af
5t
COr iTISTRY
UNIV JFORNIA
THE SILICATES
IN CHEMISTRY AND COMMERCE
THE SILICATES
IN CHEMISTRY AND COMMERCE
INCLUDING THE EXPOSITION OF A HEXITE AND
PENTITE THEORY AND OF A STEREO-CHEMICAL
THEORY OF GENERAL APPLICATION
BY
DR. W. ASCH AND DR. D. ASCH
TRANSLATED, WITH CRITICAL NOTES AND SOME ADDITIONS. BY
ALFRED B. SEARLE
AUTHOR OF "THE NATURAL HISTORY OF CLAV"
** BRITISH CLAYS, SHALES AND SANDS "
"CEMENT CONCRETE AND BRICKS" ETC. ETC.
^, R. A R Y^s>
COU.LGE Oi ;
,cn S , TY OF CM-tFORNtM
U W ' ^
'-
NEW YORK
D. VAN NOSTRAND CO.
TWENTY-FIVE PARK PLACE
1914
.
*
CONTENTS
INTKODUCTION
PAGE
The Chemistry of Carbon and Silicon . . . . . 1
SECTION I.
Historical Review of Existing Theories concerning the Constitution of
the Aluminosilicates and other Silicates . . 3
The theories of Berzelius, Smithson, and Dobereiner. The theories of
Wartha, Haushofer, Safarik. Tschermak's Felspar Theory. The concep-
tion of the acid nature of aluminosilicates by Bonsdorff, Scheerer, Ber-
zelius, Bodecker, Odling, Wartha, and Brauns. The acid nature of alumina
in aluminosilicates according to Vernadsky and the attempts made by
him to devise a general Chemical System of aluminosilicates. Modern
theories of aluminosilicates, including those of Rammelsberg, Groth,
Clarke, Tschermak, Sawtschenko, Goldschmidt, BombiccL Brauns, Mellor
and Holdcroft, Vernadsky, Pukall, Morozewicz and Dalkuhara.
SECTION II.
Critical Examination of Existing Theories concerning Alumino-silicates
Are the aluminosilicates salts of the silicic acids ? Are the alumino-
silicates double salts ? Are the aluminosilicates molecular combinations ?
Are the aluminosilicates isomorphous mixtures ? Are the alumino-
silicates complex acids or the salts of such acids ? The chemical nature
of the complex acids and their salts as shown by chemical and physio-
chemical investigations. Ostwald's definition of double salts and com-
plexes and the behaviour of silico-molybdates and sulpho-molybdates in
aqueous solutions. The course of reaction in the formation of complex
acids according to Blomstrand and Friedheim. The disadvantages of Blom-
strand and Friedheim's theories. The facts for and against the complex
nature of the aluminosilicates. The results which follow from the various
theories concerning aluminosilicates. Clarke's formulas for alumino-
silicates. The constitution of Phakelite according to Groth, Rammels-
berg, Thugutt, and Vernadsky. The constitution of Potash Felspar
according to Tschermak, Groth, Clarke, Thugutt, Rammelsberg, Wartha,
Vernadsky, Zulkowski, Haushofer and Mellor and Holdcroft. The results
of the foregoing critical examination and the possibility that the opposi-
tion of some hypotheses to the complex nature of the aluminosilicates is
only superficial.
SECTION III.
A Hypothesis concerning the Bonding of the Atoms in Aluminosilicates
and Allied Compounds . . . .. . .30
Two new radicals Hexite and Pentite. A structural chemical representa-
tion of the complex aluminosilicic acids and their anhydrides based on
the use of hexite and pentite radicals of silicon and aluminium.
viii CONTENTS
PAGE
The Consequences of the "Hexite-Pentite Theory," and the Facts . 38
I. The Reactions during Double Decomposition . . 38
Lemberg's researches.
II. The Genetic Relationship between the various Aluminosilicates 40
The researches of Lemberg, Thugutt, and Friedel. The Pseudomor-
phous processes. Table showing the changes observable in alumino-
silicates in nature.
III. The Possibility of a Chemical System of Aluminosilicates 47
The Clintonite group. The Mica group. The Scapolite group. The
Orthochlorite group. The Tourmaline group. The Felspars.
IV. The Variable Chemical Behaviour of part of the Aluminium in
Kaolin, Nepheline, and in the Epidotes . . 51
The variable chemical behaviour of part of the hydroxyl in the Topazes
and of the aluminium in the Granites.
V. The Minimum Molecular Weight of Aluminosilicates . 56
The minimum molecular weight of aluminosilicate in connection with
Lemberg's researches. The minimum molecular weight in connection
with Thugutt's work on potash, felspar, the mesolites, and the sodalites.
VI. The Constitution of Andesite . . ,- . . 62
VII. The Possibility of Isomerism . . . 63
Basic Isomerism. Ring Isomerism. Isomerism in potash and soda
felspars. Two isomeric sodalites.
VIII. Water of Crystallisation and of Constitution; Basic and Acid
Water . . . . . 65
The structural formulae of the Zeolites : Laumontite, Thomsonite,
Hydronephelite, Heulandite, Epistilbite, Stilbite, Faujasite, Scoleszites,
Foresite and Natrolite, etc., according to Clarke, Friedel, Mallard,
Rhine, Damour, Sommerfeldt, van Bemmelen, Doelter, Henry, and
others.
IX. Prognoses . . . . 73
Base Prognoses. Ring Prognoses. The theoretically possible Arden-
nites. The theoretically possible Sapphirines. The structure of How-
lite, Avasite, Milarite, Ptiolite, and Mordennite.
X. The Constitution of the Complexes of Molybdenum and Tungsten 78
a- and /3-Complexes of Molybdenum and Tungsten. Evidence in sup-
port of the structural chemical representation of molybdic and tungstic
complexes. The results of researches by Friedheim and his associates.
The action of molybdic acid on various vanadates and of vanadates on
molybdates. The action of molybdic acid on various phosphates.
The action of molybdic acid on arsenates. The genetic relationship
between the various vanadinomolybdates. The most stable types of
vanadinomolybdates and aluminosilicates. The genetic relationship
between a- and /S-phospho-molybdo complexes. The genetic relation-
ship between the arseno-molybdates. The different behaviour of the
compounds 2 R 2 O V 2 O 5 4 WO 3 and 4 R 2 O 3 V 2 O 6 12 WO 3 to-
wards acids in the light of Friedheim's and the Hexite-Pentite theories.
The constitution of "the Silicotungstates. The isomeric silicotungstic
acids and silicotungstates. The dimorphism of the potash salt K 2 O
2 H 2 O SiO 2 12 WO 9 7 H 2 O in the light of the Hexite-Pentite theory.
CONTENTS ix
PAGE
Systematic Review of a Series of /3-Complexes of Molybdenum and
Tungsten . . . . . ... 96
Aluminomolybdates R 2 O A1 2 O 3 10 MoO 3 . Borotungstates 2 R 2 O
B 2 O 3 10 WO 8 . Silicotungstates 4 R 2 O SiO 2 10 WO 3 . Platino-
molybdates 4 R 2 O PtO, 10 MoO 3 . Platinotungstates 4 R 2 O PtO 2
10 WO 3 . Alummomolybdates 3 R 2 O - A1 2 O 3 . 12 MoO 3 . Chromomolyb-
dates 3 R 2 O Cr 2 O 3 12 MoO,. Borotungstates 4 R 2 O B,,O 3 . 12 WO 3
Silicomolybrlates 2 R 2 O SiO, 12 MoO s . Silicomolybdates 4 R 2
SiO 2 12 MoO 3 . Silicotungstates 4 R 2 O SiO 2 12 WO 8 . Zirkono-
molybdates 2 R 2 O ZrO 2 12 MoO,. Titanomolybdates 2 R 2 O TiO 2
12 MoO 3 . Phosphotungstates 2 R 2 O P 2 O 5 12 WO 3 . lodomolybdates
5 R 2 O I 2 O 7 12 MoO 3 . Phosphomolybdates R 2 O* P 2 O 5 15 MoO,.
Manganomolybdates o R 2 O Mn O 3 16 MoO 3 . Phosphomolybdates
3 R 2 O P O 5 16 MoO*. Phosphotungstates 6 R O P 2 O 5 16 WO 3 .
Phosphomolybdates 3 R 2 O P ? O 5 18 MoO E . Phosphotungstates 6 R 2 6-
P 2 O 5 18 WO 3 . Arsenomolybdates 6 R 2 6 As 2 O 5 18 MoO 3 . Phos-
phomolybdates 7 R 2 O P 2 O 5 20 MoO 3 . Phosphotungstates 6 R 2 O
P 2 O 5 20 WO 3 . Arsenomolybdates 3 R 2 O AsoO 5 20 MoO 3 . Phos-
phomolybdates 7 RoO PO, 22 WO 3 . Phosphomolybdates 6 R 2 O
Pj,O 8 24 MoO s . Phosphotungstates 3 R 2 O P 2 O 5 - 24 WO a .
XI. The Constitution of Clays . . ... 102
The theoretically possible aluminosilicic acids. Hydrates and An-
hydrides. Isomeric aluminosilicic acids. Water of crystallisation and
of constitution. The minerals of the Allophane group as examples of
hydro-aluminosilicates. The water of crystallisation and of constitu-
tion in the minerals of the Allophane group. The maximum of water
of constitution in minerals of the Allophane group. Formulation of a
series of analyses of washed clays. The acid character of the clays shown
by their chemical properties. The unitary nature of clays according to
C. Mene. The behaviour of clays towards concentrated sulphuric acid.
" Clay substance." The constitution of clays according to Forch-
hammer. The value of " rational analyses " according to Mellor and
Holdcroft, Seger, Brongniart, and Malaguti. Definition of " disdyna-
mtsed " and " dynamised " substances. Vitrification of clays. Second-
ary valencies of oxygen in clays. Effect of heat on clay, according to
Rieke, and Mellor and Holdcroft. Polymerisation of Alumina. The
chemical changes occurring in the burning of clays. Isomerism and
Polymerism of Kaolin. The H.P. theory and the Facts. Pukall's re-
searches on Kaolin. The behaviour of Pukall's sodium s-kaolinates to-
wards carbonic acid and towards hydrochloric acid. Mellor and Hold-
croft's researches on Kaolin. The melting point of clays and other
aluminosilicates. Relation between Melting Point and Composition
of Clays. Mineralisers. Plasticity. A new theory of plasticity. The
Colour of Bricks.
XII. Ultramarines . . . < . . . . 136
Historical Review. A new theory of the ultramarines. Two kinds of
hydroxyls in hydro-aluminosilicates of the type H 12 H 4 (Si Al
Al Si), viz. a and s-hydroxyls. The replaceability of hydrogen in the
a-hydroxyls by acid residues. The curious property of the compounds
Na 8 H 4 (Si Al Al Si) discovered by Silber. The ultramarines as
A- and 2-aluminosilicates. The role of the group S.,O 7 in ultra-
marines. Sulphonates. The Sulphonates as Chromophores. The
changes in the intensity of colour (Schiitz). The relationship between
colour and constitution (R. Nietzki and others). The Hexite-Pentite
Theory of Ultramarines and the facts. Theoretically possible ultra-
marines. New formulse calculated from analyses of ultramarines.
Aluminosilicates from which ultramarine cannot be made. Ultra-
marines of different colours, and their constitutions. Isomeric ultra-
marines. The behaviour of ultramarines towards salt solutions. The
behaviour of ultramarines at high temperatures. The Sulphonate groups
A 2
: CONTENTS
PAGE
and the colour of ultramarines. The behaviour of ultramarine towards
acids. The maximum contents of base in ultramarines. The minimum
molecular weight of ultramarine compounds. The minimum molecular
weight of " Ultramarine blue," according to Guckelberger. The ultra-
marines as definite, single chemical compounds. Analogy between
ultramarines and sodalites,
XIII. A New Theory of Hydraulic Binding Materials and particularly
of Portland Cements . . . . . . 153
Critical and Historical review of existing theories. Vicat's theory.
Fuchs' theory. Winkler's theory. Feichtinger's theory. The hypo-
theses respecting free lime in Portland Cement. The influence of
Fuchs' theory on Heldt, on Chatoney and Rivot, and on the investiga-
tions made in order to ascertain the constitution of the Portland cements.
The theories of Le Chatelier, Newberry Bros., Kosmann, Jex, Erd-
menger, Hardt, Schonaich-Carolath, Schott, Zsigmondy, Meyer-
Mahlstatt, and Rohland. The microscopical examination of clinker.
Portland cements as definite, single chemical compounds. The chemical
constitution of Portland cements. The role of the s-hydroxyls in the
compound H 20 (Si Al Al Si) in the synthesis of Portland cements.
Hydro- and anhydro-basic side-chains. The course of reaction in the
formation of Portland cements and the influence of the time and tem-
perature of the burning. Sintered and fused cements. The changes
which take place during the granulation of slags and the production of
slag-cements. Lunge's research on granulated and non-granulated
slags. Allen and Shepherd's criticisms. The constitution of slags. A
new theory of hardening. The new theory and the facts. The role of
" soluble " silica in the hardening of cements. The causes of hardening
of Portland cements. Zulkowski's theory of hardening. The conse-
quences of the new theory of Portland cements and the facts. New
formulae calculated from analyses of Portland cements. Stoichiometric
representation of the absorption of water by cement. Regular increase
of water-content on hydration of cements. The results of Feichtinger's
researches on certain hydraulites : silicate-water, calcium hydroxide
water, and water of crystallisation. Feichtinger's researches as evidence
for the non-existence of free lime in Portland cements. The possibility
of regenerating certain hardened cements and Feichtinger's researches
thereon. Hydration and evolution of heat. Ostwald's thermo-chemical
investigations on cements. The transition of primary types into
secondary ones in Portland cements and Feichtinger's researches thereon.
The separation of lime in hydraulites in accordance with certain stoichio-
metrical laws. The hardening power of hydraulites after removal of
definite proportions of the lime. The maximum contents of silicate-
water and calcium hydroxide water. The second setting of previously
hardened masses which have been re-ground. The cause of " soluble
silica " in hydraulites. The behaviour of hydraulites towards strong
acids. The possibility of isomerism in cements. Prognoses of the pro-
portions of chalk and clay in the Taw mixture. A new solution of the
Sea water problem. The value of cements which contain no a-hydroxyls,
especially for maritime work. Prognoses of ultramarine cements.
XIV. A New Theory of the Porcelain Cements as used for Dental
Fillings . . . . . ... 19^
The first porcelain cement (Fletcher's). The use of porcelain cements
in dentistry (Morgenstern). The chemical composition of porcelain
cements. The properties of an ideal dental stopping (Miller). The
value of a scientifically-founded theory of porcelain cements for the pro-
duction of dental stoppings. Laboratory tests on porcelain cements.
The superiority of porcelain cements over ivory and natural dental
enamel so far as resistance to acids is concerned, and the use of this in
solving the problems of the course of reaction in the hardening of such
cements. Critical review of the various theories of hardening of porce-
lain cements. The chief cause of failure of porcelain cements according
CONTENTS xi
PAGE
to Jung and Morgenstern. Kulka's, Rawitzer and Apfelstadt's theories
of hardening. Are porcelain cements single, definite chemical com-
pounds ? The composition of porcelain cements as shown by Patent
Specifications. A physio-chemical theory of the hardening of porcelain
cements. The chemical constitution of porcelain cements. The role of
the s-hydrogen in hydro-aluminosilicates in the^ synthesis of porcelain
cements. The difference between Portland and porcelain cements.
The acido- and baso-philism of aluminosilicates. The acidophilism of
the a- and s-hydrogen. The different binding power of fluorine in topazes.
The acido- and baso-philism of the artificial zeolites studied by Gans.
The amphochromatophilism of Kaolin (Hundeshagen). The acido- and
basophilism of kaolin in the production of colour lakes. The acido-
and baso-philism of kaolin as deduced from the constitution of the ultra-
marines. The physico-chemical reactions during the hardening of
porcelain cements. The A- and S-porcelain cements. The course of
hydration. The course of condensation. The constitution of the
hardened A- and S-cements. The lamellar hardening of dental cements.
The consequences of the theory and the facts. Calculation of formulae
from analyses of porcelain cements. The absorption of water during
hardening must be in stoichiometric proportions. Prognoses of silicate,
basic and crystallisation water in porcelain cements. The progressive
hydration of porcelain cements. Factors which affect the time of
hardening of porcelain cements. The high resistance of porcelain
cements to acids explained by the new theory of hardening. The toxic
action of A-cements on the dental nerve-substance (pulpa). The non-
separation of base from A-cements by the cement acid. Two kinds of
zinc phosphate cements : A- and S-zinc phosphate cements. Miller's and
Black's physiologico-chemical experiences with A- and S-zinc phosphate
cements and the consequence deducible therefrom. The hardened A-
cements as " slumbering volcanoes." Cause of neurotropy found in
alumino-phosphoric acids and Ehrlich's theory. Definition of neuro-
tropy. The facts in favour of Ehrlich's theory of the chemical nature
of toxines. The chemical relationship between nerve-fibres and alumino-
phosphoric acids. Mordanting animal fibres. Siem's and Dollken's
researches on aluminous poisons. Does the acid reaction of an aqueous
solution of a metallic salt imply hydrolysis, i.e. the presence of a free
acid ? The proof of non-hydrolysis of a series of solutions with metallic
salts with an acid reaction by means of conductivity determinations
and spectrum analysis. Practical experiences of the physiologico-chemi-
cal action of A-cements. Researches made with a view to reducing the
poisonous nature of A-porcelain cements by empirical rules and the
value of such rules. Pawels' direct proof of the poisonous action of
strong acids on the pulpa by means of experiments on animals. Tech-
nical demand for improvements in A-cements. Dental decay as the
cause of diseases of other organs. The proper method of reducing the
poisonous action of the porcelain cements containing strong acids.
Practical physiologico-chemical experience of S-cements.
XV. A New Theory of Glass, Glazes, and Porcelain . . . 236
The chemical constitution of glasses. Isomerism in glasses. Explanation
of cause of variable depression of the zero point in thermometers made
of certain glasses. y com pl exes as glasses and their useful properties.
The behaviour of glasses towards water and acids. Devitrification.
The chemical constitution of coloured glasses. Witt's theory. The
H.P. theory and the facts. Calculation of formulae from a series of
analyses of glasses, glazes, and porcelains.
XVI. The Hexite-Pentite Theory as a General Theory of Chemical
Compounds . . . . . . 255
A. The H.P. Theory and the Composition of the Metal-ammonias and
allied Chemical Compounds . . . . . . 256
The disadvantages of existing structural formulae of the metal-ammonias,
cyanides, etc., according to Kohlschiitter. Werner's theory of molecular
compounds.
xii CONTENTS
PAGE
B. The H.P. Theory and "Water of Crystallisation" . . . 259
The valency of oxygen. The molecular weight of water. Water-hexite
arid pentite. Hydro-aluminosilicates. Hydro-f'errosulphates. The
water of crystallisation in alums. The water of crystallisation in chromo-
sulphuric acids.
C. The H.P. Theory and the Dissociation Hypothesis of Arrhenius . 266
D. The H.P. Theory and the Constitution of Simple Acids . . 268
Salts offthel'acids H 2 - H 4 (PO 3 ) fi , H H 4 (PO 3 ) S , and H 12 H,(PO 3 ) 16 .
Salts of the general formula 2 Pv"O 3 Na 2 O 3 P 2 O 5 aq. Hexite for-
mation of niobic and tantalic acid. Hexite and Pentite formation of
tungstic acid. Hexite and Pentite formation of the oxygen free acids.
E. The H.P. Theory and the Carbon Compounds . . . 271
Carbon and Silicon Hexites and Pentites devoid of oxygen. Chromium
hexites.
F. The H.P. Theory and the Constitution of the Chemical Atoms :
The Archid Hypothesis . . .. . . 273
The consequences of the Archid Hypothesis and the Facts.
(a) The Valencies of the chemical atoms. Atoms with constant and
variable valencies. The valency of nitrogen. The valency of
carbon. The minor valencies of carbon.
(6) Homologous series of atoms,
(c) The cause of radio-activity and the work of the alchemists.
SECTION IV.
The Conversion of the H.P. Theory into a Stereo-chemical Theory and
the Combination of the latter with the Modern Theory of the Structure
of Crystals ... . .281
(a) Critical Review of Existing Stereo-chemical Theories . . 281
The Hypotheses of van't Hoff and Le Bel. The stereo-chemical theories
of Wernerv-and Hantzsch, Schrauf, Fock, Groth, Hunt, Tutton, Herz,
Doelter and Vufriik, Vogt, van't Hoft', and Becke.
(6) The Modern Theory of the Structure of Crystals and the Possi-
bility of Combinations of the same with Structural Chemical
Theories ..... . 285
(c) Stereo-hexites and pentites, or a Stereo-chemical Theory . . 286
(d) The Hexite-Pentite Law . . . . . 289
(e) Combination of the Stereo-Hexite-Pentite Theory with Modern
Theory of Structure of Crystals . . . 289
(/) The Stereo-Hexite-Pentite Theory and the Facts . . 290
A. Dimorphism and Polymorphism and Hauy's Law r . . 290
The cause of dimorphism in compounds with the empirical formula FeS 2 .
Discussion between Berthollet and Hauy. Mitscherlich on Hauy's law.
Geuther's representation of the dimorphism of CaCO 3 . Lehmann on
Hauy's law.
B. Isomorphism in the Light of the S. H.P. Theory . . . 294
The geometric constants of isomorphous compounds. The isomorphism
of minerals of the Felspar group and Tschermak's theory. Schuster's
optical examination of plagioclase. The structure of albite and anorthite
CONTENTS xiii
PAGE
according to Clarke and Groth. Isomorphism and the theories of Jannasch
and Clarke. The structure of felspars in the light of the H.P. theory.
The cause of isomorphism in various groups of silicates according to
Retgers. The influence of Tschermak's felspar theory on the structural
representation of chemical compounds. Fock's mixed crystals of the
ammonium salt (NH 4 ) 2 O S 2 O 5 H H 2 O with salts of the general formula
R"O S 2 O 5 i H 2 O. Rammelsberg's protest against the general applica-
tion of Tschermak's felspar theory. The theories of isomorphous mixtures
and the facts opposed to it. Retgers' attempt to produce mixed crystals
from the salts KH 2 PO 4 and (NH 4 )H 2 PO 4 . Tammann's researches on
hexa- penta- and the 16-phosphoric acids. Isomorphism of minerals of
the epidote group. Sehultze's research on the production of mixed crystals
from PbMoO 4 and PbCrO 4 . Berthollet's views and the theory of isomor-
phous mixtures. The discussion between Proust and Berthollet and the
result of modern work.
C. The Dependence of the Geometric Constants on the Side-chains . 305
The influence of the water of crystallisation in the form of crystals. The
crystalline forms of urano-acetate according to Rammelsberg and to the
S.H.P. Theory. Muthmann and Becke's topical parameter and the dis-
tance of molecules from each other in a crystal. The influence of the side-
chains on the crystalline form of benzene derivatives, according to Groth.
The Structural Formula of Benzene according to the S.H.P. Theory . 309
The unequal values of the six hydrogen atoms in benzene. Ladenburg's
views on the disadvantages of Kekule"'s formula for benzene. Glaus'
formula for benzene. Armstrong's and von Baeyer's centric formula for
benzene. The stability of benzene and hydrated benzenes in the light of
the H.P. theory. The relationship between the compounds of the aromatic
and aliphatic series.
D. The Optical Properties of Crystals and the S.H.P. Theory . . 312
The relationship between crystalline forms and physical properties.
Enantiomorphic crystals. Abnormal optical behaviour of the alums. The
cause of circular polarisation in some crystals according to Groth. The
production of circular polarisation by means of sheets of mica (Reusch).
The dependence of circular polarisation on chemical constitution. The
circular polarisation of organic compounds with asymmetric carbon atoms
according to van't Hoff and Le Bel. The optical behaviour of pure and
mixed alums according to Brauns. Sohncke's explanation of the cause of
circular polarisation. The cause of circular polarisation in the light of the
S.H.P. Theory.
E. The Dependence of the Geometrical Constants on the Temperature 316
Formation of calcite from aragonite, according to Rose and Klein. The
change in crystalline form on increase of temperature, according to Leh-
mann.
F. Molecular Volumes and the S.H.P. Theory . . 317
Summary and Conclusions . ... \ . 318
The H.P. Theory and its critics. The value of the H.P. Theory. The
value of the S.H.P. Theory. The aim of Science.
Bibliography of references mentioned in text . . . . . 328
Appendix . . . . . . . 340
Formulae and Analyses . ; v . . . 341
Formulse calculated from Lemberg's experiments. Calculation of Formu-
lae of the Topazes. Calculation of Formulae of the Epidotes. Calculation of
xiv CONTENTS
FAGE
Formulae of the Granites. Calculation of Formulae of the Mesolites. Cal-
culation of Formulae of the Clintonites. Calculation of Formulae of the
Micas. Calculation of Formulae of the Scapolites. Calculation of For-
mulae of the Orthochlorites. Calculation of Formulae of the Tourmalines.
Calculation of Formulae of the Felspars. Calculation of Formulae of Clays.
Behaviour of a Series of Dried Clays towards Sulphuric acid (Bischof).
Calculation of Formulae from analyses of Ultramarines. Calculation of
Formulae from analyses of Portland cements.
Bibliography of references in Appendix . . . . 437
PREFACE
IN the year 1903, the Faculty of Philosophy in the University of
Gottingen proposed the following thesis in connection with the
Benek Bequest :
A critical examination, based on experimental evidence, is to be made
of such chemical compounds as cannot be satisfactorily explained by the
usual means. This examination should also take into special consider-
ation the extent to which the introduction of molecular additions is of
importance in the formation of such compounds, and whether it is possible
to devise a complete systematic arrangement of such compounds.
Under the motto :
" HdvTct (0eo?) fjiTp(t) Kai apiOfjLw KOI (rraOjuLw &eTae "
the authors submitted a thesis which forms part of the present volume,
viz. pp. 1 to 102 and the Appendix. The solution of the problem was
admittedly incomplete, inasmuch as only a single branch of the subject
the silicates was taken into consideration. For this reason the
Faculty did not grant the first prize to this thesis, but readily granted
the second prize " in recognition of fruitful labours leading to a single
theory covering a very important group of complex compounds."
In this way an established theory the Hexite-Pentite Theory
was devised for one highly important group of complex compounds
the silicates.
With this theory in mind, it was only natural to apply it to a series
of silicates of technical and commercial value, such as the ultramarines,
Portland, slag, dental and other siliceous cements, glass, glazes, porce-
lain, etc., in order, if possible, to elucidate their constitution. This
has been effected since the original thesis was first written, and the
results are published in the following pages.
Commencing with the assumption that Nature has formed all sub-
stances in accordance with monistic laws, the Hexite-Pentite Theory
has also been applied to the study of the structure of other complexes
as well as to that of solutions of the simpler acids, etc., and it has also
been employed, in connection with the constitution of organic com-
pounds, to form a bridge between organic and inorganic chemistry.
XV
xvi PREFACE
In order to take into consideration the positions which atoms occupy
in space (a factor which is omitted from most theories of chemical
structure) the Hexite-Pentite Theory has also been developed, in
combination with the modern theory of the structure of crystals, into
a stereo-chemical theory.
The German edition of this work was published late in 1911, but for
some unexplained reason almost every reviewer of that edition failed
to appreciate the advantages which may be derived from this theory,
and with a few exceptions they have overlooked the fact that the
Hexite-Pentite Theory as distinct from older ones is concerned
especially with inorganic chemistry, and that it has the following
characteristics :
The Hexite-Pentite Theory is a general and unitary theory ; it is
based on a single truth i.e. on a natural law found by inductive
reasoning ; it leads par excellence to prognoses, and therefore permits
of deductive reasoning the combination being a clear sign of a true
theory and it is, in addition, based on the methods of the most
famous classical chemists. Moreover, it comprehends the best of the
existing theories or explains their deficiencies, and is, above all, a
definitely stereo-chemical theory.
To enter into a complete reply to the various critics would occupy
too much space in the present volume, and as the publication of the
present edition has occupied more than a year on account of the
additional matter required much of which is due to the kind sug-
gestions of the translator the authors have decided to publish the
greater part of their reply to critics in a separate volume to be issued
shortly under the title " The Structure of Matter." At the same time it
will be noted that the chief criticisms have been met in the present
edition, though the following are conveniently noted in the Preface
rather than in the text.
A number of critics adopt the remarkable view that the compre-
hensiveness and unitary nature of the Hexite-Pentite Theory are a
disadvantage ! This is specially the case with C. H. Desch 736 ,
Allen and Shepherd 737 , C. Doelter (" Handb. d. Mineralchemie "). Yet
comprehensiveness and unitary nature are essential characteristics of
any general theory. No less an authority than Berthollet has declared
that the advantage of a general over a special theory is that the former
has certain characteristics, which are precisely the ones possessed by
the Hexite-Pentite Theory. In Gmellin-Kraut's " Handb uch " and other
classical text-books it is admitted that the object of investigation is
to produce a complete theory of chemistry from which all natural laws
affecting chemical reactions can be predicted or explained. In short,
PREFACE
xvn
the comprehensiveness of the Hexite-Pentite Theory is a positive
advantage and an indication of its truth.
The earliest opponents to a unitary nature or monism in chemistry
were the French investigators Laurent and Gerhardt. Mendelejeff and
his associates, on the contrary, are in favour of a monistic theory.
Blomstrand, Ostwald, Nernst, Markownikoff and many other well-
known chemists have often pointed out the fallacy of the conception
of the existence of molecular compounds, and these scientists are
therefore in favour of a unitary view. One of the reasons why a portion
of the present work was granted a prize by the Faculty of the Univer-
sity of Gottingen was that in it the investigation leads to a unitary
conception of the silicates.
One of the most valuable features of the Hexite-Pentite Theory is
that it effectively disposes of the necessity for any dualistic conception
of matter.
The classification of matter into chemical compounds and the so-
called isomorphous mixtures or solid solutions, as is so commonly done
at the present time, leads to the conclusion that there are some excep-
tions to natural laws. Yet when an exception is found to a natural
law this is only an indication that the terms in which the law is ex-
pressed must be altered so that it may include the apparent exception.
Where this cannot be done the " law " must be regarded as imperfectly
understood. As Spinoza has remarked, " No sane man will believe
that Nature is limited in her powers and that natural laws are of limited
and not of general application." The correctness of Spinoza's teaching
is clearly shown by the small results which have been obtained from
the application of the dualistic or pluralistic theory of matter, i.e. by
regarding certain complex compounds as mixtures. Thus, W. J.
Miiller and J. Konigsberger 779 , in studying the work of Day and his
associates in Washington and of Doelter in Vienna, point out that
notwithstanding the skill and expense involved, " the results of these
investigations do not appear to be commensurate with the labour
involved." Miiller and Konigsberger attribute this to the absence of
analogy between the materials investigated and those used in other
branches of chemistry, but the Hexite-Pentite Theory shows that there
is an abundance of analogies, and that the true reason for the paucity
of results of theoretical value from the Washington and Vienna Insti-
tutes is to be found in the erroneous pluralistic view of matter which
is held by those in charge.
The constitution of Portland cement has been the subject of investi-
gation for nearly a century, without any definitely satisfactory result.
This is due to precisely the same cause the persistent maintenance
xviii PREFACE
of a pluralistic or mixture theory and the neglect or repression of all
information or suggestions to the contrary. The attitude of many
supporters of the mixture theories of Portland cements is far from
scientific, and notwithstanding the abundance of proof of a chemical
nature in favour of the Hexite-Pentite Theory, those in favour of a
pluralistic conception of chemical substances still pin their faith to the
very slender microscopical evidence on which their theories are based.
One extraordinary " result " of following out the mixture theory in
the case of Portland cement is in the experience of two French engineers
Chatony and Rivot (see p. 156 in the text) at whose instance
extensive maritime works were constructed. The panic amongst
French and other constructional engineers which resulted from the
destruction of these structures can better be imagined than described !
The pluralistic conception of chemical substances has also been the
cause of a number of serious accidents and bad results in medical
chemistry. Thus, in the opinion of the authors, the pathology of many
diseases such as diabetes, cancer, tuberculosis, etc., must remain very
incomplete, and the nature and causes of these complaints must be
completely misunderstood, so long as the pluralistic conception of
matter is maintained. An interesting example of this is found in the
toxic action of certain dental stoppings which are fully described in
the following pages. So firmly has the mixture theory been held that
the opposition to these toxic cements was almost devoid of results, and
this theory still exerts a considerable amount of influence, notwith-
standing the fact that the authors have not merely shown the causes
of the toxic action, but the way to prevent it, and have placed perfectly
satisfactory and non-poisonous dental cements, made in accordance
with the Hexite-Pentite Theory, on the market. The continued
maintenance of the pluralistic conception of matter in medicine
is, therefore, even more dangerous than it is in industry.
Among the various critics, it is pleasing to turn from those who have
reviewed the first edition of this book in a careless or partial manner
to greater scientists like Wilhelm Ostwald 780 , who states, " The
authors commenced with an explanation of the constitution of the
clays and allied substances, but passed on from one branch of chemistry
to another until they have eventually been able to illuminate an
astonishingly large number of different facts, all of which are regarded
from the same point of view." That so able a chemist as Ostwald should
describe the present work in such glowing terms is particularly gratify-
ing to the authors, more especially as Ostwald had the opportunity, as
a student of Lemberg's, of knowing the remarkable pains which
Lemberg took in the prosecution of his investigations studies which
PREFACE
xix
have proved invaluable as a source of experimental evidence with
which the Hexite-Pentite Theory is in complete agreement. Ostwald
even goes so far as to state that " as an observer for many years of the
production and development of many scientific theories and works I
cannot avoid declaring the present one as most unusual. Let us give
a hearty welcome to these young and energetic investigators and assure
them that the further results of their work will be watched with the
greatest interest."
In this connection it is interesting to recall the regret which Landolt
expressed that his friend Kekule did not live long enough to see this
new triumph of his Benzene Theory, for the Hexite-Pentite Theory
may be very definitely regarded as an extension and development of
the Dalton-Kekule teaching. In a letter, Landolt also expressed his
definite opinion that, sooner or later, the Hexite-Pentite Theory must
be taken up by chemists in every branch of the subject. The remark-
able results which followed the synthesis of various scents, anaesthetics,
dyes, etc. all of which are primarily due to the Kekule Theory are
strong evidence in favour of the Hexite-Pentite Theory, for Kekule's
theory is essentially a part of the Hexite-Pentite Theory.
Ehrlich's Side-chain Theory is, in a similar manner, another part
of the Hexite-Pentite Theory, and the enormous value of Ehrlich's
theory in physiological chemistry is already recognised by specialists
in this subject. .
It is also interesting to observe that the facts which have led to the
Guldberg-Waage Theory are also direct consequences of the Hexite-
Pentite Theory.
Even Newton's law of gravitation has an interesting connection
with the Hexite-Pentite Theory.
The subject of colloids, which is attracting a large amount of
attention at the present time, is exceptionally well illuminated by the
Hexite-Pentite Theory, and the authors had intended to include a
considerable amount of information on this subject in the present work.
The amount of space occupied would be so great as to make the present
volume inconveniently large, however, and would so seriously delay
its publication that this subject must be dealt with in a subsequent
volume. The reader's attention is, however, called to the subjects of
cements and coloured glasses discussed somewhat fully in the present
volume for hitherto the constitution of these has usually been ex-
plained in terms of colloids. Such an explanation is highly individual-
istic and cannot be applied to cements or glasses as a whole, so that
it cannot be regarded as a really scientific hypothesis. By means of
the Hexite-Pentite Theory, on the contrary, the cause of the colour of
xx PREFACE
certain glasses is explained in a manner precisely analogous to that in
certain coloured organic compounds, wherein the colour is known to
be due to the arrangement of the atoms.
In preparing this English edition, the authors have had the inestim-
able advantage of the assistance of a well-known authority on clays
and other silicates, and they hereby wish to express their indebtedness
to him, not only for the manner in which he has executed the transla-
tion, but also for his kindness in making numerous and valuable
suggestions and criticisms and for the various additions (printed in
smaller type for their better distinction) due to his special knowledge
of the subject.
THE AUTHORS.
July, 1913.
THE
SILICATES.
Introduction
The Chemistry of Carbon and Silicon
THE remark has frequently been made that, whilst the study of
carbon compounds has reached a high state of development,
comparatively little attention has been paid to that of other elements.
A large number of chemists are engaged in studying the chemistry of
carbon because the methods of investigation have been worked out
more thoroughly than those for other elements ; because the inter-
pretation of the results is clearer, and because many carbon com-
pounds, such as the organic dyestufTs and more recently the artificial
scents, have proved to be of enormous technical value.
The majority of chemical theories put forward in recent years are
based on the characteristics of carbon compounds and are modified,
abandoned, or again become generally recognised, without the chemis-
try of other elements having any appreciable influence upon them.
There can be little doubt that if the study of other elements had
reached as high a state of development as that of carbon, not a few
facts would have been discovered which would lead to other constitu-
tional formulae and to fresh hypotheses and theories ; it is, indeed,
probable that at least as many new laws would be formulated as have
resulted from the widespread investigation of the chemistry of carbon.
These additional laws and generalisations should be of even greater
value, inasmuch as they would be based upon a wider knowledge.
Many industries should derive considerable benefit from the results
of a more thorough study of inorganic chemistry, and new products
or even new industries would probably result. The carbide industry
and that of the rare earths owe their existence to an increased study
of this branch of chemistry. Other industries such as those concerned
in the production of artificial gems, inorganic colours, the manu-
facture or employment of cement, clay, ultramarine, glass, etc. are
capable of extensive development through the application of scientific
investigation to the materials used in them.
Whilst carbon has a special interest on account of its being the
2 INTRODUCTION
essential constituent of all organic substances, its analogue, silicon,
should be no less interesting as it forms the chief material in the earth's
crust. It probably plays a far more important part in the natural
processes of the inorganic world than carbon does in the realm of
organic substances. A moment's thought will show the immense
variety of chemical reactions and the enormous scale on which they
occur in the upper layers of our planet. The form of the earth's
surface, the character of the mountain ranges, volcanic eruptions and
the phenomena of solution and decomposition are all related to such
characteristics of the widely distributed aluminosilicates as their
hardness, fusibility, heat-conductivity, resistance to pressure, etc.
These characteristics are closely related to the composition and the
chemical nature of the elements concerned, particularly silicon. How
great an interest a knowledge of the structure of these compounds
possesses, is shown by the manner in which mineralogists and chemists
study the crystallographic, physical and chemical properties of rocks
and by the great variety of theories which have been formulated in
order to give some idea of the constitution of these remarkable com-
pounds.
In spite of great intellectual effort and innumerable experiments
only a small proportion of which have been published which have
been made to draw this subject from its obscurity, little progress has
been made, and the silicon compounds, in spite of the fact that they
occur in enormous quantities and are most widely distributed, must
be included amongst those substances of whose constitution very
little is known.
For this reason it is thought that a fresh attempt to illuminate
this subject by investigating it in a purely experimental manner, as
distinct from the more theoretical considerations of other scientists,
may not be without value.
HISTORICAL SURVEY OF EXISTING THEORIES
Section I
Historical Survey of the various Theories regarding the Constitution
of the Aluminosilicates and other Silicon Compounds
THE scientific study of the constitution of the silicates commenced
in the first decade of the nineteenth century when Berzelius 1 *
Smithson 2 and Dobereiner 3 simultaneously (1811) regarded the
silicates as salts of silicic acid or silica. Previous to this, the role played
by silica was, in spite of the researches by Bergemann, Klaproth,
etc., far from clearly understood. The silicates were regarded as
complex mixtures of various oxides and as peculiar substances quite
distinct from other salts. Very few suggestions as to their true character
can be found in the earlier literature ; they remained outside the general
development of scientific knowledge, as Tachenius who regarded the
silicates as salts of silicic acid endeavoured to show in the seventeenth
century. 4
Although the suggestion that the silicates are salts of silicic acid or
silica was made simultaneously and independently by Berzelius,
Smithson and Dobereiner, as already mentioned, the chief credit
must be given to Berzelius ; Smithson contented himself with stating
that minerals do not differ from artificially prepared compounds,
and that the composition of the silicates can only be understood by
regarding them as salts, and quartz as an acid.
Dobereiner 5 worked on purely speculative lines, and argued that
as silica forms salts with bases, the oxide of silicon, Si0 2 , should be
termed " silicic acid." f
Berzelius expressed himself much less decidedly, though his meaning
was equally clear. 6 He stated that when two oxides combined, one
must be regarded as electro-negative, and suggested that the nomen-
clature of such oxides could be distinguished from that of the salts.
Several years later he classified silica compounds into bi-silicates, tri-
silicates, etc. according to the proportion of oxygen in the silica and
the base, and made some very clear suggestions regarding the formation
* References to authorities are given in the Bibliography at the end of this volume.
f The term suggested by Dobereiner, viz. " Kieselsaure/' is that used in
Germany at the present day, there being no exact equivalent in German to the English
word " silica." The word " Kieselsaure " thus represents both " silica " and " silicic
acid," the latter term expressing its meaning exactly, though seldom used excpet where
the acid nature of the substance is specially under consideration. A. B. S.
4 HISTORICAL SURVEY OF EXISTING THEORIES
of the complicated salts of silica. At that time he was so convinced of
the acid nature of silica that he believed that no mineralogist
acquainted with the chemistry of the period could have the slightest
doubt that silica was a true acid. He maintained as Smithson had
done before him that double salts existed in silicates containing
A1 2 3 and Fe 2 3 , and pointed out the analogous nature of the alums
in which silica is replaced by sulphuric acid. He also regarded the
spinels as salts in which A1 2 O 3 plays the part of an acid. These sug-
gestions were at once accepted by scientists.
By great industry, Berzelius largely extended our knowledge
of silicates. The discovery of isomorphism by Mitscherlich and the
investigations of Bonsdorff and Rose two pupils of Berzelius con-
firmed their master's theories and made it possible to provide simple
formulae for a number of silicates.
Through the use of a formula which for silica was written as
Si0 3 , Si0 2 , or SiO a great simplification occurred, though for the
silicates as a whole the expression of the results of chemical analyses
by formulae did not fulfil expectations. 7
In 1846 Laurent 8 suggested that the silicates are not salts of a
single, but of several silicates. He had proved the existence of several
tungstic acids and presumed the existence of several silicic acids of
different chemical compositions analogous to ortho- and meta-phos-
phoric acid. This hypothesis was accepted by scientists as soon as the
value of the " Type theory " had become generally recognised. Be-
tween 1855 and 1865 it was in great favour, and it is still held by some
chemists. About the time mentioned, Fremy's work on tin-acids was
published, and from this arose the idea of poly-silicic acids and anhy-
drides, which was readily adopted. This hypothesis has been pub-
lished at various times and from various points of view by Fremy 9 , St.
Hunt 10 , and Wurtz 11 , its clearest and most accurate form being due
to Wurtz. Various modifications of it have been used in theoretical
investigations by several scientific writers with greater or less effect,
and there is in existence a long series of treatises, each more or less
independent of the others, forming complex combinations of old and
new work, by Woltzien 12 , Golowkinski 13 , Odling 14 , Streng 15 , Lawrow 16 ,
Schiff 17 , Bodecker 18 , Stadeler 19 , and others. The chief result of all
these researches is to indicate that the theories put forward do not
de facto suffice to render the constitution of the silicates clear. So
far as they are concerned, the problem remains unsolved in spite of
the large amount of work done in connection with it.
A great advance was made by Damours 20 , who was the first to
suggest that the water in many silicates is of the nature of " water of
constitution," i.e. it is an integral ingredient of the salt (silicate)
itself. The importance of this observation was pointed out by Lau-
rent 21 , Bodecker 22 , and Rammelsberg 23 , and its application has greatly
increased the significance of the formulae of many silicates. More
recently, Clarke 24 has endeavoured to explain the behaviour of a
HISTORICAL SURVEY OF EXISTING THEORIES 5
series of hydrous aluminosilicates the zeolites at high temperatures
by means of structural formulae.
Many silicate formulae have been further simplified by the employ-
ment of microscopical analysis. 25
There still remained, however, a very large number of silicates
whose constitution cannot be ascertained by means of the numerous
investigations and exact analytical methods previously mentioned.
This state of affairs naturally led to further attempts to ascertain
the constitution of the silicates, and numerous new theories were
formulated. Thus, Wartha 26 , Haushofer 27 , and Safarik 28 endeavoured
in 1873-4 to explain the chemical nature of the silicates by means of
structural formulae . These attempts, which were based on theories of
the structure of carbon compounds, did not lead to any definite result
and had no appreciable influence on the development of theories
relating to silicates.
The felspar- theory published by Tschermak 29 in the " Transactions
of the Vienna Academy," in 1865, on the contrary, was of great im-
portance, but was only accepted by scientists after it had been dis-
cussed for several years.* This theory, which assumes that some of the
felspars are formed by the mixture of two substances albite and
anorthite is well supported by a large number of analyses, and was
undoubtedly of great value at the time it was introduced. It not
only facilitated the systematisation of a large number of analyses,
but explained the relationship between certain physical characters
and the chemical composition of several silicates.
In Tschermak's theory the purely chemical functions of the
silicates are not considered ; this is its great weakness, and for this
reason this theory was only accepted by scientists for want of a better
interpretation of the results of innumerable analyses of felspars. This
difficulty existed until quite recently, for in Mineralogy there are a
number of similar theories in which the chemical characteristics of the
compounds concerned are entirely disregarded, as in the ordinary
theories of the chemical nature of Scapolite 30 , Mica 31 ' 32 , Tourma-
line 33 , etc.
Towards the end of the " 'seventies " very few ideas on the con-
stitution of silicates were promulgated, the work done at that time
being chiefly in the direction of increasing the number of observed
facts and improving the "observation material" from which conclu-
sions might be drawn with greater accuracy and safety than hitherto.
Such researches as these made it possible for Vernadsky 34 to
publish his interesting treatise on "The Sillimanite Group and the
role of Aluminium in Silicates . " A considerable time before Vernadsky,
several authorities had agreed that aluminium in silicates has the
characteristics of an acid ; some presuming the existence of complex
* Special attention is directed to Reference No. 29 in the Bibliography at the end
of this volume.
6 TSCHERMAK'S AND VERNADSKY'S THEORIES
silicoaluminic acids whilst others believed that aluminium in the
aluminosilicates plays the same role as silicon. Bonsdorf 35 , as the re-
sult of investigations on hornblendes containing alumina in which
the proportions of Si0 2 and A1 2 3 vary, reached the conclusion that
silicon and aluminium each play the same role. Scheerer 36 confirmed
this view of Bonsdorff's. The view that aluminium in the natural
silicates has an acid character was also held by Berzelius 37 , Bodecker 38 ,
arid Odling 39 .
Wartha 40 was the first to publish this hypothesis in a clear form,
but he afterwards paid more attention to structural formulae and ceased
to develop this theory. About the same time, Brauns 41 attributed an
acid character to aluminium in natural silicates, but instead of the
ordinary formula, A1 2 3 , he preferred A10 2 .
Vernadsky endeavoured to show that aluminium plays the same
role as silicon in the aluminosilicates and that from the latter complex
acids (silicoaluminic acids) may be produced. Earlier observations
and experiments on aluminosilicates and the chemical changes occur-
ring in Nature completely confirmed this view. At first, Vernadsky
sought to base a chemical classification of the aluminosilicates on his
theory, but this could be applied to only a small number of com-
pounds. Most of the aluminosilicates, such as felspar, mica, etc.,
could not be brought within any scheme he could devise, and though
he repeatedly declared that the so-called " mixture theories " have
little real value from a chemical point of view, he believed that it was
unwise to abandon them.
Vernadsky 's 42 structural formulae have consequently done little
towards solving the problem of the constitution of the silicates.
The present theories as to the constitution of aluminosilicates
appear, with the exception of that of Vernadsky, to be combinations
of older theories. The existence of various ortho-, meta-, and other
silicic and poly-silicic acids, and of simple and double salts of these, is
generally accepted, and to some extent structural formulae have been
allocated. The theories of Rammelsberg 43 , Groth 44 , Clarke 45 , Tscher-
mak 46 , and others are of this kind. Those of Sawtschenkow 47 and,
more recently, of Goldschmidt 48 , differ somewhat, as they are based
on the idea that the above-mentioned silicates cannot be explained
by the foregoing theories. The researches of Bombicci 49 and Brauns 60 ,
which are based on purely hypothetical considerations, are quite
different from those previously mentioned.
The recognition of the acid nature of clays is rapidly gaining
general acceptance. Kaolin behaves in many ways precisely like an
acid, displacing carbon dioxide in carbonates, chlorine in chlorides,
etc., and Mellor and Holdcroft 708 consider it to be aluminosilicic acid
(kaolinic acid). These writers, like Vernadsky, classify the alumino-
silicates according to the ratio of A1 2 O 3 to Si0 2 and distinguish them
as alumino-raoTio-, alumino-<fo'-, alumino-n'-, alumino-tfetfra-, alumino-
penta- and alumino-^eo:a-silicates. For instance, they regard nepheline,
MODERN THEORIES OF ALUMINOSILICATES 7
Na 2 A1 2 O 3 2 Si0 2 as a salt of an alumino-di-silicic acid ; ortho-
clase, K 2 A1 2 O 3 6 SiO 2 as a salt of an alumino-hexa-silicic acid,
etc. They also suggest constitutional formulae for these substances,
but without contributing materially to any understanding of the
constitution of the aluminosilicates, as explained later.
W. Pukall 706 ' 71 also refers to the acid nature of kaolin which,
when digested on a water-bath for several days with a solution of
caustic soda, fixes a large quantity of the soda. He has also observed
that kaolin at a temperature of about 950C. causes the evolution of
chlorine from common salt and liberates a compound corresponding
to Na 2 O A1 2 3 2 SiO 2 . Among other writers who have recently
referred to the acid nature of alumina in the aluminosilicates may be
mentioned J. Morozewicz 711 , who also regards kaolin as a complex
aluminosilicic acid.
An observation by Dalkuhara 712 is highly confirmatory of the acid
nature of alumina in the aluminosilicates. It is well known that silica
which has been precipitated from solution and afterwards well washed
is neutral to litmus. Dalkuhara has examined various hydro-silicates,
particularly clays, which are acid to litmus and observed that, not-
withstanding repeated thorough washing, these silicates completely
retained their acidity, no acid passing into the wash-water. If, how-
ever, a neutral salt such as potassium chloride, ammonium sulphate
or ammonium chloride is added to the clay a soluble acid is immedi-
ately produced, the potash or ammonia being absorbed and hydrochloric
or sulphuric acid liberated. This is important in connection with
another fact established by Dalkuhara, viz. that finely divided felspar
which he regards as a neutralised kaolin on prolonged treatment
with an aqueous solution of carbon dioxide produces an acid-reacting
silicate which behaves in a manner similar to the clays just mentioned.
Section II
Critical Survey of the Existing Theories of Aluminosilicates
HpHE following hypotheses or theories have been formulated to
JL explain the constitution of the aluminosilicates :
1. The aluminosilicates are salts of silicon hydrate in which the
hydrogen is partly replaced by aluminium and partly by other metals.
2. The aluminosilicates are double salts silicic salts of aluminium
and other metals and also isomorphous mixtures of these double
salts.
3. The aluminosilicates are molecular compounds composed of
various chemical compounds which have nothing in common as
8 CRITICAL SURVEY OF EXISTING THEORIES
regards their chemical nature. The mode of combination between
the various components is very labile.
4. The aluminosilicates are isomorphous mixtures of salts of silicic
and aluminic acids.
5. The aluminosilicates are double salts of silicic and aluminic acids,
or amorphous mixtures of these double salts.
6. The aluminosilicates are, in part, silicoaluminic acids and, in
part, the salts of these acids.
Before we criticise these theories in the light of the facts, it appears
desirable to make the following statement : The aluminosilicates
constitute a single, well-defined class of compounds, the members of
which agree in the numerous observable chemical changes which they
undergo in Nature (the so-called pseudomorphic processes) and in
those of their characteristics which are best studied in the laboratory,
such as their synthesis and their behaviour towards reagents and at
high temperatures. In these ways the aluminosilicates differ con-
siderably from silicates which are free from aluminium and other
sesquioxides. No reaction is known which makes it necessary to place
any of these compounds in a special class or to give them a special
place in a separate class. They pass into each other or form the same
compounds ; they all change slowly under the influence of geological
processes into one and the same compounds of the kaolin group. In
considering these hypotheses we must take special notice of this
phenomenon ; and in explaining the chemical nature of the com-
pounds under consideration, only those hypotheses or theories should
be employed which make it possible to indicate the composition of
these compounds in a uniform manner and to exclude those silicates
which show important differences of character. That hypothesis or
theory which agrees most closely with the facts and is free from
obvious disadvantages must be regarded as the one which approaches
nearest to the truth.
(a) Critical Examination of the First Hypothesis
According to the first hypothesis the aluminosilicates are silico-
hydrates in which one part of the hydrogen is replaced by aluminium
and another part by other metals.
This theory contradicts the following facts :
1 . The relation between aluminium and the other metals contained
in these compounds remains constant no matter how soon the reaction
of the double decomposition is interrupted.
2. No reaction is known whereby it is possible to produce a hydrate
of silicic acid from the aluminosilicates and from this hydrate to
reproduce the original substance, i.e. the aluminosilicate. The separa-
tion of silica by means of strong acids is always accompanied by a
complete destruction of the whole compound. The replacement of
the metal by hydrogen usually occurs in such a manner that only
those metals can be substituted which are capable of forming oxides of
ARE ALUMINOSILICATES SALTS OF SILICIC ACID? 9
the R"O and R' 2 type, the aluminium remaining unaffected ; from
these intermediate products which appear to be acid salts of alumin-
ium it is easy to regain the original compounds. The replacement
of aluminium by hydrogen without affecting the other metals has
not yet been accomplished.
3. No instance is known in which all the hydrogen of the hypo-
thetical silicic hydrate can be replaced by a single metal, though one
metal may be substituted for one portion of it and another metal for
the remainder. Thus, the transformation of Si Al NaO 4 into Si Na 4 4 ,
or the reverse, by means of a double decomposition is impossible.
4. If it is desired to use this hypothesis in the study of the alumino-
silicates and to apply it to all of these compounds, it is necessary to
conceive the existence of highly complex and improbable silicic
hydrates or of basic salts. Even then, this hypothesis affords no
assistance for many compounds, such as the sapphires.
5. If this hypothesis is accepted, the simple reactions which occur
with these compounds cannot be explained. For example, the trans-
formation of one aluminosilicate into another has frequently been
observed, the ratio of alumina to the R"O and R' 2 O oxides remaining
unchanged and only the ratio of silica to these oxides varying ; e.g.
reactions in which an increase or diminution of Si0 2 occurs. Such
reactions are by no means uncommon: orthoclase, K 2 0-A1 2 3 -
6Si0 2 easily passes into leucite, K 2 O A1 2 3 4Si0 2 ; and later into
muscovite, K 2 -H 2 O 2 A1 2 3 4Si0 2 . Analogous changes are the
transformation of albite into kaolin and mica ; the formation of
analcime Na 2 O A1 2 3 4Si0 2 -2H 2 from nepheline ; the conver-
sion of analcime into muscovite and the artificial production of it
from orthoclase, albite and kaolin ; the transformation of andalusite,
A1 2 3 Si0 2 into muscovite 51 ; the conversion of kaolin into analcime
by means of sodium silicate 52 , the formation of kaolin from nephe-
line 53 , the conversion of elaolite, Na 2 O A1 2 3 2Si0 2 into natrolite 54 ,
Na 2 A1 2 3 3Si0 2 2H 2 0, into analcime 55 and into hydronephe-
lite 56 , Na 2 -H 2 2A1 2 3 6Si0 2 - 2H 2 ; and in the passage of
muscovite into leucite by the action of Si0 2 in the presence of alkali
carbonates 57 . These reactions, selected from a much larger number,
are quite inexplicable by the first hypothesis.
It is, therefore, scarcely conceivable that those constitutional
formulae of the aluminosilicates which are based on the first hypothesis
are in accordance with the facts.
Recently, several mineralogists, including Brogger 58 , Clarke 59 ,
Groth 60 , endeavoured to use the first hypothesis by presuming the
existence of several complex aluminium radicles such as A1C1, A1F 2 ,
A1O, etc., which replace metals and can form RO oxides. Unfor-
tunately, no chemical reactions are known in support of this hypo-
thesis, which is entirely based on the arrangement of the silicates
according to their crystalline form.
Moreover, this modified hypothesis gives little or no explanation
10 CRITICAL SURVEY OF EXISTING THEORIES
of the constitution of the chemical compounds just mentioned, and,
all things considered, it must be admitted that the first hypothesis
does not explain the reactions to which reference has been made.
(I) Critical Examination of the Second Hypothesis
The second hypothesis (that the aluminosilicates are double salts
of aluminium and other metals and that they also comprise isomorphous
mixtures of these double salts) is one of the oldest. It was originated
by Berzelius and Smithson.
The following objections to this hypothesis require consideration :
1. Any reaction in which the proportion of silica in the compound
varies whilst the proportion of aluminium to base remains constant is
inexplicable.
2. This hypothesis requires the existence of very stable double
salts of different silicic acids, or of double salts composed of both
normal and basic salts. It cannot be said that the production of double
salts from salts of different basicity or acidity is impossible, as our
knowledge of the double salts is far from complete.
The existence of such salts is, however, highly improbable and if
this hypothesis were correct it would necessitate the placing of such
salts in a class by themselves, as, amongst all the substances which
have been investigated, no such double salts have been observed.
3. How is it possible to term compounds having the general
formula :
R 2 A1 2 3 Si0 2
double salts ? These compounds occur in Nature and may also be
prepared artificially. As naturally occurring minerals : CaO 2 A1 2 3
2 Si0 2 H 2 (Margarite 61 ) and MgO A1 2 3 SiO 2 (Prismatine 62 ) may
serve as examples of this group. Artificially prepared K 2 A1 2 O 3
Si0 2 and Na 2 O A1 2 3 Si0 2 form typical synthetic products. 63
All these compounds are closely related to compounds in other
groups ; thus K 2 A1 2 3 Si0 2 and Na 2 O A1 2 O 3 Si0 2 readily
change into K 2 O A1 2 3 2 Si0 2 and Na 2 O A1 2 O 3 2 Si0 2 respec-
tively, and inversely they may both be obtained from kaolin. 64 Mar-
garite is closely related to the micas and is not infrequently formed
from them. 65 Prismatine changes into a hydrous silicate (Krypolite)
which, according to this hypothesis, must be regarded as a double
salt and in the form of phlogopite may be obtained artificially. 66
There is clearly a genetic relationship between the various alumino-
silicates, but to regard them as double salts it would be necessary to
provide a special space in the scheme of classification, as there are
many compounds of this group (which can never be termed double
salts) for which no provision is made.
4. The fact that compounds which, from the point of view of those
who accept this hypothesis, are very complex in structure are found
ARE ALUMINOSILICATES DOUBLE SALTS? 11
on experiment to be very stable, is puzzling. Thus the group R 2 O
A1 2 O 3 2 SiO 2 , into which practically all other aluminosilicates may
be readily converted, is characterised by its exceptional stability.
Those who accept this hypothesis regard the compounds of this group
as double salts, having the general formula :
3 + Al 2 Si0 5 or R' 2 Si0 3 -f R' 6 SiO 5 ,
i.e. as normal salts of meta-silicic acid with a basic salt of some other
silicic acid. It is scarcely conceivable a priori that the representatives
of the most stable substances of the whole class of aluminosilicates
are to be found in compounds of this composition.
5. To the view that the aluminosilicates are double salts there is
also the following objection : The term "double salt " is by no means
clearly defined and gives but little definite information as to the nature
of the compounds to which it is applied. This term should, therefore,
be used more cautiously than is sometimes the case and should only
be applied to those substances of which the mode of formation from
their constituent salts is clearly ascertainable. For example, it is
quite correct to term the compound K 2 Mg(SO 4 ) 2 6 aq. a double salt,
because it can be produced directly from the two constituent salts,
K 2 S0 4 and MgSO 4 . But can such syntheses be observed in the case
of aluminosilicates ? Can any analogous reaction be found among the
innumerable compounds of silica ? The syntheses which have actually
been effected suggest the exact opposite of the second hypothesis and
are most puzzling when an attempt is made to apply it to them. No
syntheses in support of this hypothesis have yet been made.
It is impossible by this hypothesis to explain the formation of
compounds such as analcime, Na 2 A1 2 3 4 Si0 2 2 H 2 (which is
produced 67 by the action of Na 2 Si0 3 on NaA10 2 ), or of other alumino-
silicates which are obtained from silicates and aluminates. 68 In
these compounds aluminates are found, but no aluminium silicates, a
circumstance which is quite contrary to the conception of alumino-
silicates as double salts.
(c) Critical Examination of the Third Hypothesis
According to the third hypothesis, the aluminosilicates may be
regarded as molecular compounds, i.e. compounds in which the unit
of combination is a molecule and not an atom.
This conception of the constitution of natural silicates has chiefly
been favoured by Bombicci 69 and V. Goldschmidt, others only having
applied it to a few specific cases, as Mallard 70 , who used it to explain
the constitution of chondrodite.
Some silicates are undoubtedly molecular compounds, particularly
those silicates which contain water of crystallisation. Some researches
of Lemberg 71 and Doelter 72 indicate that cancrinite is a molecular
compound and other investigations by Lemberg and Thugutt lead to
12 CRITICAL REVIEW OF EXISTING THEORIES
the conclusion that the sodalites are also molecular compounds.
Other natural silicates appear to confirm this view, so that at first
sight it seems as if this hypothesis would enable the facts to be satis-
factorily explained ; in reality, the facts are in direct contradiction to
the theory. A closer investigation shows that any agreement between
fact and theory which may occur is a coincidence due to the indefinite-
ness of the latter ; this indefiniteness makes a large number of sup-
positions possible. Many facts, whilst not exactly in opposition to it,
cannot be used in support of this theory because they cannot be pre-
dicted from it. For this reason, this hypothesis has not the value of a
true scientific theory or " law of Nature," one essential feature of
which is the facilities it offers for the prediction of properties of sub-
stances from a knowledge of their constitution.
The very indefiniteness of the term "molecular compound"
allows the formulation of innumerable theories and makes it ex-
tremely difficult to decide which of these are of value and which are
merely ingenious speculations. To make this clearer it may be assumed
for the moment, that the compound
K 2 A1 2 3 6 Si0 2
is composed of two or more molecules. In selecting these there is an
enormous number of possible molecular compounds to choose from,
all of which correspond to the formula of orthoclase given above.
For instance, there are
1. K 2 Al 2 Si 2 8 + 4 Si0 2 ,
2. K 2 Si0 3 + Al 2 Si0 5 -f 4 Si0 2 ,
3. K 2 Si0 3 + Al 2 Si 3 8 + 2 Si0 2 , etc.
ad infinitum.
It is clear that from the formula for orthoclase, taken as an example,
as many different molecular compounds can be written out as there
are mathematical combinations of symbols of the elements avail-
able. If one of these hypothetical formulae is found not to repre-
sent the characteristics of the substance under consideration, a second,
third, fourth, and so on, is substituted. The matter is still further
complicated by the indefiniteness of the term " molecular compound "
as used by different writers ; an indefiniteness which enables those
who use it to indulge in all manner of speculations.
Broadly speaking, there is no definite means of deciding whether
a given substance should be regarded as a molecular or as an atomic
compound. Usually, those substances are regarded as molecular
compounds which cannot be otherwise understood, 73 the subjective
conception of each individual scientist being the factor which deter-
mines whether he will regard a given chemical compound as molecular
or atomic. Some chemists regard the so-called " double salts " as
molecular compounds, whilst others regard some of these salts as
atomic and the remainder as molecular compounds. This shows that
great caution is necessary in using these terms for the solution of
ARE ALUMINOSILICATES MOLECULAR COMPOUNDS? 13
theoretical questions. In Science, it is only in rare cases that a theory
can be used which, on account of its indefiniteness and lack of clearness,
does not possess all the requirements of a scientific hypothesis.
If aluminosilicates are molecular compounds they must show
definite properties characteristic of their constitution. This is not the
case. Molecular compounds are formed of chemical compounds of
definite composition (Molecules) and must necessarily be less stable
than atomic compounds, as the force which binds molecules together
must, naturally, be weaker than that which unites atoms to form
molecules. Under many conditions, such as solution in water, or
when under the action of heat or chemicals, molecular compounds
split up into their component molecules. Many aluminosilicates show
a high degree of stability ; some can be dissolved and afterwards con-
verted into the solid state without undergoing the least decomposition
(e.g. CaO A1 2 3 2 Si0 2 , Na 2 A1 2 3 2 Si0 2 , etc.). The decom-
position-products formed when aluminosilicates are heated are usually
complex and can, more reasonably, be termed molecular compounds.
Thus, the majority of the calcareous aluminosilicates form CaO A1 2 3
2 Si0 2 , and analogous compounds. 74 The reactions of these ap-
parent components take no part in the chemical reactions of the
aluminosilicates.
The indefiniteness of the theory here criticised and the absence of
facts in support of it show definitely that it does not suffice to give
a clear idea of the constitution of the aluminosilicates. This very
indefiniteness of the hypothesis is also a reason why it is impossible to
find many facts which can be used in direct disproof of it.
(d) Critical Examination of the Fourth and Fifth Hypotheses
According to the fourth hypothesis, aluminium and silicon both
play the part of acid-forming elements ; and the aluminosilicates are
regarded as isomorphous mixtures of aluminates and silicates. As no
facts are available which show that, in natural silicates, aluminium
plays, to some extent, the part of acid- and, to some extent, that
of a base-forming element, it may be assumed that in the silicates the
aluminium is present as aluminic acid and has not replaced part of
the hydrogen of the silicic hydrate.
This view renders the constitution of a large number of alumino-
silicates quite inexplicable, particularly those with less base than is
required by the number of hydroxyl groups of the corresponding
silicic and aluminic hydrates, e.g. K 2 A1 2 3 . 4Si0 2 , K 2 O A1 2 3
6Si0 2 . This hypothesis also fails to explain the proved forma-
tion of silicates containing alumina by the decomposition of alumino-
silicates and the invariable occurrence of alumina and silica in the
products of the reaction. Indeed, this hypothesis indicates precisely
that the contrary should be expected, viz. ready decomposition into
aluminates and silicates, as the valencies of the constituents of isomor-
14 CRITICAL REVIEW OF EXISTING THEORIES
phous mixtures (of aluminates and silicates) are naturally weaker
than those of the atoms which form the components of the mixtures.
The confirmation of this hypothesis by the synthesis of alumino-
silicates from aluminates and silicates is more apparent than real, as
the ratio of base : aluminium : silica in the products of the reaction
is quite different from that which would be found if aluminates and
silicates could form isomorphous mixtures. Thus, analcime, NaAlSi 2 6
aq. and similar substances are producible from Na 2 Si0 3 and NaA10 2 .
Moreover, it has never been proved that the salts of aluminosilicic
acids are isomorphous, and to attribute this character to them is pure
hypothesis. A similarity is often observed in the forms of crystals,
e.g. chrysoberyl and olivine, but except for this single resemblance
no evidence has been given of isomorphism. No actual observations
of isomorphous mixtures produced directly from aluminates and
silicates have ever been published.
But little importance can, therefore, be attached to the fourth
hypothesis, as it is only applicable in special cases (such as those
investigated by Rammelsberg 75 , Knop 76 , and others) and has never
been of general application to the study of the constitution of the
aluminosilicates .
The foregoing hypothesis may be somewhat modified so as to
indicate that isomorphous mixtures of aluminates and silicates and
isomorphous mixtures of double salts having aluminates and silicates
as their components, may be formed along with the aluminosilicates.
This leads directly to the fifth hypothesis. Yet, even in this form, the
facts do not agree with the theory. The invariable presence of alumin-
ium and silica appears to be inexplicable the contrary appears to
be more probable the reaction products must, if this hypothesis is
correct, contain either silicon or aluminium, but not silicon and
aluminium in one and the same product.
According to the fourth and fifth hypotheses, those aluminosilicates
which consist exclusively of Si0 2 and A1 2 3 appear to occupy a special
position, yet between them and other aluminosilicates an undoubtedly
genetic relationship is shown to exist by the ease with which they
can be transformed into one another. The first contain no alkali and
cannot, for that reason, be regarded as isomorphous mixtures or
double salts of aluminates and silicates. If, however, these substances
are to be regarded as aluminium salts of silicic acid, the alumino-
silicates must, under other circumstances or in other cases, be shown
to be so constituted that, in them, the aluminium has replaced the
water of the silicic hydrate ; yet this, if true, destroys the fourth and
fifth hypotheses. The compounds last mentioned cannot be regarded
as isomorphous mixtures of A1 2 O 3 and Si0 2 , as the isomorphism of
these compounds still remains to be proved ; moreover, the existence
of an invariably simple ratio of alumina to silica is also opposed to
such an isomorphism.
Similarly, the constitution of those aluminosilicates which contain
ARE ALUMINOSILICATES ISOMORPHOUS MIXTURES? 15
water in addition to A1 2 O 3 and Si0 2 is very puzzling if studied in
connection with these hypotheses.
Hence, the fourth and fifth hypotheses cannot be used to explain
the constitution of the aluminosilicates.
(e) Critical Examination of the Sixth Hypothesis
According to the sixth hypothesis, the aluminosilicates are com-
plex acids or the salts of complex acids. They are, therefore, analogous
to the silicotungstates, arsenomolybdates, silicomolybdates, phos-
phomolybdates, etc. All the substances just mentioned have been
placed in a new group by Wolcott Gibbs 77 , though some facts which
indicated the existence of complex acids were known long before
Gibbs' work was published.
Before making any statement as to the value of this hypothesis in
the study of the constitution of the aluminosilicates the following
questions must be clearly answered :
I. To what results do previous chemical and physico-chemical
researches on the complex acids and their salts lead, as regards their
chemical nature ?
II. What theories have been formulated with regard to the chemical
constitution of the complex acids and what is the value of these
various theories ?
With regard to the first question the following statement may be
made :
(a) The properties of the complex acids producible from a series
of acids such as tungstic, molybdic, vanadic, phosphoric, arsenic,
silicic, antimonic, and other acids by the combination of two or more
of these acids (as silicic and tungstic, phosphoric and molybdic, etc.)
in definite proportions do not completely coincide with the sum of
the properties of their components.
(b) The acidity of the complex acids is seldom equal to that of
the separate acids from which the complex one has been formed.
(c) Any given acid can usually unite in variable but simple
proportions to form several complex acids.
(d) The complex acids can exist either in the free state or as salts.
(e) When complex acids take part in a double decomposition, no
separation of the component acids occurs. The latter are found in the
new product in the same proportion as they were in the original com-
plex acid.*
(/) The conversion of one complex acid into another, composed of
the same constituent acids, is easily effected by splitting off one of the
acids in the form of a salt or in the free state. Thus, the conversion of
one phospho-tungstic acid into another is accomplished by the removal
of tungstic acid or one of its salts.
* In other words a complex acid acts as a single acid and not as a mixture of
two or more separate acids. A. B. S.
16 CRITICAL REVIEW OF EXISTING THEORIES
(g) From the corresponding anhydrides a series of complex radicles
may be produced, the ratios of the constituents of the anhydrides
being always simple.
(h) Great difficulties are experienced if such compounds as the
silicotungstates, phosphotungstates, etc. are classified in accord-
ance with Ostwald's 78 definition of double salts, and if any attempt is
made to divide true complex acids into two groups according to their
behaviour in aqueous solution. The recent physico-chemical study
of these compounds made with a view to ascertaining their constitu-
tion 79 has shown that whilst some dissociate, when in aqueous
solution, into their components, others are quite stable. The former,
according to Ostwald's classification, must be regarded as "double
salts " and the latter as " complexes." In some cases, as (1) when a
" double salt " contains alkali or (2) with certain proportions of acid
and alkali, the use of the term " double salt " is permissible. With
many of these compounds this is not the case, e.g. free acids and those
which contain a much larger proportion of one of the acids than of
the other. For instance, how is it possible to represent the free acid
3 H 2 P 2 6 24 W0 3 ,
as a double salt ? Yet the physico-chemical researches of Sobolew 80
(dialysis, electrical conductivity, etc.) have shown that in aqueous
solution it dissociates into phosphoric acid and metatungstic acid and
that its salts are equally unstable in the presence of water.
The division of the compounds under consideration into two
groups according to their behaviour when in aqueous solution does not
appear to be satisfactory. On the contrary, the experimental results
make it appear far more probable that all the compounds in this group
are of analogous constitution, though they vary in their stability when
in aqueous solution. The following facts appear to confirm this view :
1. W. Asch 776 has shown by means of a physico-chemical investiga-
tion (dialysis, electrical conductivity, determination of molecular
weight, etc.) of the silico-molybdate
2 K/ 2 SiO 2 12 Mo0 3 aq.,
that in these compounds the silicic and molybdenic acids form a
complex ion. This is confirmed by the production (by the same
investigator) of readily soluble barium and calcium salts of the same
series, having the general formula
2 R"0 Si0 2 12 MoO 3 aq. (R* = Ba, Ca),
and acid salts with a composition corresponding to :
1.5 R 2 0.5 H 2 Si0 2 12 Mo0 3 aq. (R' = K, Na).
2. D. Asch 777 has prepared compounds with the general formula
2 R 2 2 S0 2 5 Mo0 3 aq. (R' = K, Na, NH 4 ),
ARE ALUMINOSILICATES COMPLEX ACIDS OR SALTS? 17
by the action of sulphurous acid on the alkalies of the paramolybdates.
These compounds, unlike the silicomolybdates, are very unstable in
water, so that the conversion of the alkali-salts just mentioned into
the corresponding salts of the alkaline earths appears to be impossible
on account of the decomposition of the latter in water. Only by the
use of concentrated alkali-paramolybdate solutions saturated with
SO 2 gas, together with the salts of the alkaline earths, was it found
possible to prepare readily soluble salts of the alkaline earths corre-
sponding: to
2 R"O 2 S0 2 - 5 Mo0 3 aq. (R" = Ba, Sr, Ca).
Consequently, there can be no doubt that the sulphurous molyb-
dates in spite of their ready decomposition when in aqueous solution
must, on account of the manner in which they form readily soluble
salts of the alkaline earths, be regarded as salts of a complex sulpho-
molybdic acid with the formula
2 H 2 2 S0 2 5 Mo0 3 ag.
It is here assumed that the compounds under consideration may
be regarded either as free complex acids or their salts, some of these
substances being stable in aqueous solution whilst the remainder are
more or less unstable.
An answer to the questions (p. 15) concerning the previous theories
of the constitution of complex acids and their salts may now be given.
It should be observed that most investigators of these complex
acids and their salts have been content to accept the chemical com-
position without making the smallest effort to theorise on the chemical
nature of these compounds. Although the number of these substances
is somewhat large, the theories of their constitution are comparatively
few, and even these are not free from objections. Amongst them,
structural formulae are of importance and have been employed by
several investigators to indicate the chemical nature of several complex
compounds. Thus, Fremery 778 endeavoured to represent by structural
formulae the arsenotungstates he prepared. Later, Friedheim 84 ,
Blomstrand 85 , Kehrmann 86 , Sprenger 87 , Michaelis 88 and others en-
deavoured to follow Fremery's example and to apply analogous
structural formulae to quite different substances. Notwithstanding
the fact that the structural formulae of Blomstrand and Friedheim are
analogous, the theories of these two investigators are quite distinct.
Blomstrand 89 compares the ability of the acid anhydrides to com-
bine in various proportions to form complex anhydrides, with that of
those salts of cobalt, rhodium, platinum and gold which can combine
with ammonia in such a manner as to form " chains " containing
1 NH 3 to 3 NH 3 .
He suggests the following equations to show the combination of
ammonia with the metallic salts mentioned :
+ NH 3 = MNH.C1,
MCI + 2 NH 3 = MNH 3 NH 3 C1, etc.
18 CRITICAL REVIEW OF EXISTING THEORIES
He regards the formation of the following complex acids as
analogous :
OX = (OH), + OM0 2 =
OX = (OH), + 2 OM0 2 = OX<M0 2 OM0 2 OH,
etc.
He considers that what occurs is the automatic opening of the
atomic complex and the introduction of the new group, member for
member, whenever this is possible without changing the general
character of the whole substance.
Friedheim 90 regards the course of the reaction in the formation of
complex acids in an entirely different manner. For instance, he
represents the first stage of the reaction of molybdic acid on
NaH 2 As0 4 as a combination of the molybdic acid with the base^of
the arsenic salt as follows :
8 -f Mo0 3 + aq. = 2 OAs(OH) 3 + Na 2 Mo0 4
+ 2 Mo0 3 + aq. = 2 OAs(OH) 3 + Na 2 Mo 2 7 , etc.
In addition to these molybdates, acid molybdates will also pass into
solution, thus :
HO Mo0 2 ONa,
HO MoO 2 OMoO, ONa,
HO MoO a OMoO, OMo0 2 ONa, etc.
These are unstable and unite with the free arsenic acid with loss
of water :
X 0|H H0| Mo0 2 ONa
OAsr-OH
IH HO
/2P
OAs^-Q|H HO
XrkTT etc.
Mo0 2 OMo0 2 ONa
Mo0 2 OMoO, ONa,
Provided that the hydroxyl groups of the acid OX=(OH) 3 do not
split off automatically with formation of water, the hydrogen of these
hydroxyl groups may be replaced by R, the following examples being
theoretically possible :
/OMo0 2 OMo0 2 ONa
OAsf-ONa
\ONa
/OMo0 2 OMoO 2 ONa
OAs;-OMoO a OMo0 2 ONa .
\ONa etc.
The foregoing structural formulae are open to the following objec-
tions :
1 . It appears as if the acidity of the complex molybdates or tung-
states is quite independent of the amount of metallic acid (molybdic
ARE ALUMINOSILICATES COMPLEX ACIDS OR SALTS? 19
or titanic acid) in the complex and is only influenced by the atomicity
of those substances with which the metallic acids combine to form a
complex. Thus, Pufahl 91 has decomposed a compound of the series
3 R 2 As 2 5 18 Mo0 3 aq.,
with silver or thallium salts, and has produced
6 Ag 2 As 2 O 5 18 Mo0 3 aq., and
6 T1 2 O As 2 5 18 Mo0 3 aq.
These compounds contain twice as much base as is theoretically
possible.
As Friedheim writes the structural formulae of the compound
3 R 2 As 2 s 18 Mo0 3
as
As = (OMo0 2 OMo0 2 OMo0 2 OR) 3
\/
As == (OMo0 2 OMo0 2 OMoO 2 OR) 3 ,
which is analogous to the structural formula previously mentioned,
he must place the compounds with 6 R 2 in a separate class on account
of their proportion of base. He denotes the constitution of such sub-
stances as molecular, i.e. he attempts an explanation which, on account
of its confused nature, is no explanation at all.
The number of such compounds with a high proportion of base is
somewhat large and it is sufficient to mention the following :
(a) 6 R 2 As 2 5 18 MoO 3 92
(6) 4 R 2 B 2 3 12 Wo0 3 93
(c) 4 R 2 O Si0 2 12 Wo0 3 "
(d) 7 R 2 O V 2 O 5 12 WoO 3 95 , etc.
To agree with Friedheim's and Blomstrand's theory, the series (a),
(b) and (d) can at most contain 3 R 2 and (c) only 2 R 2 ! There is no
real reason for placing all these compounds in a separate class, for
neither in their properties nor in their mode of formation do they
differ from those from which the above structural formulae were
derived.
2. Another weakness of the hypotheses of Blomstrand and Fried-
heim is that they do not permit of deductions being made in connection
with the compounds of the complex acids containing the elements just
mentioned, and that the composition of only a relatively small number
of the compounds in this class can be represented structurally in the
way they suggest.
Moreover, there cannot be sufficient evidence for the proposed
structural representation, as, for the majority of these compounds,
these two investigators have been contented with the use of empirical
formulae and have not made the smallest attempt to determine thek
20 CRITICAL REVIEW OF EXISTING THEORIES
constitution. This is probably due to the complexity of many of
these compounds. Thus, no hypotheses have been formulated for
compounds containing 15, 16, 17, 20 and 22 R0 3 (R=Mo, W) to one
molecule of X 2 6 (X=As, P, Vd). Some of these compounds have
been prepared from substances to which the structural formulae apply
and their molecular arrangement is then of interest. Thus, Sprenger 96 ,
working with a barium salt of the series P 2 5 24 W0 3 and Ba(OH) 2
according to the equation
3 BaO P 2 5 24 W0 3 + 6 Ba(OH) 2
= 7 BaO P 2 5 22 W0 3 + 2 BaW0 4 + 6 H 2 0,
obtained a member of the series P 2 5 22W0 3 a reaction which
admits of no explanation in terms of the above theory !
Kehrmann and Freinkel have prepared other compounds of this
series, viz. :
1. 3 BaO 4 Ag 2 P 2 5 22 W0 3 aq, and
2. 7 K 2 O P 2 5 22 W0 3 aq.
Kehrmann 97 has also prepared from the compound 2, by means of
hydrochloric acid and potassium chloride, a crystalline substance with
the formula
5 K 2 P 2 O 5 17 W0 3 .
All these compounds, of which only a small number have been
mentioned, can only be explained with great difficulty, and in many
cases are quite inexplicable, by the above-mentioned theories of
Blomstrand and Friedheim.
3. Structural formulae are of special value when definite character-
istics of the substances they represent can be deduced from them. In
this direction the structural formulae proposed by Friedheim have not
been of much service. For instance, the compounds 98
2 R 2 - V 2 5 4 WO,, and
4 R 2 3 V 2 5 12 W0 3 ,
which are formed by the action of vanadic acid on potassium, sodium or
ammonium paratungstate, are chiefly distinguished from each other
by their characteristic behaviour towards acids. Compounds of the
type
2 R 2 O V 2 O 5 4 W0 3
liberate tungstic acid on treatment with hydrochloric acid, but no such
separation is observable, when compounds of the type
4 R 2 3 V 2 6 12 W0 3
are similarly treated.
Friedheim represents the structure of these two series as follows :
1. (2R 2 0- V.O.- 4WO 3 -Jaq.)li = J H 2 3 R 2 1J V 2 6 6 WO,
2. (4R 2 O 3 V 2 6 - 12 W0 3 ' aq.) J = J H 2 2 R 2 O 1J V 2 5 6 W0 3
ARE ALUMINOSILICATES COMPLEX ACIDS OR SALTS? 21
<
V(OWO 2 OR) 3 0V- OW0 2 OW0 2 OR
OV /O W0 2 OR OV(OW0 2 OW0 2 OR) 2
\OWO 2 OW0 2 OR
Yet from these somewhat complicated formulae it is impossible to
infer the different behaviour of these two substances to acids, and
Friedheim is again compelled to resort to a molecular representation.*
The compound 100
3 K 2 P 2 5 5 Mo0 3
appears to be an exception. It is regarded by Zenker and Blomstrand
as molecular, but as atomic by Friedheim, who represents it as
X)Mo0 2 OMo0 2 OK
OP^-OK
OP^-OK
\OMo0 2 OMo0 2 OK
This structural formula shows that one-third of the potassium
should behave differently from the remaining two-thirds. This agrees
with the behaviour of this substance towards dilute nitric acid, in
which one-third of the potassium atoms are more easily separated than
the others. This is, however, quite unusual.
Friedheim and his associates also formulated other theories re-
specting the complex acids and their salts. For instance, they sought
to explain their formation by reference to that of the double salts, 101
but this hypothesis is by no means free from objection. The facts
mentioned under h (p. 16) in the description of the general character-
istics of complex compounds are quite opposed to it, and any attempt
to apply Friedheim's hypothesis to the chief members of this group is
sure to meet with many serious difficulties and contradictions. How
is it possible, for example, to use this theory to explain the nature of
compounds containing a large proportion of anhydride such as the
previously mentioned silicomolybdate
2 R 2 Si0 2 12 Mo0 3
or the corresponding silicotungstate ? In such a case it is necessary
to assume the existence of purely hypothetical molecular compounds.
* Since the above was written Friedheim 99 has abandoned the use of the formulae
1 and 2 and now uses the atomic arrangement shown below.
22 CRITICAL REVIEW OF EXISTING THEORIES
The free acids are a source of other difficulties, for how can the
constitution of the phosphotungstic acid
3 H 2 O P 2 5 24 W0 3
be represented ?
Friedheim suggested that such free acids contain an anhydride
with the character of a base, from which it would follow that the so-
called acid is really a salt. Thus, he regarded the compound
2 H 2 O P 2 6 V 2 6
as a salt of phosphoric acid, 102 namely
0(V0 2 )
and an analogous compound,
Na 2 0-P 2 6 -2V 2 5 ,
from which the first may easily be prepared, as a double salt of a vana-
dium salt of phosphoric acid and a sodium salt of vanadic acid, viz.
R 2 O P 2 5 2 V 2 5 = R 2 V 2 O 5 + V 2 5 P 2 6 .
Such a classification is obviously confusing ; whenever the analytical
results are expressed as formulae indicative of double salts, the com-
pounds must be similarly represented, or if double salts are excluded
the formulae have another meaning and represent either molecular
compounds, whose components are hypothetical, or in the case of
free acids compounds in which one of the two anhydrides is regarded
as a base.
Summary
In summarising the arguments for and against these theories with
regard to the constitution of the aluminosilicates, it should be ob-
served that the sixth hypothesis (that the aluminosilicates are complex
acids and the salts of such acids) explains a whole series of reactions
which are quite inexplicable by the other hypotheses (with the excep-
tion of the " molecular compound " theory by which " everything "
can be explained) and that most of the best-known chemical reactions
involving aluminosilicates are in agreement with it.
It is now clear that :
1. The splitting off or addition of Si0 2 is a sign of the formation
of complex anhydrides and analogous compounds.
2. The simultaneous presence of Si0 2 and A1 2 3 in the products of
the aluminosilicates and the easy conversion of one aluminosilicate
into others are comparable to the analogous reactions of phosphotung-
states, phosphomolybdates, etc.
3. The ratio Si0 2 : A1 2 O 3 remains unaltered in reactions involving
double decomposition and that no replacement of aluminium by ele-
ments capable of forming oxides of the R"0 or R' 2 O type has been
observed.
: < 4. There is a genetic relationship between all aluminosilicates, and
that they can be converted into each other.
THE ACID NATURE OF ALUMINA 23
5. Most of the aluminosilicates are convertible into stable com-
pounds by the action of geological forces.
6. The reactions of a geological nature are analogous for all the
silicates ; those which contain no A1 2 O 3 , etc. (but are almost entirely
composed of SiO 2 ) under atmospheric influences form silicic hydrates
(opals), whilst the salts of the complex aluminosilicic acids are, under
similar conditions, converted into the hydrates of the complex alumino-
silicate radicles (kaolins).
7. Highly aluminous aluminosilicates (sapphirin) as well as those
low in alumina (petalite) are known to exist.
There is also a large number of facts indicative of the acid character
of aluminium in the aluminosilicates, as previously mentioned. In
some highly aluminous slags, salts of aluminic acid (aluminates) are
known to be formed at high temperatures, and silica appears to be
unable to displace the aluminic acid from these compounds. 103 The
simultaneous formation of salts of silica and alumina, even in the
presence of an excess of free silica, has been observed ; this fact clearly
shows that aluminium has undoubtedly a much stronger acid character
than silicon. 104
Vernadsky 713 has drawn special attention to the following facts in
support of the acid nature of alumina in the aluminosilicates :
(a) The conditions in which aluminosilicates are formed both hi
the laboratory and in Nature are precisely those which are favourable
to the production of aluminates. The minerals of the spinel group
separate from molten siliceous masses at high temperatures. A separa-
tion of aluminates from such fused materials can only be explained
on the assumption that the alumina has an acid character in such
aluminates.
(b) The separation of aluminosilicates at high temperatures is
accompanied by the formation of aluminates (according to the experi-
ments of Vernadsky and Moroziewicz spinels are formed).
(c) At much lower temperatures the action of water or carbonic
acid solution not infrequently results in the decomposition of alumino-
silicates and the separation of aluminates (vide Thugutt) or hydrated
alumina, with the formation, in Nature, of bauxite or hydrargillite.
All these reactions are opposed to the conception that alumina plays
the part of a base in the aluminosilicates.
According to Zulkowski 714 the acid nature of alumina in the
aluminosilicates explains a fact which has long been regarded as
paradoxical by metallurgists, viz. whilst it is found that one molecule
of lime effects the slagging or fusion of one molecule of silica, it is also
found that just as much lime is required when the silica is combined
with alumina. This is incomprehensible if alumina is regarded as
basic, but is readily understood if alumina plays the part of an
acid.
It should also be observed that Clarke 715 has repeatedly described
aluminosilicates as possessing an acid character, and regards the
24 CRITICAL REVIEW OF EXISTING THEORIES
tourmalines as derivatives of an acid H 14 Al 5 B 3 Si 6 31 , the water in
which may be totally replaced.
Other facts are available for showing that silica when combined
with alumina behaves in a different manner chemically from what it
does in silicates devoid of alumina, and that the aluminosilicates may
rightly be regarded as " complexes " as defined by Oswald (p. 16).
Thus:
(a) Hautefeuille 105 observed that tungstic anhydride can displace
silicic acid from its salts at 900 whilst with aluminosilicates under
similar conditions the displaced material contains both silica and
alumina and not silica alone.
(b) By the action of the hydrates of aluminosilicates on carbonates
at a high temperature, C0 2 is liberated and its place is taken by both
alumina and silica.
(c) Kaolins and other clays possess acid properties and, according
to Gorgeu and Ziemjatschewsky respectively, they can decompose
haloid salts (KI, KBr, etc.) at high and moderate temperatures, with
the liberation of free haloid (acid) and the formation of salt-like
aluminosilicates .
(d) In various chemical processes both in Nature and in the la-
boratory substitution-reactions frequently occur in which the alumino-
silicic radicle remains quite unaffected. All such reactions may be
expressed by the following equation :
MX + MjA = MiX + MA,
in which X is the anhydride of an acid, M and M 1? two different metals,
and A is the aluminosilicic radicle.
The authors who have maintained the acid character of aluminium
in the aluminosilicates and who have recognised the existence of com-
plex aluminosilicic acid in some aluminosilicates have already been
mentioned in the historical section of this volume. One of these
Zulkowski states : " I have . . . also shown that alumina possesses
the previously anticipated characteristic of forming compounds which
are not salts in the ordinary meaning of this word, but which must
be regarded as aluminosilicic acids, and that these acids must occur
in certain aluminous slags and glazes."
There are, however, some objections to the hypotheses under dis-
cussion :
(a) Although in most chemical reactions, the aluminosilicates
behave in accordance with the sixth hypothesis, there are others
which are, at present, inexplicable or are in direct contradiction to it,
as the following examples will show :
1. If the aluminosilicate known as andesite 106 ,
CaO Na 2 2 A1 2 3 8 Si0 2 ,
is regarded as a salt of an aluminosilicic acid,
2 H 8 2 A1 2 3 8 Si0 2 ,
ARE ALUMINOSILICATES COMPLEX ACIDS OR SALTS? 25
it is easy to understand the formation of analcime from andesite by
treatment with Na 2 C0 3 , which, according to Lemberg, produces the
compound
2 Na 2 2 A1 2 3 8 Si0 2 (Analcime).
It is, however, difficult to see why the same chemist could not repro-
duce andesite from analcime by means of CaCl 2 . The chief product
in the latter case appears to be
2 CaO 2 A1 2 3 8 Si0 2 .
2. By investigating the behaviour of the compound
Na 2 - A1 2 3 2 Si0 2 (Nepheline)
towards gaseous hydrochloric acid and silver salts, P. Silber 107 has
shown that only one-third of the sodium is given up to gaseous hydro-
chloric acid or is replaceable by silver, the remainder of the sodium
being quite unaffected. Yet if the formula of the complex alumino-
silicic acid is
H 2 A1 2 3 2 Si0 2 ,
the sodium atoms, having replaced the whole of the hydrogen, must
behave uniformly !
3. If the sixth hypothesis that the whole of the aluminium is in
the form of an acid is accepted, it follows that all the aluminium
atoms must behave similarly to chemical agents. St. J. Thugutt 108
has, however, experimentally proved the exact opposite in a series of
aluminosilicates, and has found that one-third of the aluminium be-
haves differently from the remainder. For example, sodium nepheline
4 (Na 2 A1 2 3 2 Si0 2 ) 5 H 2 O,
on prolonged digestion at 200 with 2 per cent, potassium carbonate
solution, one-third of the alumina passes into solution in the form of
sodium aluminate and a residue of potassium natrolite,
K 2 A1 2 3 3 Si0 2 aq.,
remains, according to the following equation :
3 (4 Na 2 Al 2 Si 2 8 5 H 2 0) + 8 K 2 C0 3 + 9 H 2
= 8 Na 2 C0 3 + 8 (K 2 Al 2 Si 3 10 + 3 H 2 0) + 4 Na 2 Al 2 O 4 .
Thugutt has also experimentally proved this property of aluminium
in the kaolins, and in a series of sodalites or sodium nepheline hydrates
in which a portion of the " water of crystallisation " is replaced by
several salts such as NaCl, Na 2 S0 4 , Na 2 C0 3 , etc.
(b) The precise meaning of the term " complex acids " is by no
means perfectly clear. As has been shown in the previous pages, all
existing theories concerning the constitution of these compounds are
only applicable to a comparatively small number of these substances
and are not, in other ways, quite free from objection. Hence, the
hypothesis that the aluminosilicates are complex acids and salts gives
but little information concerning their " constitution " in the true
meaning of this word.
(c) A theory is only of value if, by its means, a large number of
26 CRITICAL REVIEW OF EXISTING THEORIES
facts can be arranged systematically. As there can be no doubt, in
the present state of our knowledge of the chemical nature of the
aluminosilicates, that a genetic relationship exists between the com-
pounds in this group this being in agreement with the sixth hypo-
thesis a general systematic arrangement in the sense of the sixth
hypothesis must be possible, e.g. one based on the composition of the
complex anhydrides. If, however, an attempt is made to apply this
arrangement to all the aluminosilicates including the felspars, micas,
clintonites, scapolites, orthochlorites, etc. a very large number of
hypothetical anhydrides is involved ; many of these are of a complex
composition and their existence has not, so far, been proved.
Vernadsky 109 has actually drawn up a scheme of classification based
on chemical properties, but he only applied it to a relatively small
number of compounds and made no attempt to arrange the micas,
felspars, clintonites and other aluminosilicates in a similar manner,
as he realised the impossibility of a complete classification on such a
basis.
Hence, although the sixth hypothesis agrees the best with the facts
of all the theories mentioned, there are several objections to it, and
these must not be under-estimated.
Consequences which follow from the previous Theories
A number of facts may now be mentioned which have a character-
istic relation to the theories concerning the aluminosilicates and may
be regarded as " consequences " of them.
A. The idea that the constitution of the aluminosilicates cannot
be expressed in the light of the previous theories has often led the
various investigators to formulate different theories in which no atten-
tion was paid to the chemical properties of the aluminates. Amongst
these are the so-called "mixture theories " of micas, 110 scapolites, 111
tourmalines, 112 etc. The various investigators differ greatly in what
they consider to be the components of the mixtures ; these are, in
most cases, only hypothetical and are often of such widely different
chemical composition that they can scarcely be described as isomorph-
ous in the strict meaning of this term. It is, therefore, impossible to
state the constituents of a "mixture" without knowing precisely
what a given investigator means by the terms he uses for such con-
stituents.
In this connection it is interesting to note that Clarke 113 has
recently suggested that the orthosilicates can form " isomorphous "
mixtures with tri-silicates and other poly-silicates. The acceptance of
this led Clarke to formulae which appear to be very improbable. For
instance, he suggests for Zinnwaldite 114 the following formulae :*
1. Al 244 Fl 167 K 224 Si 224 H 116 (AlFl 2 ) 2 o(Si 3 8 ) 1 5 6 (SiO 4 ) 3 ofl )
2. Al 239 Fl 186 Si 218 H 112 (AlFl 2 ) 209 (Si 3 8 ) 151 (Si0 4 ) 312 .
* Zinnwaldite is usually considered to be an iron-lithium silicate and not a
fluorine compound. A. B. S.
SOME CONSEQUENCES OF CURRENT THEORIES 27
By using the symbol X for both Si0 4 and Si 3 O 8 and the symbol
R for K, Li, H and A1F 2 , he obtained the following constitutional
formulae i
1. 56 (A1X 3 F1 3 R 3 ) + 53 (A1X 3 R 9 ) + 45 (A1 3 X 3 R3),
2. 62 (A1X 3 F1 3 R 3 ) + 49 (A1X 3 R 8 ) + 43 (A1 3 X 3 R 3 ).
Re-calculating an analysis of cryophillite 115 made by Riggs, Clarke
obtained the following highly complex formula :
Al 186 Fl 84 K 256 Li 324 H 146 (AlFl 2 ) 187 (Si 3 8 ) 227 (Si0 4 ) 18 5 5
and expresses this as :
31 (A1X 3 F1 3 R 3 ) + 81 (A1X 3 R 9 ) -f 25 (A1X 3 R 3 ).
Clarke has also obtained similarly complex formulae for other
silicates including stilbite, chabasite, heulandite, 116 etc. and has en-
deavoured to explain these in an analogous manner.
B. A somewhat large amount of caprice is observed in studying the
representations of the constitution of some silicates. Each investigator
selects that arrangement which he considers to be the most convenient
for his own use and it is, therefore, very difficult for anyone else to accept
any particular theory. The current hypotheses respecting the con-
stitutions of the two following aluminosilicates :
(a) K 2 A1 2 3 2 SiO 2 (Phakelite) and
(b) K 2 A1 2 3 6 Si0 2 (Orthoclase),
are typical instances.
(a) The Constitution of Phakelite
P. Groth 117 regards this compound as a simple, normal salt of
orthosilicic acid, viz. :
Si s= 3 i Al
\OK.
C. Rammelsberg 118 represents it molecularly as :
K 4 Si0 4 Al 4 Si 3 12 .
S. J. Thugutt 119 also represents it molecularly, but with other com-
ponents, viz. :
2 K 2 Al 2 Si 3 10 K 2 A1 2 4 .
Vernadsky 120 considers it as a salt of an aluminosilicic acid :
H 2 A1 2 3 2 Si0 2 .
(b) The Constitution of Potash felspar (orthoclase)
As a product of pseudomorphic processes Tschermak regards ortho-
clase molecularly as :
K 2 0-Al 2 3 (Si0 2 ) 4 -(Si0 2 ) 2 .
Tschermak 121 represents it atomically :
OK
CRITICAL REVIEW OF EXISTING THEORIES
P. Groth 122 assigns it to the following constitution :
Si _ Al
o o
0-K
Clarke 123 prefers :
/[Si 3 8 ] E= K 3
AlAsiaO,] = Al
\[SiiO.] = Al
S. J. Thugutt 124 , as the result of experiments, uses the following
constitutional formula :
2 K 2 Al 2 Si 3 10 K 2 A1 2 4 12 Si0 2 .
Rammelsberg considers it to be a multiple salt (double salt)
analogous to albite and writes the formula :
/K 2 Si 2 5 + Al 2 Si 6 15 ^
\K 2 Si0 3 + Al 2 Si 3 9 J
Wartha represents the structural formula of orthoclase as :
Vernadsky 125 regards orthoclase as a complex salt of an acid
H 2 A1 2 3 6 Si0 2 ,
and writes its structural formula :
OK
il
/\
tt
o o
Zulkowski 714 regards felspar as a salt of a complex aluminosilicic
acid and gives it the following formula :
Al SiO SiO SiO OK
/\
O
V
Al SiO SiO SiO OK
Attention may also be called to the suggestion of Haushofer 716 , who,
in order to show the genetic relationship of the felspars with granites
RESULT OF CRITICAL REVIEW 29
and micas, attributed the following constitutional formula to ortho-
clase :
O
= Si Si O AXSi OK
A
= Si Si O Al/\Si OK
O
Mellor and Holdcroft 708 regard orthoclase as a salt of an alumino-
hexa-silicic acid and suggest the formula :
O = Si O\ /O Si =
O<C >Alt\ 1=^=0
= Si O/ A X Si = O
O
= Si Si =
OK OK
C. Some aluminosilicates, viewed in the light of existing theories,
are extremely puzzling even when they are not highly complex. The
formula of ardennite, 126
10 MnO V 2 5 5 A1 2 3 10 Si0 2 5 H 2 0,
is thus described by Groth : " This formula though based on only a
few analyses indicates such a complex structure that it is highly
probable that further investigation will lead to its simplification."
This declaration was made by Groth because he was not in a posi-
tion to find a simpler formula which would agree with the theories
mentioned.
D. Another consequence of the current theories is that in many
experimental researches no analyses are calculated into formulae, the
usual view being that the substances are not true compounds, but
" isomorphous mixtures." It is clear that many interesting character-
istics are overlooked in the absence of formulae. Lemberg 127 is
typical of many other investigators who do not express their results
by means of formulae.
The Result of the Critical Examination and the Possibility that the
Objections raised to the Sixth Hypothesis are unreal
A critical examination (pp. 8-26) has shown that the alumino-
silicates and such complex compounds as the silicotungstates, the
phosphotungstates, etc. are closely related substances ; it has shown,
moreover that, in all probability, both these groups of compounds
may be regarded as members of a single class.
With regard to their constitution, this examination only shows that
30 A HYPOTHESIS RESPECTING ATOMIC BONDS
the structure of every compound is not yet known. The previous
theories on the constitution of the aluminosilicates cannot be regarded
as satisfactory, as notable objections can be raised against each, and
none of them is capable of logical application to the interpretation of
the chemical nature of the aluminosilicates as a whole, nor can any of
them be used for a systematic classification. At the same time, it
should be noted that the conception of the aluminosilicates as complex
acids or salts agrees well with the facts.
So long as no better theories are available the sixth hypothesis must
claim precedence, in spite of the objections to it already indicated.
It is, however, not improbable that these objections are only
apparent and that they would be completely overcome if the manner
in which the atoms in the anhydrides of the aluminosilicates are bound
to each other were known. By the use of a suitable hypothesis for the
structure of these anhydrides, a confirmation of this statement may be
found. The authors of this present volume have actually formulated
such a hypothesis, and its nature and the conclusions which may be
drawn from it form the subject-matter of the following pages.*
Section III
A Hypothesis to show the Bonding of the Atoms in the
Aluminosilicates and related Chemical Compounds
i
A. Two New Radicals Hexite and Pentite
1. Hexite
IF six molecules of Si(OH) 4 unite together, splitting off water and
retaining the quadrivalency of the silicon so as to form a "closed
ring," the following constitutional formula is produced :
(OH),
Ji"
2 (OH)=S/
,(OH)=Si) Si = (OH)
\/
Si
(OH) 2
Formula I.
* In sections I and II the authors have followed Vernadsky : " Uber die Gruppe
des Sillimanits und die Rolle der Tonerde in den Silicaten " (Bull, der Moskauer Gesdl-
schaft der Naturforscher, 1891, 1, 1-100).
TWO NEW RADICALS 31
If six molecules of water are split off from formula I, the constitu-
tion shown in formula II is produced :
II
Si
/\
O
= Sif 7 ^jSi =
O O
= Sil ISi =
O
\/
Si
&
Formula II.
Formula I is shown in abbreviated form by means of the following
symbols :
(OH), H 2
II II II
.(OHj-^-fOH),
(OH), H:,
Formula III. Formula IV. Formula V.
And formula II by the symbol :
| Si |
Formula VI.
In the following pages these abbreviated forms will be used in
place of formulae I and II.
If six molecules Al(OH) 3 unite together to form a "ring" after
losing six molecules H 2 O, but retaining the tri valency of the aluminium,
formula VII is obtained :
Al OH
HO A3, 7 ^Al OH
O
HO AL /Al OH
O
\/
Al OH
Formula VII.
32 TWO NEW RADICALS
By the removal of three molecules of H 2 from formula VII the
anhydride 3 A1 2 O 3 is produced.
Instead of formula VII, the symbols
OH
HO /\ OH
HO lJ OH
or
H
I
H /\ H
Al
O
H
H
or
H
Formula VIII.
Formula IX.
X
Formula X.
may be used, the atomic complex 3A1 2 3 being then represented by
\
Formula XI.
The radicals indicated by the symbols in formulae VI and XI are
termed "Hexite," 6 Si0 2 being known as "Silicon hexite " and
3 A1 2 O 3 as " Aluminium hexite."
For Silicon hexite and Aluminium hexite the respective symbols
Si and Al
will also be employed.
The hydrates of these hexites such as :
6 H 2 6 Si0 2 ,
4 H 2 O 6 Si0 2 ,
3 H 2 3 A1 2 O S , etc.,
are termed " Hydrohexites."
II. Pentite
If five molecules of Si(OH) 4 or A1(OH) 3 form " rings " in a manner
similar to hexite, the following structural formulae are produced :
(OH), (OH),
II
H 2 H 2
Si ^>=(OH)
1 1
H 2 H 2
=
Si>=
)H), (OH),
II
formula XII.
Formula XIII.
Formula XIV.
OH OH
H H
OH OH
1 i +
|AI)>
TT TT
&-
Formula XV.
Formula XVI.
Formula XVII.
A HYPOTHESIS RESPECTING ATOMIC BONDS 33
If the appropriate number of H 2 molecules is removed the anhy-
drides
Formula XVIII. Formula XIX.
are obtained.
The meaning of the symbols and formulae XII-XIX is clear from
the statement made with regard to hexite ; in addition, the sign -f in
formulae XV, XVI, etc. indicates that an even number of these
radicles must be present, as such an expression as \ (5 A1 2 O 3 ) (Formula
XIX) is impossible with existing conceptions of molecules.
The ring-forming polymerisation-products represented by formulae
XVIII and XIX are termed " Pentite," that corresponding to Si(OH) 4
being referred to as " Silicon pentite," that corresponding to A1(OH) 3
as " Aluminium pentite," and the hydrates :
5 H 2 O 5 SiO,,
3 H 2 5 SiO 2 ,
J (5 H 2 5 A1 2 3 ), etc.,
as " Hydropentites."
The pentites of silicon and aluminium will be indicated by the
symbols :
Si and Al,
respectively.
B. The Representation of the Chemical Structure of the Complex Alumino-
silicic acids and their Anhydrides by means of the Silicon and Aluminium
Pentites and Hexites.
The silicon and aluminium hexites and pentites just mentioned,
provide the " building stones " or nuclei for the acids and anhydrides
under consideration. With their aid the mode of formation of the acids
appears to be in accordance with the following rules :
(a) The hydrohexites or hydropentites of aluminium unite with
those of silica or vice versa, the two neighbouring hydroxyl groups in
the or^Ao-position in these rings splitting off the elements of water,
two other OH-groups, also in the ortho-position in the silicon ring,
losing their hydrogen atom and forming free H 2 O.
By this means :
1. From one aluminium hydrohexite and two silicon hydrohexites,
viz. from 3H 2 - 3A1 2 O 3 and 6H 2 O 6SiO 2 , is obtained the formula :
(OH), OH (OH) 2
This may be expressed in four abbreviated forms :
34 STRUCTURAL FORMULAE FOR ALUMINOSILICIC ACIDS
(OH) 2 OH (OH),
It I
(OH),=
(OH) 2 =
= (OH) 2
=(OH).
(OH) 2 OH (OH) 2
<y)
H i H
(8) H 18 (Si Al Si).
2. From a silicon hydrohexite (3H 2 6Si0 2 ) and two aluminium
hydrohexites (3H 2 3A1 2 3 ) is obtained the formula :
OH OH OH
r_/ '
OH-
or the symbols :
in in OH
OH OH OH
OH OH OH
H H H
I I I
H /\/\/\_ H
A
(7)
l|
Al ] Si | Al|
\/\/\/~
I I I
H 10 (A1 Si Al).
STRUCTURAL FORMULAE FOR ALUMINOSILICIC ACIDS 35
3. From one aluminium hydrohexite (3H 2 3A1 2 3 ) and two
silicon hydropentites (5H 2 O 5Si0 2 ) are obtained the symbols :
SiAl
\
08) H 2 (Si Al Si),
which need no further explanation.
From (a) it follows that each aluminium hydrohexite can combine
with two or at most three silicon hydrohexites or hydropentites, water
being split off. The reverse is naturally the case with the silicon hydro-
hexites ; the hydropentites on the contrary can obviously combine
with, at most, two hydrohexites.
(6) Only those types are produced, from the radicles just men-
tioned, in which the " rings " or nuclei are distributed quite sym-
metrically. From this it follows :
1. That such types as :
Si Al Si,*
Si Al - Si,
are completely excluded as they are unsymmetrical.
2. The type
Si-Al
must be doubled. It then yields two isomeric types :
Si Al Al Si,
Al Si Si A of which
(3) both ends must be formed of absolutely similar radicles, as :
Si Al Si,
Si Al - Si Al Si, etc.
It also follows that from the type
Si Al Si
no such isomer as :
Si Si Al
is possible.
(c) The types can only have a group of two similar radicles of the
same elements in the middle and not at the ends. Even in the
* If the symbols are doubled and the nuclei symmetrically placed ; such doubled
forms are theoretically possible.
I
36 STRUCTURAL FORMULAE FOR ALUMINOSILICIC ACIDS
middle they cannot have more than two similar radicles of the same
substance. The following types are therefore excluded :
Si Si Al Si - Si ,
Si Al Al Al Si,
Al Al - S A i Si - Al - Al,
Al Si Si Si Al, etc.
From what has been already stated it will be seen that the following
structural formulae are possible :
I I II
1. ~| Si | Al | Al | Si | = = H o (Si Al ' & ' Si) = 10 H 2 6 A1 2 3 12 Si0 2
iWY
_AAAA_ . A -
2. _| Si | Al | Al | Si |__ = H 2 (Si Al Al Si) = 6 H 2 6 A1 2 0, - 12 Si0 2
I I I I
n__A/\_i
3. = / Si I Al | Al | Si ^>= =H$ 6 (Si Al Al Si)=8 H 2 6 A1 2 3 10 Si0 2
Tyy-l
Si y~ = HJ (Si Al Al Si)=5 H 2 6 A1 2 3 10 Si0 2
5. ' | Al | Si | Si | Al | = H 6 (Al Si Si - M) = 8 H 2 6 A1 2 3 12 Si0 2
~\/\/\/\/
I II II I
I I
6. Al Si | Si Al | = Hg (Al Si Si Al) = 4 H 2 6 A1 2 3 12 Si0
I I
I
7. <^A1 1 Si J Si
\~\/\/
= H a (Al S"i & Al) = 6 H 2 5 A1 2 0, 12 SiO,
STRUCTURAL FORMULAE FOR ALUMINOSILICIC ACIDS 37
8.
Si Al
\
/ y^x
= H 4 Al;-S A i
12 H 2 3 A1 2 3 18 Si0 2
t<k
9. Si Al
/
| I Al^-S
v
H| Al^-S = 3 H 2 O 3 A1,O, 18 Si0 2
10. =< Si
Al
H
n-is
= 9 H 2 3 A1.0. 15 SiO,
11. =< Si
Al
H! Alf-Si = 3 H 2 3 A1 2 0, 15 SiO,
Al
Si
= H;J S A i ^Al) = 6 H a O 6 SiO, 9 A1 2 3
v
38 STRUCTURAL FORMULAE FOR ALUMINOSILICIC ACIDS
13.
I /^\
= H I S A i<- Al I = 3 H 2 6 Si0 2 9 A1 2 3
Al
6H 2 O12Si0 2 .15Al 2 0,
._ Si|Al Si |
II I II
I II
= /\/\/ N =
. _| Si | Al | Si | Al | Si L=H5. (Si-Al-Si-Al-Si)=8 H 2 6 A1 2 3 18 Si0 2
~\/\/\/\/\/~
Al Si = H% 4 (Si Al Si Al-Si)
/\/== 12 H 2 6 Al, 3 18 Si0 2
I II I II
I II I
/\/\/\/\/V
17.=<^ Si I All Si I All Si \==H? 2 (Si-Al-S A i-Al-Si)=6H a O-6 Al 2 3 -16Si0 2
\A/\/
I II I
etc. etc.
The types produced exclusively from the hexites (e.g. 15 and 16)
are termed " primary " or " major types " ; those which contain
both hexites and " penta radicles " (3, 4, 7, 10, etc.) are known as
" secondary " or " minor types."
Having now shown the chief features of the hypothesis relating to
the bonding of the atoms in the aluminosilicic acids, it is necessary
to ascertain how far the facts support this new theory.
C. Consequences which follow from the " Hexite-Pentite Theory"
I
If the aluminosilicates are really free acids or salts, of which the
anhydrides can be produced from aluminium and silicon hexites and
pentites in accordance with certain laws or rules, it follows that in
that class of reactions known as " double decomposition " the alum-
inium cannot be replaced by other elements, but that the alumina-
silica ratio must remain constant.
CONSEQUENCES OF THE H.P. THEORY 39
Hence in reactions of this kind, involving the following silicates :
(a) 6 Na 2 6 A1 2 3 12 SiO 2 = Na 12 (& - Al - Al Si),
(6) 3 Na 2 3 A1 2 3 12 Si0 2 = Na 6 (Si Al Si),
(c) 3 Na 2 3 A1 2 3 10 Si0 2 = Na 6 (T- Al - Si),
only those atoms which are outside the brackets (i.e. the sodium atoms)
can be replaced by potassium, magnesium, calcium, etc. No such
replacement can occur with the aluminium atoms and the alumina-
silica ratio must remain unchanged.
As a matter of fact, no replacement of the aluminium by elements
which form oxides of the R 2 or RO type has yet been observed either
in the so-called pseudomorphous processes or during the course of
experimental researches in the laboratory.
Lemberg (see Appendix, page following Table IV) by treating an
artificially prepared compound
0.5 Na 2 O 5 K 2 6 A1 2 3 16 Si0 2 = NaK 10 (Sl Al - Si Al Si)
with varying amounts of salt-mixtures (sodium and potassium
chlorides, potassium and magnesium chlorides, etc.) obtained the
following compounds, all having the general formula :
RnfSi Al Si Al Si),
1.
2.
Na 2 O
2Na 2
4.
3.
5K 2
5K 2 O
6
6
A1 2 3
A1 2 O 3
16SiO
16SiO
2 >
2
3.
2
.5 Na 2 O
.
3K 2 O
6
Al
2 3 -
16
SiO
2
4.
3Na 2 O
2.
5K 2 O
6
Al
2 3 -
16
SiO
2
5.
3
.5 Na 2 O
2K 2
6
Al
2 O 3 -
16
SiO
2
6.
5Na 2
0.
5K 2
6
Al
2 3 -
16
SiO
2
7.
1
.5K 2
.
4MgO
6
Al
2 3 -
16
SiO
2
8.
2K 2
3.
5MgO
6
A1 2 3
16SiO
2
9.
2
.5K 2
3MgO
6
Al
2 O 3 -
16
SiO
2
10.
3K 2 O
2.
5MgO
6
Al
2 3 -
16
SiO
2
11.
1
.5K 2
4 CaO
6
Al
2 3 -
16
SiO
2
12.
2K 2 O
3.
5 CaO
6
Al
2 3 -
16
SiO
2
13.
2.25 K 2 O
3.25 CaO
6
Al
2 3 -
16
SiO
2
From all these thirteen compounds he could only obtain a replace-
ment of the atoms outside the brackets :
NaK 10 (ST- Al-Si- Al Si),
and the alumina-silica ratio remained constant.
A large number of analogous phenomena might be mentioned, but
as they all lead to the same conclusion, the following will suffice. Thus,
the silicate
(0.5 Na 2 2.5 CaO 3 A1 2 3 18 Si0 2 17 H 2 0) 2
( / \
=jNaCa 2 . 5 Al^Sl 17 H 2
* x sV
40 CONSEQUENCES OF THE H.P. THEORY
is converted by a six weeks' treatment at 100 with KC1 (see Appendix,
Table I, No. 39a) into the compound
/ /Six
K S O 3 A1 S 3 18 SiO, 13 H 2 = K, Al(-S"i 13 H 2 0.
V W
This potassium salt is converted by a fortnight's treatment at
100 with sodium chloride solution into the sodium salt (see Appen-
dix, Table I, No. 39b)
/ Six
3 Na 2 3 A1 2 3 18 Si0 2 16 H 2 O = Na 6 Al^-Si . 16 H 2 0.
V \Y
The potassium salt
k
H S
3 K 2 3 Al a O, 18 SiO a H 2 = K, -
v x
after a week's treatment at 100 with sodium chloride solution is con-
verted into the sodium salt (see Appendix, Table I, No. 39f )
3 Na 2 3 A1 2 3 18 SiO 2 - 8 H 2 = Na
\
i I 8 H 2 0.
The sodium salt (see Appendix, Lemberg's Expts., Series B (c)
f / .Six
(3 Na 2 - 3 A1 2 3 15 Si0 2 7J H 2 0) 2 =] Na e ( Alf Si 7.5 H 2
[ V W
is converted after a hundred days' treatment with potassium chloride
solution at 200 into the potassium salt
f / A
(3 K 2 - 3 A1 2 3 15 Si0 2 1J H 2 0) 2 =] K 6 j Al(-Si 1 1J H 2
[ \ x sv
and the sodium salt
3 Na 2 O 3 A1 2 3 12 Si0 2 6 H 2 = Na 6 (Si Al Si) 6 H 2
by a three weeks' treatment at 100 with potassium chloride solution
(see Appendix, Table II, No. 45a) into the potassium salt
3 K 2 3 A1 2 3 12 Si0 2 H 2 = K 6 (Si Al Si) H 2 0,
etc., etc.
II
The new hypothesis implies a genetic relationship between the
various aluminosilicates ; under suitable conditions they must be
mutually convertible.
GENETIC RELATIONSHIPS 41
Thus the silicate
3 Na 2 3 A1 2 3 12 Si0 2 = Na 6 (Si Al Si),
can change into the silicates
(a) 3 K 2 3 A1 2 3 12 Si0 2 = K 6 (Si - Al Si),
(b) 3 MgO 3 A1 2 3 12 Si0 2 = Mg 3 (Si Al Si), and
(c) 3 CaO 3 A1 2 3 12 Si0 2 = Ca 3 (Si Al - Si),
the sodium being replaced by potassium, magnesium or calcium.
A conversion of the substance
3 Na 2 3 A1 2 3 12 Si0 2 = Na.($ Al Si),
into the compounds
(a) 3 Na 2 3 A1 2 3 10 Si0 2 = Na 6 (S~i Al Si),
(b) 3 Na 2 6 A1 2 3 12 Si0 2 = Na 6 (S_i - Al Al Si),
(c) 3 Na 2 6 A1 2 O 3 10 Si0 2 = Na 6 (Si Al Al Si),
can be effected, in case (a) by the conversion of the silicon hexite into
pentite, in (b) through the addition of an aluminium hexite and in (c)
by the simultaneous transformation of the silicon hexite in (b) into the
corresponding pentite.
In this manner a series of changes in aluminosilicates prepared
artificially by Lemberg, Thugutt and others, and the numerous
naturally occurring changes which have been observed may be clearly
represented.
Thus, Lemberg (see Appendix, Series B) :
1. By the action of caustic soda solution of various concentrations
on the silicates :
(a) 3 Na 2 3 A1 2 3 - 12 Si0 2 6 H 2 O = Na 6 (Si Al Si) 6 H 2 0,
(b) 6 Na 2 6 A1 2 O 3 12 Si0 2 = Na 12 (Si Al Al - Si),
(c) 6 H 2 -6 A1 2 3 12 Si0 2 6*H 2 = H 12 (Si Al Al Si) 6 H 2 0,
obtained, from the (a) compound, the substance
6 Na 2 O 6 A1 2 O 3 12 Si0 2 15 H 2 = Na 12 (S A i Al Al &) 15 H 2 0,
from (b) the substance
8 Na 2 O 6 A1 2 3 12 Si0 2 7 H 2 = Na 16 (S A i Al Al Si) 7 H 2 0,
and from (c) the silicates
6 Na.O 6 A1 2 3 12 Si0 2 15 H 2 = Na 12 (Si Al Al &) 15 H 2 and
8 Na 2 6 A1 2 3 12 SiO 2 - 7 H 2 O = Na^Si Al Al Si) 7 H 2 ;
2. By treating the silicates (see Appendix, Lemberg Series B).
(a) 6 Na 2 6 A1 2 3 12 Si0 2 = Na 12 (Si Al Al Si),
(6) 3 Na 2 3 A1 2 3 12 Si0 2 6 H 2 O = Na 6 (S A i Al Si) 6 H 2 0, and
(c) 3 K 2 3 A1 2 3 18 Si0 2
/
= K 6 (
v
42 CONSEQUENCES OF THE H.P. THEORY
with sodium silicate, he obtained from (a) and (6) the substance
f / /SiO
(3 Na 2 3 A1 2 3 15 Si0 2 7J H 2 0) 2 = \ Na 6 Al Si H, 15 H 2 0,
1 V X Si'J
and from (c) the compound
3 Na 2 3 A1 2 8 12 Si0 2 6 H 2 = Na 6 (S A i Al - Si) 6 H 2 O ;
3. From the silicate
(0.5 Na 2 2.5 CaO 3 A1 2 3 18 Si0 2 20 H 2 0) 2 =-
by treatment for fifteen months at 100 with 20 per cent, sodium
carbonate solution he obtained the compound (see Appendix, Table
II, No. 44)
(/ /Si\
Na 6 Alf Si
V X SI/
and by treatment for two months at 100 with a 25 per cent, solution of
sodium silicate, the substance
3 Na 2 3 A1 2 3 - 12 Si0 2 6 H 2 O = Na 6 (S A i Al Si) - 6 H 2 ;
4. From the silicates :
6 H 2 O 6 A1 2 3 12 Si0 2 6 H 2 = H 12 (Si Al Al Si) 6 H 2 O,
6 Na 2 O 6 A1 2 3 12 Si0 2 = Na 12 (Si Al Al Si),
6 Na 2 O 6 A1 2 O 3 18 SiO 2 12 H 2 ,= Na 12 (Si Al - Si Al Si) 12 H 2 0,
3 Na 2 3 A1 2 O 8 12 SiO 2 6 H 2 = Na 6 (Si Al Si) 6 H 2 0,
3 K 2 3 A1 2 3 12 SiO 2 = K 6 (Si Al S A i), and
2 -15H 2 0,
3K 2 3 A1 2 3 18 Si0 2
. / , / S K
= K 6 (Ale-Si I
v
by treatment with a mixture of sodium chloride and caustic soda
(see Appendix, Lemberg Series A) he obtained a " sodalite " :
(6 Na 2 O 6 A1 2 3 12 Si0 2 ) 4 NaCl 4 H 2
= Na 12 (Sll M M Si) 4 NaCl - 4 H 2 ;
5. From
3 K 2 3 A1 2 3 12 Si0 2 = K 6 (Si Al Si), and
/ \
3 K 2 3 A1 2 3 18 Si0 2 = K 6 Al^Si
V \QV
GENETIC RELATIONSHIPS 43
he obtained the " sodalite "
(6 K 2 6 A1 2 8 12 Si0 2 ) 2 KC1 8 H 2
= K 12 (Si - Al Al Si) 2 KC1 8 H 2 O,
by treatment with a mixture of potassium chloride and caustic potash.
6. From the silicates :
6 H 2 O -6 A1.0, 12 SiO 2 6 H 2 = BC^Si - Al Al Si) 6 H 2 0,
6 Na 2 6 A1 2 3 18 Si0 2 12 H 2 == Na 12 (Si Al Si Al Si) - 12 H 2 0,
3 Na 2 3 A1 2 O 3 12 Si0 2 6 H 2 = Na 6 (Si Al Si) 6 H 2 0,
3K 2 3 A1 2 3 12 Si0 2 = K 6 (Si Al Si),
3 Na 2 3 A1 2 3 18 SiO a = Na 6 ( Al^S'i
X S
A
3K 2 3 A1 2 3 18 Si0 2
and a mixture of sodium sulphate and caustic soda he obtained the
" sodalite "
(6 Na 2 6 A1 2 3 12 Si0 2 ) 2 Na 2 S0 4 6 H 2
= Na 12 (Si Al Al Si) 2 Na 2 S0 4 6 H 2 ;
7. From the compounds :
6 H 2 -6 A1 2 3 12 Si0 2 6 H 2 = H 12 (Si Al Al S'i) 6 H 2 0,
6 Na 2 6 A1 2 3 12 Si0 2 = Na 12 (S A i Al Al Si),
3 Na 2 3 A1 2 3 12 Si0 2 6 H 2 = Na 6 (S A i Al Si) 6 H 2 0,
3 K 2 3 A1 2 3 12 SiO a = K 6 (Si Al Si),
3 Na 2 3 A1 2 3 18 Si0 2
and sodium silicate he obtained the " sodalite "
(6 Na 2 O 6 A1 2 3 12 Si0 2 ) 2 Na 2 Si0 3 8 H 2
= Na 12 (S A i - Al Al Si) 2 Na 2 Si0 3 8 H 2 O ;
8. From the silicates :
6 H 2 O -6 A1 2 3 12 Si0 2 6 H 2 O = H 12 (Si Al Al Si) 6 H 2 0,
3 Na 2 3 A1 2 3 12 SiO 2 6 H 2 = Na 6 (Si Al Si) 6 H 2 0,
3K 2 3 A1 2 3 12 Si0 2 = K 6 (S A i Al Si),
and a mixture of sodium carbonate and caustic soda he obtained the
" sodalite "
3 (6 Na 2 O 6 A1 2 3 12 Si0 2 ) 4 Na 2 C0 3 30 H 2 O
= {Na 12 (Si Al Al Si)}, 4 Na 2 CO 3 30 H 2 0.
44 CONSEQUENCES OF THE H.P. THEORY
From these researches of Lemberg's a genetic relationship between
the compounds of the five following types :
1. S A i Al Si,
2. Si Al Al SX
3. S A i Al S A i Al Si,
4. Al^Si and
X Si
/*
5. Al^Si
Si
can be traced. This is shown in the folio whig Table :
Table showing the Results of Lemberg's Researches
(a) Series 1.
Si Al . S A i > Si Al Al Si.
(6) Series 2.
Si Al Al Si
/
S A i Al S A i
>-Al\^Si
Si
Si
Al^~Si
-> S A i Al - S A i
X S'i
(c) Series 3.
/%
/ o:
N Si
~^^S A i-Al-Si
(d) Series 4, 5, 6, 7 and 8.
Si Al Si Al Si ^^
S A i Al S A i > Si Al Ai Si
Al^Si
The experimental researches of Thugutt produce analogous results :
By digesting kaolin 139
(a) 6 H 2 6 A1 2 8 12 SiO. 6 H 2 = H ia (S A i Al Al Si) 6 H 2 0,
GENETIC RELATIONSHIPS 45
with 2 per cent, caustic potash solution at 192-202 he obtained a
compound
(6) 6 K 2 6 A1 2 O 3 18 Si0 2 18 H 2 = K 12 (Si M - Si Al Si) - 18 H 2 ;
with 1 per cent, caustic soda solution, a compound
(c) 6 Na 2 6 A1 2 3 16 Si0 2 10 H 2 = Na 12 (Si Al S'i Al - S7) -10 H 2 0;
with a mixture of caustic potash and potassium silicate two products
(d) 3 H 2 O 6 Kj.0 6 A1 2 3 15 Si0 2 6 H 2
= H 6 K 12 (Si Al Si Al Si) 6 H 2 0,
(e) 3 K 2 3 A1 2 3 10 Si0 2 aq. = K.(Si Al Si) aq.
From the above-mentioned experimental researches of Thugutt a
genetic relationship may be shown between the compounds of the
types :
(a) Si Al Al Si,
(6) Si Al Si Al S A i,
(c) Si Al Si - Al Si,
(d) Si Al Si Al Si,
(e) Si Al Si.
From these results it follows that compounds of type (a) may be
converted into those of type (&), (c), (d), and (e).
Friedel has, however, found that compounds such as
S A i Al Al Si
can also be converted into those of other types. By treating muscovite :
4 H 2 2 K 2 6 A1 2 O 3 - 12 SiO, = H 8 K 4 (S A i Al Al Si),
with a mixture of potassium silicate and potassium carbonate,
Friedel 140 obtained the compound
A
i0 2 = K 6 (^ S A i)
V \fc/
3 K 2 - 3 A1 2 8 - 18 SiO
Interesting conversions of aluminosilicates have also been observed
in Nature (pseudomorphous processes) ; these give results analogous
to the experimental researches just mentioned.
Analcime 141
3 Na 2 O 3 A1 2 3 12 Si0 2 = Na 6 (S A i Al Si)
can change into muscovite
4 H 2 2 K 2 6 Al,0 8 12 Si0 2 = ft j 4 (& Al - Al Si),
and prehnite
12 CaO 6 A1 2 0, 18 Si0 2 6 H 2 O == Ca 12 (Si Al S'i Al Si) 6 H 2 O.
46 CONSEQUENCES OF THE H.P. THEORY
The silicates :
6 Na 2 O 6 A1 2 3 12 Si0 2 (nepheline) = Na 12 (Si Al Al Si),
3K 2 3 A1 2 3 12 SiO a (leucite) = K 6 (Si Al Si),
6 Na 3 6 A1 2 3 12 Si0 2 4 NaCl (sodalite) = Na 12 (S A i Al Al Si)
4 NaCl,
3 CaO 3 A1 2 3 12 Si0 2 12 H 2 (laumontite) = Ca 3 (S A i Al Si) 12 H 2
may all change into analcime 142
3 Na 2 3 A1 2 3 12 Si0 2 = Na(Si - Al Si).
In Nature, orthoclase 143
/ /S A K
3 K 2 3 A1 2 3 18 Si0 2 = K 6 Ai(~Si I
v x sr
has also been found to change into
6 H 2 6 A1 2 3 12 Si0 2 6 H 2 (kaolin) = H 12 (Si Al Al Si) - 6 H 2
3 Na 2 3 A1 2 3 12 Si0 2 (analcime) = Na(Si Al Si)
6Na 2 6 A1 2 3 18 Si0 2 12 H 2 (natrolite) = Na 12 (S A i-Al-SVAl-S A i)-12 H 2
2 H 2 8 CaO 6 A1 2 3 12 Si0 2 (epidote) = H 4 Ca 8 (Si Al Al S'i)
3 H 2 3 A1 2 3 12 Si0 2 (pyrophillite) = H 6 (Si Al Si)
3 Na 2 3 A1 2 8 18 Si0 2 (albite) = Na
/ ,
a 6 | Al^-Sl I
4 H 2 2 K 2 6 A1 2 3 12 Si0 2 (muscovite) = H 8 K 4 (Si Al Al Si).
Natural orthoclase 144 is formed from
3 CaO 3 A1 2 3 12 Si0 2 (laumontite) = Ca,(Si Al Si),
3 Na 2 O 3 A1 2 3 12 Si0 2 (analcime) = Na 6 (Si Al S*i),
3 K 2 O 3 A1 2 3 12 Si0 2 (leucite) = K 6 (Si Al Si), and
12 CaO 6 A1 2 3 18 Si0 2 (prehnite) = Ca 12 (Si Al - S'i Al S'i).
Leucite 145
3 K 2 3 A1 2 8 12 Si0 2 = ,(Si - Al Si),
may be changed into nepheline :
6 Na 2 O 6 A1 2 3 12 Si0 2 = Na l2 (Si Al A! Si),
and nepheline into natrolite :
6 Na 2 6 A1 2 3 - 18 Si0 2 12 H 2 = Na 12 (Si Al Si Al Si) 12 H 2 0,
etc., etc.
Table showing the Natural Changes of the Aluminosilicates
1. Si-Al-Si- -^^^^^
* Si Al Si Al Si
2. Si-Al-Ai-Si-Z^? 1 '^' 8 }^' 8 '
- > Si Al Si
CHANGES IN ALUMINOSILICATES IN NATURE 47
S'i .sr Si Al Al S*i
-Si >
"Si ^ Si Al Si
3. Air- Si > Si Al S A i Al Si
4. Si - Al - Si * A^
Si-Al-Sl-Al-Si " X $
In consequence of the great variety of silicates, the various products
formed from them by the action of the weather are naturally very
numerous. The members of the felspar group are particularly dis-
tinguished by the multiplicity of their products. For instance,
potash-felspar is converted, on weathering, into kaolin, whilst other
weather-products (in the formation of which water as well as air is
necessary) are muscovite and epidote, with, less frequently, chlorite
and zeolite. Lime felspar, on weathering, forms calcareous zeolite
(chabasite, phillippsite, desmine, heulandite, and, less frequently,
laumontite, skelezite, etc.). Soda felspar forms sodic zeolites (anal-
cime, natrolite, etc.).
The scapolite minerals, on active weathering, produce epidote,
albite, biotite or muscovite and, finally, kaolin.
The tourmalines are seldom affected by the weather, but if so they
produce mica, chlorite, etc.
Some zeolites (analcime, laumontite, prehnite) are converted into
felspars on exposure to the weather. The zeolites may also be converted
into other zeolites, as natrolite into prehnite, analcime into natrolite,
and chabasite into natrolite.
The researches of Lemberg, Thugutt, and Doelter have shown that
zeolites are easily converted into other compounds by addition to,
subtraction from, or replacement of, some of their constituents.
Vernadsky 713 has observed that when granite is fused, aluminosili-
cates (e.g. anorthite) and orthosilicates (e.g. olivine) are produced, as
in the researches of Doelter and others. The granites may also be
formed by a reverse reaction from orthosilicates and aluminosilicates
at a high temperature. Granites are also converted into mica, chlorite,
minerals of the nepheline group, clays, etc.
All these changes are in accordance with the second consequence
of the new hypothesis, and the existence of a genetic relationship
between the various aluminosilicates may now be regarded as a fact
which is established beyond dispute. The nature of this relationship
can also be satisfactorily explained by the proposed theory.
Ill
The hexite-pentite hypothesis renders possible a system of com-
plete chemical classification of the aluminosilicates on the basis of
their nature as complex anhydrides.
48 CONSEQUENCES OF THE H.P. THEORY
In order to see how far the consequences of accepting this theory
agree with the facts, it was decided to calculate the formulae of a
large number of the analyses of aluminosilicates published in Hintze's
" Handbuch."
As some atoms or atomic groups can be replaced by analogous ones
e.g. the atoms K, Na, Li or Ca, Mg, Fe", or the atomic groups
A1 2 O 3 , Fe 2 3 , Cr 2 3> Mn 2 3 , etc., or Si0 2 , Ti0 2 , etc. it was con-
sidered desirable to make the calculation of the formulae in such a
manner that, instead of calculating the number of atoms of each
substance separately, the replaceable substances were taken together
in groups, thus :
Si,Al 2 (Ca, Na 2 , K 2 )0 18 6 H 2 (desmine), 146
(Si 2 5 ) 2 Al(Li, Na, H) (petalite), 147
(Si, Ti) 6 12 (Fe, Mn) (Na, K), (neptunite). 148
This method of simplifying the calculation is due to Berzelius 149 ,
who recommended its use not for all cases, but for those in which the
constituents of a substance bear no simple relation to each other.
Gerhardt 150 , who undertook a re-formulation of the silicates, did
not follow the suggestion of Berzelius, but added the various bases (such
as lime and magnesia) together, even when they bore a simple relation
to each other. The authors of the present volume prefer, however,
to adopt a grouping which more closely resembles that of Berzelius.
By this means it is possible to convert the true formula * the
interpretation of which is almost impossible on account of the presence
of a number of substances in small quantities into a formula which
is simpler, and in many cases but not all to produce a formula which
may be interpreted with ease.
In re-arranging the formulae, the authors have endeavoured to
keep as near to the true formula as possible, so as to obtain results as
quantitative as well as merely qualitative value. In many instances
this led to apparently complex formulae, but even these may be
represented atomically.
Calculations, by this means, of the formulae from a large number
of analyses of clintonite, mica, scapolite, orthochlorite, tourmaline,
and felspar, showed that many compounds of this group may be
arranged quite systematically, according to the type to which they
belong. The results of this calculation of the formulae from the
analytical figures are given in the Appendix. The following types are
selected because a large number of the compounds previously men-
tioned will be found to fit them.
* The conversion of all the analytical figures into molecular ratios is termed the
"true formula" as distinct from the approximate formula due to the simplification
proposed.
CALCULATION OF FORMULAE 49
A. Types of the Clintonite Group *
I. R Si R =6 R 2 O 8 6 Si0 2 ,
II. R-Si-R = 5R 2 3 - 6Si0 2 ,
III. Si-R-R^-Si = 6 R 2 3 12 SiO 2 ,
IV. Si-R-RT-Si = 5 R 2 3 12 Si0 25
V. Si R Si R Si = 6 R 2 8 18 Si0 2 ,
VI. Si-R -Si -R -Si = 6 R 2 3 16 Si0 2 ,
VII. R Si R Si R = 9 R 2 3 12 Si0 2 ,
VIII. R-Si-R-S A i-R = 8 R 2 O 3 12 Si0 2 ,
IX. Srr-R = 9R 2 S - 6Si0 2 ,
*
xX>
X. { Si(-R ) t =15 R 2 8 12 Si0 2 .
B.
Types of the Mica Group
S'i ft
Si
= 3
R 2 8 -
12 Si0 2 ,
SI-R-
Si
= 3
R 2 8 -
10 Si0 2 ,
.A
Rr~Si
= 3
Ra0 8 -
18 Si0 2 ,
Si
&-Si
= 3
R 2 3 -
15 SiO a ,
X Si
R-Si-
R
= 6
R 2 8 -
6 Si0 2 ,
R - S A i -
R
= 5
R 2 3 -
6 Si0 2 ,
S A i-R-
R
-Si
= 6
R 2 3 -
12 SiO 2 ,
Si-R-
R
Si
= 6
R 2 O 3 -
10 Si0 2)
Si-R-
R
Si
= 5
R 2 3 -
12 Si0 2 ,
S A i-R-
Si
R Si
= 6
R 2 3 -
18 Si0 2 ,
Si-R-
Si
R -Si
= 6
R 2 3 -
16 Si0 2 ,
Si-R-
Si
R S A i
= 5
R 2 O 3 -
18 Si0 2 ,
R-Si-
R
-Si-R
= 9
R 2 3 -
12 Si0 2 ,
I.
II.
III.
IV.
V.
VI.
VII.
VIII.
IX.
X.
XI.
XII.
XIII.
XIV. Si - R Si R Si R ST= 9 R 2 3 20 SiO 2 .
* In the Appendix the types are arranged in the order of the R 2 O 3 present ; on the
present page they are placed according to their relationship with respect to their
chemical structure.
SO CONSEQUENCES OF THE H.P. THEORY
C. Types of the Scapolite Group
I. S A i R Si =3 R 2 3 12 Si0 2 ,
II. Si R Si =3 R 2 3 10 Si0 2 ,
III. Si R R Si =6 R 2 3 12 Si0 2 ,
, IV. Si R R S A i =5 R 2 3 12 Si0 2 ,
V. Si R Si R Si =6 R 2 3 18 Si0 2 ,
VI. Si R S A i R Si =6 R 2 3 16 Si0 2 ,
VII. Si R Si R Si =5 R 2 3 18 Si0 2 ,
VIII. Si R Si Si R Si =6 R 2 3 22 Si0 2 ,
IX. Si R Si Si R Si =5 R 2 3 22 Si0 2 ,
X. Si-R-Sl-R-Si-R-Sl=9 R 2 3 20 Si0 2 ,
XI. R^-Si = 3 R 2 3 15 Si0 2 .
X Si
D. Types of the Orthochlorite Group
I. Si R Si =3 R 2 3 12 Si0 2 ,
II. Si R Si =3 R 2 3 10 Si0 2 ,
III. R^Sl = 3 R 2 3 18 Si0 2 ,
X Si
IV. R^-Si = 3 R 2 3 15 Si0 2 ,
X Si
V. R Si R =6 R 2 O 3 6 Si0 2 ,
VI. ?'Si*R =5R 2 3 - 6Si0 2 ,
VII. S'i R R S'i =6 R 2 3 12 Si0 2 ,
VIII. Si R R Si =6 R 2 O 3 10 Si0 2 ,
IX. Si R R Si =5 R 2 3 12 Si0 2 ,
X. S'i R Si R Si =6 R 2 3 18 Si0 2 ,
XL Si-R-Si-R-Si = 5 R 2 3 18 Si0 2 ,
XII. Si R S'i R Si =6 R 2 3 16 Si0 2 ,
XIII. R S'i R Si R =9 R 2 3 12 Si0 2 ,
XIV. R Si R Si R =8 R 2 3 12 Si0 2 ,
XV. Si R S'i Si R Si = 5 R 2 3 22 Si0 2 .
E. Types of the Tourmaline Group
I. R S'i R Si R = 9 R 2 3 12 Si0 2 ,
II. R S'i R S A i R = 8 R 2 3 12 Si0 2 ,
III. R-Si-R = 5R 2 3 - 6Si0 2 .
DIFFERENTIAL BEHAVIOUR OF ATOMS 51
F. Types of the Felspar Group
I. Si R Si Si R Si = 6 R 2 O 3 24 Si0 2}
II. Si R S A i Si R Si = 6 R 2 3 22 Si0 2 ,
III. Si R Si Si R Si = 6 R 2 O 3 20 Si0 2 ,
IV. Si - R Si Si R Si = 5 R 2 3 24 Si0 2 ,
V. Si R Si Si R Si = 5 R 2 3 22 Si0 2 .
A large number of aluminosilicates may be arranged according to
the authors' system (see Appendix). Whether this classification is
suitable for all aluminosilicates can only be ascertained by means
of more analyses and by calculating more formulae.
IV
The structural formulae devised by the authors show that the
aluminium and silicon atoms in an aluminosilicate do not always
behave the same in chemical and physico-chemical investigations.
Under certain circumstances some of these atoms behave differently
from the remainder, and the same is true of the monovalent and
divalent elements in these compounds.
It not infrequently happens that the hydroxyl groups which form
the "water of constitution" in the aluminosilicates are replaced by the
halogens : fluorine, and chlorine. The structural formulae show that,
in the latter case, halogen atoms may be united in various ways in a
single aluminosilicate and that these atoms must produce different
chemical or physico-chemical properties according to their position
in the whole molecule. A few examples will make this clearer.
In type I
I i
i i i i
1. \ of the aluminium,
2. J of the silicon,
3. J of the base or hydroxyl groups or the substitutes Cl, Fl, etc.
must clearly behave differently from the other f .
In type II
II.
II I I II
= /\/\/\/\ =
I| Si | A1|A1 Si
the aluminium and silicon must behave in a manner analogous to
those in type I, but J of the base (or the hydroxyl groups and their
substitutes) behaves differently from the remainder.
52 CONSEQUENCES OF THE H.P. THEORY
In type III
ill.
only J of the silicon will behave differently from the remainder.
In type IV
IV.
_AAA
YYY"
1. J of the aluminium,
2. J of the silicon,
3. J of the base (or the hydroxyl groups or their substitutes)
behave differently from the rest.
In types V and VI
V.
I l l I I
/\/\/\/\/\
"I Si | Al| Si | Al| Si |"
'YYYYY
VI.
I /\/\/\_J
<Si Al|Si|Al|Si
"YYY"
1. J of the aluminium,
2. f of the base (Type V), or f of it (Type VI) must behave
differently from the rest.
Some of these interesting results are fully confirmed by experiments
and researches already published.
In compounds of type I, such as kaolin,
6 H 2 6 A1 2 3 12 Si0 2 6 H 2 = H 12 (Si Al Al Si) 6 H 2 0,
nepheline hydrate,
6 Na 2 O 6 A1 2 3 12 Si0 2 aq. = Na 12 (Si Al Al Si)aq.,
and a number of " sodalites," i.e. derivatives of nepheline hydrate
(see p. 59), which, according to Thugutt, are so constituted that part
of their " water of crystallisation " is replaced by a given salt (NaCl,
Na 2 SO 4 , etc.). The author just mentioned reached precisely the same
conclusions as the authors of the hexite-pentite theory, viz. that one-
third of the aluminium behaves differently from the remainder.
Thugutt therefore suggests the following constitutional formulae :
2 H 2 Al 2 Si 3 O 10 H 2 A1 2 O 4 3 H 2 (kaolin),
4 (2 Na 2 Al 2 Si 3 Oio Na 2 Al 2 3 ) - 15 H 2 O (nepheline).
STRUCTURE OF KAOLINS AND EPIDOTES 53
P. Silber (p. 25) has shown that the behaviour of the compound :
6 Na 2 6 A1 2 3 12 SiO a (nepheline) = Na 12 (Si Al Al Si)
of the same type towards gaseous hydrochloric acid and silver solutions
indicates that J of the sodium behaves differently from the remainder,
and thus confirms the hexite-pentite theory.
The authors believe that confirmation of the constitution of com-
pounds of type II is to be found in a new set of formulae for the
epidotes (see Appendix). The minerals in this group are chiefly com-
pounds of type II with the general formula :
2 H 2 8 CaO 6 R 2 3 12 Si0 2 = H 4 Ca 8 (Si R R - Si)
R = Al, Fe.
The constancy of the ratio of lime to " water of constitution " in
these minerals makes it highly probable that of the hydroxyl groups
in the acids corresponding to these minerals behaves differently from
the remainder.
By replacing part of the aluminium by Fe'" in the formula
2 H 2 8 CaO 6 A1 2 3 12 Si0 25
the various epidotes are produced and no epidote has yet been found
with a higher content than is shown in the formula (see Appendix) :
2 H 2 8 CaO 2 Fe 2 3 4 A1 2 3 12 SiO a .
It appears probable that, under the conditions under which
epidotisation can occur in Nature, only those aluminium atoms which
are indicated by a dot in the formula below can be replaced by Fe==
Si Al Al Si
\/\./\./\/
For the prognosis of type III, Thugutt's work on a compound of
this type potash felspar :
3 K 2 3 A1 2 3 - 18 Si0 2 = K 6
is important. According to Thugutt, this substance, on treatment
with 2 per cent, caustic potash solution, loses silica and forms other
compounds which are incapable of exact analysis, but, so far as he has
ascertained it, their composition agrees with the theory formulated
by the authors, viz. that the constitutional formula of potash felspar
(which, according to Thugutt, is 2 K 2 Al 2 Si 3 10 K 2 A1 2 4 12 Si0 2 )
suggests that J of the silicon behaves differently from the remainder.
A partial confirmation of the prognosis of type IV appears to be
54 CONSEQUENCES OF THE H.P. THEORY
supplied by the composition of the minerals known by the general
name of " topaz." Calculations of the formulae of these compounds
from a number of analyses (see Appendix) showed that they belong,
in part, to type IV and may be represented by :
1. Si 6 Al 12 Fl 8 26 ,
2. Si 6 Al 12 Fl 9 25 . 5 ,
3. SieAl 12 Fl 10 O 25 ,
4. SioAl^Fl^O^.s,
5. Si 6 Al 12 Fl 12 O 24 .
These formulae are based on the assumption that one atom of
oxygen may be replaced by two of fluorine.
It appears probable that the hydrogen present in these compounds
has been overlooked.
If this assumption is admitted and the presence of hydrogen has
been independently proved by (a) Jannasch and Locke 128 and (b)
Penfield and Minor the topazes are derived from the hydrate :
V '
AllSilAl
I II I
SiAl 12 24 (OH) 12
The researches of Penfield and Minor showed that water in a strongly
combined state is present in the topazes. In an investigation of topaz
from Stoneham, which contained 0-98 per cent, of water, the powder
lost only 0-12 per cent, at the highest temperature obtainable by means
of a ring-burner (see Penfield and Minor, Zeitschr. f. Krystallogr. u.
Mineral. 1894, 23, 321). It is thus clear that the water contained in
topaz may easily be overlooked. The investigators just quoted have
found that the water is liberated quantitatively on fusing a topaz with
sodium carbonate. The correctness of the view that topaz contains
water in the form of OH-groups is also confirmed by the following
interesting characteristics of topaz : the specific gravity, the double
refraction, the apparent angle of the optical axes (2 e) and the crystallo-
graphic axis-ratio, all of which, according to Penfield and Minor, vary
with the proportion of hydroxyl in the topaz molecule.
Assuming, with Jannasch 128 , that the hydroxyl groups in topaz
may be replaced by fluorine, or vice versa, regarding the Stadler topaz :
Fl Fl a Fl
I u I
I Ml I
Fl F1 2 Fl
as the mother-substance and replacing the fluorine in the latter by
hydroxyl groups, the formulae of the following theoretically possible
topazes are obtained :
THE STRUCTURE OF TOPAZ AND GRANITE 55
Si 6 Al 12 24 Fl(OH) 11 ,
Si fl Al 12 24 Fl 2 (OH) 10>
Si 6 Al 12 24 Fl 3 (OH) 9 ,
Si 6 Al 12 24 Fl 4 (OH) 8 ,
Si 6 Al 12 24 Fl 12 .
In agreement with this assumption, it has been found by actual
analysis that there is a definite maximum proportion of fluorine no
topaz being known which contains a larger percentage than the Stadler
variety. There also appears to be a minimum, as no topaz is known
which contains less than eight atoms of fluorine to six atoms of silica.
This interesting result is most easily explained by stating that fluorine
atoms which are united to silicon, but not to aluminium (see the
structural formula of the Stadler topaz), are easily replaced by hydroxyl
under natural conditions, or that J of the fluorine behaves differently
from the remainder.
The probability of the authors' structural formula for topaz is
also confirmed by the chemical investigations of Rammelsberg, who
observed that on heating topazes to redness, part of the fluorine
escapes as silicon fluoride and part as aluminium fluoride.
Further investigations must show that the ratio of the fluorine lost
in the form of silicon fluoride to that lost as aluminium fluoride is 1 : 2.
The prognoses of types V and VI are partially confirmed by a
re-calculation of the analyses (see Appendix) of a number of
granites 129 by K. H. Schnerr.
This re-calculation gives the following formulae :
20 jo 90 jo 90 jk 10 90 i o
5^2^ 90 $ ^ t 90*
II I II I II ^ I II I z
i == /\./\./\./\./\ =1 o y /\./\./\
r J Si I R I Si j R I Si L| l0== \Si_| R | Si | R [Si/ =1
II i ll I ii 90 i H i 90
9 1 9 1 9 10 90 TO "
^ 2 " 2 " 2 ^ 2
18 RO 6 R 2 3 18 Si0 2 16 RO - 6 R 2 8 16 Si0 2
A. B.
These agree with the theory that J of the aluminium behaves
differently from the remainder. The aluminium atoms indicated by
dots may be replaced by Fe= ; compounds of type A may contain a
maximum of 4 Fe 2 O 3 .
Although Schnerr refers to granites in which the whole of the
* It is convenient to represent the atomic groups
OR"\ O,\
>0, _o>R', -Or (r=pl')
by 2, 1 and respectively (see also p. 166)
56 CONSEQUENCES OF THE H.P. THEORY
aluminium has been replaced by iron, experience shows that the atoms
indicated by dots are the ones most easily replaceable by iron.
It happens that those aluminium atoms in the granites which are
the most easily replaceable by iron are the very ones which, in the
epidotes, are incapable of substitution, and a closer study of the
structural formulae of these two groups of substances leads to the
conclusion that the epidotes are acid salts whilst the granites are basic
ones. The presence of a base weakens the attraction between the
silicon and aluminium ring radicles, and thereby facilitates the
substitution of the aluminium by iron at the points indicated.
The consequences of the authors' hypotheses mentioned in this
section agree with the experimental results of other investigators.
From the hexite-pentite hypothesis it follows that there must be a
minimum molecular weight for the aluminosilicates. Thus, the
formulae of the compounds
Na 2 A1 2 3 2 Si0 2 ,
Na 2 A1 2 O 3 3 Si0 2 ,
must be at least sextupled, and those of
Na 2 A1 2 3 6 Si0 2 ,
Na 2 A1 2 3 5 Si0 2 , and
Na 2 O A1 2 3 4 Si0 2 ,
must be at least tripled, in order that they may be represented in
accordance with the new theory. How does this agree with the facts ?
In many cases the theoretically minimum molecular weight may be
ascertained from an analysis of the substance or from certain definite
considerations. In this connection, one of a series of silicates :
/ A
(a) 0.5 Na 2 O 2.5 CaO 3 A1 2 3 18 Si0 2 20 H 2 = R 6 | Al Si I 20 H 2 O
V X Si'
examined by Lemberg (see Appendix, Table II) is interesting.
By treating the silicate (a) with salt solutions, Lemberg obtained
the following compounds :
.A
I. 3 K 2 3 A1 2 3 18 Si0 2 H 2 = K 6 | Ab
V X Si>
/ A\
II. 3 K 2 3 A1 2 3 18 Si0 2 13 H 2 = K 6 ( Al^-Si I 13 H 2 0,
V X Si'
(/i
Al(-Si 1 8 H 2 0,
x sV
CONSTITUTION OF THE MESOLITES 57
IV. 3 Na a O 3 A1 2 3 18 Si0 2 16 H 2 = NaJ Al^-Si | 16 H 8 0.
By treating silicate (a) with alkali he obtained
V. (3 Na 2 O 3 A1 2 3 15 Si0 2 7.5 H 2 0) 2
/ * X_\
Na 6 j Al^-Si
\ X Si/
and from the latter and potassium chloride the substance
VI. (3 K 2 - 3 A1 2 3 15 Si0 2 1.5 H 2 0) 2 =
Kefil^l)
V X Si/
15 H 2 0,
3H 2 0.
In the case of the compounds I, II, III, IV, and the silicate (a)
from which they are derived, the minimum molecular weight may be
found from the analyses ; the formation of compound V from silicate
(a) and of VI from V are quite inexplicable if a smaller molecular
weight than is required by the hexite-pentite theory is assumed for
compounds V and VI.
A second instance of interest in this connection is the mode of
formation of the potassium salt
3 K 2 3 A1 2 3 12 Si0 2 H 2 = K 6 (Si - Al - Si) H 2 0,
from the sodium salt
Na 2 A1 2 3 4 Si0 2 2 H 2 0,
as observed by Lemberg (see Appendix, Table II). This can only be
understood if the molecular weight of the original material the sodium
salt is tripled ; the theoretically minimum molecular weight is then
indicated.
The number of instances in which the theoretically minimum
molecular weight may be ascertained from analysis is somewhat large,
as may be seen from the authors' re-calculation of the formulae of a
large number of silicate analyses. From the numerous examples
available, the new formulae of the mesolites (see Appendix) may be
mentioned here.
Formulae of the Mesolites
(a) 2 Na 2 4 CaO 6 A1 2 O 3 18 Sip, -15 H 2 0^
= Na 4 Ca 4 (Si Al Si M Si) 15 H 2 0,
(6) (1.5 Na 2 5.5 CaO 6 A1 2 3 18 Si0 2 22 H 2 0) 2 ^
= {Na 3 Ca 6 . 5 (Si AL Si Al Si)} 2 44 H 2 0,
(c) (Na 2 3.5 CaO 6 A1 2 3 17 Si0 2 15 H/)),
= {Na 2 Ca 3 . 5 (Si Al Si Al Si)} 2 30 H 2 0,
(d) (2 Na 2 3.5 CaO 6 A1 2 O 3 17 Si0 2 15 H 2 0) 2
= {Na 4 Ca 3 . 5 (Si M Si Al Si)} a 30 H 2 0,
58 CONSEQUENCES OF THE H.P. THEORY
(e) 2 Na 2 4 CaO 6 A1 2 3 16 Si0 2 12 H 2
= Na 4 Ca 4 (Si Al Si Al Si) 12 H 2 0,
(/) 2 Na 2 3 CaO 6 A1 2 3 16 Si0 2 -15 H 2 0^
= Na 4 Ca,(Si Al Si Al Si) 15 H 2 0,
(g) 2.5 Na 2 3 CaO 6 A1 2 3 16 Si0 2 20 H 2
= Na Ca,(Si Al - Si Al Si) 20 H 2 0,
(h) 1.5 Na 2 3 CaO 6 A1 2 3 15 SiO^ 18 H.O
= Na 3 Ca 3 (Si Al Si Al Si) 18 H 2 0,
(*) 2.5 Na 2 3 CaO 6 A1 2 3 15 Si0 2 13 H 2 O
= Na 5 Ca 3 (Si - Al - Si Al Si) 13 H 2 0.
In all the above mesolitic silicates, with the exception of (e),
analysis indicates the theoretically minimum molecular weight, and
there is no need to doubt that the real minimum agrees with the
theoretical one, as otherwise the genetic relationship which is known
to exist between these and other members of this group would be
inexplicable.
It is, moreover, particularly interesting to observe that Thugutt 130
has, by an entirely different method, reached conclusions regarding
the minimum molecular weight of certain aluminosilicates which agree,
almost without exception, with the authors' theory. Thugutt's
conclusions are also of special value because they are based on the
results of actual experiments. On the basis of his previously mentioned
researches, Thugutt suggests the following constitutional formula :
2 K 2 Al 2 Si 3 10 K 2 A1 2 4 12 Si0 2
which is equivalent to :
3 K 2 O 3 A1 2 0, 18 Si0 2 = K e (
S A i'
the following for nepheline hydrate :
4 (2 Na 2 Al 2 Si 3 10 Na 2 Al 2 4 ) 15 H 2
corresponding to :
12 Na 2 12 A1 2 3 24 Si0 2 15 H 2 = {Na 12 (Si Al Al Si)} 2 15 H 2 O,
and the following for potash mica :
(a) K 6 H 6 Al 12 Si 18 60
= 3 K 2 3 H 2 6 A1 2 3 18 SiO 2 = K 6 H 6 (Si Al Si Al Si),
(6) K 4 H 8 Al 12 Si 18 60
= 2 K 2 4 H 2 6 A1 2 3 18 Si0 2 = K 4 H 8 (Si Al Si Al Si).
In some silicates the theoretically minimum molecular weight is
double that found by Thugutt. Thus, he attributes to potash nephe-
line the formula :
2 K 2 Al 2 Si 3 10 K 2 A1 2 4 ,
CONSTITUTION OF THE SODALITES 59
which, if doubled, gives :
6 K 2 6 A1 2 3 12 Si0 2 = K 12 (Si Al Al Si).
The same is true of Thugutt's constitutional formula for potash
mica :
H 2 K 2 Al 4 Si 6 20 H 2 A1 2 4 ,
which, if doubled, gives :
2 K 2 4 H 2 6 A1 2 3 12 Si0 2 = K 4 H 8 (Si - Al Al &).
Equally interesting in this connection are the so-called sodalites.*
According to Lemberg's 131 and Thugutt's 132 researches, these are not
atomic, but true molecular compounds. This view is opposed to that
of other investigators. It is highly probable, from the results of
Lemberg's and Thugutt's experiments, that the sodalites are deriva-
tives of the sodium nepheline hydrates, and that they are so constituted
that a portion of their " water of crystallisation " appears to be
replaceable by various salts. If this is really the case, on decomposition
they must be capable of forming products which are identical with
those from sodium nepheline hydrate.
Thugutt's researches have shown that, in reality, one-third of the
sodium and one-third of the alumina can be removed from the sodalite
in the form of aluminate of potash. Natrolite may be formed by the
action of potassium carbonate solution, chloride of sodium (or whatever
salt may be added) being set free. Thus, the blue chlorosodalite from
the elaolite-syenite from Ditro decomposes in accordance with the
equation :
3 Na 2 Al 2 Si 2 8 - 2 NaCl + 2 K 2 C0 8 + 6 H 2 O
= 2 Na 2 C0 3 + 2 NaCl + 2 (K 2 Al 2 Si 3 10 3 H 2 0) + Na 2 Al 2 4 .
(Of. the analogous behaviour of nepheline hydrate, p. 61.) As a result
of this reaction, Thugutt considers that the formula of chlorosodalite
should be :
2 Na 2 Al 2 Si 3 10 Na 2 Al 2 4 2 NaCl,
but as it is a derivative of sodium nepheline hydrate, whose constitu-
tional formula is
8 Na 2 Al 2 Si 3 O 10 4 Na 2 Al 2 4 15 H 2 0,
this being confirmed by its reaction with potassium carbonate
Thugutt's molecular weight of chlorosodalite should be at least quad-
rupled ; its constitutional formula then becomes :
8 Na 2 Al 2 Si s O 10 4 Na 2 Al 2 O 4 8 NaCl.
If 4 Na 2 SO 4 replaces the 8 NaCl, the constitutional formula of the
sulphatosodalite or norsean is obtained ; if the 8 NaCl is replaced by
4 Na 2 S 2 that of ultramarine results, and so on. Thugutt has artificially
prepared a large number of analogous substances and has allotted
molecular weights to them, as shown in the following Table.
* Another means of representing the constitutional formula of the sodalites
atomically is possible and is discussed in connection with the ultramarines (p. 152
et seq.).
60 CONSEQUENCES OF THE H.P. THEORY
Thugutt's Sodalite Series 133
12
Na 2
2
(6
A1 2 3
12 Si0 2 )
8
NaCl 4 H 2 0,
12
Na 2
2
(6
A1 2 3
12
Si0 2 )
6
NaBr,
12
Na 2 O
2
(6
A1 2 3
12
Si0 2 )
6
Nal - 6 H 2 O,
12
Na 2
2
(6
A1 2 3
12
Si0 2 )
8
NaC10 3 2 H 2 O,
12
Na 2
2
(6
A1 2 3
12
Si0 2 )
3
Na 2 0. B 2 3 8 H 2 O,
12
Na 2
2
(6
A1 2 3
12
Si0 2 )
2
Na 2 I 2 5 . 10 H 2 0,
12
Na 2
2
(6
A1 2 3
12
Si0 2 )
8
NaC10 4 4 H 2 0,
12
Na 2
2
(6
A1 2 3
12
Si0 2 >
4
Na 2 C0 3 12 H 2 0,
12
Na 2 O
2
(6
A1 2 3
12
Si0 2 )
3
Na 2 C0 3 18 H 2 0,
12
Na 2 O
2
(6
A1 2 3
12
Si0 2 )
4
Na 2 Si0 3 16 H 2 O,
12
Na 2
2
(6
A1 2 3
12 Si0 2 )
.3
Na 2 Si0 3 15 H 2 0,
12
Na a O
2
(6
A1 2 3
12
Si0 2 )
4
Na 2 S0 4 12 H 2 0,
12
Na 2
2
(6
A1 2 3
12
Si0 2 )
3
Na 2 S0 4 12 H 2 0,
12
Na 2
2
(6
A1 2 3
12
Si0 2 )
3
Na 2 Cr0 4 - 15 H 2 O,
12
Na 2
2
(6
A1 2 3
12
Si0 2 )
3
Na,Se0 4 12 H 2 0,
12
Na 2
2
(6
A1 2 3
12
Si0 2 )
3
Na 2 Mo0 4 21 H 2 0,
12
Na 2
2
(6
A1 2 3
12
Si0 2 )
Na. 2 W0 4 13 H 2 0,
12
Na 2
2
(6
A1 2 3
12
Si0 2 )
2
Na 4 P 8 5 12 H 2 0,
12
Na 2
2
(6
A1 2 3
12
Si0 2 )
8
NaN0 3 6 H 2 0,
12
Na 2 O
2
(6
A1 2 3
12
Si0 2 )
3
Na 2 P 2 5 18 H 2 0,
12
Na 2 O
2
(6
A1 2 3
12
Si0 2 )
4
Na 2 HP0 4 14 H 2 0,
12
Na 2
2
(6
A1 2 3
12
Si0 2 )
2
Na 4 P 2 7 14 H 2 0,
12
Na 2
2
(6
A1 2 3
12
Si0 2 )
3
Na 2 - Aso0 5 - 14 H 2 0,
12
Na 2
2
(6
A1 2 3
12
Si0 2 )
3
Na 2 S 2 3 9 H 2 0,
12
Na 2 O
2
(6
A1 2 3
12
Si0 2 )
8
NaOH 4 H 2 0,
12
Na 2
2
(6
A1 2 3
12
Si0 2 )
6
Nal 9 H 2 0,
12
Na 2 O
2
(6
A1 2 3
12
Si0 2 )
8
HCOONa,
12
Na 2
2
(6
A1 2 3
12
Si0 2 )
6
CH 3 COONa 3 H 2 0,
12
Na 2
2
(6
A1 2 3
12
Si0 2 )
3
Na 2 C 2 O 4 18 H 2 O.
The minimum molecular weight of any member of this series may
be ascertained from an analysis of the substance, as in the two follow-
ing sodalites :
12 Na 2 O 2 (6 A1 2 3 12 Si0 2 ) 3 Na 2 - B 2 3 8 H 2 and
12 Na 2 O 2 (6 A1 2 O 3 12 Si0 2 ) Na 2 W0 4 13 H 2 0.
The hexite-pentite theory formulated by the authors of the present
volume gives the same molecular weight. Moreover, if the salt-
content (in molecules) of a sodalite is represented by
m2
and the water- content (in molecules) by
nH,
the constitution of these substances may be ascertained from the
following formula :
{Na 12 (Si Al Al Si)} 2 m2 , nH.
For some micas, Thugutt 134 suggests constitutional formulae with
a different molecular weight from that implied by the hexite-pentite
theory. Thus, he attributes to two potash micas the formulae :
K e H 3 Al 12 Si 18 O eo H 6 A1 6 12 = 4.5 K 2 4.5^H 2 9 A1 2 3 18 Si0 2 ,
K fl H 6 Al 12 Si 18 60 H 6 A1 6 12 = 3 K 2 6 H 2 9 A1 2 3 18 Si0 2 ,
CONSTITUTION OF THE SODALITES 61
whilst the authors of the hexite-pentite theory prefer :
3 K 2 3 H 2 6 A1 2 3 12 Si0 2 = K,H 6 (Si Al Al - Si), and
2 K 2 4 H 2 O 6 A1 2 O 8 12 Si0 2 = K 4 H 8 (Si Al Al Si).
This contradiction is more apparent than real, and the fact that
J of the aluminium in these compounds behaves differently from the
remainder is equally well shown in the authors' formulae. Indeed,
there appears to be no important reason why Thugutt should not
substitute the formulae :
K e H 2 Al 8 Si 12 40 H 4 A1 4 8 , and
K 4 H 4 Al 8 Si 12 40 ' H 4 A1 4 8 ,
for those he has selected, and so obtain formulae which give the same
molecular weight as those suggested by the authors.
Another apparent contradiction to the authors' theory is the
nepheline formula calculated by Thugutt from a series of analyses in
Hintze's " Handbuch." In this calculation, notwithstanding that he
has represented nepheline hydrate and potash nepheline by formulae
in which the alumina-silica ratio is 1 : 2, and the great probability that
in nepheline itself this ratio is also 1 : 2, Thugutt selects the formula :
K 2 Na 8 Al 10 Sin0 42 = K 2 4 Na 2 5 A1 2 3 11 Si0 2 ;
and in accordance with the reaction of this substance with alkaline
carbonates he gives
8 Na 2 Al 2 Si 3 10 4 Na 2 Al 2 4 3 K 2 Al 2 Si 3 10 ,
as the constitutional formula.
This formula is quite inexplicable by the hexite-pentite theory.
As a matter of fact, the nepheline analyses by Hintze 135 do not
yield a formula in which the alumina-silica ratio is 1:2. Several
analyses approach very closely to the formula :
K 2 4 Na 2 - 5 A1 2 3 12 Si0 2 = K 2 Na 8 (Si Al Al Si).
Analyses
Molecular
Calculated
Weights
Composition
XXIII
XXV
XXIV
K 2 O = 94
5.98%
5.66o/
4.76%
5.05%
4 Na 2 = 248
15.77%
15.71%
15.97%
16.35%
5A1 2 3 = 510
32.45%
32.66%
32.06%
33.28%
12SiO 2 = 720
45.80%
45.23%
45.53%
45.10%
1572 100.00%
It is conceivable that the decomposition products of nepheline
must be the same as those of nepheline hydrate, as its constitution is
analogous, even though it contains a different alumina-silica ratio.
Thus, the consequences of the hexite-pentite theory do not, as
regards minimum molecular weight, contradict the facts.
62 CONSEQUENCES OF THE H.P. THEORY
VI
The conclusion has already (see pp. 22 to 26) been reached that,
of all the theories devised for showing the constitution of the alumino-
silicates,the one which agrees best with the facts is that which assumes
that these compounds are complex acids and their corresponding salts.
It has also been shown that, by the use of the hexite hypothesis
respecting the arrangement of the atoms, most of the objections to the
" complex acid theory " disappear. Thugutt's discovery that part of
the aluminium behaves differently from the remainder and that of
P. Silber that in nepheline J of the sodium behaves differently from the
other | are not only explicable, but are direct consequences of the
theory. A complete classification of a large number of alumino-
silicates is also rendered possible ; the felspars, micas, scapolites, etc.
need no longer be regarded as belonging to different groups of minerals,
but may be considered all to belong to a single class of compounds.
They can only be conceived as salts of a definite series of alumino-
silicic acids, and the " mixture theory " may be abandoned.
Only the behaviour of andesite now remains unexplained, and even
this will become clear if the following constitutional formula based
on the hexite-pentite theory is used :
Na Na Na
I I !
i:
Si Al j Si
\/\/\/
Ca Ca Ca
I I I
/\/\/\
I Si I Al Si)
Na Na Na
3 Na 2 3 CaO 6 A1 2 3 24 Si0 2 .
A glance at this structural formula of andesite shows that it will
react with NaCl as shown by the following equation :
Na Na Na
Na Na Na III
I I I /\/\/\
Al Si
Si | Al| Si | VVV
s/\/\/ I I I
III Na ISa Na
Ca Ca Ca+6NaCl = + 3 CaCl 2
III Na Na Na
I I
ii
I I I
N*
Na Na Na I I I
Na Na Na
THE POSSIBILITY OF ISOMERISM
63
The complex is decomposed and the re-formation of andesite by
means of CaCl 2 (double decomposition) is impossible.
The conception of the aluminosilicates as complex acids thus agrees
excellently with experimental results.
VII
From the structural formulae already given it follows that two
kinds of isomerism 136 * are possible :
1. An isomerism resulting from a different, yet still symmetrical,
arrangement of the basal atoms, or " Basis-isomerism," and
2. An isomerism due to the ring radicles, or " Ring-isomerism."
A few examples will make this clearer :
From the compound
two isomers are possible :
I. Basis isomerism
/
K/Al/Si
V
From the compound
H 4 Na 6 (Si Al Si),
two basis-isomers are also possible :
Na Na Na H Na H
III III
H /\/\/\ . H Na /\/\/\ Na
H I|s^M H Na _|siJ ^N_ Na
Na Na Na H Na H
I. II.
* For Literature with reference to Isomerism in inorganic compounds see No. 136
in Bibliography.
64 CONSEQUENCES OF THE H.P. THEORY
II. Ring isomerism
From compounds with an alumina-silica ratio of 1:2, two ring-
isomers are possible :
5i|Al[Al|Si|
/\/\/\/
Al | Si I Si Al |
\/\/\A/
I. II.
From the derivatives of this type, analogous ring-isomers produce
a secondary type :
| Si | Al| All Si I <"Af|Si Si|1fN
\/ \/ X \/\/ '
I. II.
,/\
etc.
iv.
Crystallographic and chemical investigations have already indicated
the actual existence of isomeric aluminosilicates. Thus, potash felspar
\?
is already known in two forms, viz. as orthoclase (monoclinic) and
microcline (triclinic).
Soda felspar, / Si
K Al^Si
V \T
is also known to occur in the two forms of sodium orthoclase (mono-
clinic) and albite (triclinic).
The following results of work by Thugutt confirm the existence of
ring-isomers : In the previous Section it was shown that the con-
stitutional formula of the sodalites is based upon
{Na 12 (Si Al Al Si) } 2 m 2 n H.
Hence the existence of a second series of sodalites with the formula
{Na 12 (Al Si Si Al)} 2 m 2 nH,
is theoretically possible. As a matter of fact, Thugutt has discovered
two chlorosodalites with a different behaviour towards calcium
chloride, although the chemical composition of both is identical.
The artificially prepared hydrogen sodalite behaves towards
calcium chloride in a manner quite different from that of the natural
sodalites from Arendal, Ditro, Miask, and Turkestan.
VARIOUS KINDS OF COMBINED WATER
65
The artificial variety, on treatment with calcium chloride solution,
yields a calcium chloride-sodalite according to the following equation :
3 (6 Na 2 6 A1 2 3 12 SiO 2 4 NaCl) + 22 CaCl 2
= 3 (6 CaO 6 A1 2 3 12 SiO 2 ) 4 CaCl 2 + 48 NaCl.
With natural sodalites, on the contrary, the equation is :
2 (6 Na.O 6 A1 2 3 12 Si0 2 4 NaCl) + 12 CaCl 2
= 2 (6 CaO 6 A1 2 3 12 Si0 2 ) + 32 NaCl.
It is, at present, impossible to say which formula belongs to either
of the two isomers.
^ Further researches will show how far these prognoses of the theory
are confirmed in this respect by the facts.
VIII
Water may be present either as " water of crystallisation " or
" water of constitution, " the latter being acid- or base-water. The
" acid-water " may be of various kinds : part of the hydroxyl groups
may be united to the aluminium hexite or pentite, the remainder to the
silicon hexite or pentite.
This may be seen from the following formula, in which the different
kinds of water are indicated by , ft, y, and S, respectively :
(ft)
()
(0)
(OH) 2
OH
(OH)
i
II
1
(7)
HO
Ca\
'V\/\/Ca-
OH
(r)
(ft)
HO/
Si
Al
Si
\OH
(0)
(ft)
H0\
\ .
/OH
(0)
(7)
HO
Ca/
\/
v
\/
\Ca-
OH
(7)
(OH),
OH
(OH)
i
08)
w
(ft
6H 2 (5).
Since Damour first drew attention to the change in the behaviour
of the water in hydrous aluminosilicates or zeolites at higher tempera-
tures, this subject has been studied by various investigators (see p. 4,
last line) and particularly by Clarke.
Of the zeolites examined by Clarke 138 , those relevant to the present
purpose are laumontite, thomsonite, hydronephelite, heulandite,
epistilbite, stilbite, faujasite, scolecite, foresite, and natrolite.
The Structural Formulae of the above-mentioned Zeolites, based on
their behaviour at high temperatures (after Clarke)
I. Laumonite
Al 4 (Si0 4 ) 5 Si 3 8 Ca 2 H 8 4 H 2 = 4 H 2 2 CaO 2 A1 2 3 8 Si0 2 4 H 2 0.
II. Thomsonite
Al 4 (Si0 4 ) 6 Ca 3 (AlH 2 2 ) 2 H 4 3 H 2
= 4 H 2 O 3 CaO 3 A1 2 3 6 SiO, 3 H 2 0.
66 CONSEQUENCES OF THE H.P. THEORY
These structural formulae were suggested by Clarke from a study of
the dehydration experiments of Damour, Hersch, and others, which
showed that -f- of the water must be regarded as " water of con-
stitution."
III. Hydronephelite
Al 3 (SiO 4 ) 3 -Na 2 H-3H 2 O
== \ (2 Na 2 H 2 3 A1 2 3 6 Si0 2 6 H 2 0).
IV. Heulandite
Al 4 (Si0 4 ) 3 (Si 3 O 8 ) 3 Ca 2 H 8 6 H 2
= 4 H 2 O 2 CaO 2 A1 2 3 12 Si0 2 6 H 2 0.
V. Epistilbite
Al 4 (Si0 4 ) 3 (Si 3 8 ) 3 Ca 2 H 8 6 H 2 O
= 4 H 2 2 CaO 2 A1 2 3 12 Si0 2 6 H 2 O.
Epistilbite is stated by Clarke to have the same composition as
heulandite, but the water in it appears to be more strongly bound.
VI. Stilbite
Of the same composition as epistilbite and heulandite ; behaves like
heulandite on fusion, but sometimes forms anorthite.
VII. Faujasite
Al 4 (Si0 4 ) 4 (Si 3 8 ) 2 Na 2 CaH 8 15 H 2 O
= 4 H 2 Na 2 CaO 2 A1 2 3 10 Si0 2 15 H 2 0.
VIII. Scolecite
Al 4 (Si0 4 ) 6 Ca 2 H 8 2 H 2 = 4 H 2 2 CaO 2 A1 2 3 6 Si0 2 2 H 2 0.
IX. Foresite
Al 4 (Si0 4 ) 6 CaH 8 H 2 = 4 H 2 CaO 2 A1 2 3 6 Si0 2 H 2 0.
X. Natrolite
Al 2 (Si0 4 ) 3 Na 2 H 4 = 2 H 2 Na 2 A1 2 3 3 Si0 2 .
The Structural Formulae of Laumontite, Thomsonite, etc., according to the
Hexite-Pentite Theory
The structural formulae suggested by Clarke, when rearranged in
accordance with the hexite-pentite theory, yield constitutional
formulae in which the results of Clarke's researches may also be seen,
as follows :
I. Laumontite
Clarke's formula multiplied by f gives :
THE CONSTITUTION OF THE ZEOLITES
67
6 H 3 3 CaO 3 A1 2 3 12 Si0 2 6 H 2 O = H 12 Ca 3 (Si Al Si) 6 H 2
caOH ca caOH
.(H0) =
(HO) =
= (OH),
= (OH),
6H 2 O
ca = Ca
caOH ca caOH
II. Thomsonite
Clarke's formula multiplied by 2 gives :
8 H 2 6 CaO 6 A1 2 3 12 Si0 2 6 H 2 O = H 16 Ca 6 (S A i Al Al Si) 6 H,0
HOCa-OH OHCa-OH
,(HO) =
.(H0) =
A
HO Ca-OH
=(OH) 2
Si I -6H 2
=(OH) 2
A
OH Ca-OH
III. Hydronephelite
Clarke's formula multiplied by 4 gives :
4 Na 2 2 H 2 6 A1 2 3 12 Si0 2 12 H 2 == H 4 Na 8 (ST Al Al Si) 12H 2 O
Na H H Na
I I I I
Na /\/\/\/\ Na
Na-
Si
Al
Al
Si
12H 2
I I I I
Na H H Na
Ring- and Base-isomers of this composition are clearly possible.
IV. Heulandite
Clarke's formula multiplied by f gives :
/ /A
6 H 2 3 CaO - 3 A1 2 3 - 18 Si0 2 9 H 2 = H 12 Ca 3 l Al^-Si 1 9 H 2 O
ca (OH)
ca
(OH) 2 =
9H 2 O
ca
ca -- Ca
68
CONSEQUENCES OF THE H.P. THEORY
V. Epistilbite
Epistilbite, according to Clarke, has the same composition as
heulandite, but the water is more strongly bound.
Possibly epistilbite has the following structural formula :
OH
Oca
HO Si
caO~\/
Al
__/OH
I Oca
OH
9H 2
OH
Oca
ca = i Ca
as in this the water would be bound more strongly than in heulandite.
VI. Stilbite
Clarke's formula multiplied by f may be expressed thus :
/ /Six
6 H 2 - 3 CaO 3 A1 2 3 18 Si0 2 9 H 2 = H 12 Ca 3 l Al~Si 1 9 H 8 0.
V X Si
Stilbite is either analogous to heulandite or epistilbite or it is
an isomeric product of heulandite with the following formula :
(OH) 2 ca
ca-
(OH)
Si
Al
\'
I
(OH),. 9
&/\
ca = J Ca
(OH) 2 |JX 'ca
(OH) 2 ca
VII. Faujasite
Clarke's formula multiplied first by f and then by 2 gives :
(6 H 2 1.5 CaO 1.5 Na 2 3 A1 2 3 15 Si0 2 22.5 H 2 0) 2
- 2 45 H 2
THE CONSTITUTION OF THE ZEOLITES
69
(OH), Oca
// ONa
(W
(OH).
y
^. Oca
(OH), ONa
45H 2 O
VIII. Scolecite
Clarke's formula multiplied by 3 gives :
12 H 2 O 6 CaO 6 A1 2 3 18 Si0 2 6 H 2
= H 24 Ca 6 (Si Al Si Al Si) 6 H a O
OH
(OH), OH Ca OH OH (OH),
II I \/ I II
HO-Ca, A /\ /\ X\ /\ ,Ca-OH
HO i
ca = J Ca
Al | Si |~ H .6H 2
I X\ I
i, OH
(OH), OH Ca OH OH (OH),
OH
Scolecite is of special interest, inasmuch as it must contain all the
four different kinds of theoretically possible water.
IX. Foresite
If Clarke's formula is tripled it gives :
12 H 2 3 CaO 6 A1 2 8 18 Si0 2 - 3 H 2
= H 24 Ca 3 (S A i Al Si Al Si) 3 H 2
OH
Ca OH OHOHCa OH OH OH Ca OH
V I N/ J \/
(OH), =
(OH), =
= (OH),
= (OH),
3H 2
(OH), OH (OH), OH (OH),
70 CONSEQUENCES OF THE H.P. THEORY
Foresite contains all the four kinds of water theoretically
possible.
X. Natrolite
Clarke's formula, if multiplied by 6, leads to one which is impossible
according to the hexite-pentite theory, as compounds with an alumina-
silica ratio of 1 : 3 cannot have more than 12 R 2 O. This does not
necessarily prove an objection to the theory, as Clarke, in publishing
his formula for natrolite, definitely pointed out that the character of
the water in this compound is doubtful.
Further investigations will show that this compound only contains
6 molecules of " water of constitution."
The Hexite-Pentite Theory and other Zeolites
Part of the prognosis of the theory put forward by the authors of
this volume is completely confirmed by the facts ; it will, therefore, be
of special interest to enquire whether other investigations of zeolites
such as fractional determination of water will lead to the same
conclusions as to the existence of water in four different forms of
combination in such compounds as scolecite, foresite, etc.
A number of investigators, following the researches of Friedel,
E. Mallard and E. Rhine 733 , have concluded that the zeolites form a
remarkable class of substances which differ from the hydrates. The
work of A. Damours, who showed that water can be partially absorbed
by dehydrated zeolites re-combined, supports this conclusion. There
is a general impression that the loss of water from zeolites does
not follow the laws of Dalton and Proust, though this view is in direct
contradiction to the experiments of Clarke. This view has been
specially supported by J. M. van Bemmelen 717 , E. Doelter 783 , F.
Rinne 718 , and Sommerfeldt 719 , but A. Johnson 720 adopts the contrary
view and maintains that the evolution of water is not, in principle,
different from that of normal hydrates.
J. M. van Bemmelen regarded the combination of water in zeolites
as similar to that in silica jellies. Doelter regards it as " adsorbed."
E. Rinne has found, in the case of heulandite and desmine, that
definite changes in the water-content are accompanied by equally
definite changes in the optical character of these substances. According
to him, in heulandite and desmine an equilibrium is formed at all
temperatures and the loss of water is dependent on external circum-
stances such as atmospheric pressure and temperature.
The belief that loss of water by zeolites does not follow stoichio-
metrical laws is, without doubt, based on an error. Clarke, for
instance, has conclusively shown that, in the case of heulandite, the
loss of water is quite in accordance with these laws and that in the case
of desmine the same regularity is highly probable. The apparent
irregularities are due to the use of too small molecular weights for these
THE CONSTITUTION OF THE ZEOLITES 71
compounds, whereby the regularity of the loss may be overlooked.
That this is the case with heulandite has already been shown. That it
applies equally to desmine is not difficult to prove, as follows :
Desmine has the general formula
CaO A1 2 3 Si0 2 5 H 2 0.
According to the H.P. theory, part of the water shown is " water
of constitution" and the remainder is "water of crystallisation"
(p. 65), the structural formula being :
6 H 2 6 CaO 6 A1 2 3 6 Si0 2 4 (6 H 2 0).
It is clear that a whole series of water-separation phases may
occur, such as :
1. Conversion of two hexites into pentites.
2. Conversion of the remaining hexite into pentite.
3. Separation of four pentites.
4. Separation of four hydroxyl groups.
There are at least ten phases of water-separation which lead to
forms differing from each other in crystallographic and optical charac-
ters. In short, the researches of Klnne, rightly considered, really agree
with the consequences of the H.P. theory.
The compounds
A. (CaO A1 2 3 Si0 2 5 H 2 0) 6
B. (CaO A1 2 3 Si0 2 - 4 H 2 0) 6
C. (CaO-Al 2 3 -Si0 2 -3H 2 0)e
D. (CaO A1 2 3 Si0 2 2 H.O),
E. (CaO A1 2 3 Si0 2 H 2 0)
F. (CaO-Al 2 3 -Si0 2 ) 6
are distinguished by their different optical and crystallographic
properties ; the compounds A, B, and C being monoclinic, D appears
to be rhombic, E still more clearly rhombic, and F (which has no water
of constitution) is amorphous.
Sommerfeldt considers that the zeolites, unlike the hydrates, lose
water continuously, and regards them as solid solutions. He has
applied the law of Ch. Henry and the second law of thermodynamics
to zeolites by integration, and the substitution of logarithms for
natural numbers in the formula :
(1) U =
RT'd(ln^)
C
72 CONSEQUENCES OF THE H.P. THEORY
in which the concentration of the water in the solid and vaporous
form is represented by c' and c. He devised a second formula in which
at least two temperatures are known and are proportionate to the
maximal tensions of the water vapour and that of the water occluded
in unit volume of the substance, namely c' 2 : c 2 . The heat of combina-
tion may, in this way, be calculated.
From the formula thus obtained
(2) U= +4-584 log. (^!_jjt)-j!-T, Calories,
\ Cj_ C a 7 -L2 -LI
it is possible to ascertain whether the usual laws of thermodynamics
are applicable to zeolites. If, for instance, the vapour tension of the
occluded water c' and the heat of combination U in the formula (2)
are sufficient, the zeolites may be regarded as solid solutions. E.
Sommerfeldt has determined calorimetrically the evolution of heat, 7,
following the absorption of water by analcime, and obtained, as the
result of three tests, the values 1520, 1710, and 1635 Cals. for the heat
of combination of 1 molecule of water, i.e. an average of 1622 Cals.
From the percentage of water by weight which a sample of analcime
lost on being heated from 20 to TC., whereby it is in equilibrium
with the water vapour, the maximum temperature of which can be
ascertained from G. Friedel's researches, the heat of combination U
may be found to be approximately 8530 Cals. This disagreement
shows that the formula (2) cannot be applied to zeolites. Hence,
according to E. Sommerfeldt, zeolites cannot be solid solutions ; he
regards them as adsorption products.
This conclusion of Sommerfeldt's is only partially correct, as the
disagreement of the value found with that calculated merely shows that
the zeolites are not solid solutions. It does not show that the water is
adsorbed, i.e. combined in non-stoichiometric proportions. Indeed,
the authors of the present volume have previously shown that the
available experimental material only indicates that the zeolites do not
differ essentially from other hydrates.
The objection may be raised that the chief characteristic of zeolites
their ability to re-combine with water of crystallisation, as shown by
Damour, whereby they are distinguished from other compounds con-
taining water of crystallisation is inexplicable in terms of the H.P.
theory. This anomaly is, however, merely superficial. The power of
combining with water has been exhaustively shown, elsewhere, to be
due to :
1. The number of hydroxyl groups belonging to the water of
crystallisation, and
2. The nature of the base in compounds (salts).
The more hydroxyl groups a compound contains, the closer is its
relationship to ring- water. In saline compounds the combining power
of the ring-water is also dependent on the nature of the base. Some
complex acids have a close relationship to ring-water and therefore
PROGNOSES 73
crystallise with a relatively large number of water-rings. The sodium
salts of these acids contain less water of crystallisation, the potassium
salts still less ; hence the water of crystallisation in the sodium com-
pounds is more strongly combined than in the analogous potassium
salts. It is, in fact, probable that the calcium group (O.Ca.OH) near
the OH-groups in zeolites causes the water-rings which have been
separated to re-combine. This property of re -combination so charac-
teristic of zeolites cannot properly be made a reason for separating
these compounds from others containing water of crystallisation,
and forming a separate class of compounds of a so-called " zeolitic
character."
IX
The hexite-pentite theory proposed by the authors enables prog-
noses of the chemical composition of the aluminosilicates to be made.
Two kinds of prognoses must be clearly distinguished :
1. Those founded on the proportion of base in the compound
(Base-prognoses) and
2. Those involving the presence of ring radicles (Ring-prognoses).
1. Base-prognoses
From a study of formulae of the type
Si Al Al Si = 6 A1 2 3 12 Si0 2 ,
it is possible to predict that
1. Compounds having such a formula can at most contain 10R 2 0,
and that
2. From formulae of this type the composition of an enormous
variety of salts can be predicted, including normal, acid, basic or
mixed salts, some already known and others the existence of which has
yet to be proved. By replacing the hydroxyl groups by halogens a
further series of compounds is theoretically possible.
Thus, the existence of the following compounds of this type is
readily conceivable ; the same is true of other formulae :
,__M a
I- ;; |Si|Al|Al|Si| ~ 2. |Si|Al|Al|Si
~ \/\/ JNa ~\/\/\/\/
Na Na Na Na K K
(Normal Salt) (Anhydric Salt)
Na H H Na Li H H Li
I I i I I I I I
4. ^|Si|Al|Al|SiC^ 2 2
Na H E[ lia Li Et i Li
(Acid Salt) (Acid Salt)
CONSEQUENCES OF THE H.P. THEORY
K 2 Na Na K 2
II I I II
rr-
5. *~|Si|Al|Al
H 2 =
:, Na Na K 2
(Normal Salt)
6.
Ca K K Ca
I I II
Li2== YV
Ca K K Ca
(Normal Salt)
7 - Si Al Al
M g=l A A
\/\/\/
Mg
Na 2 H H Na 2
(Acid Salt)
Na Na Na Na
I I I I
=Mg o HO-Mg-f
'HO-Mg-
Si Al
Al
Si
v/
Na Na Na
(Basic Salt)
, Mg-OH
) Mg-OH
Na
9.
2 (HOMg) =
2 (HOMg) =
Na 2 H H Na 2
II I I II
/\/\/\/\
Si I Al | Al I Si
\/\/\/\/
Na 2 H: li Na 8
(Acid and Basic Salt)
= (MgOH) 2
= (MgOH) 2
Ba H H Ba
2 (HOMg
OMg) = / \/ \/ \/ \=
(Mg OMgOH) 2
2 (HOMg-
OMg) = xxx/x/x/ =
(Mg OMgOH) 2
II 1 1 II
Ca H H Ca
(Acid and Basic Salt)
(CaOH) 2 Na Na
II 1 1
(CaOH) 2
II
11.
2 (HO-Mg-0-Mg-0-Mg) =
2 (HO-Mg-0-Mg-0-Mg)=
(CaOH) 2
K
= (Mg-0-Mg.O-Mg-OH) 2
= (Mg-0-Mg-0-Mg.OH) 2
(CaOH) 2
2. Ring-prognoses
From each primary type of formula, a series of secondary com-
pounds may be devised. Thus, from the primary type :
Si Al Al Si
PROGNOSES 75
the secondary (a) Si A! Al Si, and
(6) Si Al Al Si, may be produced ;
from the primary : Si Al Si Al Si
the secondary : (a) Si Al Si Al Si,
(6) Si Al Si Al Si,
(c) S A i Al Si Al Si,
(d) Si Al Si Al Si,
etc.
It has already been shown that a portion of the aluminium in
epidote is replaceable by Fe=. From the formula for tourmaline (see
Appendix) it may be concluded that part of the aluminium in
aluminosilicates is replaceable by boron. If it be admitted that the
aluminium in hexites and pentites may be replaced, in whole or in part,
by elements capable of forming sesquioxides and this view is highly
probable and is supported by many analyses the constitution of a
large number of compounds may be represented.
An interesting series of prognoses may be based on the properties of
the mineral " ardennite," 151 in which part of the aluminium is
replaced by vanadium. The composition of this mineral is shown by
the formula :
10 MnO V 2 5 5 A1 2 3 10 Si0 2 5 H 2 0,
which may be derived from :
Si R R Si
the structural formula being
: \ Si I Al I Al I Si ^= 5 H a O = 10 RO V 2 5 5 A1 2 3 10 Si0 2 -5 H 2 O.
\ A /<
The positions indicated by dots show the vanadium atoms in the
aluminium hexite. Vanadium hydrate is Vd Hi (OH) 5 , hence the
trivalency of the dotted positions.
It is highly probable that other " ardennites " will be found, in-
cluding the following :
1. =< Si| Al Al! Si >=-aq. = 12R 1 0-2V 1 0.-4Al I O i -10SiO i -aq.
76 CONSEQUENCES OF THE H.P. THEORY
2. I Si I Al Al | Si |_ * aq. = 12 R 2 V 2 6 5 A1 2 8 12 Si0 2 aq.
~ \/\ /\ /\/~
II I I II
II III III II
= /\/'\/"\/\ =
3. Si Al |A1 | Si I = -aq. =14R 2 0-2 V 2 5 -4Al 2 3 -12Si0 2 -aq.
=\A./\./\x =
II III III II etc.
The replacement of the silicon by allied elements, such as titanium,
zirconium, tin, etc., is also possible, and a further large variety of
compounds becomes conceivable. For instance, in the formula
(a) Al Si Al,
the aluminium atoms may be replaced by those of boron to produce
(6) B - Si B.
If the silicon in (b) is replaced by Sn
B - Sn - B,
may be produced. In a similar manner, by replacing aluminium and
silicon in substances of other types, a large number of borosilicates,
aluminostannates and borostannates become theoretically possible.
Few such compounds are known actually to exist ; among others
is nordenskioldite 152
f
6 CaO 6 B 2 3 6 SnO a = Ca 6 (B Sn B).
Apart from those aluminosilicates whose constitution has already
been described under the term " a-complexes," there is a smaller
series the " /^-complexes " which must be represented somewhat
differently, though they are quite analogous to those previously
mentioned. These include sapphirin 153
5 MgO 2 Si0 2 6 A1 2 3 .
The constitution of this compound needs some explanation, as it
has already (p. 35) been suggested that a silicon hexite can, at most,
unite with three Al. Hence the formula :
PROGNOSES 77
R 10 (A1 Si 2 Al) ; R 2 = Mg.
Sapphirin must, in fact, be regarded as a salt of an acid derived
from the hydrate :
Si S= (OH),,
>0
Si = (OH) 3
and from two hydro-aluminium-hexites by the removal of the elements
of water.
Theoretically, a sapphirin corresponding to
I _ I
Si : | Al y~
Si : |~AT V
I ~l
R 8 (Al.Si 2 -Ai); R 2 = Mg,
is possible, and, as a matter of fact, an analysis by Damour 154 and
another by W. Schluttig 155 suggest a sapphirin corresponding to
4 MgO 2 SiO a 5 A1 2 3 .
If the aluminium in sapphirin is replaced by
Fe = , Cr = , Mn E= , B = , etc,
and the silicon by
Ti, Zr, Sn, etc.,
a large number of new substances will be formed.
Howlite 156 :
Si : [B" V
I I
R 8 (B Si 2 B) aq. = 4 CaO 2 Si0 2 5 B 2 3 aq.,
* In this structural formula, the oxygen atoms are omitted for the sake of greater
clearness.
78 CONSEQUENCES OF THE H.P. THEORY
and Avasite 157 :
I __|
Si : | Fe )>-
Si:
I I
H 8 (Fe Si, Fe) 5 H 2 = 4 H 2 2 Si0 2 5 Fe 2 3 5 H 2 0,
are of this nature.
Theoretically, another class of ^-complexes is also possible, viz.
those producible from the hydrate
Al = (OH),
>O
Al = (OH),
and forming silicon hydrohexites and hydropentites in the manner
previously described. Compounds of the following types may thus be
obtained :
ii:ft" , nA
\ \/~~ Al:lJL/"
\ I \ - II
/ /\ / "
Ai:|siL ^ : |_SL>=
o \/ II
The constitution of the silicates
2 CaO - KOH A1 2 3 12 Si0 2 (milarite) 15 ',
RO A1 2 3 - 10 Si0 2 - 5 H 2 (ptioHte) 159 ,
RO A1 2 3 - 10 Si0 2 7 H 2 (mordennite) 160 , etc.,
thus becomes clearer.
If the molybdenum and tungsten complexes are truly analogous to
the aluminosilicates, they must be constituted in an analogous manner.
Assuming that, on the one hand, molybdic and tungstic acids and,
on the other hand, vanadic, phosphoric, arsenic, and antimonic acids
form hexa- and penta-radicles (hexites, pentites, hydrohexites and
hydropentites) analogous to the acids of silicon and aluminium,
complexes of molybdenum and tungsten together with their compounds
must exist or be capable|of production, which may be termed a- and
MOLYBDIC AND TUNGSTIC COMPLEXES 79
/5-complexes ; in other words it must be possible to conceive a large
number of molybdic and tungstic complexes whose constitution may be
ascertained from the hypothesis just mentioned. It is clear that the
chemical properties of the compounds should agree with the structural
formulae assigned to them. That they do so is shown below.
It is now necessary to consider what vanadium molybdates are
theoretically possible.
a-Vanadomolybdic anhydrides
Mo-V-
M5-V-
V Mo
Mo
V
= 3
= 3
= 6
V 2 6 -
V 2 5 -
V 2 5 -
12
10
G
MoO 3 ,
Mo0 3 ,
Mo0 3 ,
V Mo
V
= 5
V 2 3 -
6
Mo0 3 ,
Mo V
V-
Mo
= 6
V 2 5 -
12
Mo0 3 ,
Mo- V-
V-
Mo
= 6
V 2 5 -
10MoO 3 ,
Mo- V-
V-
Mo
= 5
V 2 5 -
12
MoO 3 ,
Mo-V-
Mo
V
Mo
= 6
V 2 5 -
18
Mo0 3 ,
Mo- V-
Mo
V
Mo
= 6
V 2 5
16
Mo0 3 ,
Mo-V-
Mo
V
Mo
= 6
V 2 5 -
15
Mo0 3 ,
Mo- V-
Mo
-V
M
= 5
V 2 5 -
18
Mo0 3 ,
V-Mo-
V-
Mo
V
-9
V 2 5
12
Mo0 3 ,
V-Mo-
V-
Mo
V
= 8
V 2 5 -
12
Mo0 3 ,
V-Mo-
V-
Mo
V
= 8
V 2 5
10
Mo0 3 ,
/Mo
V^-Mo
= 3
V 2 5
18
Mo0 33
X Mo
Mo^V
X V
= 9
V 2 5 -
6
Mo0 8 , etc. etc.
From the existence of /?-aluminosilicates it may be concluded that
the existence of analogous /2-vanadomolybdates is also theoretically
possible. These are formed (1) from the hydrate :
ViEE(OH) 4
>0
and molybdenum hydrohexites or hydropentites, and (2) from
Mo M (OH),
>0
Mo m (OH) 5 ,
80
CONSEQUENCES OF THE H.P. THEORY
and the corresponding ring-radicles of vanadic acid. In the first case
the following hydrates are produced :
I:
w;
A
Mo
V: Mo
H 12 (Mo V 2 Mb)
(b)
V : Mo >-
____ s
H 10 (Mo V, Mo)
(c)
A
1 M^ 1 \7
/\=
iv/r/-\
II II
Mo : V :
\y
Mo
\/ =
' Mo : V : Mo
\ f
II \ 1!
/ II
'
}\=
=V : Mo
=V :
Mo
1
10 H 2 V,0 5 18 Mo0 8 10 H 2 V 2 5 15 MoO,
(e)
1 1
Mo : V :
Mo
Mo : V : MO
H 16 (Mo 2 >V 2 <Mo 2 )
8 H 2 V 2 5 - 24 Mo0 3
(f)
i
Mo
: V :
Mo
H 12 (Mo 2 >V 2 <Mo 2 )
6 H 2 V 2 5 20 MoO a
MOLYBDIC AND TUNGSTIC COMPLEXES 81
When the hydrate OV 2 (OH) 8 , like the hydrohexites and hydro-
pentites, forms condensation products, acids of the following anhy-
drides :
6 V 2 5 16 Mo0 3 ,
9 V 2 5 22 Mo0 3 ,
are formed.
Similarly, a series of /2-vanadomolybdates may be formed from
OMo 2 (OH) 10 and vanadium hydrohexites or hydropentites.
If, in the a- and /2-vanadomolybdates mentioned, the vanadic acids
are represented by phosphoric, arsenious, arsenic, antimonious,
antimonic, and other acids, and the molybdic acids by tungstic acid,
the existence of vanado-, phospho-, arseno-, and other tungstates and
of phospho-, arseno-, and other molybdates becomes theoretically
possible.
Proofs of the Correctness of the above Formulae for the Representation of
the Chemical Structure of Molybdic and Tungstic Complexes
It has been repeatedly stated in the foregoing pages that the
changes which have been observed to occur in Nature in aluminosili-
cates make it highly probable that under suitable conditions they may
be converted into one another. This fact not only agrees with the
authors' hexite-pentite theory, but is a natural deduction from the
latter. In the case of the various molybdic and tungstic complexes,
also, there is the possibility that, with the same component acids,
they will be mutually convertible in the widest proportions, if their
constitution is analogous to that of the aluminosilicates. For instance,
the various vanadomolybdates are, without exception, converted
into each other under certain conditions : the vanadotungstates,
arsenomolybdates and arsenotungstates are distinguished by this
characteristic property.
The best experimental confirmation of the authors' views may be
found in the researches of Friedheim and his pupils, whose work is
characterised by the great exactitude and care with which it has been
carried out.
The above-mentioned property convertibility is shown in the
Tables on the following pages, in which a number of the results ob-
tained by Friedheim and his pupils have been summarised :
Table A. Action of a small quantity of Mo0 3 on normal vanadates.
Table B. Action of Mo0 3 on normal vanadates.
Table C Action of chlorides on NH 4 VO 3 +Mo0 3 .
Table D. Action of normal vanadates on paramolybdates.
Table E. Action of Mo0 3 on normal vanadates.
Table F. Action of Mo0 3 on phosphates.
Table G. Action of Mo0 3 on arsenates.
CONSEQUENCES OF THE H.P. THEORY
1
10 W
si
38*
HH *
II
o. 1.1
<N Tj<
oo
4*
^
ffi 1 ^
1 * 1
s
CO
.2
1 '0 1
:f
<t
q^
oj
$ P J
K* ^
t> l>
^ T
j> "7
1*
s
c8 ^ O
'o '
Q* O
o
tt
CO
q9
ws
CO"*
(M "
CO .
co .
S"
all
cs
O o^
q
1
.
.
&J
.
W O
*
*
.
q
pf
lq
U5>
-Og-
10 ifs
i
o
qj
|iV
o"
^o
4'
oF
I
HH .
&o;
TO
pq
tj"^
03
B
CO >
4^
CO
ga
o
C-J
1
N : IS
1
g
OQ W ^
o^o .
1
|
3
coo
6??
|I
1
J2
* *
*~^. IQ
Ki
^
(2
q,
t3
q e ,
2
-"co
CO
CO .
CO . X
o
q m
*r"S
0?
pf
1
o!
I
i
o q|
q!
1
I
o
cS
*"5 us
l? :
So
5>'
^
(M
RN
g<J
^
(M
CO
rl
fl"
1
in
excess
not in
excess
KC1 in
AYOAQCl
K*3
's J
"3+^
Barium chloride
WAotJoo
ZT+?
o ja
Of ""3
S O*
change of the solution formed from
kH (-f
OD
^>
(NH 4 )V0 3 + J Mol. MoO 3 with
2>
o
I
1
I
MOLYBDIC AND TUNGSTIC COMPLEXES
83
<N
4
w"
.ion products
CO
I
j
H
q
1
q
t>
Q
(M
1
1
C
J
?
4
q
<N
o
&
w"
w
"
4
<M
s.
5.
o
CM
<N
CO
^0
o
CO
1 1
CO
q
10
CO
K*
q
q
CO
q
<N
4
^
/'
q
w
g
o
M
(M
*
CO
s
o
o"
|
o
g
CO
<N
m
^
CO
i
i
&\
C<J
JS
i
^
+
_f_
a
^^
^V
kO
02
q
>"
>
>"
q
1
o
q
"*"^S
q
O N
4
M
w
g
w"
1|
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6
o
5^
tl
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CO
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O
B
S
m
i
i
q
l
W
g
s
s
O
p
o
6 s
O
1
&
1
co
+
1
M
cf
CO
1
4
P^
w i
*i
(M
W
*
n co
g
c cT
o |
CO co
C? *
*-*3
bsT
^
^
!
03 <M
*o
o
1
o
CO
J2
'1
CO
CO
"73
o
.2
a
o
q
>>
6
>
>
|
4
Q
5
.2
w"
O HH*
1
g
^H
&
The Solution
of (NH 4 )V0 3
+MoO 3 gives
by simple
evaporation
M
1
|
'S
eg O
I
Product
CONSEQUENCES OF THE H.P. THEORY
ft
o
3
^5
I
I
I
O
5
>
'o
I
s
"cS
a
i
i
^
7
? f
CJ GO
co
^H f^
9
CO CO
m
(M
^H
(M (N
U9
FH pH
O
O kO
^
q q.
(M
> >
4
^ ^-^
-5
q o o
M
kJP w **
o 1
q!
CO
. W
|
s 1
S J
1
1
I"
g,
I
M
(M
i
o:|
CO
W TH
<N
q,
W
10
CO
o
o
(O
to
q
6
M
M
CO
03
CO
CO
to
o
B
5
g
g
HH
M
1
7
t-
+
4
4
4
+
1
M
CO
I
O^H
J'" 43
CO
o
K^ -.*
<* 5
Solution of 2 NaNO 8
5
W +
H-3Na 2 O-7MoO 8
(M
(M
^
MOLYBDIC AND TUNGSTIC COMPLEXES
85
g,
B
1
eo
f'
q
'*
6
M
o
W
1
^2
00
w"
Tt*
o w
1
0*
TH
3 N
H
a
^f
o
iO
3
^^
^
* *.
a
1
4
>
?
q
CM
1
B
8
I
4
w
K
<N
CO
o
w
I 1
o
W
1 1
o
rf
1 1
q
O
W
q
w
l-H
1
4
g
o
s
(M
o"
i
o w
1
03
i
o"
1
.
1 1
(N
.
CO
C<l
00
r I
q
'
o
us
10
>
H
q
q
q
o
q
^
s
o
(M
n
1
g
4
M
w
g.
(N
4
i
n
^3*
^***
*O
(M
^o
i^
CO
bO
1
III
!
n
s^=
6
C
leo
I
4
i
J1
^H S ^
fl
d
w
*S ^
O
^^
i!
CO <D
q
o;
10
d
1
(M
eo
O
i
f
If
fl
q
Q
>"
(M
10 U9
q q
l!
*+H O
IJ
s
w*
g
4
M
B
g
4
w
Ma
O
M
^ 4
CO
IQ
P^ c^
10
86
CONSEQUENCES OF THE H.P. THEORY
O
q
W
CO
<o
is
CO
w w
CO
sw
i
9"
M
o4
1
d
1
?
pT*
10
u>
10
co O
q
2-
4s
ev
ft
w ^
q
q
<0*
1-t
4
09
M
M
M
O,
q
o
II
i
1
d
O
i
|
V18MoO 3
W
00
n
pf
co
Q
1
9
i
00
i-H
i
1
CO""
1?
7
o"
o;
i
1
*8
4 '
Q
6
pT
PH
pT
o
^i
w
\i
M
6
q
q
cT
ffi
^*
"*
CO
M
M
M
CO
CO
(N
CO
j-
CJ
w
d
o
9
1
i
i
1
|
9
i
o
O)
CO
rt<
o
O
00
^ o
O
11 O
. O
7O
'""' O
^*
O
o
dw
O HH
d
qtf
d M "
qW
i
42
S
^
PjS
pT
**?
pT
pj'S
pT
^2
s
s
6
w
4
6
"
CO
4
4
4
M
4
c5
i'
o
CO
>o
10
10
CO
10
1
1
Reacting
nbstances
1
PH
"3
^
+0
1
+d
11
P<
i
+0
* O
Q g
1
+
P
"3
He) co
4 saturated \
Mo0 3
lo-
ll
03
I
B
a
M
M
w
M
3
2.
1
MOLYBDIC AND TUNGSTIC COMPLEXES
87
10
o
H !
i
o
CO
1
i
W
4
S
1O
%
*6
<<
K
m
HH
w
Q
6"
O
co
Q
03
o qoq
*
m
|
3
a
M7s2
o
o
lo
1
!
CO
d
"B
o;w
q
03
J?
o>-
ro
w
M >O
en* *
*fl
tc* 1O
OQ 1O
1
m
<<
.
q
<J
<J
1
q
q
W*
q
q
i,
M
M
(M
M
M
a
o
6 s
o
1
f "
1
?
S
<N
q
Ml
q
^ |
o" W
6 s w
7
I
O3
M '
4""?
4S" 1 ?
6
q
q
10
6
q
M
M
M
w
<N
CO
o*
i
CO
1
CO
II
o"
i
CO
I 1
ji
^ s
q m
1C MoO 3
M
q
q
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7 o
Q 1
43
43
4S
-
w N 3
1
q
q
q
^
00
10
q
M
M
M
r- !
1 (
M
CO
10
10
10
tJO CD
*1"
II
ii
Is
1-3 C9
o m
3S
^s
qo
03 "*"*
CM
(N
CM
. CO
^
J
q ~f~
O -f
q +
. +
q +
q ^~
00
M
M
w
M
w
88
CONSEQUENCES OF THE H.P. THEORY
It is not difficult to show that the vanadomolybdates given in the
Tables A, B, C, D, and E are genetically related to each other, as
would be expected from the theory.
There must, of necessity, be a relation between vanadomolybdates
in Tables A, B, and C, as these compounds are all obtained by the same
method from different proportions of normal vanadates and Mo0 3 .
The compounds shown in Table C must be related to those in A and
B, as they are nothing more than transformation products of the
latter. Hence the following genetic relationship between the vanado-
molybdates :
(a)
(b)
(c)
(d)
(e)
(/)
(9)
(h)
(i)
(k)
(D
2R 2
V 2 5
6 MoOa,
5R 2 O
2 V 2 5
12 Mo0 3 ,
7R 2 O
3 V 2 5
18 Mo0 33
R 2
V 2 5
3Mo0 3 ,
2R 2
V 2 5
3Mo0 3
3R 2
2 V 2 5
6Mo0 3
2R 2
2 V 2 5
5Mo0 3
3R 2 O
2V 2 5
4Mo0 3
4R 2
3 Vo0 5
5MoO 3
5R 2
4 V 2 5
6Mo0 3
R 2
V 2 5
Mo0 3 .
Those shown in Table D, viz. :
(a') 3 R 2 V 2 5 6 MoO 3 ,
(b') 5 R 2 2 V 2 O 5 12 Mo0 3 ,
(c') 2R 2 0- V 2 O 5 - 4Mo0 3 ,
(d') 2R 2 0- V 2 5 - 3Mo0 3 ,
must also be related, as they have been produced in an analogous
fashion from normal vanadates and paramolybdates.
On the other hand, the vanadomolybdates (b') and (d') have a
composition analogous to (b) and (e) in Tables A, B, and C, whereby
the relationship of the various molybdates in the first four Tables
enables them to form a definite class of compounds.
Table E includes the following :
(&")
(O
(d")
(O
2R 2
5R 2
7R 2
2R 2
3R 2
V 2 5
2V 2 5
3V 2 5
V 2 5
2V 2 5
6MoO 3
12 Mo0 3
18 Mo0 3
4 MoO,
4 MoO,
From this Table (E) a relationship is shown between
1. a", b", c" ;
2. a", d" and
3. V e",
so that a", b", c", d" > and e" must be analogously constituted.
MOLYBDIC AND TUNGSTIC COMPLEXES 89
As these substances are also shown in the Summary of Tables A,
B, C, and D
a* = a,
b" = b 7 = b,
c 77 = c,
d 77 = c 7 ,
e 77 = h,
there is a definite actual relationship between all the vanadomolyb-
dates mentioned in Tables A, B, C, D, and E.
It is obvious that there can only be one theory which explains all
these vanadomolybdates satisfactorily. The authors' hexite-pentite
theory does this, and, what is more, it enables the existence of this
relationship to be predicted. A study of the following structural
formulae of these vanadomolybdates leads to the surprising result that
a large number of the theoretically constructed compounds of this
group are actually in existence, and it is to be expected that the
remaining vanadomolybdates which are theoretically possible
will be discovered sooner or later.
The vanadomolybdates just mentioned clearly possess the following
structural formulae :
. /./*h
(2 R 2 - V 2 6 6 Mo0 3 ) 3 = R 12 V^-Mo (a, a 77 ),
7 R 2 3 V 2 6 18 Mo0 3 = R 14 (v^-Mo I (c, c"),
/ /M A CK
(5 R 2 2 V 2 5 - 12 MoO.K.5 = B J V^-Mo 1 (b, b 7 , b 77 ),
V X l&/
(3R 2 0-V 2 5 -6Mo0 3 ) 3 = R 18 (vr-Mo) (a 7 ),
V XT*/
(R 2 V 2 O 5 3 Mo0 3 ) 6 = R 12 (Mo V Mo V Mo) (d),
(2 R 2 V 2 5 3 Mo0 3 ) 6 = R 24 (Mo V Mo V Mo) (d 7 , ej,
(3 R 2 2 V 2 5 6 Mo0 3 ) 3 = R 18 (Mo V Mo - V Mo) (f),
(2 R 2 2 V 2 5 5 Mo0 3 ) 3 = R 12 (Mb V Mo V So) (g),
(3 R 2 2 V 2 5 4 Mo0 3 ) 3 = ~R l6 (Mo V V Mo) (e 77 , h),
(4 R 2 3 V 2 5 5 Mo0 3 ) 2 = R 16 (Mo V V -Mo) (i),
(5 R 2 4 V 2 5 6 Mo0 3 ) 2 = R 20 (Y Mo V Mo -V) (k),
(R 2 V 2 5 Mo0 3 ) 6 = R 12 (V M A o V) (1),
(2 R 2 V 2 5 4 Mo0 3 ) 3 = R 12 (Mo V Mo) (c 7 , d 77 ).
90 CONSEQUENCES OF THE H.P. THEORY
The objection may be raised to the conception of the a-vanadomo-
lybdates as salts of complex acids : viz. the ratio of the acid components
(V 2 5 : Mo0 3 ) must remain unchanged when the acids are treated
with salts such as NaCl, KC1, etc., and the only substitution which can
take place is by means of monovalent elements such as Na, K, etc.
With the vanadomolybdates, however, this is not always the case.
For instance, it may be seen from Table A, that the compound
(a') 5 (NH 4 ) 2 4 V 2 5 - 6 Mo0 3 14 H 2 0,
on treatment with KC1 is converted into
(&') 3 K 2 - 2 V 2 O 5 4 Mo0 3 7 H 2 0.
The acid anhydride ratio in (a') is 2 : 3 and in (&') it is 1 : 2.
From the same Table it follows that
(c') 3 K 2 (NH 4 ) 2 3 V 2 5 5 Mo0 3 9 H 2 0,
on treatment with KC1 is converted into
(d f ) 3 K 2 2 V 2 5 4 Mo0 3 7 aq.
In (c') the ratio of V 2 O 5 : Mo0 3 =3 : 5 and in (d') I : 2.
In this connection it should be borne in mind that notwith-
standing the undoubted existence of free complex acids of Mo and W,
such as the silicotungstate SiO 2 12 WO 3 , silicomolybdate Si0 2
12Mo0 3 , phosphomolybdate P 2 O 5 24MoO 3 , etc. Friedheim and
his associates endeavoured to regard molybdic and tungstic complexes
as salts of related acids ; they conceived the idea that they might be
double salts and had hopes that this would suffice to explain the
remarkable conversions they had observed. And yet these reactions
are by no means so puzzling as may, at first sight, appear. Only the
a-complexes of the aluminosilicates can be distinguished by a certain
durability, e.g.
5.5 R 2 6 A1 2 3 16 Si0 2 (p. 39),
in Lemberg's series. Whatever salts are allowed to act on the com-
pounds in this series the aluminasilica ratio remains constant. In the
a-components of the molybdic and tungstic complexes this is not always
the case ; they are, to some extent, unstable. The aluminosilicates
are not all of equal stability. Of all the numerous types previously
mentioned,
SVA1-A1-SX
the kaolin type, is the most stable. It is well known that the action of
various natural (geological) processes is to convert the various alumino-
silicates into compounds of the kaolin type.
The great stability of compounds of the kaolin type is also shown
by a series of fusion experiments by Doelter 168 , who found that
MOLYBDIC AND TUNGSTIC COMPLEXES 91
1. Laumontite :
Ca 3 (Al Si Al) 12 H 2 0,
at a sufficiently high temperature, loses silica and water, forming
anorthite :
Ca 6 (S A i Al Al Si).
2. On fusion, natrolite :
Na 12 (Sl - Al - Si Al - Si) - 12 H 2 0,
produces
Na 12 (Si Al Al Si),
silica and water.
3. On fusion, scolecite :
H 24 Ca 6 (Si Al Si Al Si) 6 H 2 0,
yields
Ca,(Si Al Al Si),
silica and water.
If the vanadomolybdates and vanadotungstates are true analogues
of the aluminosilicates, the most stable of the a-compounds must be
Mo V V Mo, and
W-V-V-W.
This is actually the case, for Friedheim has shown that
(a) 6 Na 2 3 V 2 5 6 W0 8 ,
on boiling with WO 3 , is converted into
() 6 Xa0 3 V 2 6 12 W0 8 ,
and on fusing ft the a-compound
W V V W,
remains behind.
On studying the puzzling transformations of the vanadomolyb-
dates in the light of the hexite-pentite theory, it will be seen that the
less stable a-compounds are converted into the highly stable
Mo V V Mo.
The conversion of (a') into (&') and (c') into (V) may be represented
as follows :
V Mo tf - Mo - V -> Mo V - V Mo ,
(') (&')
Mo V V Mo -- > Mo V V Mo .
(O (*')
92 CONSTITUTION OF MOLYBD1C & TUNGSTIC COMPLEXES
No double decomposition can result from the action of KC1 on
(a') or (c'), because these substances are unstable in solution, as may
be found from their behaviour when attempts are made to crystallise
them from such solution. The ratio V 2 5 : Mo0 3 in compounds of the
type Mx> . V . V . Mo is not affected by reactions involving double
decomposition.
The most stable type of compound may be represented by
Mo
X Mo
deduced from the conversion of (a") and (&") into (c") (Table E).
No less interesting is Table F, all the compounds of which, with
the exception of
6 K 2 4 P 2 5 9 Mo0 3 4 H 2 0,
may be accurately represented by hexite-pentite formulae, thus :
(a) (2 R 2 P 2 O 5 4 Mo0 3 ) 3 = Ri 2 (Mo P Mo),
(6) 4 R 2 3 P 2 6 10 Mo0 3 = R 8 (Mo~ P Mo),
(c)
(R 2 0-P 2 5 -2Mo0 3 ) 6
= R 12 (Mo P P Mo),
(d)
(4R 2 O-3P 2 5 -9Mo0 3 ) 2
= R 16 (]\io P Mo P Mo),
(e)
7 R 2 5 P 2 5 16 Mo0 3
= R 14 (Mb P M A o P Mo),
(/)
(4R 2 0-3P 2 6 -4Mo0 3 ) 3
= R 24 (P Mo P Mo P),
(9)
(2R 2 0-P 2 5 -5Mo0 3 ) 3
(/MCA
P^-Mo
X Mo/
(g f ) (5 R 2 2 P 2 5 10 MoO,) l . B = R 15 | P^-Mo |
^Mo/
(f) (3R 2 0-P 2 6 -5MoO
) - R (V ;
3 ; 3 rv 18 i Jr\.
\ ^ :
(,ax
P 2 ^-M
X M A
() 2.5R 2 O-P 2 5 -24Mo0 3 =
(t") (3 R 2 - P 2 5 24 Mo0 3 ) =
Altogether this series affords one of the most interesting confirma-
tions of the hexite-pentite theory, and the advantages of grouping
together these substances on the basis of their analogous mode of
GENETIC RELATIONSHIPS OF ARSENOMOLYBDATES 93
formation are readily understood. Friedheim, on the contrary, suggests
the following, particularly with regard to the compounds (c), (d), (e),
and (/) :
" Only compound (c) of the previously unknown substance the
simplest of all those which contain phosphoric and molybdic acids is
of a simple nature . . . the other substances are undoubtedly mix-
tures."
Friedheim regards the compounds (d), (e), and (/) as " mixtures "
simply because he could not otherwise explain their composition ! The
Table is, therefore, only of value in so far as it shows a relationship
between the a- and /3-phosphomolybdate complexes !
Table G leads to the same conclusions as the others. The sub-
stances in it may clearly be expressed in the light of the hexite-pentite
theory as follows :
(a) (2 R 2 As 2 5 4 Mo0 3 ) 3 = Ri 2 (Mo As Mo),
(a') (3 R 2 As 2 5 4 Mo0 3 ) 3 = Ri 8 (Mo As - Mo),
(b) (R 2 O As 2 6 2 Mo0 3 ) = R 12 (M A Q As As Mo),
(c) (R 2 O As 2 6 6 Mo0 3 ) 8 = R 6
(3R 2 0- As 2 6 -6Mo0 3 ) 3
(d) (2R 2 0-As 2 5 -5Mo0 3 ) 3 = R 12 ( As^-Mo
|'Mo>
As^-Mo
/ /
.5==Rl 5 |AsH
(e) 5 R 2 As 2 6 16 Mo0 3
(s\ 1V1U
As 2 ^-jMo
X /Mr.
Of further interest in connection with the hexite-pentite theory
are the series of salts 170 produced by the action of V 2 5 on potassium-,
sodium- and ammomum-paratungstates :
1. 2 R 2 V 2 6 4 W0 3 ,
2. 4 R 2 O 3 V 2 5 12 W0 3 .
Of these, the first is immediately decomposed by acids even in the
cold with separation of almost the whole of the tungstic acid. On
evaporation with hydrochloric acid, the tungstic acid is precipitated
94 CONSTITUTION OF SILICOTONGSTATES
quantitatively in as complete a manner as in ordinary tungstic salts,
though in this instance it is rendered impure by the co-precipitation of
vanadic acid.
Compounds of the second series are not affected by acids.
Friedheim has endeavoured to show that the action of acids on the
compounds in the first series brings about a separation of tungstic
acid because they have, as one of their constituents, a paratungstate
which behaves in the same manner. He therefore suggested the
following equation :
(2 R 2 O V 2 5 4 W0 3 ) 3 = 5 R 2 12 W0 3 + R 2 3 V 2 5 .
( Paratungstate )
The compounds of the second series he expressed as shown below,
because the meta-tungstic acids behave in an analogous manner :
4 R 2 3 V 2 5 12 W0 3 = 3 (R 2 4 W0 3 ) + & 2 3 V 2 5 .
( Me t atungs tate )
Friedheim himself raised the following objection to his own con-
ception of the molecular structure of the compounds of the first
series 171 :
"The aqueous solution of the compound 2 R 2 V 2 5 4 WO 3
yields no precipitate on the addition of barium chloride or silver
nitrate, but on evaporation with the first of these reagents the corre-
sponding barium salt is formed; with silver nitrate a red solution,
which changes after a time to a purple-reddish crystalline compound of
the corresponding silver salt, is produced, and, if the solution is con-
centrated, the salt crystallises out in red needles."
It is scarcely likely that the compounds 2 R 2 V 2 O 5 4 W0 3
contain the components shown by such a formula, as the latter does
not indicate a substance which will form easily soluble barium and
silver salts. In another research, Friedheim regards these compounds
atomically, though even then it is scarcely possible to see, from Fried-
heim's structural formula (p. 21), that the bonds between the vanadium
and the tungsten are different in the second group from what they are
in the first. Yet this difference is at once observable in the following
structural formulae based on the authors' hexite-pentite theory :
W
W
-\/y\/
w
v
w
I II I I I
6 R 2 O - 3 V 2 6 12 W0 3 4 R 2 3 V 2 5 12 WO 3 .
Valuable confirmation of the authors' theory is also found in the
interesting researches by Marignac 172 on the silicotungstates. His
formula (Si0 2 12 WO 3 ) at once suggests hexite.
For the compound
4 H 2 Si0 2 12 WO,,
DIMORPHISM OF POTASSIUM SILICOTUNGSTATE 95
the hexite-pentite theory shows three isomers to be possible, viz. :
1.
2.
/\
w
/\=
W
w
\/
W
\/
3.
I I
,/\
W
Marignac prepared two isomeric acids and two isomeric series of
salts having the formula 4 R 2 Si0 2 12 WO 3 .
The " water of constitution " in the free acids and in some of the
salts may be demonstrated in a very accurate manner, as the acids
4 H 2 Si0 2 12 WO 3 29 H 2 O lose 25 mol. H 2 O at 100% another
6 mol. between 150 and 220, and are completely dehydrated at 350.
Hence, 8 mol. H 2 O may be regarded as the " water of constitution "
as shown in the structural formula :
W
/
W
\
The calcium salt, 2 CaO 2 H 2 O Si0 2 12 W0 8 22 H 2 0, loses 16
mol. H 2 at 100, and it also contains 8 mol. H 2 as " water of con-
stitution." This may be expressed thus :
(OH),
KO-Ca A
HO
W
:Si
(OH) 2
/\_Ca-OH
W OH
(H0) 2 = x/ \/=(OH) 2
(OH) 2 (OH) 2
The potassium salt
2 K 2 O 2 H 2 Si0 2 12 WO S 7 H,0
occurs in thick prisms and pearly hexagonal plates. Its dimorphism
may be explained by the use of the following formula :
l.
TT
H
K .]
A /
w|:Si: V
\/ \
i 1
L
\-H
V
/-H
H
I
2.
K
K
H
/\_i
W :Si
\/
i
K
The silicotungstates may also be regarded as representing the
/3-complexes which, in molybdic and tungstic compounds, are so much
96 ^-COMPLEXES OF MOLYBDENUM AND TUNGSTEN
more stable than the a-complexes. The /3-complexes usually yield free
acids and the salts are not easily converted into compounds of other
series, but will crystallise from their aqueous solution without any
decomposition. The acid component ratio also remains unaffected by
reactions involving a double decomposition.
Theoretically, the following compounds may exist :
V
4 R 2 Si0 2 10 W0 3 ,
and Marignac also prepared compounds of this series.
The following formulae for molybdic and tungstic /5-complexes are
derived from compounds mentioned in Dammer's " Handbook " :
/3-complexes
(a) R 2 (Mo A1 2 Mo),
(6) R 4 (W B 2 W),
(c) R 8 (Wj Si W),
(d) R 8 (Mo-Pt-Mo),
(e) R 8 (W Pt W).
(a) R 2 (Mo A1 2 Mo).
K 2 A1 2 3 10 Mo0 3 15 H 2 (Parmentier 173 ).
(b) R 4 (W-B 2 -W).
2 BaO B 2 3 10 W0 3 16 H 2 (Klein 174 ).
(c) R 8 (W-Si-W).
4 H 2 O Si0 2 10 W0 3 3 H 2 (Marignac 175 ),
3(NH 4 ) 2 -SiO 2 -10W0 3 - 9 H 2
4(NH 4 ) 2 O -Si0 2 -10W0 3 - 8H 2 O,
2 H 2 2 K 2 Si0 2 10 W0 3 8 H 2 O,
4 K 2 Si0 2 10 W0 3 17 H 2 0,
4Ag 2 -Si0 2 -10W0 3 - 3H 2 0,
4 BaO Si0 2 10 W0 3 22 H 2 0.
(d) R 8 (Mo-Pt-Mo).
4 Na 2 Pt0 2 10 Mo0 3 29 H 2 (Gibbs 176 ).
(e) R 8 (W-Pt-W).
4 (NH 4 ) 2 PtO 2 10 W0 3 12 H 2 O (Gibbs 177 ),
4 Na 2 O Pt0 2 10 W0 3 25 H 2 O,
4 K 2 Pt0 2 10 W0 3 12 H 2 0.
/3-COMPLEXES OF MOLYBDENUM AND TUNGSTEN 97
(a) R,(Mo A1 2 Mo),
(b) R e (Mo Cr 2 Mo),
(c) R 8 (W B 2 W),
(d) R m (Mo Si Mo), (m = 4.8)
(e) R 8 (W Si; W),
(/) R 2 (Mo Zr Mo),
(g) R 2 (Mo Ti Mo),
(h) R m (W-P 2 -W), (m = 2.4)
(t) Ri (Mo - 1 2 Mo).
(a) R 6 (Mo Ai 2 Mo).
3 (NH 4 ) 2 A1 2 3 12 Mo0 3 20 H 2 (Parmentier 178 ),
3 K 2 A1 2 3 12 MoO, 20 H 2 0,
3 Na 2 A1 2 3 12 Mo0 3 22 H 2 0.
(b) R 6 (Mo Cr 2 Mo).
3 (NH 4 ) 2 Cr 2 3 12 Mo0 3 20 H 2 O (Struve 179 , Parmentier 180 ),
3 K 2 Cr 2 3 12 Mo0 3 20 H 2 O (S.),
3 Na 2 Cr 2 3 12 Mo0 3 21 H 2 (S.).
(c) R 8 (W-B 2 -W).
2 K 2 2 H 2 B 2 3 12 W0 3 16 H 2 (Klein 181 ),
4 K 2 B 2 3 12 W0 3 21 H 2 0,
K 2 3 BaO B 2 O 3 12 W0 3 28 H 2 O.
(d) R m (Mo Si Mo) ; m = 4.8.
2 H 2 Si0 2 12 Mo0 3 24 H 2 (Parmentier 182 ),
2 H 2 Si0 2 12 Mo0 3 30 H 2 (Asch 183 ),
2(NH 4 ) 2 O Si0 2 12 MoO 3 8 H 2 (P.),
2 K 2 Si0 2 12 Mo0 3 14 H 2 O (P.),
2 K 2 Si0 2 12 Mo0 3 16 H 2 (P.),
1.5 K 2 0.5 H 2 O SiO 2 12 Mo0 3 1.35 H,O (A.),
2 Na 2 O Si0 2 12 Mo0 3 21 H 2 O
1.5 Na 2 0.5 H 2 Si0 2 12 Mo0 3 16.5 H 2 0,
2 Ag 2 O Si0 2 12 Mo0 3 12 H 2 O,
1.5 Ag 2 O 0.5 H 2 Si0 2 12 Mo0 3 10.5 H 2 O,
4 Ag 2 O Si0 2 12 Mo0 3 15 H 2 0,
2 MgO Si0 2 12 Mo0 3 30 H 2 0,
2 BaO Si0 2 12 Mo0 3 24 H 2 0,
2 CaO Si0 2 12 Mo0 3 24 H 2 0.
(e) R e (W Si W).
4 H 2 Si0 2 12 W0 3 22 and 29 H 2 (Marignac 184 ).
4 H 2 Si0 2 12 WO 3 20 H 2 0,
4 (NH 4 ) 2 Si0 2 12 W0 3 16 H 2 O,
2 (NH 4 ) 2 . 2 H 2 . Si0 2 . 12 W0 3 6 H 2 O,
98 ^-COMPLEXES OF MOLYBDENUM AND TUNGSTEN
4
K 2 0-
Si0 2 -
12 W0 3
20
H 2 0,
2K a O
2
H 2 0-
Si0 2 -
12W0 3
7
H 2 0,
2K 2 O
2
H 2 O-
Si0 2 -
12W0 3
16
H 2 0,
3K 2 O
5
H 2 O-2
(Si0 2 -
12W0 3 )
25
H 2 0,
4Na 2
'
SiO 2 -
12WO 3
7
H 2 0,
2Na 2 O
2
H 2 0-
Si0 2 -
12WO 3
10
H 2 0,
2Na 2 O
2
H 2 0-
Si0 2 -
12WO 3
11
H 2 0,
2Na 2
2
H 2 O-
SiO 2 -
12WO 3
18
H 2 0,
3 (2 Na 2 O
2
H 2 O-
Si0 2 -
12WO 3
13
H 2 0)
Na 2 O
3
H 2 O-
Si0 2 -
12 W0 3
14
H 2 0,
Na 2
3
BaO-
Si0 2 -
12WO 3
28
H 2 0,
2MgO
2
H 2 O-
Si0 2 -
12WO 3
16
H a O,
5CaO
3
H 2 O-2
(SiO 2
12 W0 3 )
47
H 2 0,
2CaO
2
H 2 0-
Si0 2 -
12WO 3
20
H 2 0,
2CaO
2
H 2 O-
Si0 2 -
12WO 3
22
H 2 0,
4 BaO
Si0 2 -
12 WO 3
27
H 2 0,
2BaO
2
H 2 O-
SiO 2 -
12 W0 3
14
H 2 0,
4 Na 2 N0 3 ,
2 BaO 2 H 2 Si0 2 12 W0 3 22 H 2 0.
(/) R 2 (Mo Zr Mo).
2 (NH 4 ) 2 O ZrO 2 12 Mo0 3 10 H 2 (Pechard 185 ),
2 K 2 Zr0 2 12 Mo0 3 18 H 2 0.
(g) K 2 (Mo Ti Mo).
2 K 2 Ti0 2 12 MoO 3 20 H 2 O (Pechard 186 ),
2(NH 4 ) 2 O-Ti0 2 -12M0 3 10 H 2 0,
2 K 2 Ti0 2 12 M0 3 16 H 2 0.
(h) R m (W-P 2
W); m
P 2
5
12
W0 3 -
42
H
2 (Pechard 187 ),
2 (NH 4 ) 2
P 2
5
12
WO 3 -
5
H
.0,
K 2 O
P 2 O
5
12
W0 3 -
9
H
.0,
2 Na 2 O
P 2
5
12
WO 3 -
18
H
2 o,
Li 2 O
P 2
5
12
W0 3 -
12
H
,0,
T1 2
P 2
5
12
WO 3 -
4
H
,0,
Ag 2
P 2
5
12
W0 3 -
8
H 2 0,
2CuO
P 2
5
12 WO,
11
H
A
2ZnO
P 2
5
12
W0 3 -
7
H
.0,
2PbO
P 2 5
12
W0 3 -
6
H
.0,
2MgO
P 2
5
12
WO 3 -
10
H
2 o,
2CaO
P 2
5
12
W0 3 -
19
H
A
2SrO
P 2 5
12
W0 3 -
17
H
2 o,
2 BaO
P 2
5
12
W0 3 -
15
H
2 0.
2.4.
(t) R 10 (Mo I 2 Mo).
5 (NH 4 ) 2 I 2 O 7 12 Mo0 3 12 H 2 O (Blomstrand 188 ),
9 K 2 H 2 O 2 (1,07 12 MoO 3 ) 24 H 2 0,
5 NaoO I 2 7 12 Mo0 3 26 HoO,
5 Na 2 I 2 7 12 Mo0 3 34 H 2 0,
^-COMPLEXES OF MOLYBDENUM AND TUNGSTEN 99
5 Li 2
5 Li 2
5 CaO
4 CaO
4 SrO Na 2 O
I 2 7
I 2 O 7
I 2 7
I 2 7
I 2 O 7
9 BaO Na0 2 (I 2 7
2 MnO 3 Na 2 I 2 7
R 2
12 Mo0 3
12 Mo0 3
12 Mo0 3
12 Mo0 3
12 MoO 3
12 MoO 3 )
15 H 2 0,
18 H 2 O,
26 H 2 0,
21 H 2 0,
20 H 2 0,
28 H 2 0,
12 Mo0 3 32 H 2 0.
(/Mo
P/M-o
^Mo
K 2 P 2 5 15 Mo0 3 (Rammelsberg 189 ).
(a) R 3
(&)
(c) R,
( / M \
\^$}
*'K|
B.f (/*);
V \w/
m = 1.2.
V ^MW
(a)
5 (NH 4 ) 2 O Mn 2 3 16 Mo0 3 12 H 2 (Struve 190 ),
5 K 2 Mn 2 3 16 MoO 3 12 H 2 0.
3(NH 4 ) 2
Mo
3 (NH 4 ) 2
2 BaO (NH 4 ),0
6 (NH 4 ) 2
3K 2
2 H 2 4 K 2 O
5 H 2 CaO
3 BaO
(a) R 6
P 2 6 16 MoO 3 14 H 2 (Kehrmann 191
(c) R n /P 2 ^w]; m = 6.i:
P 2 O 5 16 W0 3
69 H 2 (Kehrmann 192 ),
P 2 5 16 W0 3
16'H,0
P 2 5 16 W0 3
xH 2 0,
P 2 3 16 W0 3
2H 2 0,
P 2 5 16 W0 3
16 H 2 O,
P 2 5 16 WO,
19 H 2 0,
P 2 5 16 WO 3
3H 2 0,
P 2 5 16 WO,
xH 2 0.
/ ^\
*<i
100 ^-COMPLEXES OF MOLYBDENUM AND TUNGSTEN
/ W^
/ - >
(b)
(c)
(J.TJAJ>
P 2 /Mo
(3 x) Na,0 P 2 5 18 Mo0 3 (25 + x) H 2 (Finkener 193 ).
*(*<!)
6 K 2 P 2 5 18 WO 3 23 H 2 (Gibbs 194 ),
6 K 2 P.,0 5 18 W0 3 30 H 2 0,
K 2 5 H 2 P 2 5 18 W0 3 14 H 2 0.
MCK
,
(c) R 12 lAs/MoJ
As 2 5 18 Mo0 3 30 and 28 H 2 (Pufahl 196 ),
2 (NH 4 ) 2 4 H 2 As 2 5 18 MoO 3 13 H 2 (Mach 196 ),
3K 2 O-3H 2 - As 2 5 -18Mo0 3 -25H 2 O,
K 2 5 H 2 O As 2 5 18 Mo0 3 21 H 2 O,
3K 2 O-3H 2 O - As 2 5 18 MoO 3 - 21 H 2 O,
3 Li 2 3 H 2 O As 2 O 5 18 Mo0 3 31 H 2 O,
6T1 2 O As 2 5 -18Mo0 3 - x H 2 0,
3T1 2 O-3H 2 As 2 5 18 MoO 3 3 H 2 0,
6Ag 2 O As 2 O 5 18 Mo0 3 22 H 2 0,
7 Ag 2 - 5 H 2 O 2 (As 2 5 18 MoO 3 ) 22 H 2 0,
3CaO-3H 2 - As,O. 18Mo0 3 29 H 2 0,
3SrO-3H 2 O . As 2 O 5 18 MoO, 29 H 2 0,
3 MO 3 H 2 As 2 O 5 18 MoO, 33 H 2 O (M = Mg, Cd, Mn, Co),
3 MO 3 H 2 - As 2 5 18 MoO. 34 H 2 (M = Zn, Cu, Ni),
I .Vo.
t r
^-COMPLEXES OF MOLYBDENUM AND TUNGSTEN 101
3 H 2 O P 2 5 20 Mo0 3 -21, 38 & 48 H 2 (Debray 197 ),
2 Ag 2 O P 2 O 5 20 Mo0 3 7 H 2 0,
3 K 2 O P 2 O 5 20 MoO 3 3 H 2 0,
7 Ag 2 P 8 O 5 20 Mo0 3 24 H 2 0.
W\. /W
P 2 5 20 WO 3 62 H 2 (Pechard 198 ),
P 2 5 20 W0 3 50 H 2 O (P.),
6 BaO P 2 5 20 W0 3 48 H 2 O (Gibbs 199 ).
o /Mo\ o /Mo
As 2 5 20 Mo0 3 27 H 2 (Debray 200 ),
3 K 2 As 2 5 20 Mo0 3
/Mo\o /Mcr
o /oo o\
MMO>>\MO)
Mo\ /Mb-,
m = 6, 14.
3(NH 4 ) 2 O P 2 5 -22Mo0 3 9 H 2 O (Gibbs 201 ),
3 (NH 4 ) 2 O P 2 5 22 Mo0 3 12 H 2 (Rammelsberg 202 ),
3K 2 O P 2 5 -22Mo0 3 (R.),
5 K 2 O H 2 2 (P 2 O 5 22 MoO 3 ) 21 H 2 (R.),
7 Ag 2 P 2 5 22 Mo0 3 14 H 2 (G.).
^, 6,8,14.
P 2 5 22 WO 3 7 H 2 (Kehrmann 203 ) and
2 K 2 P 2 O 5 22 W0 3 6 H 2 O (Gibbs 204 ), (Freinkel),
3 (NH 4 ) 2 O P 2 O 5 22 W0 3 - 21 H 2 O (G.),
4 BaO P 2 5 22 W0 3 41 H 2 (G.),
7 K 2 P 2 5 22 WO 3 x H 2 (K. and Fr.),
7 BaO P 2 5 22 W0 3 59.5 H 2 O (Sprenger, K. and Fr.),
3 BaO 4 Ag 2 P 2 5 22 W0 3 x H 2 (K. 205 ).
*"(!><!)
102
THE CONSTITUTION OF CLAYS
3 (NH 4 ) 2
(9-x)(NH 4 ) 2
5 (NH 4 ) 2
2K 2
(3 x)Na 2
3 H 2 P 2 5 24 Mo0 3 27, 46 & 59 H 2
(Gibbs 206 ), Finkener 207 ), Kehrmann 203 ),
P 2 5 -24Mo0 3 (Hundeshagen 209 ),
(P 2 O 5 24 Mo0 3 ) (Gibbs),
P 2 5 -24Mo0 3 -16H 2 0,
P 2 5 -24Mo0 3 - 3H 2 0,
P 2 5 24 Mo0 3 - (58 + x) H 2 0.
m = 2, 4, 6.
xH 2
H 2
H0
P 2 6 24 WO
3 (NH 4 ) 2
3K 2
3Na 2 O
PA
PA
PA
40, 59 and 60 H 2 O
(Pechard 210 ), (Gibbs 211 ), (Sprenger 212 ),
24 W0 3 20 H 2 O (Gibbs),
24W0 3 - 11 or 17H 2 (Gibbs),
24 W0 3 22 H 2 O
(Brandhorst and Kraut 213 ), (Kehrmann 214 ),
2BaO
PA
24
W0 3 -
46 H 2 0,
2Na 2
PA
24
W0 3 -
27 H 2 0,
3Ag 2
P 2 5
24
WO 3 -
58 H 2 0,
Ag 2
P 2 5
24
W0 3 -
60 H 2 O,
3CaO
PA
24
WO 3 -
58 H 2 0,
3BaO
P 2 5
24
W0 3 -
58,46 H 2 0,
2BaO
PA
24
WO 3 -
59 H 2 0,
BaO
PA
24
W0 3 -
60 H 2 0,
etc. etc.
XI
The Constitution of Clays
The hexite-pentite theory shows the possible existence of a large
number of aluminosilicic acids in the form of hydrates and anhydrides.
Thus, if
Si Al Al Si,
is taken as the type, the following hydrates are possible :
, ' Y Y Y
H; 2 (Si Al Al S A i)
4.
_x\/\
Si
\/
Al
HJ 2 (Si Al
/\=
Si
\X =
Al S A i)
A
I II
\/\
Si
Al-Si)
Si A1|A1
'Y
HJ 2 (Si Al Al
6.
THE CONSTITUTION OF CLAYS
103
1 1
AA/s/V-
/\/\/\/\
Si
AlJAljSi
Si Al Al Si
\/
(Si
YY x/ ~
Al - Al S'i)
7.
1 1 1 1
H(Si Al Al
8.
A.
Si Al Aljsi
\/\/\/\/
H(Si Al - Al S A i)
9
X\/\X\/\
Si Al Al Si
HJ (S A i Al Al S A i) H(Si - Al Al Si)
10. 11.
Of the above hydrates or aluminosilicic acids, Nos. 3, 4, and 6,
also 2 and 5, also 9, 10, and 11 are isomeric. If all the contained water
is completely separated, the anhydride
Si Al Al S A i
is formed.
The above hydro-alumino-silicates may also contain a variable
proportion of " water of crystallisation," the number of hydrates being
thereby increased.
Analogous hydrates with or without water of crystallisation
may, naturally, be regarded as of other types ; by the complete loss of
their contained water, these hydrates may form a corresponding series
of anhydrides. The following hydrates and the corresponding anhy-
drides thus become theoretically possible :
Si Al Si aq.
rr
i.
2.
/
I X
! /\ I
Si [Al Si V-
r~\/
y i
-<u
<$
Al
<$
5.
6.
7.
104 THE CONSTITUTION OF CLAYS
_
<(Si Al Si > etc. etc.
These substances have seldom, if ever, been prepared synthetically,
though their occurrence in Nature is well known under such widely
different names as " Minerals of the Allophane Group," " Clays," and
" Kaolins." They have been formed out of the most diverse materials,
such as micas, felspars, chlorites, etc., by removal of the base, hydra-
tion and subsequent removal of the water under definite conditions.*
These acids are seldom found in a chemically pure state, but usually
contain small proportions of the original base. Hence some of them
may, rightly, be termed strongly acid salts.
Their formulae have seldom been calculated from analyses, as these
materials have usually been regarded as 4 ' mixtures . ' ' The formulae cal-
culations of some minerals of the allophane group 215 (see Appendix)
showed that these substances are hydro-aluminosilicates (with a small
lime content) of the type
Al Si Al and Al Si Al.
From the analyses, the following formulae were calculated :
1. 0.5 CaO 6 A1 2 3 6 Si0 2 32 H 2 0,
2 0.5 CaO 6 A1 2 3 6 Si0 2 38 H 2 0,
3. 0.75 CaO 6 A1 2 3 6 Si0 2 32 H 2 0,
4. 0.25 CaO 6 A1 2 3 5 Si0 2 32 H 2 0,
5. 0.75 CaO 6 A1 2 3 6 SiO 2 42 H 2 0.
Part of the water present is in the form of " water of crystallisa-
tion " and part as " water of constitution." It is not possible to state
a priori how much water exists in either or both these forms, but the
maximum proportion of " water of constitution " which is possible
may be predicted on theoretical grounds, as in the two following
structural formulae :
I ii I
_/\/\/\_
Al I Si Al I I Al I Si
I ii I
Maximum of H 2 O-Mols. Maximum of H 2 O-Mols.
(6) (5)
* The various theories as to the origins of clays are described in the translator's
"British Clays" 70<J and "Natural History of Clay " 732 . A. B. S.
THE CONSTITUTION OF CLAYS 105
The determination of water present after heating these substances
to a high temperature should, therefore, be of value.
Equally interesting is the calculation of the formulae of a number
of washed clays from the analyses published in C. Bischof's " Collected
Analyses of Materials used in Clay working," published in 1901 (see
Appendix 'Clays/ Section B).
These analyses agree with the theory that a number of hydro-
aluminosilicates may exist in which the alumina-silica ratio varies
within extremely wide limits, so that the hydro-aluminosilicates
themselves may be of the most widely varying nature. The analyses
indicate the following substances :
(a) Si R Si,
(6) Si R Si,
(c)
A/ Si
Si
(e) Si R R Si,
(/) Si R R Si,
(g) Si R S'i R Si,
(h) Si R Si R Sf,
() S'i-R-Si- R -Si.
More accurate calculations of the formulae from analyses by the
same investigator (see Appendix ' Clays/ Section C) gave the follow-
ing :
I. 0.5 CaO 5.5 H 2 O 3 R 2 3 15 Si0 2 = H^Ca^
II. 0.25 K 2 O 19.75 H 2 (5 R 2 O 3 12 Si0 2 ) 2 = [H$ (Si R R Si)] 2
(-(-some K.),
III. 0.5 R 2 O 15.5 H 2 O 6 R 2 O 3 16 Si0 2 = H 21 Rg. 5 (Si R Si R Si)
5 H 2 0,
IV. 0.5 CaO 15.5 H 2 6 R 2 3 16 SiO 2 = H 2l Ca. 5 (Si R Si R Si)
5 H 2 0,
VIII. 0.5 K 2 8.5 H 2 5 A1 2 3 16 Si0 2 = H; 7 K(Si Al -Si Al_-_Si),
IX. 0.5 K 2 O 9.5 H 2 O 6 R 2 3 15 Si0 2 = H? 9 K(Si R Si R Si),_
XII. 0.25 K 2 9.75 H 2 6 R 2 3 16 Si0 2 = H 20 (Si R Si R Si)
(-f- some K.),
XIII. 12 H 2 6 R 2 3 18 Si0 2 = H 4 (Si R -Si R Si),
XV. 10 H 2 5 R 2 3 12 Si0 2 = H$ 8 (Si- R R Si) H 2 O.
106 THE CONSTITUTION OF CLAYS
These compounds contain only very small proportions of base and
may, therefore, be regarded as hydro-aluminosilicates. The constitu-
tional formulae * suggested are only tentative so far as their " water
of constitution " is concerned ; it is not impossible that in some of
them a part of what is, above, included under the term " water of
constitution " may, in reality, be in the form of " water of crystallisa-
tion." The only means of ascertaining this is to make determinations
of the water left after heating the substances to various high tempera-
tures.
Further formulae calculated from the analyses of the foregoing and
other clays will show whether the other theoretically possible hydro-
aluminosilicates are known to occur in Nature or to have been prepared
artificially.
According to the authors' hexite-pentite theory, clays must have
the properties of acids. The following equation represents the action
of sodium carbonate :
Si Al Al Si -f 6Na 2 C0 3 = Na 12 (Si Al Al Si) + 6C0 2 .
According to Vernadsky 216 haloid salts (KI, KBr, etc.) decompose
clays at moderate and high temperatures, with separation of haloid
salts.
The acidity of clays is also shown by their mode of formation in
Nature. They are formed by the decomposition of aluminosilicates
under the same conditions as hydrates and anhydrides are formed by
the decomposition of their salts. Thus, in Nature, the decomposition
of simple silicates by the action of water and carbonic acid produces
opals, and a similar decomposition of aluminosilicates produces
clays.
The necessary consequence of the hexite-pentite theory that clays
are single chemical compounds and not mixtures is by no means new.
So far as certain Alsatian fireclays are concerned, this conclusion
was reached by C. Mene in a prize essay published in 1863, in which he
made the following noteworthy statement :
" The clays used for the manufacture of firebricks are compounds
of definite chemical composition and are decomposition products of
rocks of equally definite chemical composition."
This work of Mene's appears to have been overlooked, and many
modern scientists generally though erroneously regard clays as
mixtures of quartz, felspar and the so-called " clay substance." This
highly mistaken view of the chemical nature of clays is due to a
peculiarity possessed by them, easily explicable in the light of the
hexite-pentite theory, but otherwise only by assuming the existence of
a definite " clay substance." This peculiarity consists in the fact
that, like all other aluminosilicates, clays are decomposed at high
* The distribution of the OH-groups in these formulae is described at greater length
in the later sections on Ultramarine, Portland Cements, and Porcelain Cements.
ACTION OF SULPHURIC ACID ON CLAYS 107
temperatures and by some concentrated acids, forming compounds of the
most stable type possible, such as the following :
1. Si Al Al Si,
2. Si Al Al Si, and
3. S*i Al Al Si.
If, for instance, a clay of the type
Si Al S A i - Al Si = 6 A1 2 3 18 Si0 2
is treated with concentrated sulphuric acid, it loses silica or silica
and alumina, according to the temperature and duration of treatment,
forming a compound of one of the three types just mentioned.
This is also shown by the researches of C. Bischof 218 (see Appendix,
' Clays ' D), who was one of the first to study the action of sulphuric
acid on the following clays :
1. m RO 5 R 2 3 17 Si0 2 aq.
2. m RO 5 R 2 O 3 16 SiO 2 aq.
3. m RO 3 R 2 3 12 SiO 2 aq.
4. m RO 5 R 2 3 17 Si0 2 aq.
5. m RO 3 R 2 O 3 15 SiO 2 aq.
6. m RO 5 R 2 3 18 Si0 2 aq.
7. m RO 6 R 2 3 12 Si0 2 aq.
The action of sulphuric acid may be represented as follows :
1 . S'i R Si R Si > Si R R Si",
2. Si R Si R Si > Si R R Si,
3. Si-R-Si ->Si-R-R-^,
4. Si R M R S'i > Si R R Si,
/Si
5. R-Si ->Si-R-R-Si,
6. Si R Si R Si > Si R R Si,
7. Si R R Si > Si R R Si.
The above examples which may be increased indefinitely show
conclusively that clays are really converted into the highly stable
compounds stated. The alumina-silica ratio is approximately 1 : 2
which cannot be a mere coincidence and the supposition that clays
contain a " clay substance " separable by acids though erroneous is
a very natural one.
Mellor and Holdcroft 708 consider that clays are decomposed by
sulphuric acid in another manner, viz. with separation of silica and
the formation of aluminium sulphate. This view is highly improbable,
as an almost constant ratio of A1 2 3 and Si0 2 has been found in the
solution by numerous investigators, and this constancy is the founda-
tion of the theory of the so-called " clay substance."
108 THE CONSTITUTION OF CLAYS
Forchhammer 219 appears to have been the first to express any doubt
as to the unitary nature of clays. He supposed that in sulphuric acid
he had found a valuable " solvent " for clays and regarded that portion
which entered into solution as " clay " and the remainder as " un-
decomposed felspar." From time to time, doubts have been expressed*
as to the value of the so-called " rational analysis," but the remarkable
resistance of clays to strong acids is the chief reason why Forch-
hammer's conception of " clay substance " is still maintained, though
modern chemists represent it by a different formula.
Forchhammer 's theory of clays is now of merely historical interest
and must be abandoned as inconsistent with the facts.
[With it, the rational analysis must also be abandoned, at any rate as far as the
usual interpretation of its results are concerned, f]
There is, at the present time, no fact known which is not compatible
with the unitary chemical nature of clays as opposed to the view that
they are mixtures.
[This statement must be taken to refer to " purified " clays, for many materials
are commonly termed " clay " which obviously contain other constituents. Thus
" boulder clay " contains limestone and other stones, loams contain sand which may
be removed by simple washing, and many " clays " contain rock-debris of a nature
clearly distinct from clay. Unfortunately, some of these obviously " non-clay "
materials are in so fine a state that they cannot be perfectly separated by elutriation
or similar mechanical processes. It does, however, appear to be true that, quite apart
from the hexite-pentite theory, the essential constituents of clays are definite alumino-
silicates.]
Minerals of the allophane group are characterised by the ease with
which they are decomposed by acids. Other hydro-aluminosilicates,
including several clays, are only readily decomposed by dilute acids
after they have been heated very strongly. The reason for this
difference in the behaviour of substances which, according to the
authors' hexite-pentite theory, are analogous, can only be explained
in the following manner :
" Disdynamised " and " Dynamised " Compounds
It has been shown, in connection with the tungstates (p. 95), that
the presence of a base weakens the bonds in the ring-radicles of com-
plexes. Thus, tungstovanadates with a small content of base are not
decomposed by acids, but in those richer in base a precipitate of tungstic
acid readily forms when they are treated with acids. The bonds
between the ring-radicles of complex substances may also be weakened
in other ways, such as by an increase in the proportion of " water of
constitution " or " water of crystallisation " or by subjecting the
substance to a high temperature.
Compounds in which the chemical relationship between the ring-
* Seger investigated this subject and recommended it under the title of "rational
analysis " for relatively pure clays, but found it unsatisfactory for the clays used for
the manufacture of bricks, tiles, cement, etc. Brongniart and Malaguti 220 did not
question the " undoubted advantages of rational analysis," but saw in the results
obtained an uncertainty " which compels us to draw conclusions with very great care."
f Additions and comments by the translator which cannot conveniently be in-
serted as footnotes are printed in smaller type.
EFFECT OF HEAT ON CLAY 109
radicles is weakened by these means so that the substance becomes
readily decomposable by dilute acids, are said to be " disdynamised "
in order to distinguish them from the " dynamised " substances which
resist the action of dilute acids.
The reason why minerals of the allophane group are readily
decomposed by dilute acids is now clear : in them the relationship
between the silicon- and aluminium-hexites has been weakened by
the presence of a high proportion of combined water.
Clays usually contain only " water of constitution " ; on heating to
vitrification they are disdynamised and then behave like the analogous
minerals of the allophane group.
[The vitrification point of a clay is that temperature to which it must be heated
in order that sufficient fusion may occur for most of the pores in the clay to be filled
with fused matter, yet without the material losing its original shape to any appreciable
extent. In most clays there appears to be no single temperature at which this occurs
to the exclusion of others ; the material becomes vitrified gradually throughout a range
of temperature which sometimes extends over 400 C., though some clays vitrify com-
pletely in a very few moments after the fusion of some of their constituents has com-
menced. This property of vitrification is extremely important in the technical appli-
cation of clays ; further information about it will be found in the translator's " British
Clays, Shales, and Sands." 706 It is, however, possible that this range of vitrification is
due to difficulties in maintaining a perfectly constant temperature for a sufficiently long
time. If, as Doelter has suggested, the vitrification point is definable as that at which
fusion is first observed to commence, and if, further, in accordance with A. Stock's
investigations, which showed that the vitrification point and the true melting point
of a silicate are identical and that vitrification occurs on heating perfectly pure crystal-
line chemical compounds, then it should be possible to produce a completely vitrified
mass by maintaining the material for a sufficiently long time at the lowest temperature
at which fusion can be observed to occur. The cost and difficulty of doing this with
reasonably large masses of clay are very great, as the conductivity of the material is
so low, but so far as the translator's own experiments go, and in so far as he has been
able to find other similar experimental evidence, there are good reasons for believing
that the apparent range of vitrification or of fusion is merely a result of the extra-
ordinarily low conductivity of clay and of the high temperature at which fusion occurs.
Could clays be fused at temperatures as easily observed as those used in studying the
melting points of many organic compounds, there is great probability that pure clays
would be found to have a sharply defined melting point. As it is, the only means of
effecting vitrification or fusion within a reasonably short time consists in raising the
temperature considerably above that which would be necessary if time were no con-
sideration. In other words, the term " range of vitrification " indicates a practical
experience even if it may lead to the erroneous assumption that clays differ from
other definite chemical compounds in not having a sharp, well-defined melting
point.]
In order to understand the nature of the state of disdynamisation
produced when clays are heated to vitrification, it is necessary to
assume that oxygen has two kinds of valency primary and secondary
and that the bonding of the ring-radicles is due to both the primary
and the secondary valencies of oxygen. If the proportion of base or
combined water in the compound is increased, the secondary valencies
are set free either partially or completely according to the proportion
of base or water. On increasing the temperature, the bound secondary
affinities are also partially or completely liberated, according to the
temperature to which the substance is heated.
It is conceivable that as soon as the secondary valencies are set
free, a looser bond must exist between the ring-radicles of the complexes
concerned.
110 CONSEQUENCES OF THE H.P. THEORY
At the vitrification temperature, the nascent secondary oxygen
valencies of the disdynamised clay molecules at once begin to be
liberated, and this may readily lead to the formation of polymerisation
products. If the temperature increases, the liberation also increases,
and when it is complete the whole of the material is reduced to a
molten state. It is clear that as the temperature rises, the polymerisa-
tion increases, and this is, necessarily, followed by an increase in
density. When the mass is completely fused, the point of maximum
density will have been reached.
[Some highly interesting investigations by R. Rieke 707 on the temperature at
which certain clays lose their " combined water " are worth special attention. This
investigator followed Le Chatelier's observation that if a sample of kaolin is slowly
heated there is a point at which the temperature ceases to rise for some minutes, after
which it again rises steadily. If the temperature and duration of the heating are
plotted as ordinates and abscissae, the graph produced will show a marked flattening
about 500 C. Rieke examined 10 kaolins, 8 plastic fireclays, 6 non-refractory clays
(red-burning), and 2 shales, and in each case he found that a marked absorption of
heat occurred and was shown by the flattening of the graph at a temperature of 500
to 580 C. The purer the clays, the more noticeable is this break in the rise of tem-
perature.
In clays containing much free quartz the absorption of heat is obscured by the
reactions which the quartz undergoes at the temperatures mentioned, and the more
complex graphs of the impure clays may be further affected by the reactions of other
compounds present.
Rieke also found that the loss of water corresponded to the flattening of the heat-
ing curve; a notable evolution of water commences at 450 C., and almost the whole
of the water is removed at a temperature of 550 to 600 C., though for its complete
expulsion prolonged heating at a higher temperature appears to be necessary. The
rate of evolution of water is not regular, and diminishes rapidly when most of the
water has been removed. It is increased by reducing the pressure of the air surround-
ing the clay.
Mellor and Holdcroft 708 have independently confirmed Rieke's observations with
respect to china clay, and have concluded that the " china clay molecule " must have
its OH-groups placed symmetrically. They accept a slight modification of Groth's
formula,* viz. :
HO HO
More recently, Mellor has examined crystalline kaolinite in a similar manner and
finds its behaviour is identical with that of the purest Cornwall china clay.
Unlike the authors of the present volume, Mellor and Holdcroft conclude that the
" clay molecule " is decomposed into its constituent oxides alumina and silica at
500 C.,f and consider that the formation of sillimanite at higher temperatures (1200 C.)
is a confirmation of this in accordance with the equation :
A1 2 3 + Si0 2 = Al 2 Si0 5 .
They agree that polymerisation of the alumina occurs (with evolution of heat at
800 C.), but have published no formula for the polymerisation-product. In other
words, they regard the latter as though it were the simple non-polymerised substance
when (according to them) it reacts at 1200 C. with the silica to form sillimanite.
* The views of the authors of the present volume as to the distribution of the
OH-groups are described at greater length in the later sections on Ultramarine,
Portland Cements, and Porcelain Cements and the following formulae are also criti-
cised on p. 116.
t See p. 113.
BURNING CLAYS 111
W. Pukall 710 has suggested the formula :
OH
HO Si O O Al OH
HO Si O O Al OH
OH
and in opposition to all other writers indicates a double bond between the silicon
atoms. From what has been stated on previous pages, however, the bond between the
silicon atoms must contain oxygen. The view that a direct connection exists between
the silicon atoms is also held by Simmonds 721 , who studied the action of hydrogen at
high temperatures on lead meta-silicate, to which is usually assigned the formula :
He reached the conclusion that both oxygen atoms cannot occupy similar positions,
and suggested the following formula for this silicate :
Si Si Si
O O O O O O
II II
R O O R
Simmonds thus suggests that the silicon atoms are connected directly with each other
and not through the medium of oxygen atoms. Manchot and Keiser 722 were unable
to confirm Simmonds' observation on lead silicates, and rightly argue that silicon
compounds in which the silicon atoms are directly connected with each other must
evolve hydrogen when treated with hydrofluoric acid and then with alkali, yet this
reaction never occurs with the silicates now under consideration. Manchot 723 uses
this argument in criticising Pukall' s formula, and adds that such a double bond would
imply that kaolinic acid would be more easily decomposed by alkalies than by other
silicates with a single bond, whereas kaolinic acid is very resistant to alkalies.
Singer 724 has also criticised Pukall's formula unfavourably and has pointed out
that a double silicon bond, like a double carbon bond, is a source of weakness in a com-
pound rather than one of strength.
The re-combination of water with the dehydrated kaolin is also of interest as
throwing further light on the constitution of the molecule. Mellor and Holdcroft (I.e.)
found that even in an autoclave at 300 C. under a pressure of 200 atmospheres the
dehydrated china clay only absorbed 2-5% of water. Rieke found that a Bohemian
kaolin, which had been heated at 500 C. until all the water had been removed, could
only be made to re-combine with 1-1% of water. The very small proportion of re-
combination which occurs is a further proof of the remarkably high stability of the
anhydride Si Al Al Si, as pointed out by the authors of the present volume.]
Burning Clays
[" Burning " is a term used to indicate the heating of articles made of clay under
industrial conditions in kilns or ovens in order to give them the characteristics desired
in pottery, bricks, tiles, etc. It differs from simple heating (or calcination) in that the
clays have been formed into articles of the desired shape and in that the heating must
usually be prolonged and the rise in temperature must be very slow so as to avoid the
splitting and cracking of the goods.
This explanation is necessary, as the shape of the articles and the speed of the
heating are important determinants of the character of the heated material. In
" burning," clays are never supposed to be heated to such an extent as to cause them
to fuse sufficiently for loss of shape to occur. When this happens they are " over-
burned."]
So long as clays are regarded as mixtures of quartz, undecomposecl
felspar and " clay substance," no satisfactory explanation of what
occurs during the burning is possible. The great difference in the effect
of dilute acids on raw and burned clays makes it obvious that some
112 CONSEQUENCES OF THE H.P. THEORY
definite chemical reactions must occur during the burning. The nature
of these reactions has, hitherto, been inexplicable. From a " mixture,"
all kinds of simple and double salts might be formed, and these cannot
be adequately examined. Yet a correct understanding of the burning
process is not only of academic value, but of great practical importance.
Hence, the hexite-pentite theory should be of great assistance in in-
dicating the chemical reactions which take place on burning.
These reactions may be stated in terms of the Disdynamisation
Theory (p. 108) as follows :
1. On heating a clay to vitrification, part of or all the " water of
constitution " is evolved. Secondary valencies of some of the oxygen
atoms are set free, but the clay itself retains its unitary chemical nature
and is not decomposed into its constituent oxides.
2. If the temperature exceeds that necessary for vitrification, the
free valencies liberate themselves and form polymerisation products,
the clays eventually fusing either partially or completely. Hence fused
clays must possess properties chemically different from those which
have been merely vitrified. The density of fired clays must also be
higher than that of vitrified clays.
3. Vitrified clays must be more easily attacked by acids than un-
vitrified ones.
[This " consequence " is erroneous, as explained below.]
[In this connection, the extensive use of vitrified (stoneware) clays in the manu-
facture of acids and in the construction of appliances (stills, etc.) in which hot acids
are used is important. General experience appears, at first sight, to be in direct con-
tradiction to the authors' statement in this paragraph, as vessels made of clay which
has been vitrified are usually found to be amongst the most powerful resistants to all
acids except hydrofluoric.
It is probable, however, that polymerisation products and the presence of these
and of fused material of a highly resistant nature may be the cause of this anomaly,
the term " vitrified " used in the text being understood to refer to clays which have
only been heated to the lowest temperature at which vitrification can possibly occur,
and not to a temperature at which polymerisation products are formed. If this is
the case and the disdynamic action is stopped on polymerisation or partial fusion, the
apparent anomaly is destroyed and the authors' theory becomes conformable to
general experience.]
The observations of Mellor and Holdcroft 708 and others show that
clay which has been heated to a certain temperature is (in accordance
with the theory) more readily attacked by acids than that which has
not been heated. It is also a well-known fact that on further heating
at a still higher temperature a material is produced which is resistant
to acids (in contradiction to the theory). Such polymerisation as
occurs will, however, make the heated clay resistant to acids. In this
connection it must be remembered that the polymerisation brought
about by disdynamisation is itself a dynamisation and so increases the
resistance of the material to chemical influences. The rise of tempera-
ture can, in fact, only have a complete disdynamic action when no
polymerisation occurs. This fact was overlooked by the authors until
it was pointed out to them by A. B. Searle, and this oversight is the
cause of the erroneous conclusion reached in Consequence 3 of the
theory.
ISOMERISM AND POLYMERISATION OF KAOLIN 113
4. The so-called ''decomposition" (p. 107) by concentrated acids
is merely a disdynamisation.
The observation of R. Rieke that, on burning clays, their tempera-
ture does not rise steadily, but remains constant for a long time, not-
withstanding the increased temperature of the kiln, may be explained
in terms of the new theory if the constant temperature occurs at the
sintering point of the clay.
The statement made by Desch that clays heated to 700 can easily
add calcium silicate, calcium aluminate, or calcium hydrate may be
explained by the new theory of burning stated below.
The behaviour of the silicate molecule towards acids also depends on
the number of aluminium hydro xyl groups in the molecule. This must
always be borne in mind when studying this subject, and is therefore
dealt with exhaustively in the following chapter.
There can be no doubt that the rise in temperature exerts a dis-
dynamising action on clays, and that in consequence of this action
molecular changes are produced in addition to such polymerisation as
may occur. This is particularly the case with kaolin, as will be seen on
reading the following chapter. If the theory is extended in this
manner it will be found to be in complete agreement with the observed
facts.
It is not then necessary, as Mellor and Holdcroft suggest, to
assume that, on heating, clays are decomposed into free silica and
alumina and that a re-combination of these oxides occurs on further
heating.
The investigations of Richter, Bischof, Jochum, Rieke and others
have shown that the fusing point of clays is greatly influenced by the
impurities, such as quartz, alkalies, etc., present. A theory of burning
to be satisfactory must take this into consideration.
This consideration of the burning process may be allowed to suffice
as an explanation of the decomposition of slightly heated clay by
acids and its greater resistance after heating at a higher temperature.
At the same time, this theory of burning leads to no conclusions
with regard to certain properties of kaolin which are described in
the following chapter. It may, therefore, be necessary to modify
the application of the Disdynamisation theory to burning, as
further facts are observed.
The Isomerism and Polymerisation of Kaolin
From the formula 6 H 2 6 A1 2 3 12Si0 2 (kaolin) two isomeric
substances may be formed. *
* If a rule is made to name the central core first and then the side chains, the
acid A may be termed di-h-alumino-di-h- silicic acid, and the acid S di-h-silico-di-h-
aluminic acid. Hence the salts of the ,4-acid and all silicates with a central aluminium
core may be termed aluminosilicates, whilst the salts of the $-acid and all compounds
with a central silicon core may be termed silicoaluminates.
I
CONSEQUENCES OF THE H.P. THEORY
III I I I I
114
Al I Si j Si Al I
I I I I
A. S.
A number of derivatives of these two acids in which pentites replace
hexites are theoretically possible :
y\/\/\/v _AAA/'\
Si Al Al Si
and I Al j Si I Si I Al
L
\/
A'.
S'.
Si ~ and
In accordance with the foregoing nomenclature these acids may be
termed :
A' Di-p-alumino-di-h-silicic acid.
A" Di-h-alumino-di-p-silicic acid.
|' Di-p-silico-di-h-aluminic acid.
S" Di-h-silico-di-p-aluminic acid.
The acids with central aluminium rings may be shortly termed a-
kaolinic acids, and those with central silicon rings as s-kaolinic acids.
Two, three or more molecules of the acids A, A', or A" and of the
acids S, S' or S" may lose certain molecules of water and then unite to
form polymerisation products. Thus, the following compounds are
possible :
/\/
Si
Al Al
Si
Si Al Al
\AA
A 2
Si
ISOMERISM AND POLYMERISATION OF KAOLIN 115
/\/\/\/\
i /x/ YY x
I Al Si I Si I
\/\/\/\
III!
/\/\/\/
I Al | Si I Si | Al
\/\/\/\
etc. etc.
On polymerisation, separation of water can only occur in two
analogous rings, as in the centre of the S' 2 or the side rings of the S" 2
compounds.
Between the a- and s-kaolinic acids and their salts there must be a
genetic relationship, as they can be converted into each other. This
transformation may be represented as follows :
I. Conversion of the a-kaolinic acid into s-kaolinic acid :
a-kaolinic acid.
a-kaolinic acid.
a-kaolinic acid.
s-kaolinic acid. 3-kaolinic acid.
II. Conversion of the s-kaolinic acid into a-kaolinic acid
Al Si Si Al
a-kaolinic acid.
5-kaolinic acid.
-kaolinic acid.
a-kaolinic acid.
a-kaolinic acid.
116 CONSEQUENCES OF THE H.P. THEORY
In an analogous manner the polymerised a-kaolinic acids may be
converted into polymerised s-kaolinic acids and vice versa.
In the chapter on Ultramarines and Porcelain cements two kinds
of hydroxyl groups in kaolinic acids are described : termed a- and s-
hydroxyls, respectively. The former the hydroxyls of the aluminium
rings are acidophillic, and the latter the hydroxyls of the silicon
rings are basophillic. The kaolinic acids both simple and poly-
merised appear to contain more s-hydroxyls and less a-hydroxyls ;
the s-kaolinic acids, on the contrary (both simple and polymerised),
contain more a-hydroxyls and less s-hydroxyls.
These variations in the number of a- and s-hydroxyls of the a- and
s-kaolinic acids must result in these acids having a different relationship
to other acids and a different solubility in acids. The more a-hydroxyls
a-kaolinic acid contains, the more soluble must it be in acids, or in other
words, the s-kaolinic acids must usually be more soluble in acids than
the analogous isomers or a-kaolinic acids.
As the degree of polymerisation must diminish with a-hydroxyls,
it follows that, cceteris paribus, the polymerised kaolinic acids must be
less soluble in acids than the non-polymerised ones. From the theory it
follows that the anhydrides of the a-kaolinic acids have the lowest
degree of solubility in acids, and therefore the greatest resistance to
acids. If the plasticity of clays is a function of the water of constitution
(see p. 65) it follows that :
1. The a-kaolinic acids can generally have a higher degree of
plasticity than the s-kaolinic acids, as the former contain more water
of constitution.
2. The polymerised kaolinic acids have, cceteris paribus, a lower
plasticity than the non-polymerised ones.
The a- and s-kaolinic acids must also differ from each other in
physical characters, such as density, resistance to reagents, etc., as
well as in chemical structure. There is another interesting consequence
of the new theory as applied to kaolinic acids : In the salts of the
kaolinic acids, such a compound as
I II II !
'\/\_
8 Na 2 6 A1 2 3 12 Si0 2 ,
Normal sodium s-kaolinate.
must have the sodium united to the silicon ring (i.e. s-sodium)
more strongly than the a-sodium attached to the aluminium ring ;
i.e. in this compound half the sodium must be more strongly united
than the remainder. It is also probable, on a priori grounds, that this
sodium salt will behave differently towards different acids ; the
stronger acids can remove the whole of the sodium (both a- and s-
sodium), but the weaker acids can only remove the a-sodium.
PUKALUS EXPERIMENTS ON KAOLIN
117
The Hexite-Pentite Theory and the Facts
The available experimental material is in entire agreement with
the theory developed in the preceding pages. In this connection the
work of (a) W. Pukall 710 and (b) Mellor and Holdcroft 708 on kaolinisa-
tion is of special value.
The Study of Kaolinisation by W. Pukall 710
W. Pukall has endeavoured to prepare kaolin synthetically, and
from a mixture of 18-75 of quartz, 24-38 of aluminium hydrate, 150 of
caustic soda and 75 c.c. water heated in a silver crucible until the
mass became stiff, he obtained a product which, on washing, yielded a
white, crystalline substance which melted at Seger cone 7 (about 1270),
i.e. the temperature at which salt glazed ware is glazed.
Zettlitz kaolin or English china clay when melted with ten times
its weight of common salt at 950 C. evolved water and hydrochloric
acid and combined with sufficient soda (28%) to be comparable to
Na 2 O A1 2 3 2 Si0 2 . Both these kaolins are converted into a crystal-
line substance.
Multiplying the formula just mentoned by 6, the following com-
pound :
6 Na 2 6 A1 2 3 12 Si0 2 12 H 2 0,
is formed ; it may be the salt of either an a- or an s-kaolinic acid.
From Pukall's investigations it appears highly probable that the
salt he obtained is a polymerised sodium s-kaolinic acid of the following
formula :
12H 9
I
6 Na 2 6 A1 2 3 12 Si0 2 12 H 2 O.
As the ratio A1 2 3 : Si0 2 in the salt obtained by Pukall is the same
as that in kaolin, he endeavoured to remove the Na 2 O and to obtain
the free acid, i.e. the " kaolin." For this purpose he used two methods :
by treatment with (a) carbonic acid and (b) hydrochloric acid. The
results of these two experiments, whilst in agreement with the H.P.
theory, were quite different : the carbonic acid, as a weak acid, only
removes the a-sodium and converts the Si-hexites into pentites ; the
118
CONSEQUENCES OF THE H.P. THEORY
hydrochloric acid, as a strong acid, removes the whole of the a-sodium
and half the s-sodium, as may be seen from the following :
a. THE BEHAVIOUR OF PUKALL'S SODIUM S-KAOLINATE TOWARDS
CARBONIC ACID
The sodium di-s-kaolinate (6 Na 2 6 A1 2 3 12 Si0 2 12 H 2 0)
of the above-mentioned structure was heated in a Soxhlet's apparatus
for 264 hours with carbonic acid in order to remove the soda, and by
this means Pukall obtained a substance corresponding to the formula
12H 2
2 Na 2 4 H 2 10 Si0 2 6 A1 2 3 12 H 2 0.
The analyses made confirm this formula :
Na 2 H 2 A1 2 3 SiO 2
Calculated 7.63 17.76 37.68 36.94
Found 7.10 19.95 37.49 36.82
The carbonic acid converts the Si-hexite into Si-pentite as already
described. The feebly acid carbonic acid can only remove the acido-
phillic aluminium rings, and not the strongly basophillic Si-rings.
b. THE BEHAVIOUR OF PUKALL'S SODIUM S-KAOLINATE TOWARDS
HYDROCHLORIC ACID
Pukall also endeavoured to remove the Na 2 in the sodium salt
above mentioned by means of a stronger acid, for which purpose he
selected hydrochloric acid. The sodium salt dissolves in this acid
and is obtained, on treatment with ammonia, in the form of a
voluminous white precipitate corresponding to
Calculated
Found .
(R 2 4 H 2
0.5 Na 2 O
... 1.77
. 2.15
0.5 (NH 4 ) 2
1.48
1.26
12 SiO 2
12 SiO 2
41.16
42.07
6A1 2 3 ) 2
6 A1 2 3
34.99
36.33
32 H 2 0.
20 H 2 0.
20.58
20.00
PUKALL'S EXPERIMENTS ON KAOLIN 119
Pukall did not determine the proportion of Na 2 and (NH 4 ) 2 and
suggested the following formula :
3H 2 A1 2 3 2Si0 2
Calculated 19.57 36.91 43.47
Found 20.00 36.93 42.07
The hydrochloric acid, being a strong acid, removes some base from the
sodium salt, yet a small proportion of the base still remains. It is
probable that the hydrochloric acid removes half the s-sodium ; the
remainder being replaced by NH 4 .
It has already been shown that the chemical and physical properties
of any s-kaolinic acid must differ from those of any a-kaolinic acid, and
an acid s-kaolinate must differ still more widely from " kaolin " (a-
kaolinic acid). As a matter of fact, Pukall has proved that kaolin is
different from the kaolinate inasmuch as the former only loses its water
on heating to redness, but the latter parts with half its water at
temperatures below 350 C. and the remainder on heating to redness.
Other properties of these two substances also confirm the view that
they require different structural formulae. Kaolin, for example, is
very plastic on account of the many OH-groups it contains. The
number of OH-groups in the acid kaolinate is much less and part of
them are replaced by basic groups. Hence, it is not surprising that
Pukall should find this salt to be less plastic than kaolin.* When
PukalTs salt is mixed with quartz and felspar it forms a very lean
mixture, and on heating this to 1370 a beautiful, white, translucent
porcelain is produced. If the same salt is mixed with free silica and
alumina the mixture is not plastic, though kaolin, when similarly
treated, retains its plasticity. Moreover, this mixture does not produce
a true porcelain on burning.
Pukall has also prepared the above-mentioned sodium salt of
s-kaolinic acid by another method. On boiling and then fusing kaolin
with caustic soda and a little hydrated alumina, and then washing the
product, a white crystalline mass is obtained which Pukall has shown
to be the above-mentioned sodium s-kaolinate. This method is of
great theoretical importance, as it shows a definite genetic relationship
must exist between the a-kaolinic acid and the s-kaolinic acid ; one
being converted into the other under certain conditions. This agrees
with the results obtained by Mellor and Holdcroft and discussed in the
next section.
Pukall has, further, made the interesting discovery that if silica and
alumina are heated with an excess of a very strong alkali solution the
compound produced (#A1 2 3 2#SiO 2 ) always has the same molecular
ratio of alumina and silica, no matter whether the silica and alumina
are free or in a combined state.
* For notes on the relationship between plasticity and chemical constitution, see
page 133.
120
CONSEQUENCES OF THE H.P. THEORY
II
The Study of Kaolin by Mellor and Holdcroft 708
Mellor and Holdcroft have studied the structure of kaolin by
means of the purest china clay obtainable, this kaolin having a com-
position approximating very closely indeed to the formula :
A1 2 3 2 Si0 2 2 H 2 0.
The result of their investigations leads to the conclusion that in all
probability china clay is an a-kaolinic acid with a structure represented
by the formula * :
II I I II
Si
2 H 2 6 A1 2 3 12 SiO 2 10 H 2 0.
This a-kaolinic acid is converted on heating to 500-600 C. into a
derivative of s-kaolinic acid, as shown in the following diagram :
At a higher temperature (800-900 C.) the s-kaolinic anhydride is poly-
merised with a liberation of heat, and at a temperature of 1100-1200
the polymeric anhydride of the s-acid is converted into a polymeric
anhydride of the a-kaolinic acid with absorption of heat.
In this way the genetic relationship between the 6-- and the
a-kaolinic acid previously discovered by Pukall is confirmed.
The changes just mentioned are based on the following con-
siderations :
1. The heating curve plotted by Mellor and Holdcroft for pure
kaolin shows, at temperatures above 500 C., a reduction in the rate
at which the temperature rises, and this is doubtless due to the occur-
rence of an endothermic or heat-absorbing reaction. At 900 C. a
feeble exothermic reaction occurs, and between 1000 and 1200 another
strong endothermic reaction takes place. These three " critical
temperatures " are due to f :
(a) The conversion of the a-kaolinic acid into the anhydride of
s-kaolinic acid.
(b) The polymerisation of the anhydride of the s-kaolinic acid.
(c) The conversion of the polymerised anhydride of the s-kaolinic
acid into a polymerised anhydride of the a-kaolinic acid.
* Mellor and Holdcroft's formula is given on p. 110.
t Mellor and Holdcroft's interpretation of these results is given on p. 122.
MELLOR & HOLDCROFrS EXPERIMENTS ON KAOLIN
2. If this conversion of the a-kaolinic acid into an anhydride of
the s-kaolinic acid really does take place at a temperature of 500-600C.
as stated above, it follows that the product formed by heating kaolin
to this temperature must be more readily soluble than the original
kaolin. This interesting consequence of the H.P. theory has been
independently and experimentally confirmed by Mellor and Holdcroft,
who found that the dehydrated kaolin is more active than the kaolin
from which it was prepared, and its solubility in acetic, hydrochloric
and nitric acids is greater than that of the unburned kaolin.
It is probable that the anhydride of the s-kaolinic acid formed at
600 C. becomes partially hydrated when under the influence of these
acids, and the acidophillic OH-groups (the a-OH-groups) thus formed,
and twice as numerous as the OH-groups in the a-kaolinic acid mole-
cule, will make the product more closely related to acids and will
simultaneously increase its solubility in acids.
3. A glance at the structural formulae of the simple and poly-
merised a- or 5-kaolinic acids shows that :
(a) The polymerised anhydrides of the a- and s-kaolinic acids must
have a greater resistance to acids than those which are not poly-
merised.
(b) The greatest resistance to acids must be shown by the anhy-
drides of the polymerised a-kaolinic acids, and
(c) The s-kaolinic acids and their anhydrides must split off alumina
more readily than silica, when treated with acids.
These consequences of the H.P. theory are all confirmed by Mellor
and Holdcroft 's experiments ; the following being of special interest :
Samples of china clay, which had been maintained at various
temperatures, were shaken mechanically, with hydrochloric acid of
specific gravity 1-165 diluted with an equal volume of water, for two
hours, and the proportions of alumina and silica dissolved were then
determined. Pure hydrated alumina and pure hydrated silica were
similarly treated. The results are shown in the following Table :
Kaolin.
Alumina.
Silica.
Tempera-
ture.
Loss on
Heating.
Soluble Matter.
Loss on
Heating.
Soluble
Matter.
Loss on Heating.
Soluble
Matter.
%
SiO, %.
AJ.O, %
%
%
%
%
100
12.64
0.08
0.12
16.00
2.60
600
1.37
0.16
0.16
2.45
42.96
1.36
700
0.62
0.12
0.98
2.41
20.40
1.36
800
0.56
0.12
0.68
1.58
7.84
1.24
1.12
900
0.23
0.12
0.20
1.65
5.92
0.43
0.76
1000
0.25
0.06
0.16
0.05
0.00
0.05
0.68
(at 1200)
122 CONSEQUENCES OF THE H.P. THEORY
It will be observed that the solubility of the alumina in the china
clay after heating to 600 is only slightly higher than that in the clay
heated to 100. It appears as if the conversion of the a-kaolinie acid
into s-kaolinic acid commences at this temperature. At 700 there is a
notable increase in the proportion of soluble alumina ; at higher
temperatures the solubility of the alumina appears to diminish so that
at 8QO C. it is only 0-68 ; at 900 it is still lower, and, at 1000, the
solubility of both silica and alumina is very small. The solubility of
the alumina in china clay does not agree entirely with the conclusions
previously expressed (see Section I, p. 120) in which it was stated that
the conversion of the a-kaolinic acid into the anhydride of the
s-kaolinic acid occurs at 500-600 C., but the above Table clearly offers
a general confirmation of the theory inasmuch as it shows an increased
solubility in hydrochloric acid as the temperature to which china clay
is heated is increased.
4. The specific gravity of the s-kaolinic acids must, clearly,
differ from that of the a-kaolinic acids and the investigations of Mellor
and Holdcroft have shown that this is the case, the specific gravity
diminishing as the conversion of the a- into the s-kaolinic acid takes
place. The Table below shows that at 600 the specific gravity of the
clay is distinctly lower than at 110.
At high temperatures the polymerisation which occurs and the
formation of the polymerised anhydride of a-kaolinic acid must
necessarily result in a series of increases in the specific gravity of the
material. Mellor and Holdcroft have (without recognising the true
nature of the compounds with which they were dealing) determined
the specific gravity of the various a- and s-kaolinic acid derivatives, as
shown in the following Table :
Temperature.
110
600
700
800
900
1000
Specific Gravity.
2.615
2.473
2.469
2.497
2.560
2.734
Hence the various consequences of the H.P. theory as applied to
the kaolinic acids are in complete agreement with the facts.
Mellor and Holdcroft have endeavoured to explain the three
critical temperatures (500-600, 800-900, and 1100-1200), mentioned
above, which are recognisable on heating kaolin, and the abnormal
behaviour of dehydrated kaolin to wards acids, on the assumption that
(a) between 500 and 600 the substance loses all its water and is
decomposed into free silica and alumina, (6) polymerisation of the
alumina occurs at 800-900, and (c) the free silica and alumina re-com-
REVIEW OF MELLOR & HOLDCROFTS EXPERIMENTS 123
bine at 1100-1200. This explanation of Mellor and Holdcroft's is
highly improbable, and is contradicted by their experimental results.
Thus, the Table showing the solubility of kaolin, alumina, and silica
which have been heated to various temperatures (supra) shows that
at 700 only 0-98 per cent, of the alumina presumably set free from the
china clay is dissolved, whilst 20-4 per cent, of the hydrated alumina is
dissolved under similar conditions. To suggest that this low solu-
bility is due to the alumina being in the nascent state is to make the
whole experiment quite inexplicable, as alumina definitely known to be
in this state has a still higher solubility. In any case, such a difference
in solubility as Mellor and Holdcroft suppose is quite incomprehensible,
and their assumption that the alumina from the clay is more readily
converted into an insoluble modification than that existing when
hydrated alumina is heated is untenable, as the difference in solubility
is far too large. Moreover, such an assumption is unnecessary,
because, as already explained, the hexite-pentite theory gives a much
simpler interpretation which is in closer agreement with the facts.
The hygroscopicity of china clay, alumina and silica which had been
heated to various temperatures has also been determined by Mellor
and Holdcroft. The values obtained appear to be in opposition to the
assumption that china clay is dissociated into free alumina and free
silica at 500-600.
The hygroscopicity was determined by standing the materials for
24 hours at 25 over 10 per cent, sulphuric acid and noting the increase
in weight ; this was considered to be due to the water vapour absorbed.
The following results were obtained by these investigators :
Temperature.
Percentage of water absorbed.
China Clay.
Alumina.
Silica.
110
0.71
18.35
600
0.33
9.80
15.93
700
0.31
10.33
15.34
800
0.37
10.75
12.85
900
0.34
9.19
3.96
1000
0.04
0.01
0.00
The low hygroscopicity of china clay compared with that of silica
and alumina (600-900) is extremely puzzling if it is assumed that the
clay dissociates into free silica and alumina on heating. But in the light
of the H.P. theory this is readily understood. If china clay were to dis-
sociate as Mellor and Holdcroft assume, the product should have a
much higher hygroscopicity than it possesses.
Another interesting investigation of Mellor and Holdcroft is their
attempt to produce hydrous china clay from the dehydrated (heated)
material. Samples of china clay which had been maintained for a long
CONSEQUENCES OF THE H.P. THEORY
time at 600-640 and still contained 1-04 per cent, of water (approxi-
mately 1 molecule of H 2 0) were heated with water in an autoclave at
300 C. under a pressure of 200 atmospheres. The product, dried
over P 2 5 in vacuo, showed a loss on ignition of 3-63 per cent, (approxi-
mately 3-5H 2 0), the dehydrated china clay thus absorbing 2-5 per
cent, or 2-5 molecules of water. This behaviour may be predicted
from the Hexite-Pentite theory.
The Melting Points of Clays and other Aluminosilicates
[Technically, the melting point of certain aluminosilicates is of great importance.
Especially is this the case with clays used for the manufacture of furnace linings and
other refractory goods exposed to very high temperatures.]
The melting point of a substance has long been recognised as
closely related to its chemical constitution, and C. Bischof 727 was the
first to establish the existence of such a relationship. Unfortunately,
his conclusions have been found to be incorrect in detail, but this does
not prejudice his position of priority in this important subject.
[The fact should not be overlooked that the determination of the melting point
of clays is so difficult that reliable conclusions based upon it are almost impossible of
attainment in the present state of knowledge. What is usually termed the "melting
point" is merely the point at which the influence of heat is sufficient to cause the
bending of test pieces of an arbitrarily chosen shape (that of Seger Cones).
Clays do not appear to have any definite melting point, but, on heating, the
amount of fused matter gradually increases, partly by the direct action of the heat
and partly by the chemical action of the fused material on that which remains. Thus,
a clay which is maintained for a sufficiently long time at a comparatively low tempera-
ture will show a similar amount of fusion or vitrification to another clay which has
been raised to a higher temperature for a much shorter time. This fact is extensively
used in the manufacture of stoneware, paving bricks and other articles of vitrified
clay, as the loss of shape at a given temperature on prolonged heating is far less
serious than when a higher temperature is employed for a much shorter time. In
the manufacture of glazed goods, on the contrary, it is found that a little gloss, i.e.
a more complete fusion, is obtained by means of a more rapidly rising temperature to
which the goods are exposed for a comparatively short time. Hence, it is precisely
because clays behave as if they were composed of a refractory skeleton, the pores of
which are, on heating, gradually filled with a glassy material, that the manufacture
of stoneware, porcelain, etc. becomes possible. If clays melted uniformly the result
of heating them in kilns would not be the wares mentioned, but glasses and glazes.
It would remove much obscurity and many erroneous conclusions if the term
"melting point" in the literature of clays and clay- working were replaced by the term
softening point. The tests of the so-called melting point of clays and the temperatures
associated with Seger Cones do not refer to the true melting point at all, but merely
indicate the effect of the total forces acting on the material and resulting in a certain
change in shape. This change is brought about by the production in the mass of a
certain amount of fused or partially fused material and is the resultant of several
forces, the individual influence of which it is extremely difficult to calculate.
The generally accepted view of the phenomena observed in the melting point of
clays is that they point to the fusion of the least refractory materials in the clay
occurring first, this being followed by the gradual fusion of the remainder by the
fused portion. This view is confirmed by the fact that clays do not appear to have a
definite melting point like crystalline compounds, but a "range of fusion" such as is
found on heating heterogeneous mixtures.
In view of the H.P. theory, it is not impossible that the low conductivity of clay
for heat may lead to erroneous conclusions respecting the fusing points of articles
made of clay by preventing the heat reacting on the interior of the mass. The results
of prolonged heating at lower temperatures appear to confirm this view. To decide
whether a clay has a sharp melting point (like a single chemical compound) or a
MELTING POINTS OF CLAYS, ETC. 125
"melting range" (like a heterogeneous mixture) it would be necessary to keep it for
a sufficiently long time at the lowest temperature at which any fusion appears to
occur. The time required is so great that the cost of such tests becomes prohibitive,
but until they have been made it is not logical to assume that the apparent behaviour
of clays is necessarily opposed to their being definite chemical compounds and not
mixtures. It is, moreover, not impossible that the progressive decomposition of the
molecules containing substituted elements may make what are really true compounds
behave as heterogeneous mixtures, though the former suggestion appears to afford a
more probable explanation.]
That a close relationship does exist between the melting point and
chemical constitution of a compound cannot be denied, and this being
the case, the following statements are direct consequences of the H.P.
theory :
1. Clays are usually kaolinic acids which have undergone a partial
polymerisation. In the theoretically possible compound :
I I
Si I Al I Al I Si
*/V\
II I I
18 H 2 18 A1 2 3 36 Si0 2 ,
one or more hydrogen atoms may be replaced by K, Na, Ca, Mg, Fe,
etc. ; one or more aluminium atoms may be replaced by Fe, Mn, Cr, Co,
etc. ; one or more silicon atoms may be replaced by Ti, Zr, etc. By
such replacements compounds would be produced containing very
small percentages of certain elements which would, nevertheless, have a
marked influence on the melting point. It is obvious that this influence
must be different with different elements. Not only must bases have a
different effect on the melting point from that exerted by acids, but
the various bases and acids will vary in their individual influence.
Hence, the melting point of the material will be affected according as
K, Na, Ba, or Ca, etc. replaces one or more hydrogen atoms, and
whether a portion of the aluminium is replaced by Fe or Cr or Mn, etc.,
or whether Ti or Zr is substituted for part of the silicon.
Other variations in the melting point will occur according as a
portion of the hydrogen, aluminium or silicon is replaced by analogous
substances.
In all these cases the melting point is a periodic function of the
atomic weight of the substituting element, i.e. there must be a definite
relationship between the change in the melting point and the atomic
126 CONSEQUENCES OF THE H.P. THEORY
weight of the replacing element. As the atomic weight increases, the
melting point of the clay may rise or fall.
2. Clays and aluminosilicates have varying A1 2 3 : SiO 2 ratios.
With any variation in the proportion of alumina or silica the melting
point of the clay must also rise or fall.
3. The melting points of isomeric aluminosilicic acids and of the
corresponding salts must differ from each other.
(See " Basis and Ring Isomerism," p. 63.)
The H.-P. Theory and the Facts
The available experimental evidence is not sufficient to prove
completely the foregoing consequences of the H.P. theory regarding the
relationship of the melting point and the chemical constitution of
clays. Such facts as are known, however, are confirmatory of the
theory.
Consequence 1 (p. 125)
It follows from the theory that the melting point of a clay must
depend on the nature of the elements which replace some of the H,
Si or Al in the theoretically pure kaolinic acid or clay. Opposed to this
theory is the law of Bischof and Richter 726 which states that " equiva-
lent amounts of fluxes have an equal influence on the melting point of
any clay in which they occur."
[In order to obtain a numerical expression of this law, Bischof re-calculated the
analyses of the clays he examined so as to show their molecular proportions, and
arranged these as a formula of the type
O aA! 2 O 3 6SiO 2 ,
in which the amount of base is constant, the two variables being the silica and alumina.
Considering these variables alone, he suggested that the refractoriness of a clay might
be represented by a coefficient or quotient (FQ). According to Bischof :
a 2
Fire resistance Quotient (Bischof) FQg = ~r*]
According to this law, it follows that equivalent amounts of potash,
soda, ferric oxide, etc. should have an equal influence on the
melting point of clays containing them. The following compositions
of clays may be taken as an illustration :
0.5 K 2 0- 9.5 H 2 6A1 2 3 12 Si0 2 ,
0.5 Na 2 O 9.5 H 8 6 A1 2 O 3 12 Si0 2 ,
0.25 K 2 0.25 Na 2 9.5 H 2 6 A1 2 3 12 SiO 2 ,
10 H 2 5.5 A1 2 3 0.5 Fe 2 3 12 Si0 2 ,
10 H 2 5.5 A1 2 3 0.5 Mn 2 3 12 Si0 2 .
These contain the same amount of fluxes, viz. 0-5 molecules, and
should all have the same melting point. Actual determinations of the
melting points of these clays show that this is not the case.
RELATION BETWEEN MELTING POINT & COMPOSITION 127
In direct opposition to Bischof and Richter's law are the extensive
studies of Jochum 728 on a series of fireclays in connection with Seger
Cones. The data obtained by Jochum are summarised in the following
Table :
No.
SiO a
Al,0 3
Fe a 3
CaO
MgO
K a o
Na,0
Total
Fluxes
Kefractorineas
in Seger Clones
1.
53.32
44.15
0.56
0.28
0.23
0.51
1.58
36
2.
52.24
43.43
0.87
0.32
0.35
1.54
35
3.
52.50
45.22
0.81
0.54
0.50
1.85
35
4.
52.74
45.81
1.00
0.15
0.05
0.54
1.74
36
5.
52.50
46.25
0.35
0.47
0.13
0.32
1.27
36
6.
52.33
45.81
1.30
1.43
2.73
35
7.
53.11
44.63
2.34
0.86
0.65
0.22
4.07
35-36
8.
52.74
46.00
1.07
0.23
0.24
1.54
35
TiO 2
9.
53.35
44.13
0.89
0.28
1.34
1.11
3.62
35
10.
53.35
43.35
0.83
0.24
1.43
2.50
35
11.
51.45
45.23
0.55
0.30
0.41
1.78
3.03
35
12.
51.57
45.70
1.31
0.86
0.77
2.94
35
13.
51.57
45.90
1.13
0.24
0.09
0.60
2.06
35
14.
51.90
46.10
1.14
0.24
0.09
0.60
2.07
35-36
15.
51.43
45.57
1.31
0.89
0.77
2.97
35
16.
55.00
40.60
2.86
1.30 Di
ff.
4.16
35
17.
57.00
37.00
3.66
0.57
1.77
6.00
35
18.
58.19
39.37
0.85
0.09
0.41
1.14
2.49
34
19.
52.34
40.11
2.54
0.25
0.91
3.87
7.57
33
20.
52.92
39.16
2.57
0.18
1.24
3.55
7.54
30
21.
52.48
39.16
2.55
0.18
1.23
3.52
7.48
32
22.
52.90
38.40
4.80
2.40
0.80
1.00
9.00
32
A glance at this Table will show the invalidity of Bischof and
Richter's law. This is particularly noticeable with respect to clays Nos.
6, 7, and 8. The total percentage of fluxes in No. 6 clay is 2-73, in
No. 7 clay 4-07 and in No. 8 clay 1-54, but the refractoriness of all three
clays is the same (cone 35). Indeed, the clay with the lowest pro-
portion of fluxes (No. 7) has, if anything, a higher degree of refractori-
ness than the other two. The figures in connection with clays No. 17
and 18 are even more striking. Clay No. 17 contains 6-00 of fluxes
whilst No. 18 contains only 2-49, yet the refractoriness of No. 17 is a
Seger cone higher than No. 18, i.e. cone 35 as compared with cone 34,
whereas, according to the Bischof -Richter law, No. 17 should be con-
siderably more fusible than No. 18. In the case of clays No. 19 and 21,
the composition is practically identical, but the refractoriness is
different.
[Seger 730 has pointed out that the Bischof-Richter law is only applicable to clays
containing a very small proportion of basic oxides, i.e. to the most highly refractory
clays, and that it is quite useless for second-grade fireclays and clays used for building
purposes.
Richter 730 found that the form in which the silica is present in a clay, i.e. whether
combined or in the free state, has a profound influence on the melting point. Hence,
as Seger has pointed out, the resistance of clay to heat does not depend on the com-
position of the material as a whole, but on the compounds present in it and on their
state of aggregation. This fact has been repeatedly confirmed and is well known to all
128
CONSEQUENCES OF THE H.P. THEORY
manufacturers of refractory goods. Indeed, the remarkable variations in fireclay
deposits are a daily source of anxiety to those using them. For this reason, and because
he regarded the variety of minerals present in most clays as rendering abortive all
consideration of the melting point of any clay as a whole, Seger 730 insisted that it is
first necessary to free the clay as far as possible from sand, silt, and other impurities
by washing, and then to study the melting point of the purer product thus obtained.
He therefore applied Bischof's Quotient to that portion of the clay which is sufficiently
fine to be washed out by a current of water flowing at the rate of 0. 1 8 mm. per second
(i.e. on the nearest approach to " pure clay " obtainable on mechanical elutriation of
a commercial clay and termed by him " clay substance," but more accurately clayite
in the case of china clay by J. W. Mellor 708 , and pelinite in the case of plastic clays by
A. B. Searle 732 ). With this purified material Seger obtained results which agreed much
better with the actual fusion tests. As, however, serious discrepancies still existed
even among the higher-grade clays Seger eventually suggested the following formula
applied to the clayite or pelinite above mentioned, and not to the material as a whole :
Fire-resistance Quotient (Seger) FQ g = (a+b) 5.
This formula, though applicable to a larger number of clays than Bischof's, is,
like the latter, extremely limited in its application and is far from reliable, and Seger
30
25
-20
-ft
-ID
-05
\
\
\
\
*
s.c,
2 25 3 3-S
FIG. 1. Lud wig's Chart
4-5 5 55 6
himself found several fireclays and kaolins in regard to which it proved impossible to
obtain an agreement between his formula and the results of actual fusion tests. That Seger
recognised this is clearly shown in the following statements in his " Collected Papers " :
" Both Bischof's and my coefficients only give approximate figures, as the fusion of
clays involves several important physical factors which must inevitably be omitted
from any method of calculation." "It is unwise to attach much importance to any
coefficient, because it cannot include the variations in the size of the grains of clay,
this factor being quite as important as the composition of the material. Thus, silica
in an extremely finely divided state acts energetically as a flux, but coarser silica in-
creases the heat resistance of some clays to which it is added ! " Seger also laid great
stress on the irregularity of composition observed in clays, and declared them to be
" not homogeneous, but merely mixtures of various minerals of which the largest
proportion is * clay substance.' " " Hence, any figure which it is claimed represents the
melting point based on the composition of the material can only be rough approxima-
tions."
When Seger's quotient is applied to the analyses shown in the Table on page 127,
the results obtained are so conflicting that it is impossible to trace any direct con-
RELATION BETWEEN MELTING POINT & COMPOSITION 129
nection between Seger's quotient and the Seger cone numbers in the last column of
the Table. It is, however, only fair to observe that the temperatures indicated by
these Seger cones are not the true melting points of the clays, but only the " softening
points," and Bischof has shown there is no simple law connecting the temperature at
which Seger cones bend with that at which they melt.
A method of calculation similar to those of Bischof and Seger, but differing in
the manner of its representation, is that of T. Ludwig 706 , who assumed that the fluxes
in a clay are in the form of a solid solution with the clay as a solvent, and arranged
the composition of a clay as a formula with alumina as unity thus :
x RO A1 2 O 3 y SiO 2 ,
plotting x as ordinates and y as abscissae. Ludwig obtained a chart (Fig. 1) in which
the diagonal lines represent the limits of the Seger cones marked thereon, so that the
" melting point " of a clay is represented in terms of these cones. This chart is in
close agreement with the experimental observations of many fireclays and kaolins,
but is entirely unreliable for clays in which the total fluxing oxides exceed 6 per cent.
Ludwig attributed its failure to the heterogeneous nature of clays and to the irregular
distribution of the fluxes in them.
The relationship between the composition of clays and their melting point has
also been investigated by H. Seger 730 , who studied the melting point of mixtures of
silica and alumina and of silica and kaolin to which sufficient felspar was added to
keep the alkali-content of the various mixtures constant.
Seger found that mixtures of free silica and alumina behave in a manner similar
to mixtures of kaolin and pure quartz-sand, so far as the melting points are concerned.
In both cases the larger the proportion of silica the lower the melting point, until a
material is obtained with a molecular ratio of 1 A1 2 O 3 : 17 SiO 2 , after which the
addition of more silica increases the melting point until practically pure silica is
obtained. These results are summarised in the curve shown in Fig. 2 (see also
p. 132).
That some definite relationship does exist between the composition and the
softening point of clays is shown by the existence of a regular series of Seger cones.
These are composed of mixtures of pure kaolin with marble, felspar, and quartz in
atomic proportions, the whole being reduced to an exceedingly fine powder. Not-
withstanding the fact that the purest possible materials are used in the manufacture
of these cones, no definite general formula has been found for connecting the fusing
point of these cones with their composition. Seger laid special emphasis on the un-
desirability of attempting to correlate the Seger cones with definite temperatures.
" I permit the preparation of a scale of comparison between my cones and definite
temperatures," he wrote, " with the greatest unwillingness, more especially as I have
found no means of comparison for the highest cones." Seger's caution and modesty
are well known, so that it is interesting to note that later investigations have proved
that, with trifling exceptions, all the cones above No. 10 correspond very closely to
definite temperatures, provided that the rate and other conditions of heating are
favourable and constant, but that slight variations in the condition of heating cause
serious discrepancies in the behaviour of the cones. It should, however, be noted
that Seger's cones do not show the melting points of the mixtures composing them,
but only the resultant of the various forces which cause them to bend to a definite
extent. Whether there is any relationship capable of simpler expression numerically
between the bending temperatures of Seger cones and their true melting points remains
to be proved. Meanwhile, in view of the misuse of terms in the literature of the subject,
too much emphasis cannot be laid on the fact that Seger cones merely indicate the
softening points of the materials of which they are made. These softening points,
together with the molecular composition of the cones, are shown in the Table
on the next page.
130
CONSEQUENCES OF THE H.P. THEORY
SEGER CONES AND TEMPERATURES
Estimated
Temperature C.
Cone No.
Molecular Composition
K,0
CaO
Al,0,
SiO,
1320
11
.25
.58
1
10
1350
12
.21
.50
1
10
1380
13
.19
.53
1
10
1410
14
.17
.39
1
10
1435
15
.14
.33
1
10
1460
16
.13
.29
1
10
1480
17
.11
.26
1
10
1500
18
.10
.23
10
1520
19
.09
.20
10
1530
20
.08
.18
10
p
21
.07
.15
10
22
.06
.14
10
*-
23
.06
.13
10
24
.05
.12
10
25
.04
.11
10
1580
26
.04
.10
10
1610
27
.02
.03
10
1630
28
10
*
28*
9
1650
29"
8
*
29*
7
1670
30"
6
1690
31
5
1710
32f
4
1730
33
3
1750
34
2.5
1770
35
2
1920
40
* These cones are not manufactured, as their Estimated Temperatures lie too close
to neighbouring cones, and are somewhat irregular,
t Pure silica behaves like cone 32.
It will be observed that there is a fairly regular difference in temperature between
consecutive cones, but this is not sufficiently constant for any simple law to be found
from a graph of the cone numbers and temperatures.
Simonis 706 has studied mixtures of kaolin, quartz, and felspar in connection with
Seger cones and found that the felspar acts as a constant and neutral flux. He also
concluded that the softening point of such a mixture might be represented numerically
by a " refractory index," using the symbols k for the percentage of kaolin, s for that
of quartz, and / for that of felspar. According to Simonis, if k is greater than f the
" refractory index " will be R = | / + 60. For bodies high in silica, in which
J
2g
o is greater than Tc, the " refractory index " is IT k f + 60. The value of this
" refractory index " in terms of Seger cones is given in the accompanying Table :
Refractory index . .
17.5
22.6
28
33.7
39.2
44.6
50
57.6
14
15
16
17
18
19
20
26
Refractory index . .
65
72
80
89
102
114
127
141
Seger cone
27
28
29
30
31
32
33
34
RELATION BETWEEN MELTING POINT & COMPOSITION 131
It will be observed that there is no simple relationship between Simonis' Refractive
Index and the corresponding Seger Cones.
In short, the Bischof-Richter law, together with the various modi-
fications of it and the other attempts to correlate the melting points of
clays with their chemical constitution here noticed, which are not in
accordance with the H. P. theory, is shown by the above evidence to be
erroneous. Further investigations must show that, in accordance with
the H.P. theory, the true melting point of a clay (not the " softening
point ") is a periodic function of the atomic weight of the replacing
elements.
[That this relationship has not been f ound is, in part, due to the difficulties experi-
enced in melting the purer and therefore the most refractory clays, and also to the
very widespread belief that clays are heterogeneous mixtures and not true chemical
compounds. The general evidence in favour of the H.P. theory is, however, so strong
as to make this consequence of it highly probable, even though the experimental
evidence at present available in respect of melting points is of little or no assistance.
In due time the various germs of truth in Bischof's and other theories will emerge
from the obscurity in which they have so long lain, in consequence of the non-existence
of a correct theory as to the constitution of clays and allied substances.]
It is highly probable that the melting point will be lowered by the
substitution of elements of higher atomic weights. Such an effect has
been observed by G. Jantsch 729 in other complexes with the general
formula :
3Mo-X 2 3 -6N 2 5 -24H 2 0,
where Mo = MgO MnO NiO CeO ZnO, and
X 2 3 = La 2 3 Ce 2 O 3 - Pr 2 O 3 - Nd 2 3 - Sm 2 3 Gd 2 3 .
This is shown in the following Table :
Mg
Mn
Ni
Ce
Zn
La
113.5
87.2
110.5
101.8
98.0
Ce
111.5
83.7
108.5
98.5
92.8
Pr
111.2
81.0
108.0
97.0
91.5
Nd
109.0
77.0
105.6
95.5
88.5
Sm
96.2
70.2
92.2
83.2
76.5
Gd
77.5
72.5
63.2
56.5
The divalent manganese appears to behave in an exceptional
manner which cannot, at present, be explained.
Consequence 2 (see p. 126)
The melting point of silicates containing no alumina increases with
the silica-content. Thus, bisilicates fuse at a higher temperature than
monosilicates, and trisilicates are more difficult to fuse than bisilicates.
In most cases, the physical properties of complex substances differ
from those of their constituents. This is also the case with alumino-
silicates in which, according to the researches of C. Bischof, a lower
fusing point accompanies a higher silica-content, the aluminosilicates
which are rich in silica being more fusible than those relatively poor in
silica.
132
CONSEQUENCES OF THE H.P. THEORY
A glance at Fig. 2, which shows the results obtained by Seger 730
on mixtures of pure silica and alumina (see p. 129) shows :
1. An increase in the proportion of silica is accompanied by an
increased fusibility.
2. The melting point, or more strictly the softening point, di-
minishes with an increase in the proportion of silica until the mixture
with a ratio A1 2 3 : SiO 2 = l : 15 is reached, after which there is a
change in the direction of the curve until a ratio 1 : 17 is reached, after
which an increase in the proportion of silica is accompanied by an
increase in the melting point.
u red/2 Os
I 23456 7 8 9 10 II 12 13 /4 15 IB 17 IB 13 20 21 22 23 24 25
Mols.SiOz.
FIG. 2. Relation of Softening Point to Composition (Seger)
The flattening in the curve indicates the formation of a compound,
and as glasses are known with a ratio of A1 2 O 3 : SiO 2 = 2 : 36, the curve
appears to indicate the existence of a secondary type of such a glass.
The compound A1 2 O 3 , 17 Si0 2 would then have a high molecular weight
and the following structural formula :
Si | Si | Si |
\/ \/
A1 2 A1 2
A A
| Si | Si | Si
\/\/\/
Consequence 3 (see p. 126)
No experimental evidence is available for proving the correctness or
otherwise of this consequence of the H.P. theory, but further investiga-
THE CAUSE OF PLASTICITY 133
tions of clays and aluminosilicates will, in all probability, lead to the
definite confirmation of this theory.
In connection with the foregoing observations the behaviour of the
so-called mineralisers 1 may be mentioned. The ones most generally
used are the chlorides of calcium, magnesium, manganese, aluminium,
and silicon, the fluorides of calcium, sodium, potassium, magnesium
and silicon, the tungstates of potassium and lithium, the borates of mag-
nesium, calcium and sodium, the phosphates of potassium, magnesium,
etc. These mineralisers appear, in many cases, to form sodalitic com-
pounds with silicates (see Socialites p. 59) and, on adding a mineraliser
to a compound or mixture, the melting point of the substance is con-
siderably reduced.
Mineralisers play an important part in the synthesis of various
minerals and without them some minerals cannot be produced.
The Cause of Plasticity in Clay
Before concluding this chapter, a few words may be added on the
plasticity of clay.
The authors agree with Seger 221 in terming those substances plastic
which possess the power of absorbing and retaining fluids in their pores
in such a manner that the mass may be given any desired shape by
kneading or pressure, this shape being retained after the pressure has
been removed. It is a further condition that if the fluid is removed,
the substance shall retain its shape unchanged.
A number of theories 221 * have been formulated to explain the
causes of the plasticity of clays.* The authors of the present volume
consider those theories are the most probable which assign the chief
cause of plasticity to the " water of constitution " in clays.
From this it follows that :
A. The more OH-groups a clay contains in the form of " water of
constitution," the more plastic must it be.
B. By separation of the OH-groups on an increase in temperature
of the clay, or by the replacement of hydrogen by a base, the plasticity
must be reduced or completely destroyed.
These consequences of the theory are fully confirmed by facts.
Thus, Seger 221 found that if a cream or slip made of clay and water
is allowed to settle and the clear water decanted, the pasty sediment will
be so stiff that it can bear the weight of a glass rod without the latter
sinking into it. If, however, to the water used for making the slip
a few drops of caustic soda, sodium carbonate solution or water-glass
are added, so that the water is rendered feebly alkaline, a remarkable
change occurs. The slip becomes considerably thinner and more fluid,
* The chief of these are summarised in " British Clays, Shales, and Sands." 706
134 CONSEQUENCES OF THE H.P. THEORY
part of the material settles immediately to the bottom as a solid
substance and the supernatant liquid requires a very long time before
it becomes clear. If, now, a few drops of acid are added to the mass,
it becomes so stiff that the vessel in which it is contained may be
inverted without spilling the contents. On drying to a definite volume,
the acidulated mass will be found to be much more plastic than the
original clay and the alkaline mass will have lost almost all its plas-
ticity. It is highly probable that in Seger's experiment, the prolonged
action of water or acids on the clay had effected a partial separation of
the alkalies it contained, whereby an increase in plasticity resulted,
due to the cause indicated in Conclusion A above 2213 .
By the action of alkali, a partial substitution of H by the alkali may
also occur and, as indicated in Conclusion B, this is the reason the
plasticity is reduced.
E. v. Sommaruga 222 has shown, by analysis, that aluminosilicates of
the alkalies and alkaline earths lose part of their base on washing.
In agreement with Conclusion B, there is the further fact that clays
lose their plasticity at high temperatures, at which the water of con-
stitution is also driven off.
The fact that some hydrous-aluminosilicates, such as the zeolites,
are non-plastic is not in opposition to the above theory as to the
cause of plasticity, as the introduction of a definite proportion of base
so as to form a salt and zeolites are true salts completely destroys
the plasticity.
[The term plasticity, as ordinarily used, includes so many other properties that
the interpretation of experimental results is extremely difficult. Moreover, no generally
accepted method of measuring plasticity has yet been devised, all those now in use
being open to several objections, the chief of which is that they measure some property
closely allied to plasticity such as tensile strength, adhesion, viscosity, binding power,
etc., but not the plasticity itself.
Again, Drs. W. and D. Asch make no mention of the close connection between
the colloidal material present and the plasticity of clays, nor do they explain how it
is that quartz, calcium fluoride and a number of other substances of widely different
constitution and composition have been found by Flett, Atterberg and others to be
plastic when in a sufficiently finely divided state.
If it is really a fact that extremely finely divided silica which is free from con-
stitutional water can become truly plastic, the hexite-pentite theory will require
modification. In the present state of knowledge it is, however, extremely difficult to
decide whether the substances just mentioned do become truly plastic or whether
they merely become more cohesive.
Several investigations, including those by Rieke 707 , have shown that the loss of
plasticity when a clay is heated is not proportional to the loss of " water of constitu-
tion." A certain amount of plasticity remains, even when all the water has been re-
moved from the clay, provided that the removal has been effected at a low tempera-
ture. For this reason Rieke and others have concluded that the loss of plasticity
on heating is due to the physical rather than to the chemical nature of the clay. An
equally correct conclusion and one which is, moreover, in conformity with the hexite-
pentite theory, is that the loss of " water of constitution " is accompanied by poly-
merisation phenomena which materially reduces the plasticity and necessarily involves
a lack of proportionality between the loss of water and of plasticity when the clay is
heated, especially as, under such conditions, the plasticity is lost at a greater rate
than the "water of constitution."
The reader interested in this subject will find further details in the translator's
" British Clays, Shales, and Sands," in which the conclusion is reached that the plasticity
is partly due to the extreme smallness of the clay particles, partly to the shape, texture,
and physical nature of these particles, and only slightly to their chemical composition.
THE COLOUR OF BURNED CLAY 135
Considering the great stability of the clay molecule, it certainly appears to be quite
as likely that the action of a few drops of acid or alkali on a considerable weight of clay
may be due to the colloidal material in clay as to any change in the chemical com-
position of the clay molecule of the nature suggested above. Moreover, it is difficult
to understand why china clays and kaolins should be so slightly plastic compared to
ball clays yielding such remarkably similar results on analysis, unless plasticity origin-
ates largely in the physical, rather than in the chemical nature of clay. This may,
of course, be due to somewhat different chemical structure (isomerism or polymerism)
and the hexite-pentite theory is a priori in favour of such an explanation as accounting
for the physical differences.
The whole subject of plasticity is, however, so complex, that no definite theory as
to its cause has yet been found which will satisfy the whole of the facts. Under these
circumstances, the theory suggested by Drs. W. and D. Asch takes its place amongst
the numerous other serious attempts to ascertain the cause of this very elusive property
of clays. In the opinion of the translator, however, the present application of the
hexite-pentite theory to plasticity is attempting too much. The hexite-pentite theory
is so valuable in its relation to the chemical composition of clays that it would be a
pity to prejudice its acceptance by prematurely extending its application. When
more is known of the nature of plasticity, it is not improbable that the value of this
theory, in regard to plasticity, may be much greater than now appears to be the case.
The Colour of Bricks and other Articles of Burned Clay
The red colour of building bricks is usually attributed to the presence of free
ferric oxide in the burned clay ; that of Staffordshire " blue " bricks and clinkers is
generally considered to be due to the production of a ferrous silicate by the reducing
action of the kiln gases on the ferric oxide in the burned clay.
It is, however, a curious fact that the best red bricks cannot be made by adding
ferric oxide to a clay, though the use of this substance does produce a low grade of red
brick with a very irregular colour. Moreover, ordinary " red oxide of iron " dissolves
readily in hydrochloric acid, but the colour of a finely-ground red brick is not removed
by cold acid, nor can such a powder be completely bleached even by boiling with
hydrochloric acid for several hours. Again, the clay used for blue Staffordshire bricks
produces goods of a bright red colour if burned in an oxidising atmosphere, the blue
colour being only formed when reducing gases are present. If the temperature of the
kiln has not been excessive, and the atmosphere is made strongly oxidising, the blue
colour is replaced by a bright red one, this transformation of blue and red and vice
versa being capable of being repeated indefinitely as long as the temperature is care-
fully regulated.
The generally accepted opinion that a simple ferrous silicate is the cause of the
" blue " colour is not borne out by synthetic ferrous silicates, the colours of the latter
being quite different.
These facts all point to the colour of bricks being due to an aluminosilicic anhy-
dride containing iron in such a form that it can be readily converted from the ferric
to the ferrous state and vice versa. The structure of silicates in which the colour is
due to a chromophore group containing a metallic oxide is described in greater detail
in a later section on " Coloured Glasses," in which the state of combination of the metal
is explained by the aid of the H.P. theory.
Seger 730 and others have exhaustively investigated the relationship between
the iron contents of numerous clays and the colours of the bricks obtained therefrom,
but have not been able to find any definite correlation between the two. In many
instances clays which contain 5 per cent, or more of iron calculated as ferric oxide,
burn to a pale buff or primrose tint, whilst other clays with only 3 per cent, of iron oxide
produce bricks of a strong dark red colour. The lower-grade fireclays and other buff-
burning clays do not contain less iron than red-burning clays, but they must contain
it in a different form. There is evidence in support of the view that in buff-burning
clays the iron is chiefly in the form of pyrites, whilst in red -burning clays it is in the
form of a ferrosilicic or ferro-alumino-silicic acid, analogous to clay in which one or
more of the hydrogen atoms have been replaced by an atom of iron. Seger also found
that clays rich in alumina as well as iron, usually burn to a buff rather than to a red
tint.
It is interesting to note, in this connection, that if a red-burning clay is washed
with dilute hydrochloric acid a large part of the colouring matter will be removed,
and if the clay is then dried and burned it will be of a yellowish red colour. No treat-
136 CONSEQUENCES OF THE H.P. THEORY
ment with acid has yet been found, however, which will remove all the iron without
destroying the clay.
If buff-burning clays are brought into momentary contact with flame in the kiln
a reddish tint will form on their surface, as though a portion of the combined iron were
set free as ferric oxide. No satisfactory explanation of this phenomena has yet been
published, as the amount of red substance formed is too small for analysis ; the pro-
duction of such " flame-flashed " goods is, however, well known to all makers of fire-
bricks.
If chalk is mixed with a red-burning clay, the bricks produced at temperatures
below about 800 C. are red, but above this temperature the chalk reacts with the iron
compound and the bricks are quite white and might be supposed to be quite free from
iron. The nature of this white compound of lime, iron and clay has never been ascer-
tained, but in the light of the H.P. theory it would appear as if the lime had destroyed
the chromophore group forming a new ferruginous silicate and so had deprived the
iron of its colouring power.
The whole subject of the colour of burned clays is of great technical importance,
but hitherto it has been subject to so many assumptions which have passed as explana-
tions that very little scientific investigation has been made. Clay workers have been
content to accept the assumption that the red colour of certain bricks is due to the free
ferric oxide in the clay without troubling to ascertain how it is that 5 per cent, of
iron oxide is without effect on the colour of the raw clay and yet produces such an
intense colour when the clay is burned. That some change must occur in the combina-
tion of the iron is obvious and the view published some years ago by the translator of
the present work, that a large proportion of the iron occurs in the form of ferrosilicic
acid (?nontronite, H 4 Fe 2 Si 2 O 9 ) which, on heating, is decomposed into water, silica and
free ferric oxide, certainly agrees with a number of the important properties of red-
burning clays. Whether the iron is in the form of a ferrosilicic acid or of a substituted
group in an aluminosilicic acid it is, at present, almost impossible to determine ex-
perimentally.]
XII
The Ultramarines
Historical Review
Since 1828, many fruitless attempts have been made to ascertain
the true cause of the colour of the ultramarines. Those investigators
who consider ultramarine to be simply a " mixture " or a " solid
solution " have, naturally, endeavoured to find a " colouring principle,"
the nature of which varies according to the various authors. Thus,
according to Gmelin 246 and Breunlin 246 , the " colouring principle " of
ultramarine is sulphur ; Eisner 247 , Kressler 248 , Guyton Morveau 249 ,
Priikner 250 , and Varrentrapp 251 consider it to be iron sulphide, but
Brunner 252 has contradicted this by producing a blue from materials
quite free from iron, which colour is in every respect equal to that
produced from ferruginous clays. According to Unger 253 , the blue
colour of ultramarine is due to nitrogen compounds, but Biichner 254
has disproved this by showing that " ultramarine " contains no nitro-
gen. Stein 255 has suggested that ammonium sulphide, mixed with the
ground mass in a state of " molecular fineness," is the colouring matter
of "ultramarine," and Rohland 256 has stated that "ultramarine"
contains a " colour-carrying substance," or chromophore, whose
composition he has not published.
On the contrary, those investigators who consider the ultramarines
to be definite chemical compounds seek for the source of the colour in
HISTORICAL REVIEW OF ULTRAMARINES 137
the arrangement of the smallest particles of this compound, i.e. they
regard the colour of ultramarine either as a constitutional property or
seek its origin in definite atomic complexes which form definite
chemical compounds with the essential constituent (silicate) of the
ultramarines. Among others in the first class is included Hitter 257 , who
considers that " there can be no question of a colouring principle, as the
whole of the ultramarine forms a chemical compound because, as
previously shown, one form of such substances may be colourless, yet
may, under certain conditions, be converted into a coloured compound
without the introduction of any new substance a comparatively clear
indication that here, as everywhere, the colour is due to the arrange-
ment of the " smallest particles."
R. Hoffmann 258 is one of those who consider that the cause of the
colour is to be found in definite radicles contained in the ultramarine.
He has referred frankly and clearly to sulphonates which can add or
lose sodium, oxygen, and sulphur, forming various colours. 259 " These
changes occur in a similar manner to those in the side chains of organic
compounds ; addition, substitution, and subtraction changes may
occur without destroying the combination with the silicate molecule."
It is clear that Hoffmann's conception of the constitution of
ultramarine is the one which most closely resembles that of the authors
of the present volume.
In this connection, the following extracts from Hoffmann's inter-
esting work on ultramarine are of value : 26 " for the present it is
sufficient to state that the formation of green and blue ultramarines
and their behaviour towards various reagents confirm the view that the
sodium added in the form of oxide must be more firmly united to the
elements of the kaolin than is the sulphide, and that it alone takes part
in the further conversion of white into blue and green ultramarine.
Consequently, it is possible to distinguish a silicate side from a sulphide
side in the ultramarine molecule without in any way disturbing the
combination of the elements as a whole."
Hoffmann 261 was also the first to claim the chemical individuality of
ultramarine and to confirm this by means of microscopical investiga-
tion. 262 He was also the first to show that it is not correct to speak
of one ultramarine, but rather of ultramarine compounds ; he en-
deavoured to classify these into those " rich in silica " and those
" poor in silica."
The view that there are several ultramarines and that some, at least,
of these are chemical compounds, has been independently adopted by
Phillipp 263 , Szilasi 264 , Heumann 266 , Guckelberger 266 , etc. At the same
time, it should be noted that Hoffmann has doubted the chemical
individuality of several ultramarines, including " ultramarine green."
" Ultramarine green " is generally understood not to have the
properties of a chemical compound. 267 It is considered to be either a
mixture of ultramarine blue and a yellow substance or as ultramarine
blue to which sodium sulphide, etc. has adhered.
138 CONSEQUENCES OF THE H.P. THEORY
For this reason Guckelberger 268 examined " ultramarine green "
microscopically and found it to be a perfectly uniform, transparent,
sea-green substance. No traces of blue particles or of those inter-
mediate between green and blue were discernible. Hence, Guckelberger
concluded that " ultramarine green " is a single chemical compound.
It is surprising to find that, as early as 1878, B. Hoffmann 269
expressed an opinion on the nature of the bond of the sulphur-group in
the ultramarines which is very similar to that of the authors of the
present volume. He also expressed the belief that part of the oxygen
in the silicate molecule is replaceable by sulphur. " The existence of a
sodium silico-aluminate in which that part of the oxygen which is in
closer combination with sodium can be replaced by sulphur such
silico-sulphonates behaving like free sodium monosulphonate (from
which higher sulphonates may be produced by combination with
sulphur and loss of sodium, without the silicosulphonate being decom-
posed) would be sufficient to explain the formation of ultramarine by
the ordinary method of preparation and also its chemical behaviour
towards other substances."
R. Hoffmann 734 endeavoured to find satisfactory structural
formulae for white ultramarine, siliceous blue ultramarine, etc., and
for this purpose made use of the silicate formulae proposed by K.
Haushofer 736 to obtain the following :
Na O Al > Si S Na
Na Al Si Na
White ultramarine.
Al < Si S S Na
Si
O
O A]
Na O Al
Si
/0\ '
Si O
O
0_Al<0\s!
Siliceous blue ultramarine.
S Na
Hoffmann admitted, however, that these formulae were more
fantastic than probable.
THE CONSTITUTION OF ULTRAMARINES 139
A New Ultramarine Theory
The formulation of the authors' new hexite-pentite theory of the
constitution of the silicates, and the existence of an extensive literature
of ultramarine, naturally suggest the application of the theory to the
ultramarine compounds. The absence of a general theory of the
composition of the silicates appears to be the chief reason why the key to
the chemical constitution of the ultramarines has not yet been obtained,
in spite of the innumerable experiments which have been made.
For example, the following hydro -aluminosilicate :
1111
till
H 12 H 4 (Si Al - Al S A i),
contains two kinds of OH-groups :
1. Aluminium hexite hydroxyl (or a-hydroxyl).
2. Silicon hexite hydroxyl (or s-hydroxyl).
The four a-hydroxyls must obviously behave differently from the
twelve 5-hydroxyls. As a matter of fact, the hydrogen in the a-
hydroxyls is readily replaced by monovalent acid radicles such as N0 2
Cr0 2 OH, S0 2 OH, etc. The hydrogen of the s-hydroxyls is, on
the contrary, more easily replaced by basic groups.
In the hexite-pentite theory of ultramarines, the a-hydroxyls
play a special part. The substitution of acid radicles for hydrogen in
the a-hydroxyls is specially noticeable as a characteristic property of
the compound Na 8 H 4 (Si Al Al Si) first observed by Silber for which
no explanation has, hitherto, been obtainable.
On heating a mixture of kaolin with an excess of soda, to redness,
and washing the calcined product with water, Silber obtained the com-
pound :
(Si 2 Al 2 Na 2 8 ) 6 = Na 12 (Si Al Al Si).
If this substance is treated with dry hydrochloric acid gas at 150,
one-third of the sodium separates out as sodium chloride and there
remains the compound :
Na H H Na
I I I I
Na /\/\/\/\_ N a
Si Al Al Si
I i I
Na H H
This compound, contrary to the original substance, possesses the
remarkable property of not replacing its sodium by silver when treated
with a solution of silver nitrate. Instead of replacing the sodium, the
silver is precipitated as oxide.
Silber 223 gives this substance the formula Si 6 Al 6 Na 4 23 , but he has
140
CONSEQUENCES OF THE H.P. THEORY
undoubtedly overlooked the presence of hydrogen in it. The separation
of Na by the action of HC1 can only occur when the Na is replaced by
H, for a temperature of 150 is much too low for OH-groups to
separate in the form of water.
On the assumption that in the a-hydroxyls the hydrogen can be
replaced by acid radicles, the behaviour of the compound Na 8 H 4 (Si-
Al Al Si) with AgNO 3 may readily be explained. By loss of Ag 2
and H 2 the compound :
N0 2 N0 2
I I
O O
I I I
N0 2 N0 2
is formed.
If this view is correct, a maximum of four atoms of silver can be
separated for each twelve atoms of silicon. The correctness of this
consequence of the theory must be proved experimentally.
The above theory permits the prediction that the hydrogen in the
a-hydroxyls may be substituted by the most varied monovalent
inorganic or organic acid radicles, and that in all compounds of the
Si Al Al Si type, only four of these acid radicles can be taken up.
The aluminosilicates in which the hydrogen of the a-hydroxyls can
be substituted by monovalent acids or acid radicles may conveniently
be represented by the terms A -aluminosilicates or 2-aluminosilicates.
The mode of formation of the .4 -aluminosilicates may be
made clear by means of a few examples. The production of these
compounds may be explained as due to splitting off the elements
/OH
of water. Thus, from 2 or 4 mols. S0 2 <f QTJ and the hydrate
H 12 H 4 (Si Al Al Si), the following A -aluminosilicates will be pro-
duced :
HO
|OH| |OHJ
Oll|o[HJ
I I I I
so/
THE SULPHONATE GROUPS IN ULTRAMARINES 141
f\~LT TTC\
\or\
i ,-=rr/ b 2 0!Hl lOHl
O
S0 2 /\S0 2
i i
I I I
_) __)
0|H] 0|H|
so
S0 2 S0 2
c.
S0 2 \/S0 2
o
D.
The compounds A, B, C, D are acids or acid anhydrides.
The hydrogen atoms of the sulpho-groups in A and C and the s-
hydroxyl groups may be partially or completely replaced by a base,
whereby acid or normal salts will be produced.
In ultramarines, the group
so,-
= S 2 7
(a)
plays a special role. This atomic complex has the power, under certain
conditions, to split off oxygen atoms and to take them up again, or to
replace them partially or completely by sulphur atoms. Thus, there
may be formed from S 2 7 the following :
Sulphonates
o
s
S0 2 -S0 2
so/Nso
so so
s/\s
s s
SS/\SS 2
O
O
A 6
1 1
O
a A
o o
1 1
1 1
1 1
1 1
1 1
1 1
S 2 6
S 2 5
S 2 4
S 2 3
S 2 2
S 7 2
(b)
(c)
(d)
(e)
w
(g)
o
s
*-
s
ss/^ss,
ss,/\ss,
SS 2 /\SS 2
SS 2 -S
5 2 S/^
V S 2 S 2 S 2
d A
4 b
1 1
s s
s s
g
Q QJ Q
bob
1 1
1 1
1 1
1 1
1
1 1 1
S 6 3
s ? o
S 9
S 8
S 7
S 6
So
(k)
(1)
(m)
(n)
etc. etc.
142
CONSEQUENCES OF THE H.P. THEORY
The sulphonates are very labile radicles and can be converted into
one another, under certain conditions, by the loss or addition of oxygen
or sulphur atoms or by the substitution of atoms of oxygen for those of
sulphur and vice versd. The atomic complexes a, 6, c, d, e, etc. are
anhydrosulphonates, but they may also enter the above ^4-alumino-
silicates A and C as hydro-compounds.
The Sulphonates as Chromophores
The study of the A- and 2-aluminosilicates containing sulphonate
groups has shown that these substances may be regarded as chromo-
phores in the sense in which this term is used in Witt's theory.*
The introduction of a sulphonate group in this way into a hydro-
aluminosilicate is not sufficient to form a coloured body. There must
also be one part of the hydrogen of the s-hydroxyls or the total
hydrogen of the A- or 2-hydro-aluminosilicates replaced by
mono- or divalent basic atoms. Such colour-stuffs may be termed
" ultramarines."
Ultramarines are, therefore, in terms of the hexite theory, such
compounds as :
ONa ONa
etc. etc.
Following the suggestion of M. Schiitz 224 it is convenient to regard
the change from yellow to orange, red, bluish violet, violet, blue, blue-
green and green as a deepening of the colour ; the reverse change from
blue-green to blue, etc. as a lightening of the colour.
R. Nietzki 225 has formulated a law representing the relation
* Witt's theory is described in further detail in a later chapter on the chemical
constitution of coloured glasses, p. 246.
THE SULPHONATE GROUPS IN ULTRAMARINES 143
between the change of shade in a pigment and its composition. Accord-
ing to this, the pigments of the simplest constitution are yellow ; with
increasing molecular weight the yellow colour changes into red, violet
and blue. Later researches by Kriiss and S. Oeconomides 226 , H. W.
Vogel 227 , and E. Koch 228 have shown that Nietzki's law is of general
application, but that there are certain exceptions to it in which an
increase in the molecular weight accompanies a lightening instead of a
darkening of the colour.
With increasing molecular weight, the sulphonate group can
produce either a deepening or a lightening of the colour.
As it is not sufficient merely to have a sulphonate chromophore in
order to form a hydro-aluminosilicate pigment, and the introduction
of a base into an acid is necessary, it is clear that the nature of the
base must exercise an important influence on the shade. An increased
molecular weight may thus cause either a lightening or darkening of
the colour. In all probability, the molecular weight of the original
substance of the pigment (i.e. the aluminosilicate itself) is also of
importance in connection with the shade of colour produced.
Enough has been said to enable the various facts relating to ultra-
marines to be explained in a simple manner. Apart from this, however,
the theory shows the manner in which further investigations both
practical and academic may most usefully be carried out in connec-
tion with these highly important pigments.
The Hexite Theory of Ultramarines and the Facts
From the ultramarine theory developed above, a series of Conse-
quences result. It is important to see how these agree with the facts.
A
Theoretically, the composition of the ultramarines may be pre-
dicted. It is, in fact, highly interesting to calculate the formulae of a
large number of analyses in order to see how far they confirm the
Consequences of this theory.
Most analyses of ultramarine have not been calculated into formulae,
and those which have been given often show wide differences between the
calculated and ascertained values. This is considered, by most chemists,
as being less due to errors in calculating the formulae than to impurities
in the material.
The calculation of these formulae showed that ultramarines of the
following types have already been prepared (see Appendix) :
1. Si Al Al Si,
2. Si-Al-sVAl-Si,
3. Si Al . Si Al T,
4. Si-Al-Si,
5. Si Al Si.
144
CONSEQUENCES OF THE H.P. THEORY
From type 1, for example, ultramarines of the following types have
been produced :
O
SO SO
Si
Al
Al
Si
\
i
/\/'
(a) R m (Si 12 Al 12 O n )(S 2 7 ) 2 .
I I
SO SO
\/
O
(b) R m (Si 12 Al 12 O n )(S 2 5 ) 2 .
s
(c) R m (Si 12 Al 12 O n )(S 2 2 ),
(d) R m (Si 12 Al 12 O n )(S 2 0) 2 .
(e) R m (Si 12 Al 12 O n )(S 2 ) 2 .
Summary of Ultramarines obtained, arranged according to the foregoing
Types
(a) R m (Si 12 Al 12 O n )(S 2 7 ) 2 .
1. Na 12 (Si 12 Al 12 46 ) S 4 14 .
(b) R m (Si 12 Al 12 O n ) S 4 10 .
2. Na n . 5 K . 5 (Si 12 Al 12 46 ) S 4 O 10 ONa 2 ,
3. Ag 16 (Si 12 Al 12 48 ) S 4 10 ONa 2 (H 2 0) 4 ,
4. Pb 8 (Si 12 Al 12 48 ) S 4 10 ONa 2 (H 2 0) 8 ,
5. Zn 8 (Si 12 Al 12 48 ) S 4 10 ONa 2 (H 2 0) 16 ,
THE CONSTITUTION OF THE ULTRAMARINES 145
6. Ag 12 (Si 12 Al 12 46 ) S 5 9 OAgNa,
7. Ag 15 Na(Si 12 Al 12 48 ) S 5 O 9 ,
8. Na 12 (Si 12 Al 12 46 ) S 6 8 .
(c) B m (Si 12 Al 12 O n ) S 4 4 .
9. Na 16 (Si 12 Al 12 48 ) S 4 4 (H 2 0) 2 ,
10. Na 12 (Si 12 Al 12 46 ) S 5 3 ONa 2 .
(d) R m (Si 12 Al 12 O n ) - S 4 2 .
11. Na 12 (Si 12 Al 12 O 46 ) S 4 2 ,
12. Na 12 (Si 12 Al 12 46 ) S 4 2 Na 2 ,
13. Na 12 (Si 12 Al 12 46 ) S 4 2 Na 4 ,
14. Na 12 (Si 12 Al 12 46 ) S 4 2 Ag 4 ,
15. Na 6 Ag 6 (Si 12 Al 12 46 ) - S 4 2 Ag 4 .
(e) R m (Si 12 Al 12 O n ) S 4 .
16. Na n . 5 K . 5 (Si 12 Al 12 46 ) S 4 Na 2 ,
17. Na 16 (Si 12 Al 12 48 ) - S 4 Na 2 ,
18. Na 12 (Si 12 Al 12 46 ) S 4 Na 4 .
Ultramarines of other types are arranged according to their sulphonates.
The following additional pigments have been produced :
(a) R m (Al p Si r O n ) ' S 4 14 .
19. Na 14 (Si 16 Al 12 55 ) S 9 9 ,
20. Na 16 (Si 16 Al 12 56 ) S 9 9 ,
21. Na 4 (Si 12 Al 6 34 ) S 6 3 ONa 2 ,
22. Na 6 (Si 10 Al 6 81 ) S 6 3 .
(6) R m (Al p Si r O n ) S 4 10 .
23. Na 16 (Si 16 Al 12 56 ) S 10 4 2 Na 4 .
(c) R m (Al p Si r O n ) S 4 8 .
24. Na 14 (Si 18 Al 12 59 ) S 12 ,
25. Na 18 (Si 18 Al 12 61 ) S 12 ,
26. Na 20 (Si 18 Al 12 62 ) S 12 ,
27. Na 12 (Si 16 Al 12 56 )-S 12 .
146 CONSEQUENCES OF THE H.P. THEORY
(d) R m (Al p Si r O u )-S 4 2 .
28. Na 8 (Si 12 Al 6 38 ) - S ff
29. Na 16 (Si 18 Al 12 60 ) S 6 ,
30. Na 18 (Si 18 Al 12 61 ) S 5 0.
The above ultramarines exist both theoretically and actually.
Other corresponding compounds must be produced sooner or later.
If the views just expressed with regard to the constitution of
ultramarines are correct, these substances can only be produced from
hydro-aluminosilicates with a-hydroxyls, and not from acids of the
following types :
x
I. il;-Si 2. At-Si 3. Al-Si and 4.
si si
. .
X si x si x
as the latter contain no a-hydroxyls.
Ultramarines of these latter types are, as yet, unknown, and any
attempts to produce them must prove abortive if the hexite-pentite
theory is correct.
Many ultramarines of the greatest diversity of colour are in
agreement with the theory. Thus :
1. According to Zeltner 229 , violet ultramarine may be obtained
from the blue or green varieties if chlorine or other halogen and
hydrogen is passed through the given ultramarine at 160-180, NaCl
being separated.
2. According to Hoffmann 230 , a purple-red or violet pigment may
be obtained from blue or green ultramarine by treatment with acids or
salts and air at a high temperature. A separation of the base
also probably of the sulphonate group occurs.
3. J. Phillipp 231 obtained a blue ultramarine by treating green
ultramarine with water at 160, and concluded that sodium sulphide
was liberated in the process.
4. Gmelin 232 had previously shown that blue ultramarine, when
heated in a current of hydrogen, is converted into red ultramarine with
the liberation of H 2 S.
5. In the following compounds, with the same chromophore and the
same silicate nucleus, but with a variable proportion of base, the
deepening of the colour with increasing molecular weight in accord-
ance with Nietzki's law (p. 142) is readily observable.
Na 14 (Si 18 Al 12 59 )S 12 is red,
Na 18 (Si 18 Al 12 61 )S 12 violet, and
Na 20 (Si 18 Al 12 62 )S 12 blue.
THE CONSTITUTION OF ULTRAMARINES
The possible existence of isomeric ultramarines follows naturally
from the theory. Thus, there are four possible isomers for a compound
with the formula :
Na 12 (Si 12 Al 12 46 )S 6 4 Na 2 ,
as may be seen from the following structural formulae :
0-SNaO-SNa
3.
Si Al Al Si
\X\x
SNaO-SNa
2.
0-SNa-SNa
4.
The results of anumber of analyses by R. Hoffmann 233 , Heumann 234 ,
and Phillipp 235 agree with the last-mentioned formula. In spite
of the fact that all the ultramarines examined by these investigators
had the same composition, they varied in their characteristics, the
ultramarines of Hoffmann and Heumann being blue and that of
Phillipp, green. Hence at least two isomers, out of those possible, are
known.
Further studies of these pigments must eventually lead to the
discovery of new isomers, the composition of which can be predicted.
Thus, there are three possible isomers of the compound
Na 16 (Si 12 Al 12 48 ) - S 4 4 ,
with the following structural formulae :
148 CONSEQUENCES OF THE H.P. THEORY
S S 00 S S
3.
On treating a given ultramarine with an aqueous solution of a salt,
e.g. the compound
S S
Na 6 O Na
Na 2 =
Si Al
Al
Si
/\/
a O
=Na 2
!=Na 2
-i
with BaCl 2 , SrCl 2 , ZnS0 4) AgN0 3 , etc., a substitution of the sodium by
barium, strontium, zinc or silver, etc. may occur or the sulphonate
group may pass into the new compound. The sulphonates, as already
mentioned, are very labile radicles and can easily unite with or throw
off oxygen, so that it is by no means impossible that the sulphonate of a
new compound may be either rich or poor in oxygen.
Szilasi 236 and Heumann 237 have reached the same conclusion in
their investigation of the behaviour of ultramarine compounds and
solutions of salts. Szilasi studied the behaviour of three green ultra-
marines (see Appendix) one made at Budapest and the two others
at Nuremberg. As it happened, all three samples had the same com-
position, viz. :
S S
A.
_/\/\/\/\ =
Si Al Al Si I aq.
S 4 4 (H 2 0) 2 .
THE CONSTITUTION OF ULTRAMARINES
149
By treating this compound with a solution of AgN0 3 , Pb(N0 3 ) 2 and
ZnS0 4 , Szilasi obtained the following ultramarines :
ONa ONa
SO SO
B.
aq.
SO SO
o
Ag 16 (Si 12 Al 12 48 )
Pb 8 (Si 12 Al 12 48 )
Zn 8 (Si 12 Al 12 48 )
S 4 10 ONa 2 (H 2 0) 4 ,
S 4 10 ONa 2 (H 2 0) 8 ,
S 4 10 ONa 2 (H 2 0) 16 .
The mode of formation of compound B from A is easily seen. On
the silicate side there is a replacement of sodium by Ag, Pb or Zn,
whilst one sulphonate has added oxygen and the other oxygen and
Na 2 0. The addition of Na 2 O is due to the fact noted by several
investigators that sodium ultramarines, on treatment with water,
lose part of their sodium in the form of caustic soda.
That the sulphonates can lose oxygen and Na 2 in aqueous solution
is shown by the fact that Szilasi was able to reproduce the original
sodium salt A from the silver salt B 1, with the structural formula
B, by treating the latter with sodium iodide.
Heumann examined a blue ultramarine from Marienberg, the
analysis of which (see Appendix, Analysis No. 10) corresponds to the
formula :
C.
Na 12 (Si 12 Al 12 46 ) Na 2 S 5 4 .
150 CONSEQUENCES OF THE H.P. THEORY
This sodium ultramarine was heated with silver nitrate in a sealed
glass tube at 120 for seven hours and formed a yellow, silver ultra-
marine with a composition corresponding to :
SO S
O
A
B. | Si I Al Al | Si
"YYW
o o
so so
\/
s
Ag M Na(Si 12 Al 12 48 ) - S 6 9 .
The sulphonate groups in this case were oxidised ; they added
oxygen and lost Na 2 O. The silicate side took up more base than
compound C, as shown in formula D. Such cases have frequently
been observed in the formation of complex silver and thallium salts
(p. 19).
To all appearances, Heumann was able to reproduce the original
sodium salt by heating the silver salt for eight hours at 130- 140 with
a solution of sodium chloride, but, unfortunately, no analysis of this
blue compound is available.
F
If the ultramarines are really derivatives of clays and are formed
in the manner indicated by the hexite theory, the possibility of the
formation at temperatures above the vitrification point of the clay
must diminish with the amount of polymerisation which occurs and
must cease entirely at the temperature at which the clay fuses, as at
that temperature clays no longer contain a-hydroxyl. On the other
hand, it must be possible to destroy the colour of any ultramarine by
heating it to a sufficiently high temperature.
Knapp and Ebell 238 have shown that as soon as the temperature
of an ultramarine reaches that of incipient vitrification, the possibility
of its remaining blue diminishes and it ceases entirely at the fusion
point of the material.
Gmelin 239 has shown that the colour of ultramarine may easily be
destroyed by excessive or prolonged heating.
C. Stolzel 240 heated blue ultramarine to redness for a long time in
a platinum crucible and noted that the colour gradually weakened and
that a white product was finally obtained. A green ultramarine, when
similar!/" 1 ^ ated, showed no diminution in colour. At first it darkened,
THE CONSTITUTION OF ULTRAMARINES 151
but then showed so great a stability that after several hours' " powerful
heating " no further change could be noticed. In all probability, the
vitrification point of the green ultramarine examined by Stolzel was
above the " red heat " to which it was exposed ; this accounts for
the colour remaining unaffected. Further experiments will show
whether the destruction of the colour of a number of ultramarines,
which are stable at red heat, occurs at a higher temperature. Accord-
ing to the hexite theory, this must necessarily occur.
G
The separation of a sulphonate group in an ultramarine must
result in a destruction of the colour. This is necessarily the case.
Dilute acids, such as hydrochloric acid, effect a separation of the
sulphonate group and produce a colourless mass.
H
If the ultramarines are real derivatives of clays, strong acids must
not only effect a separation of the sulphonate groups, but must also
affect the silicate nucleus and convert it into a compound of the most
stable type, gelatinous silica usually separating out. No experiments
in this direction are yet available. The truth of these conclusions at
at any rate as regards the separation of gelatinous silica appears to be
confirmed by Eisner 241 , who treated two ultramarines one blue and
one green with hydrochloric acid. Both lost their colour, sulphuretted
hydrogen being evolved and gelatinous silica separated.
The authors' ultramarine theory gives a maximum content of
monovalent bases in these substances. So far as the analyses studied
by the authors are concerned, no ultramarine is known with a higher
content of bases than the maximum shown by the hexite-pentite
theory.
K
The theory also demands a minimum molecular weight for ultra-
marines. In this connection it is interesting to note that Guckel-
berger 242 in studying the ratio H 2 S : S : S0 2 in the decomposition of
ultramarines by acids has also arrived at the conclusion that the
molecular weight of " ultramarine blue " is greater than that of an
atomic complex with 6 silicon atoms, and that it is a multiple of Si 6 .
This view agrees with the theory proposed by the authors of the
present volume.
L
It also follows from the theory, that the sulphonates form definite
chemical compounds with silicate nuclei. Ritter 243 has reached the
same conclusion experimentally. By the action of chlorine gas at
152
CONSEQUENCES OF THE H.P. THEORY
300 on the so-called white ultramarine, Hitter has shown that only
a small quantity of sodium chloride is formed. From this he rightly
concluded that, in the ultramarines, the sulphonates are in true
chemical combination with the silicates, as any free sulphide com-
pounds present would be completely decomposed by chlorine.
R. Hoffmann 244 is of the opinion that the sulphonate groups
behave similarly to free sulphides, but are not quite the same as the
latter as " they show a greater stability in the silicate compounds."
Analogy between Ultramarines and Sodalites
In concluding these observations, it is interesting to note the mode
of formation of a number of compounds, the constitution of which is
analogous to that of the ultramarines.
The assumption that some normal salts, e.g. Na 2 S0 4 , Na 2 W0 4 ,
NaN0 3 , etc., contain "water of constitution," when in aqueous
solution, is quite reasonable, as the formation of such hydrates is
extremely probable (p. 267). If it is accepted, there is a possibility of
forming compounds with these salts and an aluminosilicate correspond-
ing to
Na 2 OH OH Na 2
B I I
Na.
6 Na 2 2 H 2 6 A1 2
A
12 Si0 5
If water is lost, the constitution of the resultant substances may
be represented by the formulae :
Na
2 Na 2
II ' I I II
Na _/\/\/v\
Si
Al
Al Si
Na
/\/\/\/
Na 2 OH OH Na 2
B
Na
Na 2
the sign 2 representing a molecule of a given salt (Na 2 S0 4 , Na 2 W0 4 ,
NaN0 3 , etc.).
Thugutt (p. 60) has actually obtained a series of these compounds
which may be termed " atomic compounds " (p. 59). From this atomic
expression of the constitution of the sodalites it follows that a molecule
of silicate A can combine with, at most, 4 molecules of S. This
Consequence of the theory is confirmed by the facts, and no sodalite is
CRITICAL REVIEW OF CEMENT THEORIES 153
yet known which contains more than 4 molecules of 2 to one of A (see
the series of Thugutt's sodalites on p. 60).
Theoretically it is also possible that the aluminosilicate A and other
aluminosilicates with a-hydroxyls may not only combine with simple
compounds and salts of the kinds mentioned conveniently termed A
(acid-) and 2 (salt-) sodalites but also with complex acids and their
salts.
The formation of sodalites (A- and 2-sodalites) of the latter kind
occurs in the so-called porcelain cements (p. 215).
Thugutt's sodalites and the porcelain cement sodalites may there-
fore be regarded as analogous to the ultramarines.
XIII
A New Theory of Hydraulic Binding Materials, with special reference
to Portland Cement
The various substances known as " Portland cement " form only
one division of the so-called hydraulic binding materials, the others
being known as trass, puzzolans, hydraulic limes, Roman cement, slag
cements, etc. Of all these, the Portland cements are the most important
and valuable hydraulites. * Like the ultramarines, innumerable theories
have been proposed to explain their chemical nature, but none of these
theories is completely satisfactory.
If, as may be taken for granted, the solution of the problem is to
be found in the chemical nature of the silicate cements and in the
chemical constitution of the substances (silicates) from which they
are derived, any attempt to apply the new hexite-pentite theory
to the constitution of these cements must be of exceptional interest.
If the new theory should prove to be of general applicability to the
silicate cements it would not only solve one of the most interesting
problems of inorganic chemistry, but the fact that it could afford such
a solution would be of enormous value to the new theory itself.
Before endeavouring to apply the new theory to the hydraulic
binding materials, it is desirable to review briefly and critically the
various theories now in existence concerning cement, and to state in
some detail the nature of the problem the solutions to which hitherto
suggested have proved so unsatisfactory.
Historical and Critical Notes on previous Theories relating to Cements
The artificial production of Portland cement had scarcely been
discovered when a question arose as to the cause of hardening f of
* A hydraulite is a substance which, when mixed with water to form a stiff paste,
sets and becomes hard like a cement. A. B. S.
f In English-speaking countries the " setting " and " hardening " of cements are
treated as distinct. In the present volume, the term " hardening " is used to include all
the processes which occur from the time the soft material, made by mixing the cement with
water, begins to set to the time when the mass attains its maximum hardness. A. B. S.
154 CONSEQUENCES OF THE H.-P. THEORY
cements generally. A French engineer, Vicat 270 , who had paid much
attention to cements, set to work to investigate, and eventually con-
cluded that the hardening was due to the combination of the cement
with water. A closer investigation showed that there are several
difficulties in the way of accepting this hypothesis, some substances,
which were known to combine with water, never hardening like cement.
Thus, the zeolites are hydrous aluminosilicates which, after being
deprived of water, can absorb it again from the air, though, as Fuchs
has shown, such dehydrated zeolites do not harden under water.
Again, quicklime is well known to combine with water, yet the com-
bination does not produce a hard, solid mass, but only a soft, friable
powder. Fuchs 271 therefore sought for another explanation of the
cause of the hardening, and eventually made the remarkable discovery
since repeatedly confirmed that only those aluminosilicates which,
on treatment with acids, produce gelatinous silica, possess the property
of hardening with lime and water. Fuchs concluded that hardening is
a chemical process in which part of the lime and the " attackable,"
" soluble " silica unite, on burning, to form a calcium silicate.
Indeed, Fuchs went so far as to state the composition of the silicate
which he supposed was formed. As no facts in opposition to this
theory were known, it was not only accepted readily, but was used to
great advantage. Pettenkoffer 272 an energetic supporter of this
theory even suggested that Fuchs had so completely solved the
problem that no further investigation was necessary ! Feichtinger 273 ,
however, sought for experimental proofs of Fuchs' theory, and believed
he had found it in the following fact : if the hardening is due to a com-
bination of soluble silica and free lime, the mixture must lose soluble
silica in proportion to the amount of hardening which has occurred.
This fact he confirmed on several occasions.
Fuchs' theory was published before the discovery of Portland
cement, and, when applied to the latter, difficulties at once arose. One
of these difficulties was that in Portland cement the chemical behaviour
suggests that the whole of the lime is in a combined state and that no
free lime is present to combine with the soluble silica. This was one of
the first facts observed to be opposed to Fuchs' theory. Winkler 274
then found it necessary to devise a new theory for these hydraulites,* and
at once assumed that in the newer cements the hardening was not so
much the result of a new compound of lime and silica as of the separa-
tion of lime from a compound previously formed. He retained Fuchs'
theory for silicate cements containing free lime (Roman cements) and
concluded that in Portland cements the liberation of lime occurred
until the same calcium silicate was obtained as Fuchs had found to be
necessary in the other hydraulites.
Feichtinger 275 , on the contrary, opposed Winkler 's theory, and
maintained that Portland cements contain free lime ; to this extent he
* See the first footnote on the previous page.
PORTLAND CEMENT THEORIES CRITICISED 155
supported Fuchs' theory. Nevertheless, it is possible to draw pre-
cisely the opposite conclusions from Feichtinger's experiments, i.e. the
absence of free lime in Portland cement. He endeavoured to explain
the inconsistency of his theory with the facts by means of a new and
improbable hypothesis, viz. that the particles of free lime are so
coated over with molten cement that a considerable amount of time
is needed before the presence of the free lime becomes noticeable.
Feichtinger examined various kinds of hydraulic limes, including
those, like Portland cement, in which the whole of the lime is chemi-
cally combined, and those, like Roman cements, which contain free
lime. Both are readily distinguished by their behaviour towards
water ; the former, on hydration, show a scarcely noticeable rise in
temperature, whilst the latter show an unmistakable development of
heat . Furthermore, Portland cements after a given period of hydration
show no Ca(OH) 2 , whilst in the Roman cements this substance may be
detected as soon as water is added. This is in direct contradiction to
Fuchs' theory. In order to retain this theory, Feichtinger had recourse
to the improbable hypothesis mentioned above.
Winkler 276 has argued that the behaviour of Portland cement towards
an alcoholic solution of phenolphthalein shows that the whole of the
lime is in a chemically combined state, as the smallest trace of free
lime would, if present, turn the indicator red. In reality, no such red
colour is produced. Fuchs' theory is inconsistent with the possibility
of regenerating the cement from the set or hardened mass, though this
possibility may be inferred from Feichtinger's experiments, as will be
shown later. No agreement was ever reached by Feichtinger and
Winkler : each retaining his own opinion to the last. This shows how
strong was the influence of Fuchs' theory on Feichtinger.
No absolute answer to the question, " Does Portland cement
contain free lime ? " has been given, even at the present time ; the
influence of Fuchs' theory has been so strong.
It is also interesting to note how the supporters of the " free lime "
hypothesis endeavoured to disparage the value of the phenolphthalein
reaction. Some of them suggested that the " free " lime in Portland
cement is in a crystalline state and so is incapable of reaction as an
alkali. This suggestion is futile, as Richter 277 has prepared crystallised
lime and has shown that in alcoholic solution it has an obvious alkaline
reaction.
Fremy 278 endeavoured to show the presence of free lime by treating
Portland cement with dilute acids, but Schuljatschenko 279 has rightly
shown that the behaviour of Portland cements towards dilute acids is a
most unsatisfactory premise on which to argue for the presence of free
lime, as the whole of the lime present can be removed from the cements
by means of dilute acids.
Other investigators have used other reagents 278 * such as Mg(NO s ) 2 .
* A list of reagents which have been tried for showing the presence or absence of
free lime in cement will be found in the Bibliography under No. 278.
156 CONSEQUENCES OF THE H.P. THEORY
A considerable replacement of lime then occurs, and has been con-
sidered to prove that Portland cement contains free lime. That this
conclusion is false may be readily understood when it is remembered
that such reagents are precisely those which decompose the cement.
Michselis 280 has rightly shown that the ease with which lime may be
liberated by the action of certain reagents does not prove that a
portion of the lime in Portland cement is in a weaker state of combina-
tion. The statement made by Hardt 281 , that " feebly combined lime "
is the same as " free lime," is also quite erroneous.
Nor does it follow that soluble silica plays a special part in the
hardening of cement, even though it is true that only those silicates
which contain " soluble silica " are hydraulic. Erroneous ideas as to
the part played by " soluble silica " occur throughout the literature of
cement ever since the time of Fuchs, and have, hitherto, rendered it
impossible to evolve a sufficiently comprehensive theory of hydraulites.
Many hydraulites, such as plaster, lime-aluminates, lime-borates and
several calcium and magnesium oxides, contain no silica at all. Is it
not probable that these silica-free substances harden in accordance
with the same general law as the silicate cements ? Yet no one appears
to have realised the possibility of the " soluble silica " taking no
part whatever in the hardening process, for even Jordis and
Kanter 282 , who regard all previous theories respecting the constitu-
tion of cements as without foundation and erroneous, lay great
emphasis on the importance of " soluble silica " in the hardening of
cement.
The influence of Fuchs' theory is also shown by Heldt 283 , who was
clearly of the opinion that the value of cements lies chiefly in the pro-
portion of " soluble silica " they contain and that the alumina is only
detrimental, when he wrote : " If an aluminosilicate is present in a
mortar (cement) it exists simply as a wholly inert material and takes
no part in the setting or hardening, but is harmful because it reduces the
proportion of silica present. Each per cent, of aluminosilicate which
is not combined with lime is lost, so far as the formation of a hardening
compound is concerned, and remains as an insoluble and inert
material." It is not surprising that Heldt drew the following curious
inference from this theory : " If it were possible to prepare a hydraulic
mortar (cement) containing 23 per cent, of soluble silica, all existing
cement works would be ruined, as the best Portland cement only
contains 15-16 per cent, of soluble silica, which is reduced, by the
addition of water and after hardening, to only 7 to 10 per cent, in the
final product."
Chatoney and Rivot 284 two French investigators endeavoured
to put Heldt 's theory to practical use. Schuljatschenko has published
the following comments on this interesting portion of the history of
the cement industry: "Two writers, Chatoney and Rivot 284 , the
latter a learned chemist and professor at the School of Mines, in their
treatise on materials employed in structural work on the sea coast,
PORTLAND CEMENT THEORIES CRITICISED 157
reached the remarkable conclusion that only those cements are durable
in sea-water which consist of the simplest compounds such as those
made of lime and silica. Roman cements, puzzolans and other cements
lack durability in so far as their composition is complex. ..." These
authors arranged that the sea walls in the harbours of St. Malo and La
Rochelle should be built with silicates free from alumina, and it is
easy to understand the panic which occurred among French engineers
when they noticed the rapidity with which the cement used at these
places was destroyed.
Fuchs' theory also influenced the methods of investigation of the
constitution and hardening of Portland cements. His view, that the
hardening was due to the formation of a given calcium silicate, led to
an enquiry as to which substances were formed during the hardening
of the cement. These substances were later termed the " effective
substances " of the cement. For over fifty years innumerable investi-
gators have endeavoured to find the substance which is the chief cause
of the hardening of cements,* and it is noteworthy that everyone
who was able to prepare an aluminate or silicate which possessed the
power of setting in water, at once declared that it was to this substance
that Portland cement owes its setting power ! The result is that there
are nearly as many " effective substances " as investigators. All kinds
of calcium silicates from the mono- to the hexa-silicates and many
calcium aluminates have been prepared in this connection, and, to add
to the difficulty, the silicates which one investigator declared to be
hydraulic were found by another to have no hardening power. " Hence,
almost all possible calcium silicates," write Jordis and Kanter 284b ,
" have been ' found ' in cement clinker ; indeed, some investigators
have not confined themselves within the limits of the theoretically
possible ! There is, in fact, a repletion of silicates calculated from
cement analyses, the only evidence for the existence of which is that
the (assumed) compositions of these various silicates, aluminates,
ferrates, etc., when added together in the proportions in which they
are alleged to be present, agree with those of Portland cement.
Surely this is a weak argument when it is realised what is meant by
the inclusion of all the possible combinations ! "
Fuchs' theory is also responsible for the fact that no one has
hitherto regarded the Portland cements as chemical compounds, as
this would be in direct opposition to the view that the value of a
cement lies in the (free) " soluble silica " present. It has, in fact, been
generally agreed that Portland cement is either a mixture of various
compounds (cf. the theories of Le Chatelier 285 , the Brothers Newberry 286 ,
Kosmann 287 , Jex 288 , etc.) or a fused mass of indefinable compounds.
Erdmenger 289 regards Portland cement as a "glass"; Hardt 290 as a
" solid solution," and the theories propounded by Schonaich-Caro-
lath 291 , Schott 292 , Zsigmondy 293 , Meyer-Mahlstatt 294 , Rohland 295 , etc.,
* For a list of theories of hardening the reader should refer to No. 284 a in the
Bibliography.
158 CONSEQUENCES OF THE H.P. THEORY
are of a similar nature.* These theories find a merely superficial
support from the microscopical examinations of thin sections of clinker
by Le Chatelier 296 , Feret, Tornebohm 297 and others, who have found
that commercially valuable clinker may be composed of several
different materials, f Tornebohm 297 has suggested the terms
"alite," "belite," "celite," and "/elite" for the chief of these con-
stituents.
This suggestion although at first sight it appears to be in support of
a " mixture " theory is not at all determinative, for no one has yet been
able to isolate these various constituents (e.g. by means of a mechanical
analysis), nor is there any general agreement as to the composition of
these " constituents." Thus, Le Chatelier considers that the clinker is
chiefly composed of tri-calcium silicate a substance which has not yet
been prepared, with certainty, in a crystalline state, but is a purely
hypothetical one. Tornebohm, on the contrary, regards it as a product
composed of alumina, silica, and calcium.
If alite, belite, etc. exist as real constituents of cement, each having
a different composition, it must be impossible to obtain cement clinker
of perfect uniformity. Yet Richardson 298 has produced clinkers which,
when viewed in thin sections, appear to be completely homogeneous,
and correspond exactly to good commercial clinkers. J
It is very probable that the want of uniformity observed by Le
Chatelier, Tornebohm and others in thin sections of clinker, is due to
a crystallographic and not to chemical differences in the material.
This appears all the more probable when it is remembered that it has
not yet been found possible to isolate any definitely characteristic
constituents from the clinker by means of sedimentation or mechanical
analysis. For instance, Schott 299 found that a mechanical separation
by means of moving fluid merely divided the material into grains of
different sizes, the finest having the same chemical composition as the
coarsest.
[The preparation of transparent sections of cement, as mentioned above, is ex-
tremely difficult and is not altogether satisfactory. It is much better to make a micro-
graphic analysis of pieces of polished cement clinker etched with water or 1 per cent,
hydrochloric acid and viewed by reflected light. Such pieces show that the greater
part of the cement is composed of crystals of a single constituent (" alite "), separated
by a much smaller quantity of intercrystalline material (celite ? with traces of belite ?).
Only the crystalline matter is of value, the other being quite inert. The composition
of the intercrystalline matter is uncertain ; it may be the same as that of crystals, the
material being merely in a different physical state.
Pure " alite " has been prepared by O. Schmidt and K. Unger (Der Portland
* For further information on the constitution of cement clinkers see No. 295 in
the Bibliography.
t For further information on the microscopical examination of cement see
No. 298 in the Bibliography.
J In a critique of the hexite-pentite theory made shortly after the publication of
the German edition of the present work, Allen and Shepherd stated that a reinvestiga-
tion of Richardson's clinkers with improved appliances showed that they were not
homogeneous. This discovery, which was not known to the authors when this book
was written, does not affect their argument, but only shows that Richardson was un-
able to produce, as he had hoped, a perfectly homogeneous cement. This has, however,
been obtained by Schmidt and Unger, as pointed out in the translator's note (below).
PORTLAND CEMENT THEORIES CRITICISED 159
Zement, Stuttgart, 1906, p. 102) by heating a mixture containing 67 per cent, of lime
to fusion. The " alite " crystals had a composition corresponding to :
Lime 67.33
Silica 23.50
Alumina 3.82
Iron oxide 2.28
Magnesia 2.34
Other matter 0.73
100.00
According to C. Desch 709 , " These crystals are completely homogeneous, so that
we are fully justified in regarding them as a solid solution of calcium silicate and
aluminate, but not in assigning to them a definite chemical formula."
This statement of Desch's is most peculiar. Surely the fact that the material is
crystalline is opposed to its being a " solid solution," and in any case it is not clear
why it is wrong to assign a chemical formula to crystals.
In criticising the German edition of the present work, C. Desch complains that the
authors have not paid sufficient attention to the structure of cements as revealed by
the microscope. Yet this investigator, whilst accepting the homogeneity of Schmidt
and Unger's cement, refuses to regard it as a definite chemical compound ! The " solid
solution " theory, which he prefers, has been exhaustively discussed in the general
criticism of the various theories respecting silicates (p. 13) and is further confuted by
the fact that no Portland cement has yet been found which does not conform to the
hexite-pentite theory, which states that such cements are highly basic calcium salts of
aluminosilicic acids. Besides, the properties of Portland cement do not coincide with
Desch's or any other theory of mixed crystals. (Vide pp. 13, 22 and 162.) In short,
there can be no single substance forming the essential constituent of all Portland cements
and corresponding to alite, because, as the authors' formulae show, the compositions
of cements differ greatly from each other, although they all admittedly fall within certain
limits when expressed in the form of an ultimate analysis.]
There is a sense in which all theories published on the silicate
cements are developments of that of Fuchs, and a considerable number
of investigators at the present time are still under its influence. It is,
however, impossible to find that these theories have led to any satis-
factory results, but rather to the opposite. The worthlessness of
these theories is particularly noticeable when an attempt is made to
use them in explaining the various experimental results which have
been obtained in silicate cements. Thus, in the light of the foregoing
theories, the following facts are inexplicable :
(a) It is known that the best temperature for burning a mixture
of clay and lime or chalk in the production of Portland cement is the
temperature at which the amount of vitrification is readily appreciable
to the unaided eye * and that the quality of the cement also depends
on the duration of the heating. If this is too prolonged or the tempera-
ture is too high, a cement of lesser, or of insignificant value is produced.
The theories previously mentioned afford no explanation of this
important fact.
(6) Silica cements which have been heated to the sintering point,
become gelatinous when treated with dilute acids.
This fact is well known, but not the slightest explanation has yet
been given as to its cause.
* This is sometimes termed the " sintering point." It is reached when sufficient
fusion has occurred to render the mass impervious to any suitable fluid which has no
chemical action on the material. A. B. S.
160 CONSEQUENCES OF THE H.P. THEORY
(c) It is known that in Portland cements a portion of the lime is
more readily removable than the remainder. The usual explanations
offered are that cements contain both free and combined lime, or that
part of the lime is in a state of weaker combination than the rest. The
first or " free lime " hypothesis has been shown in previous pages to be
opposed to the facts. The second is often thought to be supported by
the supposed presence of highly basic silicates and aluminates in the
cement. The behaviour of Portland cement towards certain reagents is,
however, opposed to this hypothesis. The supposition that calcium
silicates are present is founded on Winkler's experiments, which showed
the calcium silicates to be insoluble in an alcoholic solution of hydro-
chloric acid. From this it was argued that those portions of cement
which are insoluble in this reagent are composed of calcium silicate.
Calcium aluminates react alkaline to an alcoholic solution of phenol-
phthalem. Portland cements should, therefore, produce a red colour
with this reagent. As a matter of fact, they do not do so.
Hence, the ready separation of a definite proportion of lime from
Portland cements is very puzzling in the light of previous theories.
(d) By granulating furnace slags it has been found possible to
produce silicate cements which will only set or harden in the presence
of water containing lime or other alkalies in solution. None of the
theories previously mentioned can be used to explain this fact. Ac-
cording to Zulkowski 300 some Portland cements, as soon as they have
lost a certain percentage of lime, possess this characteristic of slag
cements and will only harden in the presence of alkaline fluids and not
at all with water alone. None of the existent theories show any genetic
relationship between the Portland cements and the slag cements.
As a matter of fact, there is such a relationship, as will be shown later.
(e) Lunge's 301 investigations on the resistance to alkalies of granu-
lated and ungranulated slags showed that, in the latter, the aluminium
is more strongly combined than in the former. There is no explanation
of this fact outside the present volume.
(/) The existing theories neither permit the prediction of the
following facts, nor do they provide a satisfactory explanation of them :
(1) According to Schott 302 a considerable proportion of lime may be
removed from a cement without affecting its setting and hardening power.
(2) According to Michaelis 303 , Schott, and others, it is possible to
reproduce the original cement from one which has been fully hardened.
(3) If a cement is allowed to set and is then ground to powder and
again mixed with water, it will again set hard, but not so strong as before.
(g) There can be scarcely any doubt that hardened cements are
very sensitive to certain salts, particularly to sulphates. None of
the existing theories can explain this harmful action of sulphates, nor
do they indicate any means whereby it may be avoided. When it is
remembered that an explanation of the harmful action of sulphates on
cement is probably the most likely means of overcoming the difficulties
caused by these compounds including the possible solution of the sea-
PORTLAND CEMENT THEORIES CRITICISED 161
water problem it is not difficult to imagine that the inability of
existing theories to throw any light on this important subject is one of
the gravest objections to their use. Another special weakness of
existing theories lies in the assumption made in almost all of them,
that Portland cements are not single compounds. This assumption,
which is entirely without foundation in fact, not only limits the develop-
ment of chemical knowledge of the silicate cements, but makes such
development quite impossible.
The opinion that Portland cements do not form chemical in-
dividuals is doubtless due to the prevalent ideas of the constitution of
the substances from which these cements are derived, viz. the clays.
The conception of other derivatives of clay, such as the ultramarines, as
chemical individuals is also made difficult for the same reason.
Now that it has been shown (a) that the clays and ultramarines may
be regarded as true chemical individuals (i.e. as definite chemical
compounds), (b) that by so regarding them, the whole mass of pub-
lished experiments on the silicates becomes explicable, and (c) that this
conception of them has the characteristics of a true chemical theory
one which permits a single classification for all these substances as well
as the deductive study of them it appears to be highly probable that
the Portland cements, which are nothing more than derivatives of
claj^s, may also be regarded as chemical individuals, provided that
no facts are opposed to this view.
When it is added that by thus regarding the Portland cements as
definite chemical individuals and applying the new hexite-pentite
theory to them, the meaning of the whole mass of published experi-
mental results becomes clear and that a new means of solving the
important " sea-water " problem is provided, it is hardly too much to
suppose that there will scarcely be a chemist who will continue to
regard Portland cements in the old erroneous manner as mixtures of
various substances.
In applying the new theory to Portland cements, the following
subjects must be considered :
(a) The chemical constitution of the Portland cements.
(b) The reactions which occur during the formation of Portland
cements, and the influence of the duration of heating and of the
temperature on the products.
(c) A new theory of setting and hardening.
At the suggestion of A. B. Searle the following statements, which
occur in various text-books, are dealt with more specifically than in the
original (German) edition of this treatise :
(a) The temperature in a cement kiln only effects a partial fusion of the material.
(6) Chemical reactions between solid substances take place very slowly and are
seldom complete.
(c) Cement clinker is not a homogeneous substance, but merely a mixture or a
solid solution, and correct conclusions as to its chemical constitution cannot be drawn
without studying each of the constituents separately.
(d) The chemical reactions which occur in the burning of cement are never com-
plete, and it is therefore incorrect to regard the product as a single compound, the
constituents of which are in proportions conformable to the laws of Dalton and Proust.
M
162 CONSEQUENCES OF THE H.R THEORY
(e) Cement clinker consists essentially of colloidal substances and the properties
of cement are due to the colloidal nature of its various constituents.
With respect to (a), a partial fusion of the material is not incom-
patible with the unitary nature of the clinker, i.e. it does not neces-
sarily imply that clinker is not composed of a single definite compound.
The partiality of the fusion is due to the low heat conductivity of the
material, whereby the melting point is not reached in the interior of
the mass.
[An interesting parallel to this was found by J. W. Cobb, who showed that lime
and silica enter into complete combination even though the temperature reached is far
below that required to fuse the lime and silica or the compound so formed.]
The statement (b), that the chemical reactions between solid
materials are slow and seldom complete, is by no means true at high
temperatures. Besides, there is no positive proof that on heating a
mixture of kaolin with calcium carbonate (the pure constituents of a
raw cement mix) the clinker contains free clay as well as free calcium
carbonate or rather free lime. On the contrary, the very small pro-
portion of insoluble matter in cement clinker (only 1-2%) shows that
the reaction is remarkably complete.
[Cobb's experiments, mentioned above, afford a further proof of the speed and
completeness of reactions between solid substances.]
That, as stated in (c), clinker is a mixture and not a compound is
purely an assumption and not a fact. Of the two assumptions, (1) that
cement clinker is a compound, and (2) that it is a mixture, that must
be the more probable which satisfies the most facts and enables the
prediction of the most properties to be made. This is unquestionably
true of the assumption that cement clinker is a true chemical com-
pound.
Statement (d) is sufficiently answered in the comment on statement
(b) given above.
Statement (e) that cement clinker is essentially colloidal is another
pure assumption which is quite unnecessary. It is true that cements
have some characteristics in common with colloids, especially with
regard to their behaviour on treatment with water. Any confusion
which may arise in this connection can only be due to a superficial
appreciation of the properties and structure of colloids. For, as a
matter of fact, the colloidal properties of cements and clays are by no
means incompatible with their chemical individuality, and, in the
authors' opinion, the colloids themselves are not mixtures, but definite
chemical compounds of very high molecular weight.
It is most surprising that C. Desch, on the one side, and E. T. Allen
and E. S. Shepherd, on the other, in their reviews of the German
edition of this work reproached the authors of the H.P. theory for
regarding Portland cements as definite chemical compounds and not as
mixtures. These critics believe that the microscopical investigation of
cements has shown positively that cements are heterogeneous sub-
stances. This is the sole argument which has been brought in opposi-
tion to the H.P. theory.
Unfortunately, these critics have omitted to bear a very important
PORTLAND CEMENT THEORIES CRITICISED
16$
fact in mind, namely, that a difference in crystal form does not neces-
sarily prove the presence of substances of different chemical composi-
tion. There is always a great probability of di- or poly-morphism,
whereby one and the same substance may assume different forms.
[The various forms which sulphur assumes is a particularly interesting example of
polymorphism brought about by cooling under different conditions.]
A proof of the non-identity of the various crystalline substances in
cement can only be furnished by proving that each of them has a
different chemical composition. This proof simple as it appears to be
is entirely wanting with regard to Portland cements, and all attempts
which have so far been made to separate the various crystalline con-
stituents have proved abortive.
These critics appear to adhere to one of the numerous mixture
theories of the constitution of cements, and it would be of great interest
if they would only state which is the one they prefer. If it were correct
to speak of a " fog of theories " such a term might well be applied to
the various mixture theories applied to Portland cements. Jordis and
Kanter, in their well-known work on cements, have stated that all
kinds of compounds, of possible and impossible theoretical constitution,
may be present as essential constituents, and when enquiry is made
as to what the various theories explain, it is almost impossible to find
a simple answer. The following lines will give the reader a clearer idea
as to the nature of the mixture theories :
Some writers state the composition of only a limited number of
constituents ; others give the composition of the clinker. In the
former class are Jex, Le Chatelier, Erdmenger, Rebuff at, Zulkowski,
etc. ; in the latter are Kosmann, Newberry, Jex, etc.
The constituents of cement clinker according to the writers named
below are shown in the following Table :
Alleged
Constituent
Year
Authority Quoted and Reference
Si0 2
2 CaO SiO 5
3 CaO SiO,
2-3 CaO SiO 2 .
3-4 CaO SiO 2 .
5 CaO 2 SiO 2 .
1884
1900
1893
1899
1901
1901
1856
1885
1885
1901
1901
1902
1902
1903
1856
1865
Le Chatelier, Bull de la Soc. Chim., 41, 377.
Jex, Tonind. Ztg., 1900, 1856.
Erdmenger, Chem. Ztg., 1893, 982.
Rebuffat, Gaz. Chim. ital., 28, II.
Zulkowski, Chem. Industr. 1901, 290, and Pamphlet, 1901.
Leduc, Sur la dissociation des produits hydrauliquea, Sept.,
1901.
Rivot & Chatoney, Comptes rend, 153, 302, and 785.
Le Chatelier, Bull, de la Soc. Chim., 42, 82.
Spencer & Newberry, Tonind. Ztg., 1898, 879.
A. Meyer, Bull. Boucarest, 1901, No. 6; Tonind. Ztg., 1902,
p. 1895.
Ludwig, Tonind. Ztg., 1901, p. 2084.
Kosmann, Tonind. Ztg., 1902, p. 1895.
Clifford Richardson, Tonind. Ztg., 1902, p. 1928.
Michaelis, Versammlung des Vereins der Portland Zement
fabrikanten, 1903.
Winkler, Jour. f. prakt. Chemie, 67, 444.
Heldt, Jour. f. prakt. Chemie, 94, 202-37.
164 CONSEQUENCES OF THE H.P. THEORY
The true composition of clinker is, according to Kosman (1895) :
4r\n CJi/"^ I ) ^-^2 * -*^*2^-) * ^4 (
Ca 2 biO 4 + I a 2 f g.^ 4 | ,
According to Newberry (1898) :
x (3 CaO SiO 2 ) + y (2 CaO A1 2 3 ).
According to Jex (1900) :
h c(CaSi0 3 )
ICaO
CaO
CaO
2 CaO
and according to Ludwig (1901) :
3.033 CaO -f 0.125 MeO + 0.217 A1 2 3 + 1 Si0 2 ,
or 3.158 MeO + 0.217 A1 2 3 -f 1 Si0 2 .
The published opinions as to the chemical composition of hardened
cements and of the constituents which cause this hardening are
equally divergent and confusing, as the examples in the following
Table will show :
Alleged Constituents Causing the Hardening of Cements
Alleged
Constituent
Authority Quoted and Reference
CaO Si0 2 H a O
4 CaO 3 Si0 2 H 2 O
5 CaO 3 SiO a H 2 O
3 CaO 2 Si0 2 - H 2 O
2 CaO SiO 2 H 2 O
3 CaO SiO 2 H 2 O
Le Chatelier, Bull, de la Soc. Chim., 1885, 42, 82.
Jex, Tonind. Ztg., 1900, 1856-1919.
A. Meyer, Bull. Boucarest, 1901, No. 6.
Zulkowski, Pamphlet, 1901.
Landrin, Compt. rend., 1883, 96, 156, 379, 841, 1229.
Michaelis, Jour. f. prakt. Chemie., 1867, 100, 257-303.
Michaelis, Verhandlung d. Vereins z. Beford. d. Gewerbefleizes, 1896,
317.
Rebuffat, Tonind. Ztg., 1899, 782, 823, 853, 1900.
A. Meyer, Butt. Boucarest, 1901, No. 6.
Erdmenger, Chem. Ztg., 1893, 982.
Rivot & Chatoney, Compt. rend., 1856, 153, 302, 785.
Michaelis, Jour, prakt. Chemie., 1867, 100, 257-303.
Michselis has also stated that the composition of a fully hardened
cement may be represented by :
246 (3 CaO R 2 3 +3 H 2 0)+661 (5 CaO 3 Si0 2 +5 H 2 0)+93 (CaO-J-H 2 0).
Allen and Shepherd have made the remarkable statement that the
view that Portland cement is a mixture of various constituents is
supported by ' a large amount of evidence.' It would be mostinteresting
to see this voluminous evidence, as it is entirely unknown to the authors
of the H.P. theory. Indeed, these critics appear to have overlooked
THE CONSTITUTION OF PORTLAND CEMENTS 165
a fact to which Rohland has drawn attention, namely, the undeniable
relationship between the constitution of clays, ultramarines and
Portland cements. If Portland cements were mixtures, then clays
and ultramarines could not be definite chemical compounds, yet the
available experimental evidence is entirely in support of their definite
chemical composition.
Almost all students of the constitution of Portland cements have
overlooked the following considerations :
Portland cements are, theoretically, highly basic lime salts of
aluminosilicic acids, i.e. they are basic salts of which clays are the
corresponding acids. Their general properties are in entire agreement
with this view of their constitution, and it is incomprehensible that on
treating clay with calcium carbonate in the manufacture of cement,
the product should not be a lime salt, but a mixture of various silicates
and alurninates. It must also be remembered that Vernadsky has
proved that free carbon dioxide is evolved when kaolin is heated with
sodium carbonate and that a sodium salt is formed quantitatively.
Analogous reactions occur in the synthesis of ultramarine from clay,
sodium carbonate and sulphur, wherein sulphur addition-products of
the sodium salt of the clay are formed. There is no foundation whatever
for the assumption that the reaction between calcium carbonate and
clay produces any other substances than those which the H.P. theory
demands.
(a) The Chemical Constitution of the Portland Cements
If any suitable hydro-aluminosilicate such as
_AAAA,
Si I Al I Al I Si
H 20 (Si - Al - Al Si),
which has been repeatedly mentioned on previous pages be exam-
ined, it will be found (p. 139) to possess two kinds of OH-groups, viz.
a- and s-hydroxyls. The a-hydroxyls play a special part in the forma-
tion of the ^4-aluminosilicates ; in the formation of Portland cements
the s-hydroxyls are specially important. The hydrogen of the
5-hydroxyls which may be briefly referred to as ^-hydrogen is, unlike
the a-hydrogen of the a-hydroxyls, replaceable by such groups as :
R"-OH, R"-O-R"-OH and R" O R" O R" OH,
(R" = Ba, Sr, Ca, Mg, etc.)
The basic atomic complexes are known as hydro-basic groups and as
side-chains.* If the elements of water are split off from two neighbour-
* For an explanation of side-chains a good text-book on organic chemistry
should be consulted. A. B. S.
166
CONSEQUENCES OF THE H.P. THEORY
ing (ortho) positions in the hydrobasic side-chains, anhydrobasic groups
are formed as shown :
-0-R''-|OH
R" OlH
R"
R"
O R
R\
/o
R" x
O R"
^
R"
O R"/
The hydrobasic atomic complexes
R" OH, R" O R" OH and R" R" R" OH
may be represented, according to the number of R"-atoms, by
(1), (2) and (3),
respectively, and the anhydrobasic complexes
R"\ R" \ R" R^
__ o R"/ ' O - R" - O - R"/ ' O R 7 ' R"'
O R" O R" \ O R" O R* O R"\ n
R" - O R" O R"/ ' R" R" O R"/
etc.,
O R V
may each be indicated, according to the number of R "-atoms, by
2, 3, 4, 5, 6, etc.
A few examples will make this clear :
2 K 2 O 28 R"O 6 H 2 O
6 A1 2 3 12 Si0 2
Hydrobasic Salt.
Na 2 O 20 R"O 6 H 2
H 2 6 A1 2 3 12 Si0 2
Hydrobasic Salt.
4 H 2 40 R"0 6 A1 2 3 12 Si0 2
Hydro-anhydrobasic Salt.
3=
3==
28 R"0 6 A1 2 3 12 Si0 2
Anhydrobasic Salt.
THE CONSTITUTION OF PORTLAND CEMENTS 167
What has been stated with regard to substances of the type
Si Al Al Si is equally applicable to other types, and the existence
is, therefore, possible of :
3=
4 4
- f'YA
Si |Al|Sij>=3
11 \/ II
4 4
etc. etc.
The Al may be partially or completely replaced by the sesquioxides
Fe"', Cr'", Mn'", Ce"', etc., and the Si by Sn, Ti, Zr, etc., whereby the
number of these basic salts is largely increased.
Some of these basic salts with definite hydro- or anhydro-basic side-
chains (viz. when R"=Ca, Mg) are manufactured on a large scale and
are sold commercially in a finely-powdered state under the name of
" Portland Cement." (It would be more correct to use the plural form
" Portland Cements.")
These Portland cements certainly contain 3 chains ; their maxi-
mum content of base remains to be found. Good samples appear never
to exceed a maximum corresponding to 6 side-chains. Apart from
this, these cements appear to contain a little alkali (in the aluminium
hexite), a little water (probably basic), and small quantities of such salts
as K 2 S0 4 , K 2 CO 3 , Na 2 SO 4 , CaSO 4 , etc., but only as impurities.
The following are typical examples of Portland cements :
(2)(2) OK OK (2)(2)
II I I II
4=
4=
= 4 C
+ 0.5 CaSO + 0.5 Na(K)CO,
4 ONa ONa 4
2 H 2 24 CaO 8 MgO K 2 Na 2 6 A1 2 3 12 Si0 2 +2.
5 OK 5
Si
Al Si
+ 0.5 NaCl
20 CaO 16 MgO K 2 3 A1 2 3 12 Si0 2 + 0.5 NaCl.
'\/\/\/'
168 CONSEQUENCES OF THE H.P. THEORY
+ 0.5 K 2 S0 4
5
39 CaO 3 A1 2 3 15 Si0 2 + 0.5 K 2 S0 4 , etc. etc.
(b) The Reactions occurring in the formation of Portland Cements, and the
influence of the time of heating and the temperature on the Products
Portland cements may be made by burning the most widely different
clays with definite quantities of lime or calcium carbonate. The ratio
of lime to clay naturally varies with the latter. Hitherto, the proportion
of lime and clay has been fixed empirically, i.e. it has been arranged
according to a definite rule (termed the hydraulic modulus) for each kind
of clay.
As, according to the authors' theory (p. 102), the clays are merely
aluminosilicic acids, the reactions which occur in the burning of
cement are obvious, and consist chiefly in replacing the s-hydrogen in
the clay by anhydrobasic groups. This cannot be so readily observed
in the commercial manufacture of these cements, as silica, alumina,
lime, alkali, etc. (in the form of impurities in the coal), are added to the
materials in the original mixture and produce other types than those
here described in detail.
To obtain some idea of the influence of the temperature and dura-
tion of the heating it is necessary to use the dynamisation theory
(p. 108). According to this, the oxygen valencies which are in a satur-
ated state in the raw material are set free when the clay, etc. is heated
to its vitrification point. If the heating is prolonged or the temperature
rises much above that needed to produce vitrification, polymerisation
products are formed and the free oxygen valencies again become
partially or completely bound. If the heating is still further prolonged
or the temperature is raised until the material melts, an increase in the
density of the basic silicates present may be observed. At the melting
point of the material, the polymerisation attains a maximum ; the
maximum density must, of necessity, be reached simultaneously.
This change in density under the influence of heat has been repeatedly
observed by various investigators as well as by the authors of the
present volume.
From these considerations it follows that the activity of the basic
salts (which is due to the liberation of secondary oxygen valencies at
the vitrification temperature of the material) is diminished or even
destroyed on prolonged heating at a temperature approaching the
melting point. 303a
THE CONSTITUTION OF SLAGS 169
Both consequences of the theory (a) the increase in density on
prolonged heating, attaining of a maximum at the melting point, and
(b) the diminution of activity or ability to hydrate are fully con-
firmed by the facts.
In confirmation of the second consequence of the theory, the
following facts may be cited : A properly burned cement, if crushed
to powder and then mixed with a suitable proportion of water, readily
hydrates at the ordinary temperature. This property of cement
diminishes on prolonged heating at the vitrification point and, in some
cases, ceases entirely when the cement is fused.
If the temperature is raised much above the melting point, further
reactions may occur, the polymerised molecule breaking up into its
original constituents i.e. into single cement molecules or decom-
position occurs within the cement molecule itself. In the former case,
useful cements are produced. Schmidt and linger have prepared
crystalline Portland cements from such fused substances by means
of the electric arc. Sauer has investigated the optical properties of
these crystals. When crushed and mixed with water they set rapidly,
with an appreciable development of heat.
This theory of the formation of polymerisation products of alumino-
silicates (including calcium aluminosilicates) at high temperatures,
provides a simple explanation of several facts wilich have hitherto
proved puzzling. Among several others :
The Eeactions which occur on granulating furnace slags and the
formation of Silicate Cements from them 303b
are thereby explained.
The raw materials from which iron is obtained are the iron ores.
In addition to iron, these contain other earthy constituents such as
lime, silica and alumina. The object of smelting these ores with coke
in furnaces is to separate the metallic iron from the other materials
and to remove the latter in a fluid state as slags. In order that the
slags may possess the necessary fluidity, the lime must bear a certain
ratio to the silica and the alumina, and great care is exercised by
iron-smelters to ensure that this ratio is maintained. In most cases,
the proportion of lime in the raw iron ores is too low and an addition of
limestone is, therefore, made. Under favourable conditions, the
molten iron and slag separate readily in the furnace on account of
the great difference in their specific gravities, and are allowed to flow
separately out of the furnace at two different levels. The slag carries
off all the lime, silica and alumina in the form of a calcium alumino-
silicate.
If the slag is " quenched," by allowing it to fall into cold water, a
material is obtained which, if crushed to a fine powder and mixed with
alkaline solutions (lime-water, etc.), hardens to a strong mass. The
material which has not been granulated does not possess this property.
The simplest explanation for this difference in behaviour between
170 CONSEQUENCES OF THE H.P. THEORY
slags which have been granulated and others is that the latter are
polymerised, whereas the quenched or granulated slags undergo an
" entpolymerisation," i.e. a breaking up into single cement molecules.
Against this view it may be argued that these slags are only
mixtures and not chemical compounds, but no satisfactory proof has
been found in support of this objection. On the contrary, it is obvious
that the manner in which these slags are produced is neither irregular
nor capricious, but is in accordance with definite " laws," their com-
position only varying in the several works because of differences in
the iron ores used.
Hence, if an iron ore of constant composition is used in a given
works, the composition of the slags will also be constant. This conse-
quence of the authors' new theory of the constitution of slags is adopted
by Jantzen 304 , who supports it by the following analyses of furnace
slags from the Buderus Iron Works in 1888 to 1890, 1893, 1895 and
1899 :
Si0 2 AljO, F,0, FeO MnO CaO CaSO 4 CaS MgO Alkalies
1888-90 35.20 10.02 0.21 0.55 0.30 47.10 1.56 2.17 1.20 (not determined)
1893 34.50 10.90 0.18 0.64 0.46 47.44 1.44 1.99 1.36
1895 34.23 10.28 0.33 0.64 Trace 48.26 1.87 2.07 1.13
1899 35.40 10.45 v , ' 0.37 46.74 1.72 1.81 1.20
0.91
This remarkable regularity in the composition of the slags during
so long a period cannot be a mere coincidence. It is far more character-
istic of a definite law, such as is only observed in connection with the
formation of definite chemical compounds.
Allen and Shepherd 737 deny that this constancy of composition is
due to the reason stated and regard it as caused by the constant com-
position of the mixture charged into the furnace. They endeavour to
support their contention by stating that many minerals have been
found in such slags, and protest against speculations on the structural
chemical nature of substances of which the molecular weight is un-
known. The obvious reply to such a criticism is that it is quite beside
the point. There is no evidence in support of the view that the com-
position of the slags is dependent on that of the charge, except in so
far as all chemical reactions require certain proportions of raw materials
before they can occur. The fact that the charge is constant, or
variable within certain limits, is not incompatible with the formation
of definite chemical compounds.
The further allegation that such slags contain many minerals is not
supported by facts. Jantzen, who arrived at the same conclusion as the
authors of the H.P. theory, concerning the slags he examined, must
have reached a widely different conclusion if the slags had really con-
tained numerous minerals.
If Allen and Shepherd insist on regarding slags as a kind of " glass,"
i.e. as a mixture, it is difficult to see how they can explain satisfactorily
the results of Lunge's experiments (pp. 160 and 171) on the behaviour of
granulated and ungranulated slags with alkalies. It would be a most
THE CONSTITUTION OF SLAGS
171
remarkable coincidence if such slags behaved so completely in accord-
ance with the H.P. theory, if this theory were quite erroneous.
With regard to the determination of the molecular weight of the
constituents of slags, it is one of the advantages of the H.P. theory
that (as has been previously pointed out) it furnishes for the first time
a fully established hypothesis concerning the minimum molecular
weight which a substance can possess when in the solid form. The
determination of this minimum has been impossible hitherto, as no
method yet known not even the physico-chemical ones used for
soluble compounds is applicable to solids. The published molecular
weights are, as the present writers have shown elsewhere, only applic-
able to substances in gaseous form or in solution, and cannot be used
for substances in a solid state. The charge of lack of knowledge of
molecular weight of the compounds concerned cannot, for this reason,
be urged in opposition to the H.P. theory.
Previous theories as to the nature of furnace slags have led to most
puzzling results. The theory that the chief constituent of these
slags is a definite chemical compound is confirmed by the fact that
analytical results obtained by Jantzen agree well with the formula :
26 CaO 1.5 MgO 0.25 FeO 0.25 MnO 3 A1 2 3 18 Si0 2 CaS 0.5 CaS0 4
An experimental proof of the authors' views of the constitution
of furnace slags is to be found in an investigation of slowly cooled
and of granulated slags by Lunge 305 , who obtained the following
results :
21.5 CaO 0.5 MgO 2 H 2 6 A1 2 O 3 10 Si0 2 CaS
, \\ / \/ \ ii \
j 3=<(si] Al | Al|sT>=3 CaS I
V II \/\/ II '
CaO
Calculated 47.46
Foundin \(a) 47.17
Granulated slag )(b) 47.14
Foundin l (a) 46.38
Ungranulated slag/ (6) 46.40
MgO
0.78
CaS
2.82
A1 2 3
23.93
Si0 2
23.60
H 2
1.41
t
0.73
1.82
24.36
23.38
1.06
0.72
0.73
1.82
24.20
23.60
1.25
0.84
0.81
1.79
24.64
23.29
1.21
0.98
0.81
1.79
24.82
23.50
1.17
1.10
<f> Unattacked by caustic soda or sodium carbonate.
172
CONSEQUENCES OF THE H.P. THEORY
The experiments from which these results were obtained are shown
in the following Table :
Nature of Treatment
Dissolved out of granu-
lated slags
Dissolved out of ungranu-
lated slags
iSiO,
%
Al,0,
%
Mol. SiO,
to 1 Mol.
Al,0,
SiO,
%
A1,0 S
%
Mol. SiO,
to 1 Mol.
Al,0,
I. Boiled for 2 hrs. with 30 per cent caustic f
soda solution \
6.93
6.93
1.09
0.88
2.30
2.12
1.92
1.80
3.53
3.00
3.52
3.52
1.26
1.15
1.19
1.14
5.94
2.57
2.33
3.43
3.53
2.63
2.74
4.12
4.81
4.91
4.40
1.9
0.72
0.40
1.15
1.03
1.25
1.13
1.47
1.08
1.23
1.37
7.25
7.25
1.76
1.48
2.68
2.87
2.49
2.74
4.25
4.46
4.46
4.40
4.68
4.70
5.06
5.08
6.39
6.34
0.15
0.17
0.13
0.15
0.12
0.11
0.31
0.28
1.91
1.91
II. Boiled for 2 hrs. wfth 10 per cent caustic/
soda solution . \
III. Digested for 6 hrs. on a water bath/
with 10 per cent caustic soda solution \
IV. Boiled for 2 hrs. with 5 per cent caustic/
soda solution \
V. Digested for 6 hrs. on a water bath]
with 5 per cent caustic soda solution 1
> >j ft
VI. Boiled for 2 hrs. with 5 per cent sodium/
VII. Heated for 6 hrs. on a water bath with f
5 per cent sodium carbonate solution \
It will be observed that a 30 per cent, solution of caustic soda
attacks both kinds of slag so strongly as to resemble the effect of
fusing them with soda. For this reason no importance should be
attached to the fact that rather more is dissolved from the ungranulated
slag than from the other. The relative behaviour of both slags towards
10 per cent, caustic soda solution should be noted, especially the fact
that the granulated slag is the more soluble of the two. On comparing
the structural formulae of the two slags
3=<(siJAl|Al|Si V3-CaS
Granulated Slag.
Ungranulated Slag.
CaS.
THE HARDENING OF PORTLAND CEMENTS 173
this difference is easily understood. Through the combination of a
large number of cement molecules to form a combined molecule
the strength of the bonds of the alumina in the ungranulated slags
is greatly reduced.
On the other hand, it appears as if the combination of several
silicate molecules, to form a single large one, weakens the bond in the
pentites ; otherwise, no explanation can be given for ungranulated
slags giving up 4 to 5 times as much silica to sodium carbonate solution
as do granulated slags.
(c) A New Theory of Hardening
Various theories of hardening are stated briefly in the Bibli-
ography. 3059 - None of them are entirely satisfactory, hence the need
for a fresh hypothesis based on the hexite-pentite theory.
In the following formulae is shown the composition of various
hydrated hexites, derived from one which is capable of taking up
hydroxyl progressively, i.e. at different intervals of time :
I I I ii
_/\ _/\_ _X\_ _/\_
IxF fxl
6XO a H 2 O'6X0 2 2H 2 0'6X0 2
I I I II
3H 2 0'6XOj 4H 2 O*6XO 2 5H 2 O'6XO 2 6H 2 O-6X0 2
d e f g
The conversion of a into 6, b into c, c into d, and so on, is accom-
panied by an increase in the volume of the molecules concerned, so
that the molecular volume of b is greater than that of a ; that of c is
greater than that of 6, and the compound g has the largest molecular
volume of the whole series.
In converting the compound a into b, b into c, and so on, the
separate molecules in each group take up definite positions relative
to each other, so that between b, c, d, e, etc., definite attractive, or
more correctly molecular, forces are bound to exist.
Assuming the molecules to be in the form of minute spheres, the
last statement may be expressed graphically by the following diagrams :
b Molecules c Molecules d Molecules
Each addition to the molecule of water in the form of hydroxyl
groups, 305b with a corresponding increase in the size of the molecule, is
termed a hydration phase. It is clear that any substance which is sub-
mitted to a sufficient number of hydration phases must set and harden,
because with the increase in the molecular volume the space between
the various molecules must diminish and their mutual attraction or
molecular force must correspondingly increase. Hence, every substance
174 CONSEQUENCES OF THE H.R THEORY
which can take up water progressively, i.e. which can undergo a series of
hydration phases, must be a hydraulite (see footnote p. 153).
Experience has shown that if the first hydration phases follow each
other rapidly, either no hardening occurs or what little hardening
takes place is very feeble.
These facts may be explained in accordance with the new theory,
by stating that if the hydration phases follow each other rapidly, the
spaces between the molecules are too large, or at any rate much larger
than when the hydration occurs more slowly. If this explanation is
correct, it should be possible to treat substances which hydrate rapidly
and do not harden in such a manner (as by applying pressure) that the
molecules are brought nearer together. The facts prove that when this
is done, the substance sets and hardens, thus fully confirming the
theory. Quicklime is a typical example of a material with rapid
hydration phases, and when it is slaked it falls completely to powder
with a considerable development of heat and the evolution of clouds of
steam. According to Knapp 306 , however, very finely ground quicklime
when mixed with water in a suitable, tightly closed vessel produces,
after several hours, a material which is harder than ordinary black-
board chalk.
From the foregoing statements, the following conditions and
characteristics of good hydraulites may be deduced :
1. The earlier hydration phases must occur at sufficiently long
intervals.
2. The material must undergo a large number of hydration phases.
Of several substances, under similar conditions, the one which under-
goes the most hydration phases will eventually be the hardest and
the most dense.
3. The smaller the distance between the molecules of a hydraulite
during the first hydration phases, the harder and denser will be the
mass produced.
The New Theory of Hardening and the Facts
I. According to this theory, setting must be prevented if the
particles of hydraulite are too far apart, as when too much water is
used. 307 An excess of water may also bring about too rapid an
addition of OH-groups and this, according to the new theory, must
have a detrimental effect.
II. It also follows from the theory that the smallness of the hydrau-
lite particles must play a special part in setting and hardening.
The smaller the particles the easier and more rapid will be the
hydration ; the larger the particles the more difficult will it be to
hydrate them. A definite degree of fineness is, therefore, an essential
condition of hydration, and it is theoretically, as well as practically,
necessary to regulate the intervals of time between the hydration
phases (i.e. the rate of combination with water) by means of the fine-
ness of the particles of cement.
THE HARDENING OF PORTLAND CEMENTS 175
III. According to Knapp 308 , anhydrous magnesia (prepared by
calcining magnesium chloride) absorbs water with no development of
heat and with extreme slowness, a stony mass is produced with a hard-
ness somewhat greater than that of marble. The lighter, more porous
magnesia (obtained from the hydrous carbonate) combines rapidly
with water and finally forms a porous, talc-like mass.
Richter 309 maintained finely powdered, anhydrous calcium nitrate
at a white heat for six hours in a platinum crucible and obtained a
vitrified porcelain-like mass, with a clearly defined crystalline texture
on the fractured surface. When ground with water this crystalline
CaO sets like cement. If the lime is insufficiently heated it is found to
crack badly on cooling.
Allen and Shepherd 737 state that only large pieces of fused lime are
indifferent to water, and that finely powdered, fused lime does
not differ from ordinary quicklime. This " fact," which requires con-
firmation as it contradicts the results of Richter's investigations, is used
by Allen and Shepherd as evidence against the H.P. theory. These
critics consider that the reduced reacting power of the burned material
is not due to polymerisation, but to the size of the pieces, i.e. to the
surface area. If this were really the case, calcium aluminosilicates
(cements) must behave exactly the same when burned hard or soft,
provided that the material is ground to the same degree of fineness
in both cases. Direct experiments show, however, that this is not the
case.
These interesting instances of isomeric lime and magnesia are
readily understood in the light of the authors' theory ; both the MgO
from magnesium chloride and the crystalline CaO are polymerisation
products which have hydration phases like the hydraulites and harden
in a similar manner.
According to the authors' theory, the cause of disintegration in
some materials is due to hydration phases following each other too
rapidly, owing to the material not having been properly burned. In
this connection it must be admitted that disintegration may also be
due to other causes.
For instance, Michaelis 310 attributes the cracking or " expansion "
of cements to a subsequent increase in volume, this being due to three
causes : first and foremost to a high percentage of lime, second to the
presence of calcium sulphate, and, finally, to irregular particles and
coarse grains in the cement.
That too high a percentage of lime may bring about the destruction
of the mass is a simple inference from the authors' theory, as lime and
alkalies effect an intense and rapid hydration, and a sufficiently large
proportion of lime will cause the hydration phases to follow each other
very rapidly.
An irregular distribution of coarse and fine grains in the cement,
resulting in disintegration, may be explained in terms of the authors'
theory because, as already mentioned, a fine powder is hydrated more
176 CONSEQUEiNCES OF THE H.P. THEORY
rapidly than a coarser one and forces differing in intensity are thereby
set to work in various portions of the material, with the result that the
latter is broken up.
The harmful effect of gypsum or plaster of Paris in silicate cements
is described later.
IV. Quartz crushed to an impalpable powder and then levigated,
will not form a hard mass with lime and water. 311 Opal, similarly
treated, hardens slowly, but well. Calcined silica, such as that obtained
in silicate analyses, when mixed with lime, hardens rapidly but badly.
According to the authors' theory, lime effects a hydration of the
opal and calcined silica, so that they harden ; but, as lime does not
behave in this way towards quartz, with the last-named substance no
hardening occurs.
According to Winkler 312 , if a mixture of three parts of quartz and
one part of lime is strongly heated and the sintered mass is then
crushed with six times its weight of lime and a suitable quantity of
water, the mass hardens slowly and strongly. It is clear that in this
case a series of hydration phases occurs at long intervals.
V. The authors' dynamisation theory also explains why it is
necessary for most silicates to be heated to redness before they will
harden in water (like Portland cements), or with lime and water (like
puzzolans). In the case of clays it has already been shown that, on
heating them to redness, or on causing them to combine with a base,
the bond between the hexites or pentites of silicon and aluminium is
weakened, and, for this reason, such silicates precipitate gelatinous
silica when treated with dilute acids.
The authors' theory agrees with the discovery of Fuchs that only
those silicates harden which contain " soluble silica," with the one
difference that the " soluble silica " plays absolutely no part in the
hardening process.
Different silicates must be heated 314 to very different temperatures
or for various periods before they will harden with lime and water.
For some of them a short heating to redness is sufficient ; others must
be strongly heated for a considerable time, and others must be almost
melted. According to Fuchs, the following substances harden with
lime and water after they have been sufficiently heated at a suitable
temperature : felspars, leucite, various magnesium silicates such as
talc and steatite, analcime, natrolite, clays, etc. All these silicates
harden because the heating and subsequent treatment with lime and
water produce hydration phases in the manner already explained.
The cause of the hardening of " trass " and " puzzolans " with lime
and water may be explained in an analogous manner. The trasses and
puzzolans are simply clays, and only differ from ordinary clays in the
alterations they have undergone in consequence of volcanic action.
In the course of time these substances may again lose their free
secondary valencies. Such trasses or puzzolans are improved by being
heated to redness.
THE HARDENING OF PORTLAND CEMENTS
177
A considerable number of hydraulites of the most widely different
composition have already been prepared. Thus, various aluminates,
ferrites, ferromanganese oxides and silicates, borates, calcium sul-
phates, etc., have marked hydraulic properties. A further study of the
hardening of these compounds must eventually lead to the proof of
the existence of hydration phases.
VI. The Causes of Hardening of Portland Cements. If a definite
silicate cement is selected, e.g. the compound
4=
Si Al Al Si
the following substances may be formed from it :
-f 2 Ca(OH),
(2)
+4 Ca(OH) 2
etc. etc.
If the hydration occurs as indicated in the above formulae at definite
intervals and with a definite increase in volume, hydraulites are pro-
duced in accordance with the authors' theory. The absorption of
water does actually occur in this manner, as will be explained in the
next chapter ; Zulkowski 315 has experimentally proved the increase in
volume. He treated ground slag with water, and obtained a flocculent
178 CONSEQUENCES OF THE H.P. THEORY
mass and a deposit of a sandy nature. The volume of the deposit
increased in process of time. The microscopical appearance of this
ground slag after treatment with water differed but little from that of
the dry (untreated) material.
The action of alkaline fluids was much more energetic. The volume
of the deposit was three to five times that of the original slag-powder.
Under the microscope the appearanceof the material gradually changes,
and after several months the original, small, glassy grains were no
longer observable, their place being taken by much larger, irregular
rounded grains or masses.
In the case of Portland cement, water alone will effect a change in
shape similar to that which occurs with slag-meal and alkaline solu-
tions. Zulkowski was the first to point out these changes in shape
and volume in the case of silicate cements, and in these changes he
saw the true cause of the hardening of hydraulic materials. The
hardening itself he explains as follows : " The cement grains which, at
the commencement, lie over and amongst each other and without any
definite relationship to each other, combine chemically with the water
present in the pores ; from them is produced a new substance, a
hydrosilicate, the material thereby changing its shape and increasing in
volume. The particles which expand in this manner occupy all the
available space, lie closely together, increase continually in volume,
and eventually convert the whole of the original loose particles into a
compact mass."
[W. Michaelis (Chem. Zeit., 1893, 17, 982) has suggested that hardening is mainly
due to the formation of a colloidal calcium hydrosilicate. According to Desch 709 ,
" this theory so well explains the phenomena observed and is in such good accordance
with the results of microscopical investigation of cements during and after setting
that it must be held to contain the greater part of the truth." Desch further adds
that " the course of events when Portland cement is mixed with water may be described
as follows : The essential hydraulic constituent is alite, which is a solid solution of
three components. The action of the water is, at first, confined to the alite, which
is partly decomposed, the aluminates being first hydrolysed. The solution thus pro-
duced is supersaturated and soon deposits tricalcium aluminate partly in colloidal
form and partly in crystals, according to the amount of water in the mixture, a larger
proportion of water favouring crystals and a smaller one the formation of a gel. The
excess of lime remains in solution or a part may be deposited as crystals of calcium
hydroxide. This corresponds to the ' initial set.'
" The action of the water on the calcium silicate contained in the alite is much
slower, and when hydrolysis occurs the calcium silicate is separated in colloidal form.
The gel produced forms a coating round the particles and prevents further action.
The colloidal matter is easily seen in a polished and etched specimen, and its definitely
colloidal nature may be shown by immersion in a dye such as eosin. Colloidal sub-
stances adsorb dyes, but crystals do not do so."
Desch attributes the hardening of cement which has been hardened and re-ground
to the large proportion of non-hydrated matter present in all cements, owing to the
slowness of the hydration.
The suggestion of W. Michaelis that the hardening of cements is due to their
colloidal nature cannot per se be regarded as of more than limited value, even when
supported by the statement of C. Desch that it " is in such good accordance with the
results of microscopical investigation." It does not coincide with the results of
Feichtinger's studies of hydration, given on another page, nor with the thermal in-
vestigations of Oswald and the multitude of facts which have been published in
support of various other theories, and is therefore inapplicable to any general theory
relative to cements. There is an analogy between the action of water on cements
and on colloids, as has been pointed out on a previous page, and any theory (if
FORMULA OF PORTLAND CEMENTS
179
correct) must therefore be capable of extension to organic cements in which hydrosols
are converted into hydrogels, forming cementitious substances, just as inorganic
cements pass through definite hydration phases into stone-like masses.
Bone-substance, which is essentially a highly basic calcium carbo-phosphate
(p. 271), is probably derived from an organic cement whose hardening phases are
analogous to those of Portland cement.]
The Consequences of the New Theory of Portland Cement
and the Facts
From the foregoing theory of the chemical constitution of the
Portland cements and the corresponding hardening theory, a series of
interesting consequences may be inferred, the value of which may be
proved by means of the experimental material available.
From the theory it follows that the calculation of the formulae
of Portland cements from their analyses must lead to compounds, the
existence of which is theoretically possible. The calculation of the
formulae from a series of cement analyses fully confirms this conse-
quence of the theory ; the high content of bases is particularly notice-
able in some analyses. Whether the whole of the base is in actual
combination is doubtful ; further investigations are needed to decide
it.
The formulae calculated from cement analyses (see Appendix) are
shown in the following Tables :
(a) n MO 3 R 2 O 3 - 12 Si0 2 - 2.
Al,0,
Fe,0,
CaO
MgO
K,0
Na,O
SO,
CO,
H,0
I. 24 MO 3 R 2 3 12 SiO 2 2
1.50
.50
26.00
1.00
0.25
0.25
0.5
3
2
II. 34 MO 3 R 2 3 12 SiO 2
2.00
.00
34.00
III. 35 MO 3 R 2 3 12 SiO 2
2.00
.00
35.00
k IV. 36 MO 3 R 2 3 12 SiO 2 2
2.00
.00
36.00
0.50
0.5
V. 37 MO 3 R 2 O 3 12 SiO 2 2
2.00
.00
36.00
1.50
0.5
VI. 37 MO 3 R 2 O 3 12 SiO 2 S
2.00
.00
36.25
1.25
0.5
VII. 37 MO 3 R 2 O 3 12 SiO 2 S
2.25
0.75
36.00
2.00
1.0
VIII. 38 MO 3 R 2 O 3 12 SiO 2 S
2.25
0.75
38.00
0.50
0.5
IX. 39 MO 3 R 2 O 3 12 SiO 2 S
2.00
1.00
38.25
1.25
0.5
X. 39 MO 3 R 2 O 3 12 SiO 2 2
2.50
0.50
39.00
1.00
1.0
(b) n MO 3 R 2 3 10 Si0 2 .
Al,0,
Fe,0,
CaO
MgO
K,0
Na,0
SO,
CO,
H,0
XI. 29 MO 3 R 2 8 - 10 SiO 2
XII. 34 MO 3 R 2 O 3 10 SiO 2
XIII. 35 MO 3 R 2 O 3 10 SiO 2
3.00
2.25
2.25
0.75
0.75
29.0
31.5
32.5
2.5
1.5
0.5
0.5
_ __
2
(c) n MO 3 R 2 O 3 18 Si0 2
. v
j.
|lAl,0,
Fe,0,
CaO
MgO K,O
Na,0
SO,
CO,
H,0
XIV. 52 MO 3 R 2 O 3 18 SiO 2
XV. 54 MO 3 R 2 O 3 18 SiO 2 S
2.25
3.00
0.75
52.00
53.75
1.25
___
1
__
___
180 CONSEQUENCES OF THE H.P. THEORY
(d) n MO 3 R 2 3 15 SiO 2 2.
Al a O,
Fe,0,
CaO
MgO
K t o
Na,O
SO,
co, |H,O
XVI. 20 MO 3 B 2 O 3 15 SiO 2 S
2.00
1.00
22.0
1.0
0.25
0.25
0.50) 3.0
1
XVII. 21 MO 3 R 2 O 3 15 SiO 2 S
2.00
1.00
22.0
0.5
0.50
1.0
2
XVIII. 21 MO 3 R 2 3 15 SiO 2 S
2.00
1.00
22.5
1.0
0.25
0.25
0.50
2.5
1
XIX. 22 MO 3 R 2 O 3 15 SiO 2 S
2.00
1.00
22.0
0.5
0.25
0.25
0.50
0.5
2
XX. 24 MO 3 R 2 O 3 15 SiO 2 - S
1.50
1.50
26.5
.5
0.25
0.25
4.0
2
XXI. 25 MO 3 R 2 O 3 15 SiO 2 S
1.50
1.50
27.0
1.5
0.25
0.25
4.0
2
XXII. 39 MO 3 R 2 O 3 15 SiO 2 S
2.50
0.50
36.0
2.5
0.50
0.50
1.00
O.SMnO
XXIII. 42 MO 3 R 2 O S 15 SiO 3 S
2.00
1.00
42.5
.5
0.50
0.50
0.50
2.5
2
XXIV. 45 MO 3 R 2 O 3 15 SiO 2 S
2.50
0.50
45.0
.0
1.00
XXV. 45 MO 3 R 2 O 3 15 SiO 2 S
2.25
0.75
44.0
1.0
0.25
0.75
1.00
XXVI. 46 MO 3 R 2 O 3 15 SiO 2 S
2.25
0.75
45.5
.0
0.50
XXVII. 46 MO 3 R 2 O 3 15 SiO 2 S
2.25
0.75
46.0
.0
1.00
(e) n MO - 6 R 2 3 12 SiO 2 2.
A1,O,
Fe,0,
\C&0
MgO
K,0
Na,o|
SO,
CO, H,0
XXVIII.
92 MO-
6 R 2 3
12 SiO 2 2 | 5
1
I 89
6
-1- 1
3 |10
(f) n MO - 6 R 2 O 3 18 Si0 2 2.
Fe,0, | CaO | MgO | K,O |Na,O | SO, CO,
XXIX. 38 MO - 6 R 2 O 3 18 SiO 2 S
3.5
2.5
40.0
_
0.5
0.5
2
2
XXX. 39 MO 6 R 2 O 3 18 SiO 2 S
3.5
2.5
40.5
0.5
0.5
0.5
2
2
XXXI. 74 MO 6 R 2 O 3 - 18 SiO 2 S
5.0
1.0
71.0
6.0
3
8
XXXII. 76 MO 6 R 2 O 3 18 SiO 2 S
5.0
1.0
72.0
5.0
1
4
XXXIII. 90 MO 6 R 2 O 3 18 SiO 2 S
5.0
1.0
86.0
8.0
4
10
(g) n MO 6 R 2 3 16 Si0
Fe,0, CaO MgO K,O Na,O SO, CO,
XXXIV. 36MO-6R 2 3 -16Si0 2 -2
6
35.50
3.50
1,0
2.00
30
XXXV. 38MO-6R 2 3 -16Si0 2 -2
6
35.75
3.25
0.50
0.50
1.5
1.50
36
0.5
0.5
XXXVI. 39MO-6R 2 3 -16Si0 2 -2
6
34.00
3.00
1.00
1.00
1.0
0.5
0.5
XXXVII. 39MO-6R 2 3 -16Si0 2 -2
6
35.75
3.25J 0.50
1.00
1.5
1.00
30
0.5
0.5
XXXVIII. 40MO-6R 2 3 -16Si0 2 -S
6
34.75
3.25 0.75
1.00
0.5
0.25
0.5
0.5
(h) n MO 5 R 2 O 3 18 SiO 2 . 2.
Al,0, | Fe,0, | CaO JMgO | K,O [N%0 j SO, | CO, |H,O
XXXIX. 44 MO 5 R 2 3 18 SiO, S
XL. 50 MO 5 R 2 O 3 18 SiO 2 S
3.5
4.0
1.5
1.0
44.5
50.0
1.0
1.0
0.5
1.5
0.5
1.0
o
2.5
(i) n MO R 2 3 12 Si0 2 .
Al,0, Fe,0 s CaO MgO K,O Na,O SO, CO, H,O
XLI. 30 MO - R 2 3 12 SiO 2
0.75
0.25
29.5
0.5
XLII. 32 MO R 2 3 - 12 SiO 2
0.75
0.25
32.0
XLIII. 34 MO R 2 O 3 12 SiO 2
1.00
33.5
0.5
XLIV. 39 MO R 2 O 3 - 12 SiO 2
1.00
39.0
The water which enters into combination must, in any case, be
capable of representation by stoichiometrical figures, i.e. in molecules.
That this can be done is seen from the following examples :
HYDRATION OF PORTLAND CEMENTS
181
I. Von Teicheck 316 has studied the hydration of a Portland cement
of the formula
45 MO 3 R 2 3
15 SKX
/ 45 MO = 44 CaO 1 MgO,
\ 3 Ra o 3 = 2.25 A1 2 3 0.75 Fe 2 3 ,
R;0= 0,75 Na 2 0.25 K 2
(see Appendix, Analysis XXV).
Al
5V ^ 5
After 21 or 30 days 14-44 per cent, of hydration-water was found,
which, according to theory, represents the addition of 36 mols. of water,
as shown in the following equation :
45 MO 3 R 2 3 15 Si0 2 R' 2 SO 4 + 36 H 2 O
= 18 MO 9 H 2 3 R 2 O 3 15 SiO 2 + 27 M(OH) 2 -f R 2 S0 4
In this case, the chief products of the reaction may be represented
by:
(1)
(1)
4- 27 M(OH) 2
The percentage of water represented by the above formula is 14*21,
which is in sufficiently close agreement with that found by experiment.
II. Zulkowski 317 produced a cement by burning, at a white heat in
a Seger furnace, a mixture of lime and Zettlitzer kaolin, the latter
having a composition corresponding to A1 2 O 3 2Si0 2 2H 2 O. His
results suggest one of the two following formulae for the cement he
prepared :
4=
4=
5 5
II II
'\/V\/\ =4 o
Si|Al|Al Si'
\/\/\/\/
II II
5 5
36 CaO - 6 A1 2 O 3 12 SiO
!=4 C
or
I AI| si |_;
\/y-
4
36 CaO 6 A1 2 3 12 SiO
182
CONSEQUENCES OF THE H.P. THEORY
Zulkowski studied the hydration of this compound by reducing it
to a powder, mixing it with water and forming balls ; these set when
warmed gently for a quarter of an hour and became quite hard after
one and half hours. These balls were then placed in water and were
found to have become much harder after the lapse of several months.
Zulkowski also found that a given cement after 7 days contained
16-19% and after 30 days 17-05% of hydration- water. According to
theory, 36 mols. of water should enter into combination according to the
following equation :
36 CaO 6 A1 2 3 12 Si0 2 + 36 H 2
H0(l)
OH /\/\/\/\ OH
(1)
28 Ca(OH) 2 *
(1)OH H0(l)
The value 16-19% calculated from this formula agrees sufficiently
well with the amount found by experiment.
C
The hydration of cements must take place very gradually. In
determining the amount of water entering into combination during the
hardening it is, therefore, necessary to be able to trace a gradual
increase in the proportion of water in the material. This is confirmed
by the results of a series of hydration experiments by Feichtinger 319 ,
who studied the behaviour, towards water, of the following hydraulic
materials :
3=< Si
3=
^
2 3
21 MO 3 R 2 3 - 15 Si0 2 2f 22 CaO 3 R 2 O 3 15 Si0 2 2J
(Analysis XVIII, Appendix) (Analysis XIX, Appendix)
1 (B) 2 (c)
* 4000.8 gms. of the hardened cement mass contain 18x36 = 648 gms. water or
4000 8 =16>19 per cent * water -
t 2=2.5 R'COs + 0.5 R 2 SO 4 +H 2 O.
j 2=0.5 MgCOs + 0.5 R 2 SO 4 + 2 H 2 O.
HYDRATION OF PORTLAND CEMENTS 183
4 4 3 3
Si Al Si Al Si go -2
4 4 4
44 CaO 5 R 2 3 18 Si0 2 2* 26 CaO 6 R 2 3 18 SiO 2 -2f
(Analysis XXXIX, Appendix) (Analysis XXX, Appendix)
3 (A) 4 (D)
Samples B, C and D were Bavarian hydraulic limes, obtained by
burning marl ; A was a Portland cement. The sample D con-
tained 13 mols. free lime (as shown by Feichtinger's experiments),
but in the other silicates the whole of the lime was in a combined
state.
The hydration experiments were carried out as follows : a small
quantity of cement was placed in a suitable vessel and weighed accu-
rately. It was then mixed with a little water and was afterwards
immersed in water. To determine the amount of water which had
entered into combination, the samples were dried at 100 C. and the
increase in weight was attributed to the combined water.
Calcium hydrate only loses all its water at a red heat ; at 300 C.
only a portion of it is removed. According to Feichtinger, the silicate-
water is also driven off at this temperature. By determining the
proportion of water evolved at 300 C. and deducting it from the
total combined water, the difference shows the proportion of water in
combination with the lime.
The following Tables which are based on Feichtinger's researches
show the manner in which the water was evolved.
In Table I :
<7=the total weight of water which combines with 100 parts of
cement in time t.
s=the weight of water which is evolved at a red heat from
100 parts of the mixture of cement and water at 300 C, i.e.
water combined with the silicate.
g s= the weight of water which is evolved at red heat from
100 parts of the mixture of cement and water, i.e. water com-
bined with lime as Ca(OH) 2 .
* 2=1.5 R"CO 3 +1.5 R 2 CO 3 +0.5 R 2 SO 4 +2.5 H 8 O.
t 2=2 R*CO 3 +0.5 Na 2 SO 4 +13 CaO + 2 H 2 O.
184
CONSEQUENCES OF THE H.P. THEORY
Table I
1(B)
2(C)
MA)
(
4)D
t
g
s
gs
9
8
9 s
9
8
9 8
9
8
9 *
Immediately
after mixing
with water.
1.28
1.28
0.61
0.61
0.99
0.99
6.79
1.40
5.39
After 4 hrs.
1.67
1.67
0.71
0.71
1.41
1.41
7.80
2.42
5.38
, 20
2.08
2.08
1.14
1.14
2.29
1.60
0.69
8.26
3.08
5.18
, 3 days
3.42
3.42
1.82
1.82
5.62
3.80
1.82
8.87
3.30
5.57
, 7
3.85
3.85
2.15
2.15
6.58
4.76
1.82
11.20
4.20
7.00
, 14
4.46
4.46
2.63
2.63
7.96
5.90
2.06
11.80
4.64
7.16
, 18
5.00
4.40
0.60
2.84
2.84
8.45
6.20
2.25
11.86
4.60
7.26
, 21
5.84
4.50
1.34
3.46
3.46
8.91
6.43
2.48
12.75
5.30
7.45
, 24
5.89
4.42
1.47
4.36
4.36
10.40
6.60
3.80
13.68
5.60
8.08
, 28
6.86
4.46
2.40
4.90
4.30
0.60
10.52
6.50
4.02
13.92
5.82
8.10
, 35
7.68
4.52
3.16
5.56
4.25
1.31
11.43
6.63
4.80
14.30
6.18
8.12
, 42
8.30
4.48
3.82
6.20
4.30
1.90
11.35
6.60
4.75
14.68
6.60
8.08
, 49
8.92
4.40
4.52
7.08
4.20
2.88
11.50
6.58
4.92
14.50
6.56
7.94
, 56
9.13
4.46
4.67
7.34
4.25
3.09
11.60
6.64
4.96
14.73
6.60
8.13
, 80
9.50
4.40
5.10
7.40
4.20
3.20
11.56
6.60
4.96
14.65
6.56
8.09
In Table II :
MJ ^i> M2 an d MS are the molecular weights of the hydraulic
binding materials.
y=the number of molecules of water which combine with /UL, /z 1?
etc., parts of cement in time t.
<r=the amount of water, in gramme-molecules, lost by /x> Mi> e ^ c ->
parts of the mixture of cement and water at 300, i.e. water
combined with the silicate.
y cr=the number of molecules of water which are only evolved at
a red heat from/*, Mi> etc -> parts of the mixture of cement and
water, i.e. water combined with lime as Ca(OH) 2 .
Table II
M=2777.4
/ii=2659.4
/* 2 =4585
^3=4327
1 (B)
2 (C)
3 (A)
4(D)
t
7
<r
7 - G
7
<r \y-ff
7
ff
y-ff
7 I <f
y-<T
Immediately
1
after mixing
with water.
1.97
1.97
0.90
0.90
2.50
2.50
16.30
3.36
12.94
After 4 hrs.
2.58
2.58
1.04
1.04
3.59
3.59
18.75
5.82J 12.93
20
3.21
3.21
1.68
1.68
5.97
4.07
1.90
19.86
7.40 12.46
3 days
5.27
5.27
2.69
2.69
14.32
9.68
4.64
21.33
7.931 13.40
7
5.94
5.94
3.17
3.17
16.77
12.13
4.64
26.93
10.19
16.74
14
6.88
6.88
3.97
3.97
20.28
15.04
5.24
28.37
11.16117.21
18
7.73
6.79
0.94
4.19
4.19
21.53
15.80
5.73
28.51
11.06
17.45
,, 21
9.01
6.94
2.07
5.11
5.11
22.70
16.38
6.32
30.65
12.74
17.91
24
9.08
6.82
2.26
6.44
6.44
26.50
16.82
9.68
32.89
13.46 19.43
28
10.58
6.88
3.70
7.24
6.35
0.89
26.80
16.95
9.85
33.46
13.99
19.47
35
11.85
6.97
4.88
8.21
6.28
1.93
29.13
16.89
12.24
34.38
14.85
19.53
42
12.81
6.91
5.90
9.16
6.35
2.81
28.92
16.82
12.10
35.29
15.87
19.42
49
13.76
6.79
6.97
10.46
6.20
4.26
29.30
16.77
12.53
34.83
15.77
19.08
56
14.09
6.88
7.21
10.85
6.28
4.57
29.56
16.92
12.64
35.41
15.87
19.54
80
14.66
6.79
7.87
10.93
6.20
4.73
29.45
16.82
12.63
35.22
15.77 19.45
HYDRATION OF PORTLAND CEMENTS 185
These Tables agree with the theory in showing a gradual absorption
of water. Thus 1 B, Table II, shows that on mixing the cement and
water together only 2 mols. H 2 enter into combination, but that after
20 hours 3 mols., and after 18 days 7 mols. of water are combined. A
gradual combination of water may also be observed in the case of
silicates 2(0), 3(A) and 4(D).
It should be noticed that, according to Table II, some of the CaO
in the materials studied by Feichtinger split off before the silicates
had taken up the maximum quantity of water. Thus 1(B) can bind a
maximum of 9 mols. of water, but the lime splits off when only 7 mols.
(after 18 days) are combined. After 80 days this silicate took up no
further quantity of water. A similar result is observable with 2(0),
which is analogously constituted. In this case, the lime separates
when 6 mols. have entered into combination, but only after 28 days.
With Portland cement 3(A) the lime separates after the combination
of 4 mols. of water, i.e. after 20 hours. In the compound 4(D) the
hydration of the silicate molecule occurs somewhat rapidly, on account
of the presence of free lime. After 20 hours the silicate molecule
combined with about 7-5 mols. H 2 0. The separation of the lime began
only after 3 days, after 8 mols. of water had entered into combination.
The structural formulae 1(B), 2(0), 3(A) and 4(D) show clearly the
reason for the separation of the lime at an earlier stage than is the
case with other hydraulites. The larger the basic side-chains the
weaker must be the bond of a portion of the lime. The structural
formula of Portland cement shows 4- and 5- side-chains, whereas the
structural formulae of the other compounds show at most only 2- or
3- side-chains.
The figures 16. 82 and 15.77 molecules of o-water,* which are taken
up, after 80 days, from the compounds 3(A) and 4(D), at first appear to
be opposed to the authors' theory, as for the latter the maximum is 10
mols. a- water (or 11 or 12 mols. if the Al-OH-groups are included).
From Feichtinger 's results it is, however, clear that part of the water
he regarded as o-water was really in the form of " water of crystallisa-
tion." Feichtinger re-heated the cement masses 1(B), 2(C), 3(A) and
4(D) to redness and obtained a fresh hydration. These results are
shown in Tables III and IV. From Table IV it will be seen that the
cements 3(A) and 4(D) give similar results for a-. But, shortly after mix-
ing, the cement 3(A) took up 7.49, and cement 4(D) 3.6 mols. of water, so
that this portion of the water behaves differently from the remainder.
If these amounts are regarded as " water of crystallisation," the
remainder (16.82- 7.49=9.33, and 15.77-3.6=12.17) may be termed
* 4 water of constitution," i.e. the compound 3(A) has taken 9, and 4(D)
about 12 mols. of silicate-water into combination in the form of
hydroxyl groups.
For definition of <r- water sea previous page.
186
CONSEQUENCES OF THE H.P. THEORY
In silicate cements, such as Portland cement, which are devoid of
free lime there can only be one, or at most two forms of water present at
the beginning of hydration, viz. silicate-water and " water of crystallis-
ation." After a short time a third form of water that in the calcium
hydroxide Ca(OH) 2 may be present. If, on the contrary, the cements
contain free lime, the calcium hydroxide water is present at first in
addition to the silicate-water and the " water of crystallisation " just
mentioned.
These theoretical deductions are confirmed by Feichtinger's results
previously mentioned. A glance at Tables I and II will show that
Feichtinger found no calcium hydroxide water in cements 1(B), 2(C)
and 3(A) (which contain chemically combined lime), but in cement
4(D), on the contrary, he found it shortly after the commencement of
the hydration. 319 *
E
From the hardened masses it must be possible, by burning under
certain conditions, to reproduce the original hydraulite with exactly
the same hydrating (hardening) properties, so long as water is the sole
hardening agent, as was the case in Feichtinger's experiments.
Several investigators, and particularly Michaelis 320 , have drawn
special attention to the possibility of reproducing the original cement
powder from the hardened mass. This possibility of regenerating
cements is, however, a simple deduction from the results 321 obtained
by Feichtinger, who endeavoured to ascertain experimentally whether
a hardened cement mortar when heated to redness and again mixed
with water will re-set and harden. He also measured the amount of
water taken up. His results are shown in the following Tables, in
which the letters are the same as those in Tables I and II.
TABLE III
1(B)
2(C)
i
MA)
4(D)
t
g
8
9-8
9
s
g-s
g
8
g-s
g
s
g-s
Immediately
after mixing
with water.
4.00
1.20
2.80
1.24
0.50
0.74
7.84
2.94
4.90
8.30
1.50
6.80
After 5 hrs.
4.20
1.60
2.60
2.30
0.70
1.60
7.89
3.02
4.87
36
5.16
1.96
3.20
3.12
1.20
1.92
8.60
3.68
4.92
9.56
2.35
7.21
60
5.48
2.02
3.46
3.80
1.40
2.40
9.20
4.35
4.85
5 days
6.24
2.30
3.94
4.25
2.20
2.05
9.80
4.87
4.93
10.98
3.88
7.10
8
6.56
2.58
3.98
4.40
2.32
2.08
10.50
5.60
4.90
12
6.90
3.15
3.75
4.60
2.40
2.20
11.04
6.20
4.84
12.81
4.66
8.15
20
7.75
3.84
3.91
5.48
3.35
2.13
11.84
6.56
5.28
14.60
6.52
8.08
24
7.80
3.84
3.96
6.48
4.02
2.46
11.60
6.66
4.94
40
8.32
4.11
4.21
7.06
4.22
2.84
60
9.02
4.42
4.60
7.20
4.18
3.02
HYDRATION OF PORTLAND CEMENTS
187
TABLE IV
/i=2777.4
fij_ = 2659.4
M 2 =4585
^3=4327
1 (B)
2(C)
3 (A)
4(D)
t
7
cr
y-<r
7
<r
7-0-
7
0-
y-a-
7
or
7-<r
Directly
after mixing
with water.
6.17
1.85
4.32
1.83
0.73
1.10
19.97
7.49
12.48
19.96
3.60
16.36
After 5 hrs.
6.48
2.47
4.01
3.39
1.03
2.36
20.10
7.69
12.41
36 ,
7.96
3.02
4.94
4.61
1.77
2.84
21.91
9.38
12.53
22.98
5.65
17.33
60 ,
8.46
3.11
5.35
5.61
2.06
3.54
23.44
11.08
12.36
5 days
9.63
3.54
6.09
6.28
3.25
3.03
24.97
12.40
12.57
26.39
9.39
17.06
8
10.12
3.98
6.14
6.50
3.43
3.07
26.75
14.27
12.48
12
10.65
4.86
5.79
6.79
3.54
3.25
28.13
15.80
12.33
30.79
11.20
19.59
20
11.96
5.92
6.03
8.09
4.95
3.14
30.17
16.71
13.46
24
12.03
5.93
6.11
9.57
5.94
3.63
29.56
16.97
12.59
40
12.84
6.34
6.50
10.43
6.23
4.20
60
13.92
6.82
7.10
10.64
6.17
4.47
'
A comparison of the figures in Tables III and IV shows that the
hydration phases of the regenerated hydraulite (made from a hardened
cement by re-heating) follow each other more rapidly than do those of
the original cement. From this it may be concluded that the hardened
masses were not properly burned, as otherwise the hydration phases
in the regenerated cement would occur in precisely the same manner as
in the original cement. These results make the possibility of repro-
ducing fresh cement from hardened masses highly probable.
As the hydration phases follow each other more rapidly than in the
original cement (Tables I and II) a much lower degree of hardness must
be obtained in the case of regenerated cements when they are mixed
with water and allowed to set and harden . This was actually the case in
Feichtinger's experiments.
Thermo-chemical studies of hydration and hardening processes must
lead, in the case of cements which contain free lime, to results which
are different from those in which the whole of the lime is in a com-
bined state.
In cements of the former kind there are theoretical reasons why a
development of heat must occur at the commencement of hydration
(the hydration heat of the CaO) ; and in cements devoid of free lime a
perceptible development of heat can only occur after an interval, viz.
at the moment when the separation and hydration of the first CaO
molecule occurs.
As a matter of fact, Feichtinger did observe a noticeable develop-
ment of heat during the hydration of cement 4(D), which contains free
lime.
In this connection the results of W. Ostwald's thermo-chemical
studies 322 on the following cements are particularly interesting :
188
CONSEQUENCES OF THE H.P. THEORY
A <UMO
in^n OTT n
Si0 2 2 H 2
Analysis XII.*
34MO
31.5 CaO 2.5 MgO
8
Analysis XXVIII.
B. 9 2 M0.6R 2 <V12Si0 2 .3MgC0 3 10H 2 {
SMgO
3 = 5 A1 2 3 - Fe 2 3 .
p 74. Mn . a p n . i A Qin <*
C. 74 MO 6 R 2 3 18 Si0 2 3
Analysis XXXI.
Q TT n
8 H0
R Q =
O,.
Analysis XXXII.
D. 76 MO 6 R 2 3 18 Si0 2 MgC0 3 4 H 2
Analysis XXXIII.
E. 90 MO - 6 R 2 3 18 Si0 2 4 MgC0 3 10 H 2 O
These results are summarised in the following Table :
Time
D
E
2 hours
7.53
20.53
9.94
34.01
20.47
6
10.09
37.05
12.23
35.46
29.57
1 day
18.79
41.35
15.32
38.39
39.78
4 days
46.16
29.72
5 ,,
47.17
32.10
6
57.96
33.56
__
44.34
7
65.63
40.21
51.55
Ostwald drew attention to the great increase in heat evolved on the
5th, 6th and 7th days and suggested that after this time a new stage in
the hardening process occurs and is accompanied by a fresh develop-
ment of heat. This noticeable development of heat for which,
hitherto, no satisfactory explanation has been given is readily under-
stood in the light of the new theory. It is the moment of hydration of
the calcium oxide liberated from the silicate molecule.
Further references to the development of heat during hardening will be found in
the Bibliography under No. 322.
G
As the most important hydraulic limes are aluminosilicates, it
must, theoretically, be possible to observe the conversion of primary
into secondary types by the action of alkaline solutions of definite
concentration. This deduction has been confirmed by some experi-
mental results obtained by Feichtinger 323 . He treated the hydraulic
mortars A, B, C and D (both in the fresh state and after they had been
allowed to harden for some time)with aqueous solutions of sodium and
potassium carbonates, and allowed these reagents to act for some time.
* For the analytical figures, see the corresponding numbers in the section on
Portland cements in the Appendix.
ACTION OF ACIDS AND ALKALIES ON CEMENTS 189
A definite quantity of silica and a little alumina was dissolved, the
amounts being expressed in percentages and molecules in the following
Table :
TABLE V
% Si0 2
Molecules SiO 2
A
B
C
D
A
B
C
D
In fresh state .
After 14 days .
,, 3 months
5 .
2.63
1.66
1.42
1.04
5.09
3.72
2.50
2.10
6.78
6.05
5.80
5.26
4.24
2.86
2.40
2.12
2.17
1.34
1.14
0.84
4.11
3.00
2.02
1.70
2.98
2.66
2.55
2.31
2.13
1.90
1.82
1.65
From this Table it may be seen that the Portland cement A is a
basic salt of the type
Si M S A i Al Si
and, in the fresh state, parts with 2 mols. Si0 2 , forming
ST-Al-Sl-Al-Si.
Similarly, the alkaline solution reacts on the hydraulic lime D,
which is a compound of the type
Si Al - S A i - M - Si.
It forms a compound of the type
ST-Al-Si-Al-ST,
and it is interesting to note that the cements B and C, which are both
basic salts of the type,
/SI
Al^ST
X Si
do not, when in the fresh state, part with the same number of mole-
cules.
From B with the liberation of 4 mols. Si0 2 a compound
Si-Al-Si-Si-Al-Si,
and from C a salt of the anhydride
S A i - Al - Si,
are produced. The last-named shows that hexa-compounds may, in
some cases, be produced by the action of alkalies on penta-com-
pounds.
Table V also shows that the solubility of the silica diminishes as
the cement mass hardens. This fact is also in agreement with the
theory, according to which a separation of CaO from the hydraulites
A, B, C and D should occur and the combination between the alumina
and silica radicles should be intensified.
190
CONSEQUENCES OF THE H.P. THEORY
H
The separation of CaO in hydraulic binding materials, which is a
result of the action of dilute hydrochloric, sulphuric, carbonic and other
acids, of alkaline carbonates or, in some cases, of water alone (Portland
cements), must take place in accordance with certain definite stoichio-
metrical laws. Valuable contributions to the support of this statement
have been made by Feichtinger 324 and Schott 325 .
Feichtinger has studied the action of water containing carbonic
acid on the cements 1(B), 2(0), 3 (A), 4(D) and also on the silicates :
=3 C
24 CaO 3 K 2 3 15 Si0 2 2* 24 CaO 3 R 2 O 3 12 Si0 2 - 2 f
Analysis XX, Appendix. Analysis I, Appendix.
5 (E). 6 (F).
Feichtinger's object was to discover whether the whole of the lime
in the hardened material could, in this way, be converted into calcium
carbonate or whether this conversion was confined to a portion of the
lime. Although he allowed CO 2 - water to act on the hardened material
for 1 J years, he was unable to convert the whole of the lime into CaC0 3 ;
a part of the lime remained combined with the silica. Unfortunately,
Feichtinger did not publish the data on which he bases his conclusions
regarding the proportions of lime in the free and combined state after
1J years. The following Table shows the progress of the decom-
position, studied by Feichtinger, during only 5 months :
TABLE VI
Conditions of Experiments
Percentage of CO 2
A
B
The mortar lay 3 months in clean wate
After this for 1 month in CO 2 -water
2 months
>
* > >
5
p
4.2
14.4
16.7
18.2
20.8
20.9
8.1
16.3
19.2
19.4
19.4
19.4
* 2 = 4 RCO 8 + 0.25 Na 2 SO 4 + 2 H 2 O.
3 R,O 3 = 1.5 A1 2 O S 1.5 Fe 2 O 3 .
4 RCO 3 = 2.5 CaCO 3 1.5 MgCO 3 .
1 2 = 3 RCO 3 + 0.5 R 2 SO 4 + 2 H 2 O.
3 R a O 3 = 1.5 A1 2 O 3 1.5 Fe 3 O 3 .
3 RCO 3 = 2 CaC0 3 MgCO 3 .
ACTION OF ACIDS AND ALKALIES ON CEMENTS 191
TABLE VII
lli
eS fl
II
41.36
38.12
37.48
39.56
43.84
41.13
40.90
36.13
37.10
36.80
42.30
41.70
22.5
19.4
21.2
21.3
20.9
24.0
16
12
16
15
26
27
24
21
22
24
44
26
8
9
6
9
18
12
23.45
19.30
21.59
22.29
22.27
23.14
2860.8
2777.4
2659.4
3090.9
4585.0
4327.0
13
19.0
14.5
16.5
19.0
29.0
29.0
Table VII is of special value, as it allows the inference that the
following products have been formed by the action of carbonic acid on
the hydraulites F, B, C, E, A and D :
1
8CaO-3Al 2 3 -12SiO s
F.
9CaO-3Al 2 O 3 -15Si0 2
B and E.
6CaO-3Al 2 3 -15Si0 2 .
C. '
= 1
18 CaO 5 A1 2 3 18 SiO s
A.
12 CaO 6 A1 2
D.
1
18 Si0 2
A glance at the above structural formulae shows that the separation
of CaO must be in accordance with quite definite laws. Hence it
follows from the structural formulae A and D that :
1. The lime is combined more strongly with the middle hexite and
cannot be so easily separated as it can from the side hexites, and
192
CONSEQUENCES OF THE H.P. THEORY
2. In the neighbouring positions 2 and 3, the lime is more feebly
bound than in the positions 1 and 4.
It appears to be unlikely that the 2 side-chains in the compound
A are in neighbouring positions (2, 3).
A comparison of the structural formulae B, C and E shows that the
lime in positions 1 and 3 in the pentites is more strongly combined than
in position 2. The possibility that the lime in C forms a 2 side-chain
in position 2 is improbable.
Schott 326 studied the reaction of a cement :
42 CaO 3 R 2 3 15 SiO, 2*.
Molecular Weight=3974.4
G.
137.4 parts of cement hardened by (NH 4 ) 2 CO 3 gave :
CaC0 3 MgC0 3 CaS0 4 CaO Fe 2 3 A1 2 3 Si0 2 H 2 Insol. Total.
79.20 2.90 1.30 15.10 4.30 4.50 22.70 6.10 1.30 137.40
57.56 2.10 0.98 10.99 3.14 3.28 16.53 4.44 0.98 100.00%
These results lead to the formula :
11 CaO Fe 2 3 2 A1 2 3 15 SiO 2 31 CaC0 3 1.5 MgC0 3 0.5 CaS0 4 14 H 2 O
Calcd. 11.34
Found 10.99
2.95
3.14
3.75
3.28
16.68
16.53
57.06
57.56
2.32
2.10
1.25 4.64
0.98 4.44
0.98 (Insol.)
(9H 2
+ 32.5 RC0 3 -
^ (1)
OH OH
9 CaO 3 R 2 3 15 Si0 2 )
2 Ca(OH) 2 + 3 H 2 O + 0.5 CaS0 4
H.
2.5 RCO 8 0.5 CaSO 4 2 H 2 O.
2.5 KC0 3 = 1.5 MgCOs + 0.5 K.CO, + 0.5 Na 2 CO 8 .
3 B 2 O S = 2 A1 2 O 3 Fe 2 O 8 .
PROGNOSES RELATING TO CEMENTS 193
The structural formula H suggests a comparison with the formula
B previously given. The decomposition, so far as the separation of
lime is concerned, occurs in a similar manner ; this can scarcely be a
mere coincidence.
More hydration phases occur under the action of alkaline carbonates
of certain concentration than with water alone. Hence, in such cases,
the cement masses must attain a greater hardness, as Schott has shown
experimentally.
It is, therefore, very important to ascertain the nature of the
action of carbonic acid on hardened mortar, as a clear conception of the
changes which occur to cement mortars hardening in air may then be
obtained. The secondary hardening of cements allowed to set in air
must be chiefly referred to the action of carbon dioxide and moisture
in the air.
As the cement mortar, in such a case, undergoes a large number of
hydration phases which follow each other very slowly, storing in air
ought to give a harder product than is obtained by storage underwater.
J
In a hydraulite of the composition
5 5
II II
4=/\/\/\ == 4
4 oJSi|^Al|SiJ =4C
'\/
5
it is possible to remove a portion of the lime by means of hydrochloric,
carbonic or other dilute acids, or of dilute ammonium carbonate
solution. The following compounds may be produced in this manner :
3 3
II II
CJSi| Al|Si]^ 3 o 2 oII|Si|Al Si C 2 o etc.
1. 2. 3.
These compounds may, in the presence of water or dilute alkalies,
undergo a series of hydration phases. Hence, if a portion of the lime
is removed from combination with the cement by means of dilute acids,
it must, to a certain extent, retain its hydraulic properties.
Fremy 327 has experimentally removed a portion of the lime from
hydraulic limes, and has treated the residue with dissolved lime, with
the result that the mixture hardened. Zulkowski 328 repeated Fremy 's
experiment, and found that as much as 14 per cent, may be removed
from some Portland cements without destroying the power of the
residue to harden when mixed with water.
194 CONSEQUENCES OF THE H.P. THEORY
Such hydraulites as
I Si | Al | Al | Si
cannot contain more than 8 molecules of silicate-water, but, in addition
to this, A can have a theoretical maximum of 20 Ca(OH) 2 , or 20 H 2
which is driven off at a red heat. B, under similar circumstances,
cannot have more than 16 mols. Ca(OH) 2 , or 16 H 2 O volatilised at a
red heat. In other words, there is for each cement molecule a maximum
proportion of silicate-water and of calcium hydroxide water. This
statement is also true of all analogously constituted silicate cements.
It will be interesting to observe how far this inference from the
theory is supported by the facts.
If a hardened mass of cement containing free basic lime-salts is
crushed, it will harden into a stony mass if mixed with a suitable
quantity of water or dilute solution of alkali. These lime-salts are
particularly likely to be present where hydration is effected by the
action of alkali-free or acid-free water. As the number of hydration
phases in such partially decomposed silicates is large, especially in the
presence of a little alkali and water, it should be possible to produce
materials or articles of great hardness from such silicates.
Schott 329 has experimentally obtained a second setting and harden-
ing by mixing a pulverised hardened cement mass with water.
M
As the bond between the aluminium hexite and the silicon hexites is
weakened by heating aluminosilicates and by their combination with
lime, it should be possible to observe that when the material is treated
with dilute acids, a separation of lime and of gelatinous silica occurs, as
in clays (p. 107).
This is actually the case, and Fuchs made this fact the basis of
his cement theory.
N
If hydraulic limes are treated with concentrated hydrochloric,
sulphuric, or other acids, it should be possible to observe a decom-
position of the silicate molecule in addition to the separation of the
PORTLAND CEMENTS AND SEA WATER 195
lime. The silicate molecules, being derivatives of clays, must be
resolved into compounds of the type
S A i-Al-Al-sX Si-Al-Al-Sl, or sVAT-H-Si
(see p. 107).
So far as the authors are aware, no experiments to prove this have
yet been made.
From the theory, the possible existence of isomers of the silicate
cements may also be inferred. Thus the compounds
are isomeric. Up to the present these isomers have not been investi-
gated.
Good hydraulites ought only to be producible by mixing hydro-
aluminosilicates (clays) with limestone or chalk in theoretical stoichio-
metric proportions, the ash of the fuel (alumina, silica, lime and alkali)
used being also taken into consideration.
As a matter of experience it is well known that for each mixture
only definite proportions of clay and lime can be used to produce good
cements. These proportions are usually found empirically, but the
formulae given by the authors show that these empirical proportions
agree with the ones theoretically the most suitable and that the
empirical proportions are scientifically correct.
Q
A New Investigation of the Sea Water Question
Schuljatschenko 330 correctly states that it is very difficult
to ascertain accurately the cause of the destruction of masonry
exposed to the action of the sea ; i.e. whether it is due to the pro-
perties of the bonding material (cement), to external influences such
as sand, to incorrect proportions of the materials used in the concrete,
to the porosity or to the low density of the cement blocks, etc. There
can be no doubt that all these factors have some influence, but the facts
seem to show that, in many cases, the chief cause of the decomposition
of maritime masonry is the action of sulphur compounds. That this
inference is generally true is shown by the fact that a large number of
196 CONSEQUENCES OF THE H.P. THEORY
investigators have, for many years, endeavoured to ascertain what
substances are formed by the action of calcium sulphate on
cements.
It is generally agreed that Portland cements contain compounds of
lime and alumina, and Candelot 331 and Michaelis 332 have concluded
that, by the action of gypsum or plaster of Paris on hardened cement
masses, certain calcium sulpho-aluminates are formed, and that these
are one of the causes of swelling of cements. Schott 333 also investi-
gated the action of gypsum (plaster of Paris) on normal Portland
cement and on analogous cements in which the alumina is replaced by
iron oxide. In both cases he noticed that decomposition occurred, so
that the formation of a calcium sulpho-aluminate or sulpho-ferrate
appears to be probable. Schott did not, however, agree with the
investigators just named that the swelling action of gypsum (plaster)
is due to the formation of sulpho-aluminates or sulpho-ferrates. Le
Chatelier 334 , on the contrary, is in favour of the formation of a definite
calcium sulpho-aluminate and, like Deval 335 , endeavoured to ascertain
the action of various sulphates on cements containing various propor-
tions of alumina.
Rebuffat 336 also found that there is a number of different calcium
sulpho-aluminates. He doubted, however, whether the destruction of
maritime masonry could be referred to the formation of these com-
pounds. Here again, it should be noticed, the swelling and disinte-
grating effects which occur when gypsum (plaster) is present in the
cement were also attributed to the last-named substance. The chief
description of the disadvantages of sulphates on cements is that of
Schiffner 337 , who had collected a number of instances in which the
decomposition was unquestionably due to the action of sulphur com-
pounds on the hardened cement masses. Some of these interesting
examples may be mentioned here :
1. In the walls of a railway tunnel, the effects of some destructive
action were observed. The mortar came out of the joints in the form
of a milky fluid and carried with it all the sulphate, so that the cement
was considered to be bad. It was only after a very careful examination
that it was found that the overlying rocks contained sulphurous lignite
which became oxidised to sulphates, the latter causing the destruction
of the cement.
2. In a concreted gallery in a mine in Alsace-Lorraine the walls
became moist and porous in parts. The greater portion of the
structure was in exceptionally good condition, so that it was im-
possible to blame the cement, but in some portions boil-like swellings
appeared, the mortar becoming semi-fluid and the joints loose.
A closer examination showed that the nature of the water in the
neighbourhood of the gallery contained calcium and magnesium
sulphates in sufficient quantities to effect a partial decomposition of
the concrete.
3. According to Grauer, cracks and characteristic white crystals
PORTLAND CEMENTS AND SEA WATER 197
appeared in the joints of a sewer built of bricks laid in cement. In
this instance the sulphates were introduced by the sewage.
4. According to Le Chatelier, defects appeared in the cement used
in the Paris fortifications because this was quite close to the famous
gypsum beds. In this instance the sulphuric acid in the cement rose
from 0.4 to 3.75 per cent.
5. In a tunnel near Almeria (Spain) the mortar swelled a few
months after it had been finished. The sulphuric acid content rose
from 0.3 to 2.3 per cent. The ground water contained 2 g. calcium
sulphate and 1 J g. magnesium sulphate per litre (or 140 and 105 grams
per gallon respectively).
6. A railway viaduct, which passed through a clay deposit con-
taining gypsum and through gypsum beds, suffered seriously because
the drainage water was saturated with gypsum.
These instances are sufficient to show the serious action of sulphur
compounds on cement, and the question arises as to whether any
information may be gained from a study of the constitution of the
cements, or from the observations and experiments which have been
made, whereby this action may be explained, and, if possible, prevented.
The reader may be surprised to learn that this question can be answered
in the affirmative in the following manner :
If water is allowed to act on a typical Portland cement such as :
4 OK OK 4
II I I II
oo f 01 1 Al Al Si I c
6 kX ~ A ' *
YY
4 OK
KOK4
A.
a hard, cement mass with the formula
(2) OH OH (2)
I I
+ x Ca(OH) 2 + 2
(2)
B.
is formed.
From the formula B it may be seen that the silicate of the hardened
cement contains a-hydrogen (marked with a +), and on p. 140 it
was shown that the a-hydrogen tends to be replaced by monovalent
acid radicles such as SO 2 OH, SO OH, etc.
In this manner all kinds of A- and Z-aluminosilicates such as the
ultramarines (p. 140 et seq.) may be formed. If the cement mass B
comes into contact with solutions of salts such as gypsum, it is by no
198
CONSEQUENCES OF THE H.P. THEORY
means improbable that 2-aluminosilicates will be formed. High
temperatures are unnecessary, as Thugutt has shown that the formation
of the 2-aluminosilicates (sodalites) may take place at low tempera-
tures in the presence of solutions of suitable salts. As the formation
of these substances is accompanied by a change in volume, it is clear
that the hardened cement, such as B, must crack if its hydrogen is
replaced by acids or acid radicles (p. 152) and that it may be completely
destroyed.
Hence it follows that the authors' cement theory permits the
prediction that the action of sulphates on cement will be accompanied
by disastrous results. The possibility of the disintegration of maritime
masonry by the action of the sulphates of calcium, magnesium, etc., in
the sea water is thereby explained.
There now remains the question as to whether this serious action of
sea water can be, in any way, prevented. In cases where the destruc-
tion of the cement work is exclusively confined to the action of the
sea water, the most satisfactory solution of the problem will be found
in the use of cements in which no a-hydroxyls can be formed, i.e.
cements of the types :
AlSi,
X
All-Si and AU-S
Si
(p. 189)
If this inference from the theory can be proved experimentally and
the practical observations and experimental results previously men-
tioned almost amount to such a proof an interesting and important
practical result would be obtained from purely theoretical reasoning,
and would form a notable step in the direction of a solution of the
" sea- water problem."
R
From the theory it follows that, from clays containing a-hydroxyls,
compounds must be producible which contain both hydraulites and A-
or 2-aluminates or ultramarines, i.e. pigments with hydraulic pro-
perties such as :
CONSTITUTION OF THE PORCELAIN CEMENTS
S
199
= (2)
etc.
(2)
SO, S0 2
ONa
ON
It will be interesting to learn whether this prognosis can be proved
by the actual production of such substances.
XIV
A New Theory of the Silicate or Porcelain Cements
Certain kinds of transparent silicate cements, which are conveni-
ently known as porcelain cements, have been used for some years
as dental-stopping materials. The first of these porcelain cements was
discovered and patented in 1878 by T. Fletcher 338 , but it did not
fulfil his anticipations and rapidly fell out of use. 339 An interval of 25
years appears to have elapsed before any other porcelain cements were
produced, and these were of a different composition. Those placed
on the market in 1904 by Ascher and others were heartily welcomed
as new discoveries in dentistry, and they rapidly attained great
popularity on account of their valuable characteristics.
It may be here pointed out that the porcelain cements appear
likely not only to replace the zinc phosphate cements and amalgams,
but also the burned enamels and the " queen " of stoppings gold in
practical dentistry ! Morgenstern has expressed himself as follows
respecting these new stopping materials : 34 " Porcelain cement, when
properly selected and prepared, sets to form a mass with a remarkable
resemblance to natural teeth, both in colour and transparency and
possessing a gloss which is confusingly like that of natural dentitic
enamel. These stoppings have no objectionable features, and in no
way harm the teeth, and they have a great advantage over gold and
the burned enamels in that they save the dentist thousands of hours of
work and greatly economise his health and power. They save the
patients many a painful hour and have great pecuniary advantages."
Porcelain cements consist of two ingredients a powder and a fluid.
According to Sanderson, Fletcher's powder was composed of aluminium
hydrate, zinc oxide or magnesia and a basic zinc silicate. The powders
200 CONSEQUENCES OF THE H.P. THEORY
of the new porcelain cements consist chiefly of calcium alumino-
silicates.
The fluids of the new cements differ from that of Fletcher chiefly
in their consistency. Fletcher's fluid was a syrupy solution of alu-
minium phosphate in phosphoric acid, whilst the newer ones are less
syrupy and consist chiefly of alumina and phosphoric acid. There was,
until recently, a cement of which the powder resembled that of Fletcher
and consisted chiefly of calcium aluminosilicate and zinc oxide. The
fluid had a consistency resembling that of Fletcher's fluid, but was
chiefly composed of alumina and phosphoric acid with a large pro-
portion of zinc oxide. It differed from Fletcher's cement because it
was a practicable, dental-stopping material.
On mixing the silicate powder with the fluid, there is immediately
formed a transparent mass which is at first plastic in distinction from
the earlier zinc phosphate dental cements but rapidly becomes quite
hard.
The powder of the new cements contains the same constituents as
the Portland and slag cements, but instead of the fluid being pure water
or alkaline water, acids (aluminophosphoric acids), or solutions of acid
salts (aluminophosphates), are employed.
From a scientific point of view it is highly important that an
investigation should be made with a view to ascertaining the constitu-
tion of the porcelain cements in order to solve a number of physical
and chemical problems in connection with their setting. This investiga-
tion appears to be all the more necessary when the available experi-
mental results and the theories already formulated are critically
examined. If the new hexite theory proves of use in this investigation,
it will not only add to the value of the theory itself, but will clear many
problems of enormous and pressing importance in surgery and particu-
larly in dentistry.
The ijew silicate cements with the exception of those containing
a large proportion of zinc oxide both in the powder and in the fluid
portion have one serious drawback : they have a destructive action
on the nerves (pulpa) of the teeth. For this reason there has long been
a dispute as to the best means of preventing this poisonous action.
In regard to this and to several other problems e.g. the best
methods of testing the durability, density and hardness of such cements,
both in the laboratory and in the mouth much remains to be done.
It is, however, clear, that in all investigations of this kind, a knowledge
of the constitution of the cements and of the changes which take place
during their setting, must be of the greatest importance.
The porcelain cements must possess a number of very definite
characteristics, such as unchangeableness of shape and size in the
mouth, resistance to the action of saliva, etc., if they are to fill a useful
place in applied dentistry.
Miller 341 considers that an ideal dental stopping should have the
following characteristics :
LABORATORY TESTS ON PORCELAIN CEMENTS 201
1. Sufficient hardness so as not to be worn away unduly by
mechanical forces in the mouth.
2. Unchangeability in saliva, food-stuffs and other decomposition
products (chemical indestructability).
3. Constancy of form and volume when placed in the teeth.
4. Low heat conductivity, so that any changes in the temperature
of the mouth are not transmitted to the nerves of the teeth.
5. A high degree of plasticity in order that the stopping may be
water-tight and may properly fit the teeth.
6. Colour as similar as possible to that of the teeth.
7. Absence of detrimental action on the tooth material, nerves,
mucous membrane and the general health.
8. Easy manipulation.
9. Minimum sensitiveness to moisture.
10. Adhesiveness to the tooth- wall.
11. Antiseptic, at any rate during fitting.
12. Easy removal, if necessary.
The possibility of producing ideal stopping materials depends
chiefly on a knowledge of the chemical constitution and on a clear
understanding of the reaction which occurs during the hardening of
these substances. If no scientific basis no scientifically grounded
theory of the porcelain cements is possible, the manufacturers of
these substances can only work in an arbitrary manner in attempting
to improve the quality. To do this is, however, risky, as it is possible
that some manufacturers may even produce inferior products instead
of " improvements " ; the final material may, in fact, be worse than
the original one, though it may be sold as " greatly improved." In
one case a porcelain cement was so much " improved " that it was
eventually agreed that the material made five years previously was by
far the " best," and the manufacturers were obliged to forego their
" improvements " and to use the older recipe !
A large amount of theoretical, and especially of experimental work,
has been done in connection with porcelain cements, but it cannot be
said that this has made the most important properties, such as the
poisonous nature of some of these cements, more comprehensible. The
solution of this problem of poisoning undoubtedly one of the most
important is made particularly difficult by the absence of any well-
established theory, and even more serious are the effects of false and
purely speculative theories and especially of wrong explanations and
faulty interpretations of experimental results.
In this connection the litmus experiment of Rawitzer 348 is pecu-
liarly typical. This investigator endeavoured to show, by means of
strips of paper soaked in blue litmus solution, that the porcelain
cements containing zinc oxide are poisonous, whereas their innocuous-
ness has been proved by laboratory tests and is obvious from a study
of their chemical constitution. Rawitzer appears to have overlooked
the fact that a substance may turn blue litmus red and yet may not be
202 CONSEQUENCES OF THE H.P. THEORY
prejudicial to health ; it all depends on the amount of acidity present.
A substance may even be acid and yet may not have any detrimental
action on the teeth. For instance, concentrated hydrochloric acid is
unquestionably a violent poison, but dilute hydrochloric acid is, on the
contrary, an internal medicine of great value. Yet both solutions turn
blue litmus red ! Litmus alone cannot give any clue as to the amount
of acidity, and is, therefore, useless for determining poisonous qualities.
Rawitzer had not, apparently, a clear view of the meaning of the term
" acid reaction," and was but partially informed with regard to the
structure of the hardened cement masses ; consequently he had an
erroneous idea of the physico-chemical reactions occurring during
the hardening.
The absence of more definite knowledge of the nature of the
porcelain cements has led to several false and meaningless investiga-
tions by Dreschfeld 342 , Strumpel 343 , Robert Richter 344 , and Kulka 345 .
These have been criticised by Schreiber 346 .
For instance, Dreschfeld, Strumpel and Richter 347 digested the raw
cement (composed of a solid aluminosilicate and a fluid containing
alumino-phosphoric acid and aluminophosphate of zinc) with water
for various periods of time. According to the length of this digestion a
proportionate quantity of the uncombined cement would be decom-
posed, the result being a partial splitting up of the cement mass into its
components. These acid-reacting decomposition products were titrated
and regarded as "free phosphoric acid " by the investigators named.
Yet what is the use of showing the presence of acid in the
decomposition products of a substance which is known to have an
acid as one of its original constituents ?
The same authors also studied the action of freshly mixed (and
therefore uncombined) cements on various colourless solutions as well
as solutions of aniline dyes, fruit juices (bilberry juice), etc. They
regarded a cement which produced no colour in the presence of aniline
dye-stuffs as perfect ! Yet it is clear that even the " densest cement,"
in a fresh (unhardened) state, must necessarily form a compound of an
intense colour if such cements form a lake by combining with the dye-
stuff. It is a well-known fact that a valuable series of aniline lakes are
produced from aluminosilicates and certain basic aniline dye-stuffs ; is
it reasonable to suggest that, because an aluminosilicate forms a lake
with a certain aniline dye-stuff, it is, therefore, unsuitable as a dental
stopping ?
Kulka falls into a similar error in his experiments, and he appears
to have paid no attention to the physico-chemical reactions of harden-
ing in his studies, although Morgenstern 349 and Schreiber 350 had called
attention to them. Morgenstern was, therefore, induced to issue a
warning in regard to the experiments of Kulka and to the general
manner in which investigations on silicate cements are carried out.
In this warning Schreiber joined. Both these authorities believe that
it may be safely assumed that Kulka would never have carried out
LABORATORY TESTS ON PORCELAIN CEMENTS 203
his experiments on imperfectly hardened cements if he had been clear as
to the constitution of these substances and the changes in their physical
and chemical properties which occur during the different hardening
phases.
As Morgenstern 351 rightly says : " It is incorrect to stop the various
chemical and mechanical processes in cements prepared for experi-
mental purposes before the hardening is complete. The cements so
treated lose very valuable properties and lead to erroneous results.
" If this were a matter of purely theoretical or academic interest I
should not write about it, but would modestly express my contrary
opinion. This is, however, a case where the conclusions are of great
practical and technical importance, and Kulka's theories may have a
most important influence on the use of silicate cements in dentistry and
on their production by the manufacturers. It is because I am con-
vinced that this influence may be profitless and even harmful that I
feel right to call ' Halt ! ' to those colleagues who are following these
new paths."
Morgenstern himself treated the cements with chemical agents from
half to three hours after hardening. He agrees, however, that he could
not, in this way, definitely ascertain the true properties of the cements
he examined : "I treated," he says, 352 " my cements with water at
35 C. for one-half to three hours, and found that their adhesion,
durability, density and resistance to acids and alkalies were such that
the results obtained cannot be regarded as showing the inherent good
characteristics or their value as dental stoppings."
Morgenstern 353 rightly says that in many of his experiments Kulka
paid too little attention to the time required for hardening the cements :
" Before commencing his special experiments, he (Kulka) treated his
cement fillings (30 minutes after they had set) with a mixture of saliva
and water and allowed them to remain in it for seven days, the fluid being
renewed occasionally. He found that some cements showed no change,
others a little change, and others again were much altered, and that one
cement was completely destroyed. These changes in structure and
hardness are good evidence that the different cements take different
times to complete hardening."
As Kulka, in his researches, did not pay any attention to the
hardening phases in his cements, he found, as Morgenstern has shown,
that as great a loss of material occurred when the cement was treated
with a 0.5 per cent, solution of lactic acid as is only produced in three
weeks in a properly hardened cement.
Schreiber 354 has pointed out the interesting fact that Kulka's
phosphate cements possessed no adhesion, so that Kulka's conclusions
based on too early a treatment of the cements with saliva, i.e. before
they had properly hardened must, necessarily, be erroneous. As a
matter of fact, Kulka covered the ends of small pieces of ivory with
cement, and after an hour's standing placed them in saliva- water, where
they remained for six days. At the end of this period he found " to his
204 CONSEQUENCES OF THE H.P. THEORY
astonishment " that the ivory could be completely withdrawn from
the cement covering with comparative ease. From this experiment
Kulka drew his erroneous conclusions.
Another serious omission in the records of experiments mentioned
on the last two pages is that none of the investigators named mentions
the proportion of powder to fluid which he used in his tests. Hence it
is not difficult to understand that, as Schreiber 355 has shown, under
apparently identical conditions a cement mass x is, according to one
investigator, only ^ih as resistant as the mass y ; according to another
investigator it is only Jth as resistant as the same mass y ; according
to a third it has the same resistance to acids as y, and, finally, a fourth
reports it as being more resistant than y ! Clearly, these different men
have worked with cements of widely differing degrees of hardness and
therefore with very different proportions of powder to fluid. Schreiber
has correctly stated, in regard to this remarkable result of the study
of these experiments with silicate cements : " Are not these results
significant ? Can any reliance be placed on experiments which give
such contradictory results ? It is impossible to believe that any
substance can behave so differently in analogous experiments."
In spite of Morgenstern's warning and Schreiber's severe criticism,
Kulka has continued to pay no attention to the hardening phases and
other important properties of the silicate cements. In his latest work
on the possibility of chemical and pathological actions of cement
stoppings 356 he endeavours to determine the acidity of various
silicate masses shortly after they have been produced, i.e. during the
first stages of hardening. This is a very important problem ; yet how
does Kulka attempt its solution ? He mixes the powder with the fluid
and, either at once or after 20 to 40 minutes, during which the mass
is kept at a temperature of 35, he grinds it to a fine powder. He then
treats about 1 g. of this powder with 150c.c. distilled water for 24 to
48 hours. At the end of this period the powder is removed by filtration
and the liquid titrated with rr potassium hydrate. The alkali
neutralised is expressed in terms of " free phosphoric acid."
A further study of this so-called " quantitative determination " of
the ** free phosphoric acid " shows that this method is not merely
objectionable, but is entirely erroneous because :
1. By adding a larger quantity of water to the finely powdered
but unhardened cement mass, and especially if it is also stirred con-
tinuously for 24 to 48 hours, not only is the cement decomposed, but,
in the case of cements in which the fluid is a solution of zinc salts,
these salts separate out as new constituents ! Acid decomposition
products of the most varied nature enter partially into solution. On
titrating the filtrate assuming that it can be titrated (see 2 below)
what is really determined is the proportion of substances which are, to
a large extent, of secondary origin and are not contained in the original
material !
CRITICISM OF EXISTING THEORIES 205
2. It is entirely wrong in principle to titrate acid-reacting solutions
of metallic salts (zinc salts of aluminophosphoric acid) and to determine
the " free acid " by means of the amount of potassium hydrate
required, because many solutions of metallic salts react like acids, but
contain no trace of free acid. Copper sulphate, cobalt chloride, nickel
sulphate, etc., are typical in this respect.
3. None of the fluid portions of silicate cements contained free
phosphoric acid, but phosphoric acid combined with alumina, i.e.
aluminophosphoric acid and their zinc salts.
These complex aluminophosphoric acids and their salts have
entirely different chemical and physiological properties from those of
free phosphoric acid and must not be confused with it. This is the more
important as the alumina, as will be shown later, plays a very important
part in the physiologico-chemical action of these acids.
Yet Kulka, in his determination of the " free acid," entirely over-
looks this alumina and regards the cement fluid as consisting of
" orthophosphoric acid " in which one atom of hydrogen has been
replaced by a base. This view is quite erroneous and unfounded.
Under these conditions it is not surprising that Kulka's " deter-
minations of acidity," in various silicate masses, led him to regard
what are known in practice as highly poisonous cements as " harmless "
and those which are entirely free from danger as " the most poisonous."
From the experiments of Morgenstern, Kulka and others it was
discovered that the porcelain cements have a far higher resistance to
acids than have ivory 357 and the enamel of natural teeth. 358
This fact is of special importance inasmuch as it provides the key
to the constitution of the silicate cements. It is also important to
observe that some of these cements possess this high resistance even
before they are fully hardened ! This fact also provides means for
studying the course of reactions which occur during the hardening and
in this way excludes a priori a number of hypotheses which will be
mentioned presently.
Critical Examination of various Hypotheses concerning the Course of
Reaction during the Hardening of the Porcelain Cements
Experimental results are available from which it is possible to
learn the course of the chemical reactions which occur in the hardening
of porcelain cements. It is clear that so long as no scientific and well-
founded theory was put forward, these results must remain in the
background. Several of these hypotheses must, however, be aban-
doned, if the high resistance of the half -hardened cement to acids is to
be taken into consideration.
Jung 359 was one of the first to endeavour to explain the chemical
changes which result in the hardening of the porcelain cements. He
first assumed that the powders are " chemical compounds of silica,
alumina, lime," etc., but found an "important error" in the com-
position of these cements and was led to conclude that, on mixing the
206 CONSEQUENCES OF THE H.P. THEORY
powder with the fluid, a separation of lime and magnesia in the form
of calcium and magnesium phosphate i.e. a separation of readily
soluble substances must occur. " The solubility of these substances
in acids," says Jung, " may be reduced by the admixture of alumina,
silica, etc., but it can never be removed altogether."
The proved slight solubility of the porcelain cements in acids is
clearly opposed to the separation of lime and magnesia as just sug-
gested.
Morgenstern 360 also appears to have discovered the same " import-
ant error " as Jung. " We know," he says, " that the general chemical
composition of the cements is due to their calcium and magnesium
contents, and that the reaction between the powder and the fluid
results in the formation of calcium and magnesium phosphates, which
are known to be readily soluble in acids. This naturally leads us to
fear that dental stoppings made of such cements cannot have much
resistance to the acids present in the human mouth . ' ' Yet Morgenstern
has, himself, shown the great resistance of these cements to acids, and
has further demonstrated that the reactions which take place during
hardening must be different from those mentioned in the above
quotation. 357 ' 358
Kulka 361 , in 1909, published a theory concerning the chemical
reactions occurring during the hardening of porcelain cements, accord-
ing to which the action of the acid on the powder produces successively
primary, secondary and tertiary calcium phosphates. This theory is,
however, opposed to the resistance of the silicate masses to acids
which Kulka has, himself, proved 1
Schreiber 362 has severely criticised Kulka's theory, and has rightly
demanded that any theory of the hardening of a cement must neces-
sarily explain why the calcium compounds produced do harden.
Any theory to be satisfactory must, for example, explain why a cement
fluid which has been diluted with water effects a more rapid hardening
than the concentrated fluid, and so forth. For this fact the Kulka
theory affords no explanation.
Rawitzer 363 has also attempted to explain the course of the re-
actions which produce a hardening of the porcelain cements ; but his
suggestion that the phosphoric acid in the cement fluid causes the
precipitation of the whole of the silica in the aluminosilicate powder
in an insoluble form is directly opposed to general experience with
regard to the behaviour of aluminosilicates. Moreover, silica pre-
cipitated in an insoluble form from aluminosilicates must usually be in
the form of a gelatinous mass, yet in porcelain cements this form is not
produced.
Somewhat more noteworthy is the hardening theory suggested by
Apfelstadt 364 , who considers the powder to be composed of a mixture of
alumina and clay. On mixing this powder with the fluid, the alumina
combines with the "free phosphoric acid" in the latter, A1 2 (P0 4 ) 2
being precipitated. This precipitate " cements the previously formed
ARE PORCELAIN CEMENTS MIXTURES? 207
aluminium phosphate and the clay substance together." This investi-
gator also attributes the poisonous action of the silicate cements to
the presence of " free phosphoric acid." His theory affords no explana-
tion of the great resistance of the fully hardened cements to acids.
It is well known that clay substance is resistant to acids, yet the
alumina and the " cemented aluminium phosphate " must be readily
soluble in acids. What, also, is to be said about the lime and mag-
nesia ? To this question, Apfelstadt's theory affords no answer.
Moreover, the expression " cemented " is by no means a clear one.
In short, Apfelstadt gives no satisfactory explanation of hardening,
and his opinion that porcelain cements are mixtures of alumina and
clay substance is without foundation.
From the foregoing pages it will be readily understood how feeble
and unsatisfactory are the theories criticised and that the investiga-
tions hitherto made have led to no results of importance. Hence there
are reasons for supposing that an application of the H.P. theory of
silicate constitution to the hardening of porcelain cements is not with-
out interest.
Before attempting this, however, it is desirable to enquire whether
the porcelain cements, as such, are single chemical compounds, as it is
only then that they can be elucidated in the light of the silicate
theory.
As the result of numerous investigations made by them in the
manufacture of porcelain cements and of their studies of such cements
as are now obtainable commercially, the authors of the present volume
have reached the conclusion that these substances are really single
chemical compounds, chiefly calcium aluminosilicates.
The chief reason for supposing them to possess this unitary
character is the manner in which they are produced : useful cements
can only be made from clays (hydro-aluminosilicates) and lime or other
bases mixed in definite stoichiometric proportions and heated to
redness.
It is also impossible to separate a porcelain cement into different
ingredients by mechanical treatment, such as washing with an inert
fluid. Such fractions as are obtained in this manner all have the same
composition.
The unitary character of these compounds is confirmed by the
following : It might be supposed that the silicate powder is composed
of mixtures of calcium aluminate and calcium silicate or calcium
aluminate and aluminosilicate, or of silica, calcium aluminate and
aluminosilicate. These constituents could then be readily separated
on account of their different specific gravities. But no such separation
is possible ! The high resistance to acids of such mixtures in the form
of half -hardened cements, as found by Morgenstern and Kulka, would
be inexplicable. The contrary is really the case ! Furthermore, the
presence of some constituents, such as calcium aluminate or calcium
silicate, is thereby excluded, as these products, even after being heated
208 CONSEQUENCES OF THE H.P. THEORY
to redness, readily absorb C0 2 from the air. On mixing a given
porcelain cement with the cement acid an evolution of C0 2 should
therefore be observable, but this is not the case.
The objection may be raised that a study of the Patent Specifica-
tions leads to the conclusion that many porcelains cannot be single
compounds. Thus 0. Hoffmann (German patent No. 199,664, Kl. 30h
of 7th April, 1907) claims a " Method of producing dental cements
characterised by the use of aluminosilicates alone or in admixture
with other substances."
A suggestion of the non-unitary character of porcelain cements is
also given in Rawitzer's German patent, No. 196,510, Kl. 30h of 20th
November, 1905, in which he claims " the production of a dental
cement-powder for transparent dental stoppings which is to be mixed
with phosphoric acid before use." This powder is made by " mixing
heated but unfused aluminium silicate A1 2 O 3 Si0 2 with a previously
melted mixture of calcium aluminum oxide and silica."
The study of commercial porcelain cements made by the manu-
facturers previously indicated show beyond all doubt that their
dental cements were not made according to this recipe ! For instance,
a " cement " which contained a large proportion of precipitated
aluminosilicate was entirely useless as a dental cement on account
of the ready solubility of the precipitated aluminosilicate in acids, and
the ready decomposition of the " cement " by acids. The ordinary
porcelain cement made by the same manufacturer is, like all other
cements of clay, very resistant to acids, so that these cements cannot
contain a large proportion of precipitated aluminosilicate.
There is no doubt that the various porcelain cements do contain
admixtures of salts (basic and acid) and, possibly, small quantities of
precipitated aluminosilicate, these being added to give certain definite
characteristics to the material and to regulate the time of setting and
hardening.
It is also well known that only in the rarest cases are the recipes
in the Patent Specifications correct for making commercial products.
For instance, the patentee of the well known Rostaing cement was the
first to use zinc phosphate for dental purposes. Yet Rostaing was,
after Jung's 365 recommendations, so careful and took such pains to
express himself so broadly and in such an incomprehensible manner
that it has not, so far, been found possible to produce a cement having
all the properties possessed by Rostaing's own preparation by follow-
ing the directions in the Patent Specification.
Hence the Patent Specifications cannot be regarded as being
opposed to the unitary nature of the porcelain cements.
A physico-chemical Theory of the Hardening of Porcelain Cements
In formulating a theory of the hardening of porcelain cements, the
following matters must receive special attention :
(a) The chemical constitution of the porcelain cements.
ARE PORCELAIN CEMENTS MIXTURES? 209
(6) The attraction of aluminosilicates for acids and bases.*
' (c) The physico-chemical progress of the hardening.
(a) The Chemical Constitution of the Porcelain Cements
It has already been shown that a hydro-aluminosilicate of the
formula
II
I I
H 20 (Si-Al-Al-Si)
contains two kinds of hydroxyls : a- and s-hydroxyls ; the former
playing the most important part in ultramarines and the latter in
Portland cements.
In Portland cements the hydrogen of s-hydroxyls the s-hydrogen
may be substituted by monovalent basic groups, viz. R" OH,
R" O R" - OH, etc., where R"=Ca. These are termed " hydrobasic
groups " and according to the number of R"-atoms are indicated by
(1), (2), etc. By separation of the elements of water in two neighbour-
ing, i.e. ortho-hydrobasic, side-chains, the anhydrobasic groups :
- R"\ -O - R" O - R"\ t
O R"/ O R' O R"/
are formed and are distinguished according to the number of
R"-atoms by 2, 3, 4, etc. (p. 166).
The porcelain cement powders differ from the above silicate
cements inasmuch as they contain only a few silicate side-chains ;
and the number of R"-atoms is 1.
The following are typical porcelain cements :
R'O 6 A1O 6 Si0 R"0 6 A10 5 Si0 2 R'O 3 Al 0* 10 Si0
23 2 23
jo__/ \/ \/ \/ \ 1
10= |Si|Al|Al|Si| =1 o etc.
4R"O-6Al 2 3 -12SiO 2
These porcelain cements also differ from other silicate cements in
that they only form transparent, stone-like masses when mixed with
certain acids, viz. aluminophosphoric acids, or such of their salts as
have a certain composition, to be mentioned later.
* The authors of the present volume use the term acido- or baso-phile (from philos
=fond of) for any substance which has an attraction for an acid or basic dye-stuff.
A. B. S.
210 CONSEQUENCES OF- THE H.P. THEORY
The Attraction of the Aluminosilicates for Acids and Bases
The acido- and baso-philism of the aluminosilicates must be
specially considered, as this property of the aluminosilicates plays an
important part in the reactions under consideration.
For example, in the hydro-aluminosilicate
I I il I
H 12 (Si Al Al S A i),
both the a- and s-hydroxyls are acido- and baso-philic, i.e. the a-
hydrogen and the s-hydrogen may be substituted by monovalent acid
and basic radicles. There is a great difference between the degree of
acido- and baso-philism * of these hydrogen atoms : the a-hydrogen
atoms are strongly acidophilic and only feebly basophilic, but the
5-hydrogen atoms are strongly basophilic and are only feebly acido-
philic.
These properties of hydro-aluminosilicates, which are very im-
portant in connection with the reactions which occur in the hardening
of cements, may be further shown in the following :
1 . The topaz molecule
Fl FL Fl
il I
Fl F1 2 Fl
must, if the foregoing hypothesis is correct, have the monovalent
fluoric acid radicle strongly bound to the aluminium radicle and only
feebly to the weakly acidophilic silicon radicle. In any case the
fluorine must be bound more strongly to the aluminium radicle than
to the silicon radicle.
The fact that the topazes contain at least 8 fluorine atoms, shows
that when natural changes occur the fluorine splits off from the
silicon ring and not from the aluminium one, i.e. the fluorine is bound
more strongly to the aluminium than to the silicon ring, as the theory
implies.
2. The relatively feeble basophilism of the a-hydroxyls and the
strong basophilism of the s-hydroxyls are shown by the interesting
studies of Gans 367 on the " artificial zeolites " or " permutites." Gans
found that the aluminosilicates showed a variation in the strength of
the bond between them and the alkalies and alkaline earths,
the bases in some cases being readily and completely replaced by
* See footnote on p. 209.
ACIDO- AND BASO-PHILISM 211
others, whilst in others, substitution could only be effected with
difficulty.
Gans inferred (in agreement with the theory stated above) that the
readily replaceable alkalies and alkaline earths are combined with
alumina, those bases which are replaced with greater difficulty being
attached to the silicon. In other words, he concluded that the a-
hydroxyls are feebly basophilic and the s-OH groups are strongly
basophilic.
Gans has applied this ready replaceability of the a-bases of the
aluminosilicates in an ingenious and practical manner. For instance,
in the sodium silicate A, viz. :
Na Na Na Na
I I I I
Na /\/\/\/\_ Na
** | Si | Al| All Si |
~~
Na Na Na ISTa
A.
the a-sodium must be readily replaced on treatment with aqueous
solutions of Ca, Fe", Mn, etc., forming B, viz. :
Na R"
I I
N
ia
B.
R"=Ca, Fe, Mn, etc.
Conversely* the compound A may readily be formed by treating B
with an aqueous solution of sodium chloride.
The great technical importance of such properties of the a-bases is
obvious. Thus, by suitable treatment of the sodium silicate A with
water, it can remove calcium and magnesium bases from solution, i.e.
it can be made use of in softening hard water.
The a-bases may also be used for other industrial purposes, e.g.
to replace potassium in molasses and syrups in the sugar industry by
sodium or calcium.
For this reason the following patents (see Siedler 368 ) are interesting :
(a) An invention for treating water for domestic and technical
purposes, distinguished by filtering the water through hydrous alumino-
silicates, whereby the undesired bases such as iron oxide, manganese
oxide, lime, magnesia, etc., are replaced by others which are desirable
or at least harmless.
(b) An invention for replacing the potash, in sugar syrups and
molasses, by other bases, distinguished by filtering the said syrups and
CONSEQUENCES OF THE H.P. THEORY
molasses through aluminosilicates, whereby an exchange of bases
occurs, the potassium in the syrups being replaced.
3. The acido- and baso-philism of the aluminosilicates are also
shown by their amphichromatophilism, i.e. their relation to both acid
and basic dye-stuffs, as has been shown by Hundeshagen 369 in the case
of kaolin. Concerning this, Hundeshagen wrote : "A peculiar form
of amphichromatophilism is observable in kaolin, which behaves as
though the silica and alumina could act independently towards dye-
stuffs. The influence of the silica is by far the strongest, and it is to
this that clay owes its very basophilic character ; almost equal, in fact,
to that of amorphous silica. At the same time there is a weaker, yet
still distinct, oxyphilism which is completely analogous to the oxy-
philism of free alumina."
Hundeshagen therefore considers that in the kaolin molecule there
are both alumina-hydroxyls (=a-hydroxyls) and silica-hydroxyls
(=s-hydroxyls).
4. The acido- and baso-philism of kaolin may also be observed in
the colours known as "kaolin-lakes," which are formed by the action
of kaolin on acid and basic dye-stuffs. The basophilism is stronger than
the acidophilism, so the kaolin lakes with basic dye-stuffs play a highly
important part in technology of lakes, whilst kaolin-lakes containing
acid dye-stuffs have a much feebler colouring power and are, technically,
of much less importance.
5. According to Hundeshagen, the acido- and baso-philism of
kaolin are due to the fact that kaolin can withdraw acids from acid
solutions and bases from alkaline ones.
6. The acidophilism of the a-hydroxyls of kaolin is shown by the
constitution of ultramarine, and particularly from the behaviour
(observed by Silber) of the compound :
Na 12 (Si-Al-A A l-S A i)
towards HC1 and that of the product thus formed,
Na 8 H 4 (Si-Al-Al-Si),
towards AgN0 3 , as well as by the formation of the sodalites (p. 152).
The somewhat strong acidophilism of the a-hydroxyls and the very
strong basophilism of the s-hydroxyls are of importance in connection
with physio-chemical reactions which take place during the hardening
of the porcelain cements, as described in the next section.
(c) The Physio-chemical Eeactions occurring during Hardening
The hardening of porcelain cements is physio-chemically analogous
to that of other silicate cements, such as Portland and slag cements,
the molecules undergoing a series of hydration phases, just as do those
of Portland cement (p. 173). The porcelain cements are also " hydrau-
lites " (p. 174), but, unlike the Portland and slag cements, they only
harden in the presence of certain acids. If the powdered portion of a
THE HARDENING OF DENTAL CEMENTS
213
porcelain cement is more basic than usual, acid salt solutions may
induce hydration phases.
Two classes of porcelain cements may, conveniently, be dis-
tinguished :
1. Porcelain cements of which the fluid portion is acid acid
cements or ^.-cements.
2. Porcelain cements of which the fluid portion is an acid salt
solution * saline or E-cements.
The 2-cements have several advantages over the A -cements.
The chemical reactions involved in hardening porcelain cements
consist chiefly of two parts :
(a) Hydration, and
(6) Condensation, or formation of an acid or salt with simultaneous
loss of water.
(a) Hydration
Hydration consists, as in the hardening of Portland cement, in a
series of hydration phases as shown in the following example :
10== Si I All All Si I _
4 RO 6 A1 2 3 12 Si0 2
(a)
I I
= SiAlAlSi
I I
RO 2 H 2 . 6 A1 2 3 12 Si0 2
(b)
1 I
\/
Si I Al I Al I Si
I I I I
1 o == /\/\/\/\ ==1 o
r J Si | Al | Al | Si] =io
I I I I I I
4 RO 3 H 2 6 A1 2 3 12 Si0 2 4 RO 4 H 2 6 A1 2 3 12 Si0 2
(c) (d)
4 RO - 5 H a O 6 A1 2 3 12 SiO,
(e)
* Although the term ' ' acid salt solutions ' ' is used for convenience, it should be under-
stood that acid-reacting salts are really meant, and not the true acid salts which con-
tain H-ions. Solutions of metallic salts are known (p. 228), which do not appear to
contain H-ions and yet have an acid reaction.
Even if the acid reaction of these fluids is referred to the presence of H-ions, or
if these ions should be found in some of them, there still remains a large difference
between a porcelain cement containing free acid and one containing an acid salt, par-
ticularly when the physiological action of the cement is considered.
CONSEQUENCES OF THE H.P. THEORY
111
\/\/\
SilAllAl Si
I! I I II
! /\/\/\/\
-
1 o _ ' I I I I _ i o /-\\ _ I _ /I \
II I I II II I I II
4 RO 6 H 2 6 A1 2 3 12 Si0 2 4 RO 10 H 2 6 A1 2 3 12 Si0 2
(*) (g)
This large number of hydration phases is accompanied by a notable
development of heat, particularly at the beginning.
(b) Condensation
As soon as the hydration assisted by the acid or acid salt solution
ceases, the second stage of hardening condensation commences.
If the fluid portion of the cement is a complex acid, as shown by
the acidophilic a-hydroxyls, water will be separated and the acid
radicle will attach itself to the silica molecule.
On account of the somewhat strong acidophilism of the a-hydroxyls
on the one hand and the very strong basophilism of the s-hydroxyls
on the other, it is highly probable that acids will attach themselves
to the silica ring without any separation of base from the silica side of
the molecule.
The constitution of a hardened mass of an -4-cement will, thus, be :
m
A A
According to this constitution, if, for instance, A is an alumino-
phosphoric acid, such a substance must be a strongly acid salt of a
triple acid.
The addition of a complex acid to a cement powder is by no means
a neutralisation of the former in the ordinary sense of this word,
although on account of its insolubility the hardened mass may react
neutral to litmus. There is, in fact, a large number of substances
which, being insoluble, react neutral to litmus and yet are, constitu-
tionally, acids. Kaolin is a typical substance of this kind.
A hardened 2-cement has probably an analogous constitution :
aq.
THE HARDENING OF DENTAL CEMENTS 215
A completely saturated substance of this kind is, therefore,
analogous to Thugutt's sodalites (p. 60) and the E-ultramarines whose
mode of formation has been shown in previous pages to be due to the
formation of condensation products. The ^4-cements, on the contrary,
are analogous to the ^4 -ultramarines (p. 140).
These structural formulae indicate that a molecule of a cement may
be combined with four molecules of acid or of 2, but this can only
be the case occasionally.
The above structural formulae for fully saturated dental cements
are only for a given case, as the structure of these substances must,
naturally, vary with the ratio of powder to fluid. Some of these
cements may, for example, have the formula
(1)=
(1)=
OH OH
others contain an excess of acid (2) or of uncombined A or 2. The
constitution of hardened cements of other compositions may be
regarded as analogous.
The physio-chemical reactions occurring during hardening are
thus clearly shown by means of this theory. On the physical side, the
following may be added :
If the cement mass is regarded as a sphere composed of different
layers as in Fig. 3, 370 the hardening takes place from the circum-
ference towards the centre. The outer layer a
hardens without any external pressure, but in the
case of 6, any expansion is opposed by the harden-
ing outer layer a. The same occurs with layers c and
d, only they cannot expand so much. Hence the
hardness and density of the mass must increase as
the interior is approached and the outermost layer
must be the softest. An examination of phos-
phate cements confirms this view, the outer portion of an old dental
stopping being more or less worn, whilst the interior is found to be
much harder.
Consequences of the Theory and the Facts
A
From the theory it follows that the formulae calculated from the
analyses of the porcelain cements must be arranged to represent
compounds whose existence is theoretically possible. Unfortunately,
very few analyses of porcelain cements have been published. The
216 CONSEQUENCES OF THE H.P. THEORY
investigations of the authors 371 have shown that the powders contain
approximately
CaO A1 2 3 Si0 2
6-12% 38-50% 40-44%
One analysis leads to the formula
ca ca
/\/\_l
Al|Si)>=l (Ca=JCaO)
~
3 CaO 6 A1 2 3 10 Si0 2 Loss on ignition
Calcd. 11.20 40.80 40.60 8.00
Found 12.10 38.19 40.60 8.23
The 6-12% CaO in the porcelain cements shows that the powder
contains fewer R" side-chains than the Portland cements. This
relatively small proportion of CaO also explains the great resistance of
these cements to acids, as experiments with complex acids have shown
that the power of the molecule for combining with a base increases
inversely as the amount of base present (pp. 94, 108, 262, 263, 265,
etc.). The non-separation of this CaO by the action of the fluid
portion of the cement may also be regarded as being due, in all
probability, to the acidophilism of the Al- and the basophilism of the
Si-rings.
B
The absorption of water during hardening must be capable of being
represented stoichiometrically, as it is in Portland cements. The
hardened mass must contain various forms of combined water : water
as R" OH, water in the form of OH-groups attached to the silicon
ring and " water of crystallisation." Of these, the maximum amount of
water combined with R" and with silicon respectively must
a priori be capable of prediction. No direct determinations of these
forms of water have been published.
C
The hydration of the porcelain cements must proceed gradually
like that of the Portland cements. It must, therefore, be possible to
prove a gradual growth of the various OH-groups by determining the
amount of water in the porcelain cements at various periods during
the hardening.
This consequence of the theory was confirmed, in the case of
Portland cements, by a series of hydration experiments by v. Teicheck
and others (p. 180), but no such determinations have, as yet, been
made with porcelain cements.
THE HARDENING OF DENTAL CEMENTS 217
D
The duration of the various hydration phases is a very interesting
subject. In the case of the porcelain cement powders, with their
relatively low content of base, the duration of the hydration phases
must, cceteris paribus, depend on the following factors :
1. The constitution of the silicate molecule.
2. The acidity of the cement acid.
3. The temperature at which the hardening occurs.
4. The proportion of water in the cement fluid.
5. The physical conditions of the cement powder.
As regards the first factor the constitution of the silicate molecule
it is clear that the various silicate molecules must hydrate at
different rates.
As an increase in the acidity of the cement fluid must increase the
speed of hydration, it is clear that, cceteris paribus , those porcelain
cements of which the fluids contain more acid must harden more
rapidly than those with a less acid fluid.
As, on the contrary, the hydration begins more readily when the
basic content of the silicate molecule is increased, a reduction of the
acidity of the cement fluid must effect a corresponding increase in
the basic content of the silicate molecule if a definite rate of hardening
is to be reached.
The temperature at which the hardening occurs exercises an
important influence on the rate of hardening, the higher the tempera-
ture the quicker the hardening, and vice, versa. The extent to which
the rate of hardening is increased by a rise of (say) 10 in temperature
must be determined by direct experiment.
For a definite acidity in the fluid portion of the cement, the rate
of hardening must naturally depend on the proportion of water in
the fluid : the larger the proportion of water the more rapid the
hardening, and vice versa, as in the former a quicker, and in the latter
a slower hydration occurs.
The ability of the silicate molecule to undergo hydration also
depends, cceteris paribus, on the physical condition of the cement
powder : the coarser the powder the slower and feebler the hydration,
the finer the texture the greater its reactability.
This consequence of the theory is fully confirmed by experience.
With some ^4 -cements the hardening is so rapid that the powder must
contain coarse grains as well as fine ones in order to reduce the rate of
hardening within convenient limits, or special instructions must be
issued to users that the fluid must be added in small quantities and
very slowly.
There is a possibility, in the case of some of the slower 2-cements,
of so regulating the rate of hardening that at blood heat (37 C.) they
harden at a normal rate and can thus be used for dental purposes. This
is effected by arranging the size of the grains in the powder and the
concentration of the fluid portion of the cement.
218 CONSEQUENCES OF THE H.P. THEORY
At the ordinary temperature, the 2-cements usually harden more
slowly than the JL-cements, and a number of writers have considered
this to be a defect in the E-cements. As a result of this slower harden-
ing of the E-cements they contain uncombined 2 (i.e. uncombined,
feebly acid salts) in solution for a longer time after the commencement
of the hardening than do the ^t-cements, and, consequently, they have
an acid-like reaction towards litmus for a longer period. This has led
to the false conclusion that the 2-cements are detrimental to the
pulpa.
In reaching this conclusion the following have been overlooked :
1. That the dental cements should not harden at the ordinary
temperature, but at blood heat, and this is, as already shown, the
temperature at which they harden best.
2. No importance can be attached to the suggestion that these
cements are harmful to the pulpa, as the reddening of litmus by them
is not due to a strong A -acid, but to a weakly 2-acid salt solution.
E
It also follows from the theory, that the hardening of a porcelain
cement must occur in a series of phases. This consequence of the
theory is fully confirmed by practical experience. Morgenstern 372 has
shown that, in most cements, the first hardening is followed by molecu-
lar changes, which in some cases are completed within 3 hours, but in
others are not fully completed in 24 hours. In confirmation of this is
the fact, proved by Morgenstern, that the strength of these cements
increases if, after the first period of 3 to 24 hours, they are kept out of
contact with air or moisture.
Wege 373 has also distinguished two stages in the hardening of
porcelain cements.
1. The setting stage, which, according to Wege, "lasts 15 to 20
minutes. If it takes place at blood heat, it is accompanied by a
marked evolution of heat owing to the rapidity with which the physio-
chemical changes occur. During this stage these cements become so
hard that they may be cut and polished. At ordinary room temperature
the hardening takes place much more slowly.
" The sensitiveness of the freshly mixed cement to moisture and
to saliva is characteristic of the first stage of the hardening of a
porcelain cement. It is, therefore, necessary to perform the operation
of tooth-stopping in such a manner that all saliva is excluded until the
cement is hardened."
2. The stone-forming stage commences " after 15 to 30 minutes (at
blood heat). The chemico-physical reactions which occur during this
second stage of the hardening are less energetic than those in the first
stage, and the heat evolved is so small as to be scarcely measurable."
11 The mass in the second stage is less sensitive to moisture and
saliva. This sensitiveness which shows itself by ' killing ' any cement
TOXIC ACTION OF J-CEMENTS 219
mass mixed with saliva diminishes more and more until it eventually
ceases completely.
" The c stone-forming ' process may be completed in a few hours
or it may take 2 to 3 days, different cements varying considerably. It is
during this second stage that the cement attains its maximum hardness
and density."
Schreiber 374 , in his critical studies, has also repeatedly called
attention to the various phases of hardening of the porcelain cements.
The inference from the theory that the hardening of the porcelain
cements occurs in a series of phases is thus in agreement with the facts.
It is clear that, previous to the " stone-forming " stage, the
hardening of the porcelain cements may be hindered by the action of
water, alkalies, and diluted acids, and it is a serious error, in studying
the resistance of these cements to acids and alkalies, to treat them with
these reagents before the stone-forming stage of the hardening is com-
pleted. As already mentioned, Morgenstern and Schreiber have
clearly shown the nature of this error in a series of experimental studies
made by them.
F
In the light of the H.P. theory, the fact that porcelain cement masses
have a higher resistance to dilute acids than is possessed by ivory or
the enamel of natural teeth is explicable. The acid in the fluid portion
of the cement does not decompose the silicate molecule ; it does not
cause the separation of any bases which can form easily soluble salts
with phosphoric acid or aluminophosphoric acid. The acid in these
cements only assists the hydration of the silicate molecule and adds
itself to the latter. Dilute acid, if it does not act on the hardened
molecule, may, if it has as great an affinity for the silicate molecule as
the cement acid, effect a further hydration and may replace it, though
this is seldom the case, with dilute lactic and acetic acids.
This indicates that the cement mass is not readily attacked by
acids, a fact which has been proved experimentally.
The Toxic Action of the ^-cements in the Light of the New Theory
From what has been written in the foregoing pages, the constitu-
tion and properties of the porcelain cements must, undoubtedly, be
regarded as new members of the great class of silicate compounds. It
is therefore desirable, in the light of the H.P. theory, to find an answer
to a question which is both theoretically and practically of the greatest
importance. It has been stated that some porcelain cements have a
serious disadvantage in that they cause dangerous inflammation and
destroy the nerves (pulpa) of the teeth, with all the consequences which
follow these actions.
For several years there has been a bitter fight as to whether the
toxic character of these silicates may be prevented. The chief difficulty
in solving this problem appears to lie in the lack of knowledge of their
CONSEQUENCES OF THE H.P. THEORY
constitution and the course of the reactions during the hardening of
the material. Moreover, the question as to the toxic action of porce-
lain cements containing strong acids the A -cements are the only
ones which have been found to affect the pulpa is purely a physio-
logico-chemical one, and yet no one has endeavoured to answer it
with the assistance of physiological chemists and their discoveries of
toxines, although this would seem to be a conditio sine qua non to any
satisfactory solution.
The following lines contain the results of an effort to ascertain the
cause of the harmful action of some cements and to find a means of
preventing it. This effort is based on a consideration of the constitu-
tion and the reactions occurring in the hardening of ^.-cements and on
a study, of the manner in which the toxines have been found to react
physiologically.
In studying the causes of the toxic action of the A -cements the
following consequences of the theory are important :
1. The action of the acids in the fluid portion of the A -cements
the aluminophosphoric acids results, primarily, in the hydration of
the silicate molecule, i.e. in the formation of a-, s- and basic-hydroxyls.
The combination of the acid with the molecule is a secondary result,
and is due to the acidophilic OH-groups.
The cement, prepared by mixing the powder and the fluid together
into a plastic mass, is at once forced into the dental cavity under con-
siderable pressure. It is, therefore, clear that it must contain a
considerable amount of free aluminophosphoric acid which may
gradually find its way to the pulpa.
2. According to the theory, which is based on the fact of the strong
basophilism of the silicate ring and the weak acidophilism of the
alumina ring, it follows that, in all probability, the free alumino-
phosphoric acid will not cause the separation of the least particle of base.
This highly probable consequence of the theory becomes a certainty
when the repeatedly observed high resistance to acids of the un-
combined or incompletely combined A -cements is taken into considera-
tion.
This consequence of the theory, which is in complete agreement
with the observed properties of the cement masses, is of great import-
ance in studying the causes of the toxic action of the ,4-cements.
Thus, it might be assumed that the 6-12% lime in the A -cement
powders would be separated on mixing the powder with the acid fluid,
and that if the lime present reached a definite proportion it might, in
this way, completely prevent the toxic action of the acid owing to the
combination of the acid and lime. From both the theory and the
observed behaviour of the ^4-cements towards acids it follows that no
such separation of the base can occur.
The improbability of any separation of lime being brought about
by the aluminophosphoric acid on simply mixing the silicate powder
and the acid fluid together, is confirmed by the behaviour of highly
TOXIC ACTION OF ^-CEMENTS
basic cements which have been hardened by treatment with acid, such
as the zinc phosphate cements, the powdered portion of which contains
90% of zinc oxide.
In commerce, as may readily be seen from a study of the literature
of the subject, there are two kinds of zinc phosphate cements :
(a) Those in which the fluid portion contains a strong, free acid ;
and
(6) Those in which the fluid portion contains a considerable amount
of a stronger base, e.g. zinc oxide.
The difference is shown in the following Table, due to H. Paschkis :
Composition of Zinc Cements
Name
" Fluid Portion "
Contains
Poulson
fluid
no zinc
Entrop
Ash
,,
Griinbaum
little zinc
Poulson
Rostaing
crystalline
fluid
much zinc
It is clear that these two kinds of zinc phosphate cement may have
different chemico-physiological properties. In this connection it is
interesting to notice that one of the most famous workers Miller,
Professor of Dentistry at Berlin University 376 comments on the
repeatedly observed destruction of pulpse by zinc phosphate cements
(p. 232), whilst another equally famous operator Prof . Black 377 has
observed no such destruction by zinc phosphate cements. These
contradictory opinions can only be explained by assuming that
Miller used cements containing free acid, whilst Black used those in
which the fluid portion contained salts. Other operators have also
reported contradictory results, some recommending the use of a
protective medium below the cement stopping and others advising the
direct use of zinc phosphate cement as providing the most suitable
protection for the pulpa. 378
The destructive action, on the nerves, of zinc phosphate cements
containing strong acids in a free state in the fluid portion can only be
explained by supposing that not merely the 6-12% of base in porcelain
cements, but even the 90% of base in the zinc cement powder, cannot
prevent the destructive action of the free acid on the nerves at the
moment when the mass is introduced into the cavity in the tooth.
This surprising fact admits of a complete explanation : the harden-
ing of a cement is essentially a slow physio-chemical process and it
cannot, by the time the mass is introduced into the cavity, have
proceeded far enough for the neutralisation of the strong acid to effect
the separation of the base. This behaviour of the highly basic zinc
222 CONSEQUENCES OF THE H.P. THEORY
phosphate cements thus affords a further confirmation of the im-
probability of any separation of the base by the action of the cement
acids on silicate powders so poor in basic material as are the A -cements
at the moment of their introduction into the dental cavity.
3. In the light of the H.P. theory, the fully hardened A -cements are
really " sodalites " (p. 214). The acid is added to the silicate molecule
because of the acidophilism of the a-hydroxyls. Experience has shown
that this acidophilism of the silicate molecule is never strong, and in
the case of acid dye-stuffs the " lakes " produced are, technically, of
minor importance.
There is a danger on account of the low acidophilism of the a-
hydroxyls, that after a long time a separation of free acid may occur
and the pulpa be destroyed, the A -cements thus resembling a sleeping
volcano which may start its destructive action at any moment.
According to the new theory, the completion of the hardening of
the A -cements need not prevent the acid in them from acting detri-
mentally. Definite reports made by various practical dentists show
that the deleterious action has been observed a long time after the
" stopping " had been inserted ; in some instances after an interval
of a whole year. In one case, disease of the pulpa, resulting in the
death of the patient, set in more than a year after a shallow cavity had
been stopped with ^4-cement.
The toxic action of the A -cements has now been shown to be due to
that of the free aluminophosphoric acid present. The question arises
as to whether this toxic action can be proved by chemico-physio-
logical experiments in which these free acids are compared with other
toxic substances. The answer to this question forms the subject of the
following section :
The Causes of the Neurotropism of Aluminophosphoric Acids
(Ehrlich's Theory)
The term " neurotropism " was suggested by Ehrlich 379 to in-
dicate the poisonous action of any material on nerve-substance.
Before it can be stated that a given substance is, theoretically, a
neurotrope it is necessary to understand why modern physiological
chemists consider that neurotropism is the result of chemical action.
The famous physiologist and bacteriologist, P. Ehrlich, was the first to
suggest that only those chemical substances are neurotropic which
form a definite chemical compound with the nerve-fibres 380 (side-chain
theory). Erhlich reached this conclusion as a result of his study of
the so-called vital colour processes. Ehrlich has shown that the various
dye-stuffs become localised in the organism according to their chemical
constitution. For instance, methylene blue has a special attraction
for living nerve-fibres ; other dye-stuffs are chiefly retained by the fatty
organs and still others by the substance forming the kidneys.
As the theory of the chemical combination of the toxines is of
fundamental importance if a satisfactory theory which will explain the
THE CAUSES OF NEUROTROPISM 223
observed properties of porcelain cements is to be obtained, it is neces-
sary to mention briefly those facts having any bearing on the
theory which have been observed by all well-known physiological
chemists.
Ehrlich's theory is confirmed by the following facts :
1. Analysis of cases of poisoning by toxines. It is well known, for
instance, that when toxines are introduced directly into the blood-
stream they rapidly disappear. 381 The rapid combination of injected
toxines with the blood has also been observed by von Behring 382 ,
A. Knorr 383 , Bomstein 384 , de Croly 385 and others.
2. The investigations of von Behring 386 on tetanus afford a special
confirmation of the theory of the chemical combination of the toxines.
If animals which are peculiarly liable to tetanus are inoculated with
tetanus poison, this is found in all the organs except the central
nervous system. In other words, the poison is only feebly combined
in the organs first mentioned, but it enters into definite chemical
combination with the nerve-substance and cannot then be detected.
The following fact also supports Erhlich's theory : Knorr has
drawn up a '* Scale of Sensitiveness to Tetanus," and finds that the
poisonous dose for a hen is 200,000 times that for a horse, the amount
being calculated in grammes of poison per gramme of animal weight.
Hens have been found by Kitasato to be practically immune from
tetanus.
The very slight sensitiveness of hens as compared with horses may
be explained by Ehrlich's theory as due to lack of combining power.
This is confirmed by the experiments of Metschnikoff 387 , Azakawa 388 ,
and of Fermi and Pernossi 389 , which show that insensitiveness to
certain poisons is accompanied by the easy recognisability of the
toxine in the organism for a long time after its introduction.
4. The well-known experiment of Robert Koch 390 is a particularly
valuable confirmation of the theory of the chemical combination of the
toxines. Koch wished to sterilise infected animals with corrosive
sublimate, but found that the largest practicable doses had no influence
on the parasites, the animals being killed more easily than the para-
sites. This can be readily understood in the light of Ehrlich's theory ;
the sublimate is organotropic, but not parasitotropic, i.e. it forms
definite chemical compounds with the substances forming the important
organs of the infected animals, but has no chemical action on the cells
of the parasites.
5. Low's experiments on the action of oxalic acid on plants, is
another interesting and valuable confirmation of Ehrlich's theory.
Oxalic acid is well known as a powerful poison to both animals
and plants, and its action was found by Low to be due to its forming
definite compounds with lime salts. Hence, according to Low, oxalic
acid is only poisonous to those plants whose cells contain lime salts,
and it can have no poisonous action on plants, the cells of which are
free from calcium compounds. Low has fully proved by direct experi-
224 CONSEQUENCES OF THE H.P. THEORY
ments that plants which contain no lime salts are not poisoned by
oxalic acids.
Further important confirmation may be found in the results of a
large number of experiments, all of which are fully indicative of the
production of definite chemical compounds. 391
Amongst others, Pasteur's Immunisation Therapy, Behring's
Serum Therapy (Diphtheria serum), Chemicotherapy, the work of Koch
and Uhlenhut on the use of atoxyl in the cure of malaria, and the
chemical treatment of infectious diseases (syphilis) by Ehrlich and
Hata all yield therapeutic results in support of Ehrlich's side-chain
theory.
There can, therefore, be no doubt that the theory of the chemical
combination of the toxines is fully established.
If it is desired to explain the neurotropism of the ^1-cements (i.e.
the poisonous action of the aluminophosphoric acids on nerve-sub-
stance) it must be clearly shown that these substances form definite
chemical compounds with the nerve-fibres.
In order to do this it is clearly necessary to :
1. Have a clear idea of the chemical constitution of the nerve-
fibres, and
2. Produce facts which show the existence of a chemical relation-
ship between the aluminophosphoric acids and the nerve-fibres.
I. The Chemical Constitution of the Nerve-fibres
The nerve-fibres, like all other animal fibres such as wool and silk,
belong to the proteins, 392 i.e. to those substances whose constitutions
have been so admirably studied by Emil Fischer and his students. These
investigators 393 claim that it has been positively proved that the
proteins contain amino-acids, the same fundamental substances
appearing in the most widely differing proteins, but in very varying
proportions, so that one or other amino-acid may be entirely
wanting. This constitution of the proteins is reminiscent of the
aluminosilicates which also contain a few fundamental substances
combined in the most varied proportions. For instance, in the pro-
teins, the following amino-acids are found : glycoeol, d-alanine,
Z-leucine, d-glutaminic acid, amino-oxysuccinic acid, diaminoacetic
acid, etc.
As the complete hydrolysis of proteins by acids and alkalies
always yields the same results, E. Fischer and his associates concluded
that the amino-acids in them are not secondary, but are an integral
part of the protein molecules. Hence the proteins are complex acids
and must behave towards acids and bases in a manner analogous to
other complex acids. As a matter of fact, the albumens are usually
represented as multiple acid bases and multiple basic acids, i.e. they
have a marked baso- and acido-philism and form compounds with both
acids and bases. This ability of the albumens to combine with acids
and bases has been investigated by several methods. 394
THE CAUSES OF NEUROTROPISM 225
II. The Chemical Relationship between the Nerve-fibres and the
Aluminophosphoric Acids
If it may be accepted as a definite fact that the nerve-fibres, like
animal fibres generally, are chiefly proteins (amino-acids), it is clear
that such substances may form definite compounds with either simple
or complex acids, especially as Friedheim and his associates have
found, as the result of a large number of experiments, that complex
acids can not only combine with bases, but also with other acids, and
other chemists have proved the existence of amino groups.
That the facts fully confirm the possibility suggested by theory
is shown by the mordanting of animal fibres by sesquioxide compounds
such as aluminosulphates (alums), aluminoacetates, etc., i.e. by the
various complex alumino-acids. 395 The properties of the alumino-
phosphates such as the existence of aluminophosphates with very
different proportions of phosphoric acid and alumina, which can pass
into one another ; the impossibility of replacing the alumina by other
bases by double decomposition ; the masking of the phosphoric acid
by alumina in agriculture, etc. show that their constitution is
analogous to that of the aluminophosphates and aluminoacetates, and
there can be no doubt that they have a special chemical relationship
to the nerve-fibres. In short, the aluminophosphoric acids are, in
accordance with Ehrlich's theory, neurotropes or nerve poisons.
It is very probable that the proteins, like the aluminosilicates,
have a cyclic constitution, i.e. they apparently consist of N- and C-
hexites and pentites. The combination of animal (nerve) fibres and
the complex alumino-acids the corrosives is most probably analo-
gous to that of the complex acids : two neighbouring OH-groups in
the animal fibre combining with two similar (ortho) OH-groups in the
alumino-acid with loss of water. The resultant complex can then, in
an analogous manner (i.e. on losing water), unite with dye-stuffs, the
combination of these being thus effected by means of the OH-groups
in the alumino-acids. From this it follows that only dye-stuffs with
ortho-hydroxyl groups can combine with alumino-acids and can be
used as dyes. This interesting consequence of the theory has been
fully confirmed by the experiments of C. Liebermann and St. Kon-
stanecki 396 , who have shown that the only oxyanthracinones which are
fixed dyes are those containing two ortho-hydroxyl groups. C.
Liebermann has converted non-dyeing colours into strong dyes by the
introduction of two ortho-hydroxyl groups, particularly in the case of
fluorescines, eosines, 397 malachite green, 398 fluorines, 399 oxyaurenes, 400
etc.
What can be said in regard to the physiologico-chemical action of
the 2-cements ?
The experience of Black and Schreiber with S-phosphate cements
shows that the 2-silica cements are non-poisonous to the nerves of the
teeth. The plastic mass of Z-cement does not contain free alumino
226 CONSEQUENCES OF THE H.P. THEORY
phosphoric acid, but an acid saturated with zinc oxide, i.e. a zinc salt,
which must, naturally, behave in a different physiologico-chemical
manner towards the nerves. According to Ehrlich's theory, all toxic
action is excluded in the case of 2-cements, as investigations on the
dyeing of animal fibres show 401 that, in the absence of mordants, the
colour can only be fixed on wool and silk when the dye-bath is acid,
i.e. only when the dyestuff-acid is in a free state. From this it follows
that only free acids have any action on the nerve-fibres, salts being
inert in this respect ; in other words, solutions of zinc salts can form
no definite chemical compound with nerve-fibres, i.e. they are not
neurotropic.
It is very remarkable that, according to Siem's investigations, 738
complex compounds of aluminium (sodium alumino-lactate), when
injected subcutaneously into animals, are found to be highly poisonous.
On injecting relatively large doses of these compounds into the blood,
death occurred after seven to ten days. The daily subcutaneous in-
jection of small quantities into dogs, cats and rabbits, caused death
within three to four weeks after the introduction of a total weight of
0.25 to 0.30 grammes A1 2 3 per kilog. of animal weight.
The fact discovered by Dollken 739 in repeating Siem's experiments
is even more interesting. Dollken confirmed Siem's conclusions and
also found that, in accordance with the H.P. theory, these poisonous
aluminium compounds are essentially nerve poisons. He found that in
animals which had died from injections of these substances the nerve-
roots were degenerated and that marked changes had occurred in the
nerve-cells. The central nervous system is the part most affected by
these poisonous aluminium compounds ; the outlying nerves not being
appreciably affected.
Siem and Dollken have also shown that it is a further characteristic
of aluminium poisoning that time is required before any symptoms of
poisoning are observable. Neither investigator noticed any acute
symptoms of poisoning, even when large doses were administered.
This experience is a complete agreement with the symptoms accom-
panying poisoning by silicate cements of the " A " type, in which, as
previously stated, the action of poison does not make itself observable
until after weeks, months, or, in some cases, more than a year.
The objection may be raised that, according to the H.P. theory,
neutral salts of complex alumino-acids and particularly sodium
alumino-lactate, should be wcw-poisonous, as the harmlessness of the
zinc aluminophosphates (i.e. of the 2-cements) was thus explained.
This objection is not well taken, as it is necessary to remember that
some salts, like the sodium compounds of complex acids, readily
dissociate and their anions can then enter into reaction. For this reason
the feebly dissociable zinc salt possesses advantages over the free
acids. Moreover, it is especially important to observe that Siem used
extremely dilute solutions, whilst the fluid portion of the 2-cements is
highly viscous and is thus different from the ^4-cements. The prob-
THE ACID REACTION OF Z-CEMENTS 227
ability of extensive dissociation or decomposition of the fluid portion
of the 2-cements in hollow teeth is very remote.
It should also be noted that, apart from any particular theory, there
can be no doubt that free acids can combine with nerve-substance far
more readily than can salts, and from this point of view the Z-cements
must be more advantageous than the A -cements for physiologico-
chemical purposes.
The objection may be raised that the fluid portion of the 2-por-
celain cements is very concentrated, and that the acid reaction is
due to a hydrolysis of the salt, i.e. that these salts must contain free
aluminophosphoric acid, even if only in small quantity. This objection
is quite erroneous, as the acid reaction of metallic salts is not neces-
sarily a sign of hydrolysis, because many metallic salts (including
nickel sulphate, manganese chloride and copper sulphate) which, hi
aqueous solution, react strongly acid may be shown, on physio-
chemical grounds, to be quite free from hydrolysis.
As the question whether the acid reaction of an aqueous solution
is a definite sign of the presence of free acid has not been clearly
answered, an attempt is made, in the folio whig lines, to deal with it in
accordance with the experimental material available.
Does the Acid Reaction of an Aqueous Solution of an Acid Salt always
indicate Hydrolysis and the Presence of Free Acid ?
The non-hydrolysis of a number of acid-reacting solutions of
metallic salts may be shown :
(a) By determining their coefficient of conductivity, and
(b) By spectrum analysis of the solution.
(a) Conductivity Determinations
The following simple means of determining whether a salt is hydro-
lysed in aqueous solution is due to Ostwald. If the molecular con-
ductivity of a solution of one gramme-molecule of a salt in 1024 litres
of water at 25 C. is represented by yui 02 4 an d the conductivity of the
same weight of the salt in 32 litres of water at the same temperature
is represented by ^ 82 , from the difference A between these two numbers
it can at once be seen whether the substance is hydrolysed or not. If,
for instance, the difference A is approximately 20, no hydrolysis has
occurred, but if A is considerably above 20, a hydrolysed salt is
present. 402
A number of salts, such as nickel sulphate, cobalt chloride, man-
ganese chloride, copper chloride and copper nitrate, when in aqueous
solutions react like acids, yet the value of A shows that according to
Ostwald 's rule they are not hydrolysed, as may be seen from the
following Table, 403 in which no number is significantly above 20.
228 CONSEQUENCES OF THE H.P. THEORY
Conductivity Difference
Salt A
Nickel sulphate 18.6
Manganese chloride 18.5
Cobalt chloride 18.2
Copper chloride 20.5
Copper nitrate 18.6
Copper sulphate also has an acid reaction, yet the determination
of the conductivity of a number of aqueous solutions of copper sulphate
show, according to Ostwald 404 , that this substance is not hydrolysed.
Ostwald has shown that the conductivity increases steadily with the
dilution of the solution, and from this and from the conductivity of an
infinitely dilute solution he concludes that solutions of copper sulphate
contain Cu- and S0 4 - ions, but no H- ions.
(b) Spectrum Analysis
According to Knoblauch 405 and Nernst 406 , spectrum analysis affords
a very delicate method for showing the constancy, or otherwise, of the
constitution of a substance. If the absorption spectrum of a solution
of the substance changes with the concentration a change must have
occurred in the constitution of the substance. According to Nernst 407 ,
innumerable tests have shown that a very small change in the consti-
tution is readily shown by the difference in the absorption spectrum.
If acid-reacting solutions of metallic salts, such as copper sulphate,
underwent the slightest hydrolysis this could be detected by the change
in the absorption spectrum, so that by examining the spectrum of
solutions of different strengths it is possible to ascertain whether the
slightest hydrolysis has taken place.
Acid-reacting copper sulphate which, according to its conductivity,
is not hydrolysed in aqueous solution, has also been spectroscopically
examined by several investigators, including P. Glan 408 , H. W. Vogel 409 ,
and Knoblauch 410 . Glan and Vogel found that the solid and dissolved
substances both have the same absorption spectrum, so that no change
in its constitution and therefore no hydrolysis occurs when acid-
reacting copper sulphate is dissolved in water.
Knoblauch dissolved half a gramme-molecule of copper sulphate in
0.37 litres of water and an equal quantity in 325 litres of water ; the
character of the spectrum of both these solutions was identical and
Knoblauch therefore concluded that in neither case did water effect
any hydrolysis of the salt.
In these ways, the best methods of physical chemistry have shown
that a number of acid-reacting metallic salts are not hydrolysed when
in aqueous solution, i.e. they do not contain any free acid.
The objection may be raised that (a) Carrara and Vespignani in
measuring the rate of saponification of methyl acetate at 25 C. by
THE ACID REACTION OF Z-CEMENTS 229
means of copper sulphate, and (b) Davis and Fowler by inverting sugar
with copper sulphate solution, 411 have shown quantitatively that the
hydrolysis of the copper sulphate does occur and that the investiga-
tions of these scientists, at first sight, appear to show a slight though
definite hydrolysis. These experiments must, nevertheless, be re-
garded as useless, as Donnan 412 , who first introduced them, found that
they were by no means free from objection inasmuch as they contradict
the results of conductivity determinations. They are specially
erroneous as their authors worked on the false assumption that the
saponification or inversion was effected exclusively by hydrogen-ions.
If this assumption were correct it must follow that :
1. The inversion of the sugar must increase with the dilution of
the acid, as the number of the H-ions increases as the solution becomes
more dilute. Precisely the opposite is the case : the inversion pro-
ceeding more rapidly with the stronger acid. 413
2. The rate of inversion must be reduced by adding neutral salts
of the acid used, as this would reduce the number of H-ions. Yet
according to Nernst the opposite is the case : the presence of an
equivalent amount of potassium salt of the given acid increasing
the rate of inversion by about 10 per cent.
3. Salts which react acid to indicators must also invert sugar, as
they should (on the assumption named) contain H-ions. Yet H. Ley 414
has observed that many salts which react acid to indicators behave
like neutral salts as regards sugar.
4. Salts which contain no H-ions should never invert sugar, yet
H. Ley and others 415 have found that many so-called neutral salts,
e.g. chlorides of strong bases, invert sugar to a small yet measurable
extent . The contradiction between practice and the theory that H-ions
are necessary for the inversion of sugar was explained long ago,
Arrhenius 416 having shown that other ions greatly increase the action
of the H-ions. If, however, the inversion of sugar may be effected or
increased by other ions it is clearly useless to employ this method to
ascertain what hydrolysis (if any) has taken place in a given solution.
The above-mentioned facts are also opposed to the assumption that
sugar inversion can only occur in the presence of H-ions, as Ley and
others have effected it in complete absence of these ions. If, on the
other hand, it is agreed that anions may influence the inversion, it is
impossible to understand why the inversion cannot be due to the S0' 4 -
ion in the copper sulphate, as two absolutely unexceptionable methods
electrical conductivity and spectrum analysis have shown the non-
hydrolysis of the solution.
There can be no doubt that there are some metallic salts which
react like acids and yet do not contain a trace of free acid. Hence
the acid reaction of the Z-cement fluids cannot be used as an argument
for the presence in them of free acid ; in other words, the acid reaction
of the Z-cement fluids does not in any way imply the possibility of a
chemical combination of the cement fluid and the nerve-fibres.
230 CONSEQUENCES OF THE H.P. THEORY
The physiologico-chemical properties of the A- and 2-cements
fully agree with the properties which have been observed in practice.
Practical Experiences with A- and --cements in regard to their
Physiologico-chemical Behaviour
The numerous experiments already referred to leave but little
doubt that the -4-cements are nerve-poisons and that the Z-cements
are harmless.
In the year 1904 or 1905, shortly after the silicate cements had
been placed on the market, several attempts were made to prevent the
poisonous action of the A -cements. For this purpose Selowsky 417 ,
Hentze 418 , Sachs 419 , Bruck 420 , Detzner 421 , Scheuer 422 , Escher 423 and
others recommended that :
1. A very thick cement mixture should be used so that any excess
of poisonous acid in the fluid would eventually combine with the
excess of powder.
2. Before inserting the cement, a neutral material should be
introduced into the dental cavity, so as to prevent the acid from
reaching the pulpa.
In spite of the most careful use of these protective materials,
dental literature contains many reports of destroyed pulpse and of
some deaths due to the acid. Thus, in 1906 the following (German)
dentists reported cases of poisoning and the uselessness of a stiff paste
and of protecting pieces : Heinsheimer 424 , Silbermann 425 , Reissner 426 ,
and in 1908, Schreiber 427 . In 1909 Baldus 428 confirmed this view. Of
the many (German) dentists who in 1909 reported deaths due to
pulpa poisoning caused by A -cements, only the following need be
mentioned : C. Wolff, Aachen 429 , Marx 430 , Horstmann 431 , Schulte 432 ,
Gerhardt, Leipzig 433 , Wild 434 , Albrecht 435 , Peckert 436 , Stein-Mann-
heim 437 , Gunzert 438 and Port 439 .
Of these, Wild alone found 30 deaths due to ^4-cements. Still more
recently, Feiler 440 has reported that in spite of the greatest care, 11
cases of poisoning occurred, and enquired whether it was right to use
silicate cements of so dangerous a nature to patients. " I must say
that to me each case is a peculiarly unpleasant memory, so that I am
constantly asking myself whether we are justified in using a material
which, in spite of the greatest care and skill, places the patient in so
much danger."
Feiler has also reported a fatal case following the use of an A-
cement as follows : " The following incident, told to me by Privy
Councillor Partsch, is worth careful consideration. I take the following
from the official medical report : ' On the 16th December, 1906, a year
after the stopping of a superficial cavity in the right upper incisor with
original Ascher's silicate cement, R. G. (22 years of age) began to suffer
indefinable pains in the right side of his face, and several days later a
pronounced swelling of the right cheek and of the upper and lower
PHYSIOLOGICAL BEHAVIOUR OF PORCELAIN CEMENTS 231
eyelids was observed ; fever also commenced. On the 20th December
an elastic swelling, very sensitive to the touch, was easily observable ;
the teeth were very painful when pressed, and a similar swelling near the
fossa cannia was seen. The temperature rose to 40 C. with the pulse
at 120. General condition much disturbed ; no mental symptoms.
The dentist trepanned two, whereupon pus discharged from the pulum
cavum, the swelling increased around the roots of the teeth and con-
tained an evil-smelling pus. In the evening the temperature was still
38.5C.; the pain somewhat reduced. Next day, a general improvement.
On the 23rd and 24th no pain experienced ; patient taken in closed
carriage to the dentist for further treatment. On the 25th he made
a long journey unknown to the doctor. On the 26th headache re-
commenced and on the 27th the doctor was sent for and found con-
siderable feverishness and headache, but no trouble with the mouth,
apart from three vomitings. The doctor diagnosed influenza, but the
symptoms increased daily, the lid of the right eye swelled, the eye-
ball was protruded ; general mental symptoms observable ; the pulse
sank to 56 and became irregular, the knee reflexion was unsatisfactory,
and considerable deep hyperaesthesia of the legs was found.
" On the 4th of January an operation showed that the processes had
extended through the fissura orbitalis inferior to the eye-socket, and
notwithstanding a wider opening it was impossible to prevent the
spread of the processes. The temperature fell for a short time, but on
the 7th of January it rose to 40.4 C., with feverish shivering, and
remained fairly constant with increasing brain disturbance until the
exitus letalis on the 18th of January."
Schreiber 441 in 1910, after reporting a whole series of fresh deaths
from diseased pulpse due to the use of A -cements, wrote in strong terms
condemning the impracticability of the preventive methods recom-
mended.
Freund 442 , of Breslau, encouraged the use of ^4-cements, and
attributed the toxic action of some specimens to the presence of
arsenic and not to the free acid. A year later (in 1909), 443 after some
unfortunate experiences with -4-cements, he openly joined those who
accept the acid theory and discussed the question as to who were
responsible for these {C accidents " the manufacturers who guaranteed
their products to be harmless, or the dentist.
Lartschneider 444 distinguishes between an irritation of the pulpa
and destroying it. Under the term " pulpa irritation " he groups all
the cases in which pain is felt soon after the insertion of the cement.
In most cases the pain soon ceased, but in some instances it continued
for several hours. He has observed these symptoms in 6 to 8 per cent.
of his patients. They were often quite independent of the depth of the
cavity, and many of the worst cases were those where no trouble was
anticipated. He noticed that young, delicate, anaemic patients
suffered most, and considered that the fatal cases might be due to
anaemia.
232 CONSEQUENCES OF THE H.P. THEORY
Robert Richter 445 also attributes the harm done by these cements
to the presence of arsenic, and points out the seriously poisonous
nature of this material. He goes so far as to suggest that the A-
cements should always be labelled as " poison."
Schreiber 446 also regarded the A -cements as poisonous, and urged
that they should be scheduled accordingly. He also suggested that in
the case of an " accident " the dentist should be held to be legally
responsible.
It is interesting to observe that most investigators consider that the
poisonous action is due to the free acid.
A. Masur 447 reports observations made by the Breslau dentists on
the destruction of the pulpa a short time after the use of A -cements,
the patients suffering from acute periodontitis. Masur also considers
that the cause of the symptoms observed is to be found in the cement
acid. Reissner 448 also attributes the periostitis observed by him to
the action of free acid.
Silbermann 449 definitely assumes that the detrimental action of the
^4-cements on the pulpa is due to the acid they contain, and has
endeavoured to prove this assumption experimentally. Later, he
considered that the arsenic in the cements was the cause of their toxic
action, but " the difference observed in the pulpa after the application
of arsenic and of an Ascher's stopping, which had resulted in peri-
odontitis," led him to conclude that the damage was done by the acid
in the cement and not by the arsenic. Moreover, arsenic-free A-
cements have the same toxic action as others ; hence it is not generally
agreed that the acid is the poisonous ingredient.
Kulka 450 has pointed out that, according to Miller 451 , the destruc-
tion of the pulpa (p. 221) is by no means unusual with zinc phosphate
cements, and is apparently due to the phosphoric acid in the cement
fluid. Kulka accepts this suggestion and also the similar one made by
Ottolenguis 453 ; he also considers it possible that the free acid removes
lime from the tooth-ivory and affects the pulpa by partial destruction of
the dentine.
Feiler 454 does not accept this view, as he found that on drilling
through the stopping the dentine above the pulpa was unaffected, and
that no lime had been removed from it ; he does, however, agree that
the detrimental action of the A -cements is due to the free acid present,
and refers to Pawel's 455 work in support of this. Pawel found, by
actual experiments on animals, that the acid in these cements can
penetrate thick layers of dentine and can then damage the pulpa.
According to Feiler, the chemical irritation of the excess of acid
affects the vitality of the pulpa through pores or channels in the dentine
and destroys its power of resistance to bacteria. The latter are thus
able to pass through the channels in the dentine and to enter the blood-
stream, thus bringing about violent processes, the intensity of which
depends on the virulence or pathogenity of the germs present.
The destruction of the pulpa which results from the use of porcelain
PHYSIOLOGICAL BEHAVIOUR OF PORCELAIN CEMENTS
cements containing free acids is attributed to the strong acids in the
cement fluid by the following (additional) authorities : Biel 456 ,
Hentze 457 , Sachs 458 , Bruck 459 , Apfelstadt 460 , Schreiber 461 , Wege 462 ,
Schachtel 463 , etc.
Lartschneider 464 has expressed a doubt as to the action of free
acid in A -cements on the pulpa. He placed small pellets of cotton-
wool saturated with the fluid portion of these cements (i.e. with
cement-acid) in the cavities in infected teeth and closed the cavity
with a Fletcher's cap. In some instances temporary pain was ex-
perienced by the patient, but it ceased after a few hours. In no case
did he find any appreciable destruction of the pulpa or any periostitic
symptoms, even though some of these " acid fillings " were retained
in the teeth for nine weeks.
This investigation is of value, but it does not invalidate the " acid
theory " for the following reasons :
1. Symptoms are, in many cases, only observed after a very long
time, sometimes as much as a year or more after the introduction of
the stopping, and the observations made by Lartschneider were made
in too short a time for the action of the acid to become noticeable. In
this connection the experience of another dentist Albrecht 465 is
interesting. Albrecht was one of the first to use A -cements extensively,
and he could not understand why so many of his colleagues complained
of their deleterious action. More recently, however, he has realised
that several " accidents " are due to old cases, the damage to the
pulpa taking some months before it became noticeable. Two cases in
particular, in which he filled quite shallow cavities with A -cements,
resulted in the destruction of the pulpa and in periodontitis after more
than a year, have made him pessimistic with regard to these cements.
The eventual destruction of the pulpa in the cases quoted by
Lartschneider is, therefore, by no means excluded.
2. The plastic silicate mass is pressed into the dental cavity under
considerable pressure, whereby the free acid may the more readily
penetrate the pores or channels in the dentine and so reach the pulpa.
If a pellet of cotton- wool saturated with acid is used, there is little
or no pressure exerted, and the acid cannot so readily reach the pulpa :
it may, in fact, combine with the Fletcher cement.
3. It is not impossible that only certain people are sensitive to
the action of the aluminophosphoric acids, and that in his experi-
ments Lartschneider had patients who were not likely to develop
pulpitis.
If the harmlessness of the aluminophosphoric acids is assumed,
to what is the destruction of the pulpa due ? Moreover, Pawel has
shown the harmful action of strong acids on the pulpa by direct
experiments on animals as previously noted (p. 232).
The most direct proof that the toxic action of the A -cements is
solely due to the free acid they contain is found in the 2 -cements,
which only differ from the former in the substitution of a salt for the
234 CONSEQUENCES OF THE H.P. THEORY
free acid, yet are found in practice as well as in theory to be perfectly
harmless.
No sooner had the poisonous nature of the A -cements been realised
than an urgent demand was made for their improvement in such a
manner that they should lose their toxic action completely. Thus
Heinsheimer 466 has stated that " Beautiful and valuable though the
Ascher cements are, they have one property which is absolutely neces-
sary to remove, viz. the toxic action on the pulpa. Otherwise, these
almost ideal materials must be discarded. These views are held by a
number of my colleagues, and I may frankly say that this serious dis-
advantage is not due to the use of too soft a mixture or to badly
prepared material."
Greve expresses himself to the same effect : " Some of the new
silicate cements produce excellent results under suitable conditions,
but an improvement is essential. If this cannot be effected they will
never attain the popularity which has been prophesied."
The warnings of Heinsheimer, Greve and others are all the more
significant when it is remembered that, according to Pfaff 467 , diseases
of the pulpa are the cause of other diseases of important organs
particularly of the eyes and ears. Thus, deposits of decomposed matter
on the pulpa, diseases of the pulpa itself and of the membranes sur-
rounding the fangs, frequently cause neuralgia of the trigeminus, or
neuritis ascending to the ganglion gasseri (Karewski). The clinical
observation that the eyes are affected in many diseases of the teeth
has been made by numerous ophthalmologists. Acute pulpit is, peri-
ostitis and empyemia of the antrum highmori are stated to be the causes
of many eye complaints by Alexander, Keyser, Wacher, Lardin,
Birch-Hirschfeld and others. Pagenstecher and Vossius have also
reported numerous cases. Amongst other diseases of the eyes which
have their origin in defective teeth are changes in the optic nerves and
in the retina ; inflammation of the cornea and of the conjunctiva, or
of the whole eye-ball ; diminished sensitiveness in the apparatus for
accommodation and in the iris, affections of the muscles which move
the eye-ball and eyelids, diseases of the tear-glands and ducts. These
have been observed by Decaisne, Blank, Schmidt, Schulek, Wedl and
others. The manner in which these diseases are brought about must
be sought in the nerves and in the mucous lining of the mouth ; the
latter extends to the jaw from the ostium pharyngeum tubce. to the drum
of the ear, so that inflammatory processes in the mouth may also
extend their action for a considerable distance. Otitis media and the
related ascending neuralgia may also be due to diseases of the teeth,
according to Boke, Ziem and Winkler.
Greve 468 , in 1906, attributed the poisonous nature of the A -cements
to their irrational composition. He considered that the composition of
the silicate powder does not permit it to neutralise the cement acid,
and he attributed the dangerous irritation of the pulpa to an excess of
free acid. It has been shown that in the highly basic zinc phosphate
RELATIVE DIFFUSIBILITY OF A- AND 2-CEMENTS 235
cements (p. 221) the use of less acid will not avoid the danger, because
no separation of the base has occurred by the time the plastic mass is
placed in the cavity. Nevertheless, Greve's work is important because
he showed the value of bases for reducing the poisonous nature of A-
cements. The right way to destroy the poisonous nature of the silicate
cements is shown, both by theory and practical experience, to consist
in saturating the cement acid with a strong basis before the fluid
portion of the cement is mixed with the powder ; in other words, by the
conversion of -4-cements into 2-cements.
W. and D. Asch 469 , in 1908, published the results of some experi-
ments with a transparent 2-cement, i.e. with a silicate cement in which
the fluid portion consists of an acid-reacting salt solution. Use of this
cement in practical dentistry appears to be highly satisfactory : the
mass proved, in accordance with theory, to be perfectly harmless to
the pulpa. The practical experiences of Oppler 470 , Wege 471 , Schach-
tel 472 , Schreiber 473 , Baldus 474 , etc., with this cement have further
confirmed its absolute harmlessness.
Baldus has used this cement for more than a year, Wege and
Schreiber for several years. Schachtel has laid this cement on almost
translucent pulpae, which were very painful at the time of the opera-
tion, but after a long time no harmful symptoms could be observed.
Oppler has brought this cement into direct contact with the free pulpa,
yet though the patients were under observation for a long time, he
observed no irritating symptoms, a result which, according to Schreiber,
is incredible if A -cements are used.
Hence, practical experience is in full accord with theory in regard
to the absolute harmlessness of the 2-cements, just as both are agreed
as to the essential poisonous nature of the A -cements.
The 2-cements have, in their physiologico-chemical relations, other
advantages over the ^4-cements. It is open to argument whether an
excess of cement fluid diffuses more rapidly through the dental capil-
laries and into the pulpa more rapidly when it is in the form of a
solution of a salt or an acid. The facts established by Graham 740
afford valuable evidence in this connection. According to Graham, the
acids and acid salts diffuse more rapidly from a mixture of basic,
neutral and acid fluids than do the basic and neutral ones. The fluid
portions of the A -cements which are usually free, or practically free
aluminophosphoricjacids diffuse, cceteris paribus, more rapidly than the
2-cements, as the latter are usually saturated with bases. Should an
excess of the fluid portion of the S-cements eventually diffuse towards
the pulpa, it is by no means improbable that during this time it would
come into contact with cement powder and so would become fully
neutralised. In this way the slow diffusibility of fluid portions of the
2-cements is a great advantage, for physiologico-chemical purposes,
over the more readily diffusible portion of the A -cements.
When it is remembered that in the commercial 2-cements the fluid
is highly viscous, whilst in the ^4-cements the fluid is very mobile, it is
236 CONSEQUENCES OF THE H.P. THEORY
clear that, cceteris paribus, the Z-cement fluid must diffuse more slowly
than that of the A -cements, and therefore the former cements are
preferable to the latter.
XV
A New Theory of Glasses, Glazes,* and Porcelains
A definite part of the silicates known as glasses, glazes and porce-
lains are, without doubt, definite chemical compounds in the structure
of which hexites and pentites play an important part.
Some of the " glasses " are compounds of simple acids, others,
like most glazes and the porcelains, are, in so far as they are single
chemical compounds, complex acids or the corresponding salts.
Dumas 475 considered that glass has as definite a composition as
certain minerals or that it is a mixture of certain silicates ; the glasses
he examined corresponded to the formula Na 2 CaO 4SiO 2 , but,
as Berthier 476 has shown, a higher silica content in the glass makes it
harder and less fusible, whilst lime increases its resistance to chemical
influences ; Benrath 477 regards as " glasses " those silicates which
correspond to the general formula RO 2 Si0 2 . It is important to
observe that it was Benrath who showed that the most suitable
composition for all useful glasses (excluding optical ones) lies within
the limits of Na 2 CaO 6 Si0 2 and 5 Na 2 7 CaO 36 Si0 2 , in
which Na may be replaced by K and Ca by Pb. The occurrence of the
figure 6 and its multiples is highly significant.
Zulkowski 741 has studied the relationship between the chemical
composition and the physical properties of glass, and, for certain
specimens prepared by him, he suggests the following empirical
formula :
M' 2 M"0 6 Si0 2 ,
and the following structural formula :
/0-SiO-SiO-O-SiO-OM'
MX
X SiO SiO O SiO OM'
In this manner Zulkowski regards glasses as definite chemical
compounds. At the same time, he regards the refining stage in the
manufacture of glass as a chemical process and not, as is customary,
as a purely physical one in which the dross particles are separated on
account of their higher specific gravity.
That the 6 SiO 2 in the above formula plays an important part in
glasses is recognised by Zulkowski, and based on the investigations
of Schwarz, which showed that the resistance of glasses to the action
* Glazes are carefully prepared mixtures of minerals which are applied to articles
in order to impart a glossy surface or glaze, the covering material being melted into a
kind of glass by heating the article in a kiln or suitable oven. Opaque glazes are termed
enamels, but both words are used somewhat loosely.
THE CONSTITUTION OF GLASSES, ETC. 237
of 10 per cent, hydrochloric acid reaches a satisfactory value with
glasses of the character examined by Zulkowski. The investigations of
Stas and others have also shown that glasses only become resistant to
the action of water when their composition is in accordance with the
above formula.
It is also of interest to observe that Zulkowski has studied glasses
with 5 Si0 2 in the molecule to which he attributes an analogous
formula.
In reality, it is not the number 6, but a multiple of this number
which is essential, and glasses containing 36SiO 2 are particularly
important. Thus, the normal composition of glass is stated by
Fischer 742 to be :
5 Na 2 7 CaO 36 Si0 2 ,
5 K 2 7 CaO 36 SiO,,
5 K 2 7 PbO 36 Si0 2 .
Normal glasses of the following formulae have also been reported : 743
6 K 2 2 PbO 2 ZnO 2 BaO 36 Si0 2 ,
3 Na 2 3 K 2 3 PbO 3 CaO 36 Si0 2 ,
3 Na 2 3 K 2 6 PbO 36 Si0 2 .
It cannot be said that the three latter formulae represent the mini-
mum molecular weights, as formulae can be constructed from the same
data with less than 36 Si0 2 . Yet if the above formulae are regarded
as representing the minimum molecular weights, then glasses must
clearly have at least 36 molecules of Si0 2 in each glass molecule.
There are many people who believe that glasses are not single
chemical compounds, but mixtures or solid solutions. Zulkowski holds
the opposite view, and has drawn attention to the experiments of
Mylius and Foerster 744 , which show that glasses are not mixtures, but
true chemical compounds. Zulkowski regards glasses as acid di-
silicates, because he is not in a position to give a formula similar to
those suggested by the H.P. theory.
Of special interest is the composition of alabaster-glass, which,
according to Zulkowski, is not a double silicate, but a pure potassium
meta-silicate which belongs to the siliceous glasses. The composition
of this glass he represents by K 2 0, 8 Si0 2 . It is highly probable that
this glass has a molecular weight at least four times as large as corre-
sponds to the above, i.e. that the true formula contains 32 SiO 2 .
In addition to those glasses which may, possibly, be regarded
as simple silicates, there are the glazes and porcelains which may be
regarded as fused aluminosilicates or salts of other complex silicates,
such as salts of borosilicic acid. Zulkowski also considers that " on
fusing 4 SiO 2 , 2 B 2 O 3 with one molecule of CaC0 3 and one molecule
of soda, the product is not a glassy mixture, but a homogeneous
glass." He attributes to the material obtained in this manner a
structural formula analogous to that which he assigns to normal glass.
Assuming that the minimum weight of the chemical compounds
238 CONSEQUENCES OF THE H.P. THEORY
known as " glass " corresponds to a formula with 36 Si0 2 and that this
substance is an acid with the constitution
11
14 H a O 36 Si0 2 ,
in which the positions marked with a -f are either direct bonds between
the Si-hexites or are those to which dibasic or sesquioxide-forming
elements may be attached, by means of this constitutional formula
many hitherto puzzling properties of the " glasses " may be explained.
It should be observed that in this formula the maximum of
OH-groups is shown. A series of acids with fewer OH-groups is
theoretically possible ; from these a series of salts can be produced
as in the case of the complex acids.
The following lines deal with some properties of " glasses " which
are explicable by means of this theory :
1. Schott 478 has examined " best Thuringian glass " with a com-
position corresponding to
8 Na 2 K a O 4 CaO A1 2 O, 36 Si0 2
Calcd. 16.05 3.04 7.25 3.30 70.36
Found 16.01 3.38 7.24 3.00 69.02 (0.42 Fe 2 3 and 0.26 MgO)
in a threefold manner, viz :
(a) After two years' exposure to air,
(b) After heating to 100 C., and
(c) After heating to the softening point.
The glasses were carefully cleaned with water, alcohol and ether,
dried by prolonged standing over sulphuric acid, weighed before and
after treatment with water and finally after heating in an air bath at
150 C. The loss of weight was calculated to milligrammes per sq. cm.
Experiment I : Loss of weight in water 3-5 mg.
at 150 C. 0-8 mg.
After heating in water the glass appeared to be unchanged, but after
heating in an air bath the whole surface became covered with very fine
cracks, but no flakes were split off.
Experiment II : Loss of weight in water 2-5 mg.
at 150 C. 0-8 mg.
The cracks produced in the air bath were very fine and could scarcely
be seen with the naked eye.
Experiment III : Loss of weight in water 1-8 mg.
at 150 C. 0-6 mg.
In this case no cracks could be observed even with a lens.
THE CONSTITUTION OF GLASSES, ETC.
239
From the results of these experiments it follows that the constitu-
tion of the glasses tested must differ, and it should be specially noted
that heating this glass to its softening point had notably improved its
quality, as is shown by Experiment III. If it is assumed that the
dibasic elements and the sesquioxide are strongly bound, but that the
alkali-atoms are labile, the following isomers of the original formula
may be conceived ; these appear to confirm the three foregoing
experiments :
=Na,
=Na 2
=Ca
=Ca
=Na,
Na a Na a Na a
B.
Na a Na 3 Na a
II II II
K- X V S
Si I Si I Si
Ca=
Na a =
fa a Na a Na a
C.
It is very probable that, in Experiment III, the compound A is
formed, as this has a symmetrical distribution of the atoms in the
molecule which would account for its greater stability than the
compounds B and C.
It is here assumed that on storing or heating the glasses examined,
only the alkali-atoms change places, the dibasic and Al-atoms not
being affected. This assumption is justified by the fact, proved by
Weber, that very little depression* is shown by thermometer glasses
which contain potassium, but no sodium. If this depression is due to a
* When some kinds of glass are used in the manufacture of thermometers, these
instruments are found, in course of time, to indicate lower temperatures than they
should do. This is referred to as the "depression" of the thermometer; it is com-
monly understood to be due, in some way, to the chemical composition of the glass
employed.
240 CONSEQUENCES OF THE H.P. THEORY
rearrangement of the alkali-atoms within the molecule, those glasses
which contain sodium, but no potassium, should show no depression at
all. Experiments made by Schott 480 show that this is actually the
case.
Thus, glass w r hich contains unmixed alkali (i.e. a pure potash-lime
glass) when used for thermometers shows a much smaller error owing
to changes in volume than a glass containing mixed alkalies (i.e. con-
taining both potash and soda). Thus, a glass which contains unmixed
alkali 745 showed, after a given time, a depression of only 0-04, whilst
a glass containing mixed alkali had a tenfold depression, viz. 0.40.
It is a well-known fact that thermometers made of glass containing
both potash and soda are erroneous on account of this depression,
whilst those made of potash alone are quite satisfactory ; this was first
pointed out by Weber in a lecture before the Prussian Academy of
Science, in December, 1883.
2. It is a well-known fact that the behaviour of various kinds of
glass under the heat of a glass-blower's lamp varies greatly : one
kind of glass (window glass) turns matt and rough shortly after it has
become hot, whilst the glass made in the Thuringian Forest can with-
stand repeated heating and cooling, and may be blown into various
shapes and re-melted without showing any signs of physical change.
Schott's 481 experiments on Thuringian glass have shown that it has
the following composition :
8.25 Na 2 1.25 K 2 0.25 MgO 4.25 CaO A1 2 3 36 SiO,
Calcd. 16.21 3.72 0.37 7.54 3.23 68.93
Found 16.01 3.38 0.27 7.38 3.38 67.74
An analysis of the sand used in its manufacture showed :
SiO a A1 2 3 Fe 2 3 CaO MgO K 2 Na 2
91.38 3.66 0.47 0.31 Trace 2.99 0.50
Schott therefore assumed that this glass owes its valuable
properties to the alumina it contains, this being derived from the sand.
He has confirmed this by preparing various glasses synthetically from
pure quartz to which various quantities of alumina were added, and
found that the latter enabled the glass to be worked satisfactorily
in the blower's lamp whilst the former left much to be desired. The
value of alumina has also been confirmed on the large scale ; the
addition of felspar or alumina to a glass mixture invariably improved
the working qualities of the glass.
Seger 746 , also, made exact experiments on the action of alumina in
glass mixtures, and has shown that it increases the fusibility of the
mixture and that the tendency to de vitrify is reduced. Weber, in an
exhaustive treatise on " Depression Phenomena in Thermometers,"
has stated that alumina is highly important in the manufacture of
glass : it increases the fusibility and makes it easier to work.
Schott has also repeatedly observed that the tendency to crystallise
or devitrify, shown by many glasses with a high percentage of alkaline
THE CONSTITUTION OF GLASSES, ETC. 241
earths, may be diminished by the addition of alumina. This peculiar
property of small amounts of alumina (2% to 3%) is readily understood
in the light of the H.P. theory of the constitution of glasses ; it is due
to the bonding of the silicon hexites by the Al-atoms. Definite com-
plexes are formed and may be conveniently termed y-complexes.
The presence of very small proportions of one substance in another
has frequently a very marked effect on the latter. Thus, Marignac 484
has shown the enormous influence of 2 per cent, of silica in silico-
tungstates ; W. Asche 485 and Parmentier have shown the equal
importance of 2 per cent, of silica in the silico-molybdates, and it is
very probable that the small amounts of Ce 2 3 in the rare-earths used
for gas-mantles, 486 phosphoric acid in the blood, and carbon, tungsten
and other " impurities " in steel play a highly important part in the
characteristics of these substances.
3. Forster 482 and Kohlrausch 483 have independently proved
experimentally that glass is attacked by pure water more strongly
than by acids. Forster has also found that a given glass will lose the
same weight when treated with sulphuric, hydrochloric, nitric or acetic
acid, of either one-thousandth of the normal,* or ten times the normal
strength. With concentrated acids, Forster found the action to be
weaker than with more dilute ones.
This property may be explained in the light of the H.P. theory, as
follows : The water causes primary alkali to become separated from the
molecule, and this, to some extent, reacts in a secondary manner on the
hexite and partially converts it into pentite, as the authors of the
present volume have frequently observed in studying the complex
salts. With acids, on the contrary, only the acid-water reacts and
causes a partial separation of the alkali in the glass. This alkali is at
once neutralised by the acid and so is prevented from having any
secondary action. In this manner the more powerful action of water,
as compared with acids, may be explained.
4. The cause of the phenomenon known as " devitrification " was,
until quite recently, extremely puzzling and has not been ascertained
with certainty. For instance, Zulkowski considered that devitrifica-
tion is due to the presence of subsidiary silicates. Thus, a glass made
from a mixture corresponding to the formula :
9 Na 2 + 10 CaO + 60 SiO a ,
is stated by Zulkowski to be :
8 (CaO Na 2 6 SiO 2 ) + 2 (CaO 4 Si0 2 ) -f Na 2 4 Si0 2
True glass. Subsidiary silicates.
The glass is thus regarded by Zulkowski as composed of 8 molecules
of normal glass with 2 molecules of calcium tetra-silicate and 1 mole-
* "Normal acid " is of such a strength that 1 c.c. of it will exactly neutralise 0-040
gramme of NaOH or 0-053 gramme of Na 2 CO 3 , hence 1 c.c. of " one- thousandth normal "
or milli-normal acid will exactly neutralise 0-000040 gramme NaOH and 1 c.c. of " ten
times normal " acid will neutralise 0-400 gramme NaOH or the equivalent weight of
any other alkali.
242 CONSEQUENCES OF THE H.P. THEORY
cule of sodium tetra-silicate. These subsidiary silicates are, according
to Zulkowski, the cause of devitrification.
In the opinion of the authors of the H.P. theory, the experiments
of M. Groger 748 throw a special light on the subject of devitrification
and lead to the true causes of this phenomenon. Groger examined a
devitrified bottle glass made in the works of the Austrian Glasshiitten-
gesellschaft at Aiissig. It consisted of crystalline nodules which, on
fracture, were composed of radial fibres of a matt greenish-white tint.
In these nodules completely transparent, dark green masses are
embedded. Groger analysed both the transparent masses and the less
transparent devitrified portions and found that their chemical com-
position was identical and corresponded to the general formula :
2.5 R 2 O 4.5 RO A1 2 3 15 Si0 8 ,
0.25 K S 2.25 Na 2 O 0.25 MgO 3.5 CaO 0.5 MnO 0.25 FeO A1 2 0, 15 SiO,
Theory :
1.64 9.75 0.70 13.70 2.48 1.24 7.13 63.36
Found in devitrified portion :
1.52 9.76 0.61 13.38 2.49 1.39 7.73 63.79
Found in transparent portion :
1.45 9.78 0.73 12.81 2.47 1.39 7.42 64.39
In this manner Groger confirmed the statement of Pelouze that the
devitrified portions are of the same composition as the glass itself, and
also that of Benrath in which the errors in the view previously held, that
a devitrified glass is more siliceous than a normal glass, were exploded.
Groger also investigated the physical and chemical properties of
both portions in order to ascertain the cause of the devitrification.
He showed that the two portions differed considerably in both physical
and chemical properties. For instance, the transparent portion is
much more fusible than the devitrified portion.
Again, when treated with concentrated hydrochloric acid the
devitrified portion was almost dissolved completely, whilst the
transparent portion remained unattacked. From this, Groger con-
cluded that the devitrified portion consisted of two different substances
and endeavoured to separate them by digesting for twelve hours with
concentrated hydrochloric acid. Both portions the soluble and the
insoluble were analysed and conformed to the following formulae :
For the soluble portion :
10.25 RO 0.75 R a O 0.12 Si0 2 .
For the insoluble portion :
1.75 RO - 2.25 R,0 A1 2 3 12 Si0 2 .
These figures were deduced from the following data :
0.25 FeO 9.5 CaO 0.5 MgO 0.75 Na 2 12 SiO a
Theory 1.35 39.80 1.49 3.48 53.88
Found 1.16 39.30 1.33 3.57 52.89 0.27 MnO 0.36 K 2
THE CONSTITUTION OF GLASSES, ETC.
0.25 FeO 0.25 MnO CaO 0.25 MgO 2 Na 8 0.25 K,0 A1 2 0, 12 SiO,
Theory 1.67 1.65 5.20 0.92 11.53 2.18 9.48 67.37
Found 1.88 2.60 5.83 0.73 11.27 1.28 9.44 66.97
In the light of the H.P. theory, the devitrification of this mass is
readily explained. The clear portion consists of a perfectly stable
penta-compound which, in time, parts with a simple silicate and is
converted into a hexa-compound. Groger interpreted his results in a
similar manner and considers that the devitrification is due to an
unmixing of the glassy mass. In other words, devitrification is not a
molecular change, such as occurs when amorphous arsenic acid is
converted into the crystalline modification (Pelouze), but the con-
version of an unstable compound into a stable one by the separation of
a definite constituent. This conclusion agrees completely with the
interesting results obtained by O. Schott 749 in the microscopical
examination of numerous de vitrified products. Schott found that
de vitrified glasses contain crystals of wollastonite (calcium silicate),
and the existence of this substance as an integral part of devitrified
glass is shown in the above analysis.
As far back as the year 1900, Zulkowski 741 endeavoured to refer
the properties of glass to its chemical constitution and found that, at
that time, the only properties to which glass manufacturers and others
paid much attention were of an aesthetic nature, such as the shape of
the articles made, and the colour, transparency and light refractivity
power of the glass. The chemical properties of glass, i.e. its resistance
to weather, water and various chemicals, had scarcely been studied at
all, and Zulkowski very wisely pointed out that many articles of a
domestic or aesthetic nature, to say nothing of the innumerable
technical and optical articles made of glass, and those used in the
experimental sciences, require that glass should possess not only certain
physical properties, but the still more important chemical ones, and
yet the study of the latter has been almost entirely neglected.
Nevertheless, the chemical structure attributed to glass by Zul-
kowski does not sufficiently explain the various properties which have
been mentioned in the present chapter, whereas the H.P. theory does
explain them satisfactorily.
The Chemical Constitution of Coloured Glasses
Coloured glasses of the most varied tints may be prepared by
means of suitable preparations of copper, silver, gold and kon, and
attempts to learn the chemical constitution of these glasses have been
made by numerous chemists. Zulkowski, for instance, regards them
as mixtures of various silicates, one of which contains the colouring
244
CONSEQUENCES OF THE H.P. THEORY
oxide. Thus, according to him, the ferrous oxide in a glass is contained
in a silicate of the following formula :
/\
Si n O S n_i< /Fe or
Si n O
in 1
-ONaNaO
S Fe
>Si n 2n _i
The constitution of coloured glasses is of extreme importance, both
scientifically and artistically. The most widely adopted view is that
glasses are colloids and that the colouration is of a colloidal nature.
That the source of the colour of glasses is analogous to that of organic
compounds does not appear to have been suggested, and it is therefore
of great interest to consider it with the assistance of the H.P. theory.
When this is done the surprising conclusion is reached that coloured
glasses possess a structure analogous to that of the organic dye-stuffs
and that the colour of the glass is due to the chromophore groups and
salt-forming groups in accordance with the theory which Witt devised
for organic dye-stuffs.
Glasses do not belong to a single class, but, as their analyses
indicate, to several classes of compounds, some of which are simple
and others highly complex. This may be readily observed in the
following types of glasses :
8 R 2 6 RO 36 SiO,
A.
8 R 2 2 RO A1 2 S 36 SiO,
B.
4 R 2 RO 6 B 2 8 24 SiO,
C.
(3 R 2 7.5 B 2 8 6 SiO,) 2 etc,
D.
THE CONSTITUTION OF GLASSES, ETC. 245
In the positions marked -f not only acid groups, but also groups
of metallic oxides (in either -ous or -ic form) may enter. The intro-
duction of such acid or metallic oxide groups may conveniently be
termed central acidising or central metallising and the groups them-
selves may be termed centralisers.
All these centralisers have an important influence on the rings, as
will be shown later. At the moment, however, the metallic central-
isers are the most interesting, as they give to compounds containing
them the property of absorbing certain selected rays of light, i.e.
the metallic centralisers are excellent chromophores.
The structure of these chromophore groups may be explained as
follows : The positions marked + in the foregoing structural formulae
are supposed, for the moment, to be occupied by CuO. One of these
positions may then be represented by :
Si
/\
O
Cu
/\
O
V
Si
This group may lose oxygen and so be converted into the group
B.
246 CONSEQUENCES OF THE H.P. THEORY
On further reduction, group B forms the group :
Si-
O
Cu
Cu
O
Si
c.
Group C can also part with oxygen or copper.
Group B is the chromophore group which, on reduction, forms the
leuco-group C. The latter, on oxidation, again forms the chromophore
group B. If, during this re-oxidation, a little of the separated metal
remains unoxidised, a coloured glass will be obtained in which small
quantities of free metal occur simultaneously with the chromophore
group.
Decolouration by reduction and re-colouration by oxidation have
been repeatedly observed in organic dye-stuffs. It was first pointed
out by C. Grabe and C. Liebermann 750 , who found that all the coloured
organic compounds which they examined became colourless on
reduction. The reduction may cause the direct addition of hydrogen
without the loss of any element from the molecule, or it may be effected
by the simple removal of oxygen from the compound.
Besides the chromophore groups, the side-chains have also an
important influence on the colour. In coloured glasses these side-
chains are of a basic nature, and, in accordance with Witt's theory,
these glasses should be classified as " basic colours."
Witt's Theory. According to 0. N. Witt 751 , the colour of aromatic
compounds is due to the simultaneous presence of a colour group or
chromophore, and of a salt-forming group. The chromophore is more
active, i.e. it produces a stronger colour, when the dye is a salt than
when it is in the state of either a free acid or a free base.
In organic dyes and colours, the colour-substances must contain
chromophore centralisers such as are required for coloured silicates by
the H.P. theory. Such colour-substances are typified by some dyes
containing the so-called triphenylmethane group. The oxidation
products of the compounds :
/C,H 4 NH Z xC 6 H 4 NH 2
eCH 4 NH 2 C(OH)^C 8 H 4 NH 2
\C 6 H 4 NH 8 \C,H 3 (CH 8 ) NH,
Paraleucaniline. Rosaniline.
THE CONSTITUTION OF GLASSES, ETC.
and the substances
247
C 6 H 4 NH t
NH 2
I \C,H 4 NH HC1
and
/C,H 4 - NH,
C C,H 4 NH 2
\CeH,CH 8 - NH HC1
are basic dyes on account of the basic groups, though the materials
from which they are prepared paraleucaniline and rosaniline are
colourless. The structure of these colours may, according to the H.P.
theory, be written as follows :
NH,
NH,
These new structural formulae are in as complete agreement with
the properties of these substances as the ones generally seen in text-
books and have, in addition, the following advantages :
1. They show a complete analogy with the coloured glasses,
inasmuch as both the organic compounds and the glasses are shown to
contain chromophore centralisers ; in the former case, carbonic
centralisers.
2. As distinct from the usual structural formulae, the new ones
show definite symmetry, which makes the new formulae more probably
correct than the older ones.
3. The difficulties connected with difference in behaviour between
the central ring and the two others in the older formulae do not occur
in the new formulae, as in the latter the groups are arranged differently.
There are many other instances in which this difficulty, encountered
when the text-book formulae are used, is avoided by the employment
of the new formulae.
With the assistance of the H.P. theory in combination with that of
248 CONSEQUENCES OF THE H.P. THEORY
Witt, the possible existence of the following coloured glasses containing
copper may be predicted :
Type
A.
B.
C.
D.
E.
F.
G.
I.
8
8
8
8
8
8
8
R 2 0-
R 2 0-
R 2 O-
R 2 0-
R 2 0-
R 2 0-
R 2 0-
6 R'O
10 R'O
12 R'O
16 R'O
17 R'O
nR'O
nR'O
3 Cu 2
3 Cu 2
3 Cu 2
3 Cu 2 O
3 Cu 2
2 Cu 2
Cu 2
36 Si0 2
36 Si0 2
- 36 Si0 2
36 Si0 2
36 Si0 2
36 Si0 2
36 Si0 2
H. p(8 R 2 nR'O 36 Si0 2 ) + q(8 R 2 nR'O Cu 2 36 Si0 2 )
Type II.
A. 6 R 2 4 R'O Cu 2 B 2 3 36 SiO
B. p(6 R 2 O 4 R'O Cu 2 B 2 3 36 Si0 2 ) + q(6 R 2 4 R'O B 2 3
- 36 Si0 2 )
Type III.
A. 7 R 2 7 R'O Cu a O A1,O, 36 Si0 2 + 7 R 2 7 R'O A1 2 3
- 36 Si0 2 + Cu,
B. p(7 R 2 7 R'O Cu 2 A1 2 3 36 Si0 2 ) -f q(7 R,0 7 R'O A1 2 3
- 36 Si0 2 ) -f- rCu a , etc. etc.
These three types of glass must obviously differ in their properties.
The glasses in the first group are simple silicates, those in the second
group are the Gamma Complexes, in which the copper is more strongly
combined than in group I. In the third group the glasses are also
Gamma Complexes, in which free metallic copper occurs in addition to
the copper in combination.
[The existence of coloured glasses containing other metals in place of copper and
of a completely analogous constitution is equally possible.]
The H.F. Theory and the Facts
Only one glass in the first group mentioned above has yet been
prepared, namely Porpora,* which, according to Zulkowski 752 , corre-
sponds to the formula :
8 R 2 17 R'O - 3 Cu 2 36 Si0 2 .
* Porpora glass is defined as a glass which has a rusty red colour by reflected light
and a purple-blue colour by transmitted light, the colour being due to a small proportion
of copper added to the batch.
THE CONSTITUTION OF COLOURED GLASSES 249
The analysis of this glass when re-calculated, in accordance with
formulae suggested by the H.P. theory, is as follows :
6.25 Na,O 1.75 K,O 4.5 CaO 10.5 PbO IFeO 1 MnO 3Cu 2 O 36SiO 2
Theory 6.57 2.79 4.27 39.74 1.22 1.20 7-28 36.91
Found 6.31 2.60 4.31 39.06 1.29 1.50 7.89 35.80
Trace A1 2 3
Zulkowski has also analysed a glass belonging to the second group
and known commercially as Copper Ruby. This analysis corresponds
to the formula :
6 R 2 4 R'O 0.5 Cu 2 B 2 3 36 Si0 2
3.25 K,O 2.75Na,O O.SSnO 0.75MnO 1.75 PbO ICaO 0.5Cu,0 B,0, 36SiO f
Theory 9.10 5.07 1.99 1.59 11.62 1.67 2.12 2.08 64.76
Found 9.11 5.13 2.16 1.91 10.71 1.52 1.63 2.53 64.80
Traces of FeO A1 2 3 MgO
Zulkowski has also analysed aventurine, a glass belonging to the
third group. Part of the copper in aventurine glass is in the free state,
but if all the copper is considered to be in combination the analysis
corresponds to the formula :
7 R,0 7 R'O - Cu,0 Al.O, 36 SiO,
1.5 K,O 5.5Na,O O.SPbO 0.25 FeO 5CaO 1.25 MgO Cu,0 Al0 36SIO,
Theory 4.19 10.15 3.22 0.53 8.33 1.49 4.25 3.03 64.71
Found 4.46 10.22 3.07 0.68 8.74 1.57 4.90 2.16 64.52
The structural formulae of these glasses when arranged in accordance
with the H.P. theory are as follow :
Porpora glass
323
11 OL
Si I Si Si
Cu 2 Cu 2 Cu 2
I I
Si Si
Si
"\/\/\/"
II II II
333
250
CONSEQUENCES OF THE H.P. THEORY
Copper Ruby glass
I II I
Aventurine glass
Cu 2
II II
A large series of facts which have, hitherto, been inexplicable is in
complete agreement with these structural formulae. For example :
(a) On comparing the structure of the ruby glass with that of the
porpora, it is clear that the chromophore
>Si Cu 2 Si<'
in the ruby glass is in the first y-complex, whilst the corresponding
chromophore groups in the porpora glass are combined with a simple
polymerised silicate.
From the H.P. theory, a masking of the Cu 2 in copper ruby glass
may be predicted, i.e. this oxide will not be recognised by ordinary
tests so readily as it is in the porpora glass. This interesting conse-
quence of the theory is found to be in complete agreement with the
experimental evidence.
According to Rose and Hampe 753 , cuprous oxide and silver nitrate
react as follows :
3 Cu 2 O -f 6 AgN0 3 4- 3 H 2 = 2 Cu 2 H 3 N0 6 -j- 2 Cu(N0 8 ) a + 6 Ag.
Zulkowski 752 used this reaction in his studies of the copper ruby
and porpora glasses and found that whilst the porpora glass effected
a separation of metallic silver in accordance with the equation, the
copper ruby glass showed no such separation, even after many weeks.
(b) From the structural formulae of these three glasses it follows
that only the aventurine contains free metallic copper. The facts fully
confirm this consequence of the theory. For example, Wohler found
THE CONSTITUTION OF COLOURED GLASSES 251
that on placing this glass in a solution of mercuric chloride it became
white and copper entered into solution a clear sign of the presence of
metallic copper. It might, of course, be argued that cuprous oxide,
which is also present in aventurine glass, would produce the same
result, but this argument has been met by Zulkowski 752 , who treated
the powdered glass with an ammoniacal solution of copper. In the
presence of metallic copper the reaction with this solution would be
Cu + CuO = Cu 2 0,
and the solution must be decolourised. Zulkowski placed a weighed
quantity of finely powdered aventurine glass in a test tube and then
added an ammoniacal solution of copper sulphate in such an amount
that the metal in it was equal to one-quarter of the copper in the glass.
The tube was then sealed and heated on a water bath. After 15 hours
the deep blue colour of the solution was entirely discharged, thus
proving beyond all doubt that aventurine glass contains free copper.
Zulkowski has also shown by similar tests that porpora and copper
red glasses contain no free copper. In the case of porpora the colour
of the solution was not affected in the least nor was the tint of the glass
changed, even after three years. The test was not so prolonged with the
copper red glass, but even after several weeks the colour of the
solution was not changed in the least. These tests show beyond all
question that the porpora and copper red glasses contain no free
metallic copper, but that it is present in aventurine glass. They also
shatter the opinion, commonly held, that the colour of the two glasses
first named is due to their ability to dissolve metallic copper and re-
tain it in solution in its metallic state.
(c) The structural formulae of porpora, copper red and aventurine
glasses also show that the colour is due to a definite chromophore
group and not merely to dissolved cuprous oxide as is frequently
stated. The investigations made by Seger 754 on coloured cuprous
glasses are in full agreement with this consequence. This investigator
showed that an alternately reducing and oxidising atmosphere is
necessary in the production of these glasses, and that the difficulties
in manufacture were not so much due to the glass itself as to the correct
atmosphere in the furnace. Seger found that the same glass-mixture
would produce all shades, from black, through brown, to bright red or
yellowish green, and that different parts in the same melt would vary
enormously in colour, according to the nature of the gases which
entered the crucible ; that some melts would be of good colour whilst
others of the same batch would be quite devoid of red and would,
instead, be black or grey.
All these variations show that red glass must have a definite chemical
constitution, that it must contain certain chromophore groups, and not
be merely a solution of copper or cuprous oxide. Seger confirmed
this view when he added 1 percent, of cupric oxide to a glass correspond-
ing in composition to
3 Na 2 3 CaO 3 B 2 3 15 Si0 2 .
252
CONSEQUENCES OF THE H.P. THEORY
This mixture was placed in a porcelain crucible which was then placed
in a platinum one. The platinum crucible was fitted with a porcelain
lid through which protruded a porcelain tube of small bore. On
heating the crucible to 400 to 500 and passing a stream of hydrogen
or carbon monoxide through the tube, the copper oxide was reduced,
but the glass did not fuse ; it merely formed a red clinker. On raising
the temperature to 950 and continuing the stream of reducing gas, the
metallic copper previously formed disappeared, the particles dissolving
in the molten glass, and the colour of the glass changed from red to a
greenish grey. On powdering this grey glass and re-heating with
white glass to which a little oxidising agent, such as 1 per cent, iron
oxide, tin oxide or a sulphate like gypsum, had been added and sub-
stituting a stream of air for the former reducing gas, Seger obtained
a red glass.
He explained this phenomenon by supposing that the oxygen con-
verted the black metallic copper * into red cuprous oxide and the latter
gave the glass its red colour. Seger suggested the three following
equations as showing what occurred with different oxidants :
2 Cu + Fe 2 3 = Cu 2 + 2 FeO
2 Cu + Sn0 2 = Cu 2 + SnO
2 Cu + S0 3 = Cu 2 + S0 2 .
The correctness of the last equation is confirmed by the voluminous
development of gas during the fusion.
The red glass thus formed may clearly be represented by the
following formula :
B Si > Cu 2 < Si B
in which it is assumed that only a portion of the glass contains the
chromophore shown. Otherwise, the proportion of cuprous oxide would
have to be higher than that actually present.
The phenomena observed by Seger are in complete conformity
with the consequences of the application of the H.P. theory to coloured
glasses.
(d) It has, hitherto, been impossible to understand why coloured
glasses should contain such small quantities of free metallic con-
stituents. Not only can this fact now be explained, but it is a direct
consequence of the H.P. theory.
* Strictly, this is not metallic copper at all, but the leuco-compound or the reduced
leuco-compound (p. 246).
ARE GLASSES SOLID SOLUTIONS? 253
(e) According to the theory there is a definite maximum for the
metallic constituents to which the colour of glasses, etc., is due. This
maximum is not exceeded in the glasses mentioned on preceding pages,
and further investigations will only show that it must not be
exceeded.
It is highly probable that glasses containing silver and gold are
completely analogous to those containing copper, but to prove this it
will be necessary to re-calculate the analyses of these glasses and to
consider their characteristics and properties with the aid of the H.P.
theory.
In reviewing the German edition of the present work, C. Desch 736
urged that the use of " definite formulae " for glass and porcelain is
unjustifiable. This is not surprising, as Desch has so strongly com-
mitted himself to the view that cements, glasses and porcelains are
all " solid solutions." Of various theories, that one is most likely to be
correct which explains the most facts and permits the prediction of
the most properties, and on this basis the H.P. theory, like all
others, must be judged. The authors of the H.P. theory have never
suggested that the structural formulae they assign to various substances
are in any sense " final," and they readily admit that they must be
altered whenever other formulae which correspond with more proper-
ties are discovered. Meanwhile, the fact that, at present, they
explain more properties than any other formulae yet devised is a
sufficient reason for the formulae deduced from the H.P. theory.
Moreover, so far as the authors of this theory are aware, there is, at
present, no real ground for doubting the correctness of their conclusions.
On the other hand, what good does it do to assume that glasses are
mixtures or solid solutions ? Such a view, which is held by many
chemists, including all the chief critics of the H.P. theory, does not in
any way advance the cause of science, because it fails to explain more
than a very small proportion of the facts, whilst an enormously large
number of them are fully explicable in accordance with the H.P.
theory. Under these circumstances, is it too much to say that the
deductions from the H.P. theory approximate far more closely to the
true structure of the substances concerned than do the " mixture "
and " solid solution " hypotheses ?
It should be observed that in this volume the authors have made
no attempt to show that all commercial glazes, glasses and porcelains
are definite chemical individuals, though, without doubt, many of them
are such. In the following pages the analyses of a number of glasses,
glazes, and porcelains have been calculated into the molecular form,
those materials being selected which, on account of their excellent
physical and other properties, appeared likely to consist of definite
chemical compounds. This calculation of the formulae should prove
of value in the further study of these materials.
254
CONSEQUENCES OF THE H.P. THEORY
Formulae of Glasses, Glazes, and Porcelains
The following analyses of three Jena glasses are taken from
Hovestadt's book on the subject :
(a) Jena glass 3 III has the following composition :
3 Na 2 O 3 CaO 0.25 A1 2 3 0.75 B 2 3 12 Si0 2
Calcd. 16.07 14.52 2.20 4.53 62.67
Found 16 16 2 4 62
(b) Jena glass 6 III has the following composition :
3 Na 2 0.5 K 2 0.75 A1 2 3 0.25 B 2 8 15 SiO,
Calcd. 15.18 3.84 4.17 2.84 73.97
Found 15 5 5 2 73
(c) Jena glass 13 III has the folio whig composition :
1,5 K 2 2.5 ZnO B 2 O 3 10 Si0 2
Calcd. 13.86 19.91 6.86 59.37
Found 15 20 7 58
(d) The composition of a glass highly prized for champagne bottles,
analysed by Maumene 487 , is :
4 CaO 2 Na 2 - 0.25 K 2 0.25 A1 2 3 0.75 Fe 2 3 12 Si0 2
Calcd. 18.05 9.98 1.89 2.05 9.66 58.37
Found 18.60 9.90 1.80 2.10 8.90 58.40
According to F. Fischer 488 , the composition of the glaze ordinarily
used for porcelain corresponds to the formula :
RO 1 to 1.25 A1 2 O 3 10 to 12 Si0 2 .
The folio wing Tables have been calculated from various analyses of
porcelain and porcelain glazes published by Seger 489 .
I. Formulae of Porcelain Glazes
1
SiO, | TiO, | Al,0,
Perec
Fe,0
ntage o
CaO
I
MgO
K,0
NajO
H a O
Mole
E,O|E,O,
culea
EO,
H,0
Sources of glazes
1.
73.24
13.97
0.31
2.57
0.51
4.81
1.71
3.83
2.0
2
18
3.0
Berlin porcelain
glaze (old, prob-
ably of Dr. Eis-
ner's period).
2.
76.11
14.61
0.66
1.44
0.42
2.99
3.03
1.23
1.5
2
18
1.0
Pegmatite glaze
from L. Sazerat
in Limoges.
3.
74.99
14.80
0.37
1.09
0.36
4.31
3.49
0.65
2.0
2
17
0.5
Porcelain glaze
from Limoges
(per Held & Co.,
Mayence).
4.
64.96
12.74
0.80
8.78
1.95
2.30
9.19
3.5
2
17
8.0
Japanese porce-
lain glaze from
Arita. No. 2.
5.
61.97
12.92
0.39
9.59
4.17
1.12
9.91
3.5
2
16
8.5
Japanese porce-
lain glaze from
Arita. No. 1.
6.
64.88
1.39
14.33
1.39
10.09
1.55
5.61
4.5
2
15
Chinese celadon
(FeO)
glaze.
FORMULA OF PORCELAIN GLAZES
II. Formula of Porcelains 490
255
No
SiO,
Al,0,
Per
F ej 3
centage
MgO
of
K,0
Na a O
H 2 O
E 4 O
Mole
R.O,
culea
SiO a
H a O
Source of the Porcelains
1.
63.95
25.59
0.69
0.54
2.07
0.98
6.62
0.5
3
12
4.0
Soci6te anonyme de
Hal (Belgium).
2.
63.07
24.67
0.59
0.40
4.25
7.00
0.5
3
12
4.5
Berlin porcelain, 187 7
Alk.
3.
63.48
25.00
0.51
1.06
2.26
1.19
6.76
0.5
3
12
4.0
A. Hache & Pepin,
CaO
Schalleur, Vierzon.
4.
60.53
26.37
0.75
0.69
2.95
1.44
6.39
0.5
3
12
4.0
L. Sazerat, Limoges,
CaO
body for heavy
porcelain.
5.
60.42
26.47
0.52
1.37
2.75
1.60
7.19
1.0
3
12
5.0
L. Sazaret, Limogea,
CaO
ordinary body
6.
76.75
18.44
1.17
0.02
4.23
0.17
0.5
3
18
Japan IV, Biscuit of
CaO
egg-shell porcelain.
7.
71.31
19.74
0.73
0.17
4.04
0.1
4.01
1.0
3
18
3.0
Japanese Body II.
CaO
8.
71.60
18.71
1.19
4.16
0.18
4.68
1.0
3
18
4.0
Japanese Body III.
&org.
Subst.
9.
65.79
23.51
0.31
1.59
2.01
1.73
5.89
1.0
3
15
4.5
Guerin & Co. (Body
CaO
for figures).
10.
69.32
23.64
0.83
0.86
2.66
1.82
5.98
1.0
3
15
4.5
Guerin & Co. (su-
CaO
perior body).
11.
65.61
23.07
0.65
0.80
2.94
2.72
4.50
1.0
3
15
3.5
Guerin & Co.) (su-
CaO
perior body).
12.
66.00
22.59
0.36
1.68
2.71
1.80
5.59
1.0
3
15
4.0
Guerin & Co. (ordin-
CaO
ary body).
13.
64.52
22.07
0.97
2.10
1.35
3.13
5.60
1.0
3
15
4.0
J. Poyat, Limoges
CaO
(ordinary body).
14.
66.78
22.70
0.55
0.97
1.07
1.51
6.07
0.5
3
15
4.5
Carlsbad Body I.
CaO
15.
65.17
23.63
0.51
1.09
2.92
0.90
5.98
0.5
3
15
4.5
Carlsbad Body II.
CaO
16.
64.28
23.49
0.87
1.77
1.11
3.07
5.48
1.0
3
15
4.0
J. Poyat, Limoges
CaO
(superior body).
17.
66.97
20.92
0.64
2.06
2.75
0.41
5.43
1.0
3
16
4.0
A. Hache & Pepin
CaO
(superior body).
18.
52.94
28.91
0.48
3.99
1.7
0.68
9.12
2.0
6
18
10.0
Sevres, Body for
CaO
2.48
table-ware.
0.17
C0 2
MgO
19.
74.53
16.09
1.03
0.06
4.37
1.19
2.83
1.0
2
15
2.0
Japanese Body I.
CaO
0.25
MgO
,
From a study of the foregoing formulae it will be seen that there
is a great probability of the hexites or pentites playing an important
part in the structure of the substances under consideration.
XVI. The Eexite-Pentite Theory as a General Theory of Chemical
Compounds
The following facts make it appear probable that the new hexite-
pentite, or more briefly the H.P. theory, which originated in connection
with the aluminosilicates, is capable of application as a general theory
of chemical compounds.
256 CONSEQUENCES OF THE H.P. THEORY
A. The H.P. Theory and the Composition of the Metal-ammonias and the
Belated Compounds
The H.P. theory appears to be of special value with regard to the
constitution of the metal-ammonias and the related compounds. In
Gmelin-Kraut's " Handbuch " (1909. V, p. 337) a number of compounds
termed metal-ammonias are described, and from the empirical formulae
there given, the following may be selected as being likely to contain
hexite or pentite radicles :
[Co(NH 3 )J 2 Cl 4 (PtCl 6 ) J H 2 0, [Co(NH 3 ) 6 ] 2 (PtCl 6 )Cl 4 2 H 2 0,
[Co(NH,).][Cr(CN).], [Co(NH 3 ) 6 ][Fe(CN) 6 ) 3 [Co(NH 3 ) 6 ][Co(CN) 6 ],
[Co(NH 3 ) 5 ][Fe(CN) 6 ] - 1 J H 2 O, [Co(NH 3 ) 5 ][Co(CN 6 )],
[Co(NH 3 ) 5 N0 2 ] 3 [Co(N0 2 ) .] [Co(NH 3 ) 4 NO 2 ]S0 4 H 2 0,
[Co 2 2 (NH 3 ) 10 ](NH 3 ) 4 2 H 2 0, etc.
Of special interest are the compounds :
f /Co 2 NH(NH 3 ) 8 "| x
L\Co 2 NH(NH 3 ) 8 J A '
X = N0 3 , Br, a, etc.
Co 4 (NH 3 ) 10 (N0 2 ) 12 H 2 0, Co 4 (NH 3 ) 20 (N0 3 ) 10 ,
Co 4 (NH 3 ) 10 (N0 2 ) 12 H 2 0, Co 2 (NH 3 ) 10 (S0 4 ) 2 C0 3 4 H 2 0.
Also the compounds :
2 Na 2 Co 2 3 5 N 2 3 H 2 0,
3 Na 2 Co 2 3 6 N 2 3 H 2 0,
and the cobalt oxalates :
Na 3 (NH 4 ) 3 Co 2 (C 2 4 ), 7 H 2 0,
K 3 Na 3 Co 2 (C 2 4 ) 6 6H 2 0,
K 5 Na 19 Co 8 (C 2 4 ) 24 - 32 H 2 0, etc.
The hexites clearly play an important part in the following com-
plexes of nitric acid, prepared by Oppenheim 491 :
K 4 Ni(N0 2 ) 6 , K 2 BaNi(N0 2 ) 6 , K 2 SrNi(N0 2 ), K 2 CaNi(N0 2 ) 6 ,
K 2 PbNi(N0 2 ) and Ba 2 Ni(N0 2 ),,
from which it is impossible to substitute another metal for the Ni by
any of the ordinary methods of double decomposition.
The following penta-compounds :
K 3 Cu(N0 2 ) 5 , K 3 Zn(N0 2 ) 5 -6H 2 and K 3 Hg(N0 2 ) 5 H 2 0,
also prepared by Oppenheim, are interesting, inasmuch as they show
that three-fifths of the OH-groups in pentanitrites behave differently
from the others.
Hexites clearly occur, also, in the following compounds prepared
by Soenderop 492 :
2 (K 2 Co 2 Cy 12 )HgJ 2 , Hg 3 Co 2 Cy 12 K 6 Co 2 Cy 12 , Hg 3 Co 2 Cy 12 Na 6 Co 2 Cy lz ,
K 3 CoCy,, Na 3 CoCy 6 2 H 2 0, (NH 4 ),Co 2 Cy 12 H 2 0,
(NH 4 ) 6 Co 2 Cy 12 HgCy 2 H 2 0.
METAL-AMMONIAS AND RELATED COMPOUNDS 257
The hexites also play an important part in the yellow and red
ferrocyanides, K 4 Fe(CN 6 ) and K 3 Fe(CN 6 ) and in the double salts
FeCl 3 3 KC1, CdCl 2 4 KC1, etc. *
The number of compounds whose composition indicates the possi-
bility of hexites and pentites playing an important part is very large,
and all attempts to represent these atomically have hitherto proved
unsatisfactory. 493 For some of them, structural formulae have been
devised, as Erlenmeyer's 494 and Friedel's 495 formulae for the ferro-
cyanides ; Blomstrand's 496 formulae for ferrocyanides and metal-
ammonias ; Jorgensen's 497 formulae for the metal-ammonias and
Remsen's 498 for the double salts. Kohlschutter 499 has shown that the
defects in all these suggested formulae are due to their limited applic-
ability ; instead of a broad general principle, these formulae are only
related to special compounds, and it is not infrequently found that
they do not apply to apparently closely related compounds.
A. Werner 500 was one of the first to call attention to the repeated
occurrence of the number 6 in inorganic compounds and to utilise this
in the formulation of a theory of molecular compounds in which an
attempt was made to construct structural formulae.
[Werner discovered a remarkable series of optically active compounds of cobalt
and chromium, whose activity he traced, in this case, to the hexavalency of the elements
in question.
He regarded an element as possessing, in addition to its usual or " principal "
valencies, what he designated " auxiliary " valencies, i.e. a land of fractional valency
capable of effecting the union of otherwise independently acting molecules like NH 3
and H 2 O. For the present purpose it will be convenient to distinguish between these
two types of valency, though the manifestation of the latter is understood by Werner
to be independent of units, being variable within wide limits with the nature of the
atoms combined and the external physical conditions. Under the influence of both
principal and auxiliary valencies, the components of a complex molecular compound
arrange themselves into zones around the central element. The first zone comprises a
maximum of four or six univalent atoms or groups, this number going by the name of
" co-ordination number," and each additional component of the complex is relegated
to the second zone, where it takes upon itself certain peculiarities in behaviour, notably
that of mobility and consequent tendency to ionisation.
For instance, the structure of the well-known complex CoCl 2 6 NH 3 was formerly
written
Cl NH 3 NH 3 - NH 3 Co NH 3 NH 3 - NH 3 Cl,
a representation at once unwieldy and inadequate, though consistent with the then
prevalent ideas of valency. Werner, however, regards it as possessing the structure :
[
NH 3
NH 3 Co
NH 3
in which the ammonia molecules are united with the cobalt atom by auxiliary valencies
and comprise a first zone (usually marked by square brackets), whilst the two ionisable
chlorine atoms fall into a second. The six constituents of the first zone may be supposed
to be arranged symmetrically around the metallic atom, so as to be situated at the corners
of a regular octahedron (Fig. 4), the position of the chlorine atoms remaining undefined
by Werner.
Other groups than NH 3 may be included in the first zone, in which case it is easy
to see that isomerism becomes possible with compounds of the type
A ~l
Me
B *_
Xn
258
CONSEQUENCES OF THE H.P. THEORY
This hypothetical tetrahedral grouping permits the prediction of the possibility
of two isomers, whose space formulae are not superposable ; both such substances should
therefore be optically active. By submitting to resolution certain compounds of the
two types :
tA I" A 2 Co en 2 ~|
Co en. I and I
w
in which A or B represents Cl, Br, NH 3 , NO 2 , SCN or H 2 O and en=ethylene diamine
or two molecular radicles NH 3 , Werner obtained isomers with a very appreciable
rotation. In one isomer containing a single atom of cobalt, a specific rotation of 200
was obtained, whilst another with two cobalt atoms gave the very high value of 840.
Some of these compounds maintain their optical activity unchanged in solution
for several months, others exhibit a phenomenon akin to muta-rotation. The sub-
stitution of certain components of the complex by different groups sometimes produces
racemisation, whilst in others the activity is preserved. A few of these complexes give
a very considerable rotary dispersion. The peculiar feature about the chromium com-
pounds is that the value of the rotary power always lies about 150 below that of the
corresponding cobalt compound, indicating that the metal must play the master-role
in the production of the activity. In his book, "New Ideas on Inorganic Chemistry "
(translated by Hedley), Werner fully states the evidence in favour of his theory so far
as it could be produced at the time when his book was published.]
NH 3
FIG. 4.
Werner 501 states that : " If, in accordance with (his) proposed
structural formulae, the elementary atoms forming the molecules have
their valencies saturated, they must, nevertheless, have some un-
saturated valencies, as only in this way is it possible to explain how
the apparently saturated molecules can unite with each other to
form molecular compounds. It was formerly the general belief, and
even now this same view is largely held, that the structure of molecular
compounds is unprovable as they consist of the combination of the
molecules to form complexes quite apart from the relationship of the
atoms concerned. Recent discoveries have, however, shown that this
combination of molecule with molecule seldom, if ever, occurs, and
that, even in molecular compounds, the combination is really between
definite atoms. Hence, it is possible to devise structural formulae for
the so-called molecular compounds in the same manner as for the
valency compounds."
WATER OF CRYSTALLISATION 259
The difference between the valency compounds and the molecular
ones is due, according to Werner's co-ordination theory, to the valency
compounds being derived from compounds in which the chief valencies
are saturated, whilst the molecular compounds are formed by satura-
tion of minor valencies. According to this theory the molecular
compounds should be less stable than the valency compounds, yet this
is by no means always the case : a very large number of the so-called
molecular compounds being amongst the most stable substances known !
The representation of the constitution of the compounds under
consideration by means of the H.P. theory overcomes the difficulty
introduced by the use of major and minor valencies, as in Werner's
theory, as the H.P. theory is one of valency compounds and not of
molecular ones and is in full agreement with the high stability which
has been observed.
B. The H.P. Theory and the so-called "Water of Crystallisation"
The frequent occurrence of 6 and 5 H 2 O molecules in compounds
containing " water of crystallisation " suggests that this water may be
in the form of hexites or pentites and may thus form the foundation of
a theory to explain the occurrence of water of crystallisation.
The view that the H 2 0-molecules can form hexites and pentites
requires a higher valency for oxygen than that usually ascribed to it.
Various writers have shown that oxygen has, at times, a higher
valency than 2, and the physical properties of water confirm this.
Thomsen 502 has pointed out that the water molecules of salts often
separate in pairs at the same temperature, from which he concluded
that either the water molecules are arranged symmetrically about
the molecule of the salt or the molecular weight of water is double
that of steam. The latter view requires oxygen to have a valency
greater than 2.
A number of other investigations imply that water is capable of
becoming polymerised. Thus, Paternos' experiments 503 suggest that
the molecular weight of water in acetic acid is 18 or 36, according to
the solidifying temperature of the mixture. According to Eykmann 504 ,
water in paratoluidine has one-half, but in phenol the full normal
molecular pressure. Walker 505 has measured the heat of liquefaction
of ice in ethereal solution and concludes that the molecular weight of
water is 36. Ramsay and Aston 506 consider that water and some other
substances containing hydroxyl, such as alcohol, acids, etc., are
molecular aggregates when in a fluid condition.
[W. R. Bousfield and T. Martin Lowry 771 have advocated the view that liquid
water is a ternary mixture of " ice molecules," " water molecules," and " steam
molecules," these three varieties being perhaps identical with Sutherland's 772 " trihy-
drol." Armstrong 773 has added to this theory the conception of isomeric molecules,
of equal size, but different structure. Moreover, Tamman 774 has prepared at least
four polymeric forms of ice :
dihydrone" V) = OC with
H/ X H
260 CONSEQUENCES OF THE H.P. THEORY
H\ /OH
" hydronol " >O<
H/ X H
and BO forth. Such extensions as these have been found to be necessary, in order to
explain the experimental data that have been accumulated in recent years, and must
now be regarded as essential parts of the theory of the constitution of water.
Even steam, so long considered as a uniform material that could be represented
accurately by the much-beloved and greatly over- worked formula H 2 O, has been shown
by the careful measurements of Bose 776 to be a mixture of simple and polymerised
molecules, e.g.
H 4 O 2 2 H 2 O
the proportion of the substance in the simpler form being reckoned at 91 per cent, in
the neighbourhood of the boiling point.]
Kohlrausch and Heydweiller 507 and H. Ley 508 have found that the
electrolytic dissociation of water is greatly increased on raising the
temperature. The " acidity," which is very feeble at the ordinary
temperature, increases to such an extent that at 100 C. it is almost
equal in strength to that of phenol. This 509 is clearly shown in the
following Table, in which t is the temperature, d the degree of dissocia-
tion and K the affinity coefficient :
t d K
0.35 10- 7 0.12 10- 14
10 0.56 10- 7 0.31 10- 14
18 0.80 10- 7 0.64 10- 14
34 1.47 - 10- 7 2.20 10" 14
50 2.48 10- 7 6.20 10~ 14
The strength (K) of the water increases considerably in the interval
between and 50, and at 100 has a value at least a thousand times that
at zero. This enormous increase in the strength at higher temperatures
is explicable on the assumption that polymerisation occurs in the sense
of the H.P. theory.
Assuming that oxygen has a higher valency than 2 and that
water can form polymerisation products, the constitution of water-
hexite and water-pentite may be represented graphically by :
\/
6 H 2 5 H 2
which may be abbreviated to H or H or to A and -.
Such compounds may then be represented in more complex ones as
follows :
ii T ii
2 Si | Al | Si C
I 1 i I 1
9 H 2 3 A1 2 3 12 Si0 2 4 H 2 H.
WATER OF CRYSTALLISATION 261
The bonds between the rings in this aluminosilicate are loosened by
the manner in which the cyclic water (or water of crystallisation) is
attached, and the position and mode of attachment of the water of
crystallisation weakens or destroys the bonds between the base and
the remainder of the molecule.
The Theory and the Facts
I. Hydro-aluminosilicates
The structural formulae shown below may be derived from the
hydro-aluminosilicates given on page 105.
I II I
_/\/\/\_
Ill I i I
\/\/\_, ,__ /\/\/\_,
All Si | All |Al|Si|Al| or A1 Si Al
--\/\/\/ ' \/\/\/~' ~\/\
I II I I II I I II
H? 2 (A1 S A i Al) 4 H H H? 2 (Al Si Al) 4 H - 2 H
I Al Si Al| or
XV J >
HJ,(A1 Si Ai) 6 H
I II I I II I
.x\/\/\_, _/\/\/\.
|A1 Si All or I All Si All
II J_ |_
H 10 (Al-Sl- Al) -4H-H.
The position of the various water-rings implies (in agreement
with theory) that these aluminosilicates are readily decomposed by
acids. 510 A further study of these compounds must show that the
easily separable water the cyclic water must be attached with
varying degrees of strength.
II. Hydro-ferrosulphates
0. Kuntze 511 has studied the loss of water undergone by a mineral
of the composition
6 Fe,0 3 18 SO, 62 H,0
CONSEQUENCES OF THE H.P. THEORY
at different temperatures. If the results obtained by him are calculated
into formulae, they agree surprisingly well with the structural formula :
Fe
_ l
as may be seen from the following figures :
Calcd.
Found
40H 2
20.48%
21. 04% split off at 105 C.
8H 2
4.07%
fr.UO /o }, ,,
110
2H 2
1.030/0
0.790/0
130
8H 2
4.090/0
4,060/0
140
4H 2
2.050/0
2.38% ,, ,,
red heat
6 Fe 2 3
27.30%
26.86%
18 SO,
40.950/0
39.01%
A1 2 3 0.27%
Insoluble 1.79.
This shows that the water pentites are split off at 105, the weakly
bound "water of constitution" of the S0 3 side-chains at 110, the
more strongly bound " water of constitution " of the middle S0 3 -ring
at 130, the remainder of the " water of constitution " of the S0 3 side-
chains at 140, and the " water of constitution " of the iron-ring and
the remainder of the water of the middle S0 3 -ring at red heat.
III. The Water of Crystallisation in the Alums
In the light of the above theory of water of crystallisation, the
alums possess the following structural formula :
iiii
3 K 2 12 H 2 O 3 R 2 8 12 S0 3 10 H.
From this structural formula it follows that :
1. Five-sixths of the water (the hexite water) must be bound more
loosely than the rest.
2. The bond between the rings on the one part, and between the
rings and the base on the other, must increase with the amount of
water split off.
These consequences of the theory agree with the facts, as Van
Cleef 512 has shown that the gradual and steady loss of water molecules
which occurs in the alums when the heating is continued after five-
sixths of the total water have been removed, is very noticeable.
Recoura 513 and Whitney 514 have found that on heating chrome-alum
WATER OF CRYSTALLISATION IN ALUMS 263
at 1 10 to constant weight, a new alum with new properties is obtained.
This new compound is readily soluble in water, but, unlike the true
alums, is not precipitated by barium chloride, i.e. the new compounds
contain no S0 4 -ions ; the bond between the S0 3 and Cr 2 O 3 is strength-
ened by the loss of H.
Water-free chrome alum may clearly occur in two isomeric forms
as shown in the following structural formulae :
I til
S Cr
|s|"
\/~~
A.
Ortho compound.
It is interesting to note that the free acids of this chrome alum
have been prepared by both Recoura and Whitney.
A glance at the structural formulae of the compounds A and B
shows that these substances behave very differently in both chemical
and physical properties. The basic or H-atoms in the ortho-compound
are more easily separated than those in the para-compound. As a
matter of fact, the ortho-compound (the green modification) has a
measurable electrical conductivity, whilst the yellowish brown or para-
compound shows no such conductivity.
The lowering of the freezing point of the green acid (A compound)
is 0.24, that of the yellowish brown or B compound is 0.07. Accord-
ing to Whitney the green modification can be converted into the
yellowish brown one which, in aqueous solution, has the appearance
of absinthe. It gelatinises after a few days.
IV. The Water of Crystallisation of Chromo -Sulphuric Acids
According to the new theory of water of crystallisation enunciated
above, the two chromo-sulphuric acids studied by Recoura,* namely :
12 H 2 6 Cr 2 3 18 SO 3 96 H 2 (violet chromo-sulphuric acid) and
12 H 2 6 Cr 2 O 3 18 S0 3 36 H 2 O (green chromo-sulphuric acid)
must have the following structural formulae :
fl 1 V I fl II j jl j )l
<= /\/\/\/\/\ > == /\/\/\/\/\ ==
<= | S | Cr | S | Cr S ~ > J S | Cr | S | Cr | S | =
VVVVV VY x ii x j j
Violet Chromo-sulphuric acid. Green Chromo-sulphuric acid.
A. B.
* When chromic hydrate is dissolved in sulphuric acid the solution is at first green,
but after a while changes to violet and deposits violet-blue, regular octohedra to which
is ordinarily assigned the formula Cr 2 (SO 4 ) 3 15 H 2 O, the proportion of water being some-
what uncertain. In the corresponding salts, the green variety gradually changes to
violet at ordinary temperatures when in solution, but on boiling the violet changes
rapidly into the green variety. It is generally stated that the green variety does not
crystallise, and there is good reason to suppose that it is colloidal. A. B. S.
264 CONSEQUENCES OF THE H.P. THEORY
I ii
or
A glance at the structural formulae of the compounds A, B and C
will show that the A compound must be less stable than B and C as it
contains more water hexites. The Cr and S rings of the B and C
compounds must be more strongly bound than those in compound A .
This consequence of the theory is confirmed by the discovery of
Recoura, that the addition of barium chloride to the violet solution
produces an immediate precipitate, whilst the green solution, when
similarly treated, undergoes no apparent change.
The theory also explains the following behaviour of the green acid :
In the air it appears to remain unchanged for several years, but its
aqueous solution is very unstable and. on the addition of barium
chloride, only a weak precipitate forms even after an hour. In time, a
more labile bond is formed between the rings of the acid by the
addition of water hexites.
If the nature of the separation of the water hexites in the A
compound is compared with that of the ferrosulphuric acid, a definite
analogy is observed. Here, also, the water hexites in the chrome and
middle S0 3 -rings are more firmly bound than the water hexites in the
side S0 3 -rings.
On heating to 90, or more rapidly when boiled, the violet acid, or
A compound, forms a green solution the composition of which, as
Recoura's experiments have shown, has nothing in common with the
solid green acid.
The fact that the colour of a compound can be changed by the
addition of water to its molecule, closely agrees with the view that a
change of colour may occur in a dilute aqueous solution on account of
the combination of water hexites or pentites.
Recoura has studied the chemical reactions of the solution in a
thermo-chemical manner. If increasing amounts of sodium are added
to the green solution, the heat evolved on the addition of an amount
of sodium equivalent to one-sixth of the sulphuric acid of the sulphate
will be equal to the heat evolved when sodium combines with an acid,
whereas all other proportions of sodium evolve much less heat.
From this it follows that on boiling a compound of the type
S Cr S Cr S it is converted into the penta-compound S Cr S
Cr S with resulting separation of three molecules of sulphuric acid. On
treating the green sulphate S Cr - S Cr S with BaCl 2 a very stable
compound of the type S Cr Cr S is formed, as already noticed in
connection with other complexes, and according to Recoura only one-
fifth of the penta-acid is precipitated.
WATER OF CRYSTALLISATION IN ACIDS 265
If the mixture of green penta-acid is allowed to stand a long time,
the penta- is converted into the violet hexa-acid. The penta-acid has
not yet been prepared.
Whitney has tested Recoura's results by modern physio -chemical
methods and has fully confirmed them.
Attention may also be directed, in this connection, to the hydrates
of the cerium, praesodymium and neodymium sulphates studied
by Roelig 515 . For instance, a concentrated solution of cerium sulphate
at 25 forms the duodecihydrate Ce 2 (SO 4 ) 3 12 H 2 O ; between 30 and
40 C. the octohydrate Ce 2 (S0 4 ) 3 8 H 2 0, and at temperatures above 74
the pentahydrate Ce 2 (S0 4 ) 3 5 H 2 O.
The structural formulae of these acids, according to the H.P.
theory, are :
fi i ii i ii it i it i ii ii i ii i ii
"III SjOe| SJCeJ S |^ l!| S |Ce| S J OeJ S jjl I] S]Ce[SjCeJ SjII
I 1 I IJ I I] H I II I II II I II I II
"Duodecihydrate." "Octohydrate." "Pentahydrate."
That the bond between the rings and the base is weakened by the
addition of water radicles hexite and pentite is shown by the
following facts :
1. According to an article in the "Papierzeitung" 516 , two-thirds
of the acid in a saturated solution of aluminosulphuric acid (366 g.
aluminium sulphate per litre) may be neutralised with trinomial
caustic soda solution, a permanent precipitate being formed. If the
original solution is diluted ten times, only as much base is taken up as
will correspond to one- third of the sulphuric acid.
From this it follows that in a concentrated solution all the H-atoms
of the acid may be replaced by a base, but in a dilute solution only
half of these atoms can be so replaced.
The structural formula of the aluminosulphuric acid under con-
sideration is :
-AAAAA=
"| 8 I All S | All S |~~ *<!
\/\A/\/\/~~
H i it i H
In a concentrated solution, 24 OH-groups are replaced by OR', but
only 12 hydroxyls are replaced in a dilute solution.
2. Gittelson 517 has found that by treating concentrated cerium
solutions with concentrated phosphate solutions, salts are produced
such as
3 Na 2 - 6 Ce 2 8 - 6 P a 5 24 H a O,
but with dilute solutions of these substances free acids are produced.
266 CONSEQUENCES OF THE H.P. THEORY
C. The H.P. Theory and the Dissociation Theory of Arrhenius
It has been shown in the foregoing pages that the addition of
cyclic water affects the bond of the rings and the ions. On the addition
of water of crystallisation the bond between the rings is reduced and the
ionisation increased. This fact is of great value in formulating a new
theory of solutions. It leads to the " Dissociation Theory " of Ar-
rhenius and gives it a new experimental basis.
According to Nernst 518 , it is always questionable whether a mole-
cule in solution adds water molecules or not, as the Raoult and van't
Hoff methods give no definite results in this respect. Yet in view of the
strong disdynamic action of water there can be no doubt that the
dissociation of a solution of a salt on increasing dilution is accompanied
by the addition of water.
Hence the fundamental law of van't Hoff in regard to solutions
viz. that in highly dilute solutions substances assume a condition
similar to gases 519 appears in a new light. Van't Hoff first suggested
that the osmotic pressure of a solution (e.g. sugar in water) is as great
as the pressure produced by an equal quantity of the dissolved sub-
stance if the latter were in the form of a gas occupying the same
space as the solution. Yet no one had ever explained why dissolved
substances should behave in this manner and no reason was known as
to how the osmotic pressure was created. The authors' view (that
an addition of water molecules to the molecules of the substance in
solution occurs) indicates the existence of a definite attractive force
between the molecules dissociated by the water and the water outside
the semi-permeable membrane, and that that attractive force is the
cause of the osmotic pressure.
Numerous other facts may be equally easily explained in the light
of this new theory ; amongst others are the formation of hydrates in
solutions, 520 the presence of molecular aggregates in concentrated
solutions and their destruction on dilution, e.g. the dissociation of the
ether molecular aggregate (CH 3 O CH 3 ) n , the aggregate CH 3 CO
NH 2 in aqueous solution and several thermo-chemical phenomena.
The view that hydrates are formed in aqueous solutions is held by
a number of authorities, some of whom have supported their opinion
by experimental evidence, as : A. Werner 521 , Abegg and Bodlander 522 ,
Euler 523 , Hantzsch 524 , Lowry 525 , Tournier d'Albe 526 , Jones and his
associates 527 , V. Kohlschiitter 528 , Vaillant 529 , R. J. Caldwell 530 , H. E.
Armstrong and J. A. Watson 531 , E. H. Renni, A. J. Higgin and W. F.
Cooke 532 and others.
A. Werner 533 , as early as 1893, expressed his opinion that electro-
lytic dissociation is necessarily accompanied by the formation of a
compound with the solvent used. "According to the results shown
by our experiments," says Werner, " the existence of hydrates in
aqueous solution is not merely an inference from the hydrate theory ;
these hydrates form an essential condition of electrolytic dissociation.
THE DISSOCIATION THEORY OF ARRHENIUS 267
In an aqueous solution the ions are not metallic atoms, but
metallic atoms combined with six water molecules, the whole forming
definite radicles. This shows clearly why the electrical conductivity
and the dissociation of a salt are so closely related to the solvent."
Abegg and Bodlander suggested that a hydration of the anions and
cathions occurs. The degree of hydration of the alkali-ions increases in
the following order : K, Na, Li, etc. Feebly dissociating solvents are
those with feeble affinity for ions, and vice versa.
Euler also adopted the idea of a hydration of ions taking place in
aqueous solutions, and attributed to nickel, copper and cobalt ions
the formulae :
[Ni(H 2 0) 4 ]++, [Cu(H 2 0) 4 ]++and [Co(H 2 0) 6 ]++.
An acid in aqueous solution is, according to Hantzsch, a " hydronium-
salt." The ions of hydrochloric acid in aqueous solution are, according
to him :
HC1 + H 2 = [H 2 0, H]C1 = (H 3 0)+ + C1-.
This reaction is analogous to the formation of an ammonium salt from
an acid and ammonia :
HC1 + NH 3 = NH 3 HQ = (NH 4 )+ + C1-.
Lowry also regards the nature of electrolytic dissociation from
the point of view of a hydration theory.
Tournier d'Albe touched upon the problem of hydrated ions in his
work on the theory of electrons and expressed the opinion that each
molecule draws molecules of the solvent to itself and becomes hydrated.
According to the most recent results published by Jones and his
associates, the lowering of the freezing point of concentrated solutions
shows, beyond a doubt, that hydrates exist in solution. Vaillant has
definitely discovered the existence of hydrates in aqueous solution by
means of spectrometric investigations.
R. J. Caldwell has shown that the speed of inversion of raw sugar
by hydrochloric acid may be increased by the presence of various
chlorides. To explain this phenomenon Caldwell supposes the salt to
be hydrated in solution, a portion of the water thereby losing some
of its solvent power, and thus effects a " concentrated " action on the
sugar. To determine the " average hydration " of a given salt it is only
necessary to ascertain experimentally how much water may be added
to the salt solution in order to reduce the speed of reaction to its
original amount.
H. E. Armstrong and J. A. Watson investigated the action of salts
on the speed of hydrolysis of methyl acetate by nitric and hydrochloric
acids. They found that in most cases the presence of a salt increased
the speed and attributed this to the hydration of the salt.
E. H. Rennie, A. J. Higgin and F. W. Cooke examined the effect of
various nitrates on the speed of solution of copper in nitric acid, and
found that the presence of sodium nitrate, and particularly lithium
268 CONSEQUENCES OF THE H.P. THEORY
nitrate, caused a considerable increase in the rate of solution. Potas-
sium nitrate was without effect and calcium nitrate and rubidium
nitrate diminished the rate of solution. Beginning with the nitrate
possessing the greatest accelerative power the salts may be arranged
thus : Li, Na, K, Rb, Cs, which is the same order as Wymper found for
their action on the speed of inversion of cane sugar, and these authors
attributed it to the same cause, viz. the " concentrated action " which
these salts possess on account of their hydration. The same authorities
also conclude that the investigations mentioned form a further proof of
the combination of the solvent with the dissolved substance.
The experimental investigations of a number of other authorities
and the opinions expressed by them all point to the necessity of a
complete agreement between any theory of " water of crystallisation "
and any theory of " solution."
D. The H.P. Theory and the Constitution of Simple Acids
As the complex acids may be formed from simple ones, it must also
be possible to form cyclic compounds including those in which an acid
is not combined with other acids. A number of facts in support of
this application of the new theory of the simple acids may be men-
tioned :
1. Tammann 534 prepared the following salts of a hexa-phosphoric
acid :
K 2 Ag 4 (P0 3 )cH 2 0,
K 4 Ag 2 (P0 3 ) 6 ,
K 2 Na 4 (P0 3 ) 6 ,
K 4 Na 2 (P0 3 ) 6 ,
3[K 2 Sr 2 (P0 3 ) 6 ]4H 2 0,
Li 2 (NH 4 ) 4 (P0 3 ),8H 2 0,
Li 2 H 4 (P0 3 ) 6 4H 2 0,
Li 2 Na 4 (P0 3 ) 6 6H 2 0.
And the following from a penta-phosphoric acid :
(NH 4 )K 4 (P0 3 ) 5 *6H 2 0,
(NH 4 )Na 4 (P0 3 ) 5 ,
(NH 4 )Li 4 (P0 3 ) 5 ,
(NH 4 )K 4 (P0 3 ),
The following compounds, also prepared by Tammann, are also of
interest, and are clearly related to a di-, penta-, hexa-phosphoric acid :
Mg,Na 4 (PO,) 18 ,
Ca 6 Na 4 (P0 3 ) 16 ,
Mn 6 Na 4 (P0 3 )i,.
From the theory of the constitution of complex acids formulated
by the authors of the present volume, it follows that the hydroxyls of
the hexa- or penta-radicles are partly acido- and partly baso-philic,
i.e. the water they contain is not all bound to the radicles with the same
THE CONSTITUTION OF SIMPLE ACIDS 269
degree of force. This consequence of the theory also follows from the
physio-chemical investigations of the above acids by Tammann.
In the compounds
(a) K 2 Na 4 (P0 3 ).,
and
(b) Na 2 Na 4 (P0 3 ),
a positive current only removes one-third of the base.
By the prolonged action of AgN0 3 on K 6 (P0 3 ) 6 , Tammann was
able to replace two-thirds of the base by Ag.
The behaviour of the compound (NH 4 ) 5 (P0 3 ) 5 towards sodium and
potassium shows that one-fifth of the base in it behaves differently
from the remainder. The same is shown by the molecular conduc-
tivity of this ammonium salt and the conductivity of other salts
obtained from it, such as :
(NH 4 )(NH 4 ) 4 (P0 3 ) 6 ,
(NH 4 )Na 4 (P0 8 ) 6 ,
(NH 4 )Li 4 (PO,) 6 .
If the absolute speeds of the ions are calculated by Kohlrausch's
method (by the addition of the maximum values) the following maxima
are obtained :
(NH 4 )(NH 4 ) 4 (P0 3 ) 6 (NH 4 )Na 4 (P0 8 ) 8 (NH 4 )Li 4 (PO s ) 5
A. oo = 300 A co = 230 A co = 210
The maximum values actually found are for the ammonium salt 125,
for the ammonium-sodium salt 96, and for the ammonium-lithium
salt 90.
These figures can be most easily understood by assuming that
one-fifth of the base passes away in the form of cathions whilst the
remainder, with the acid, has the function of anions.
2. The hexitic structure of phosphoric acid in simple salts is
shown in the following compounds, prepared by Gluhmann 535 :
2 BaO 3 Na 2 3 P 2 5 11 H 2 0,
2 CaO 3 Na 2 3 P 2 5 6 H 2 O,
2 CuO 3 Na 2 3 P 2 5 12 H 2 0,
2 FeO 3 Na 2 3 P 2 5 12 H 2 0,
2 MnO 3 Na 2 O 3 P 2 O 5 12 H 2 O,
2 NiO 3 Na 2 O 3 P 2 O 5 24 H 2 0,
2 CoO 3 Na 2 3 P 2 O 5 24 H 2 O,
2 MgO 3 Na 2 O 3 P 2 O 5 12 H 2 0.
In these compounds two-fifths of the OH-groups clearly behave in
a manner different from the rest. Analogous compounds of niobic and
tantalic acid with a small proportion of base have been obtained by
Marignac 536 :
4 H 2 4 K 2 O 3 Nb 2 5 12 H 2 0,
Na 2 0-3K 2 -3Nb 2 5 * 9 H 2 0,
K 2 O -3Nb 2 5 - 5H 2 0,
4 K 2 3 Ta 2 5 16 H 2 0,
270 CONSEQUENCES OF THE H.P. THEORY
4
Na 2 O
3Ta
2 5 24
H 2 0,
4
Ag 2
3
Ta
2 5
3
H
A
4
BaO
3
Ta
2 5 -
6
H
.0,
4
MgO
3
Ta
2 5
9
H
.0,
4
HgO
3
Ta
2 5
5
H
,0.
3. The composition of the following compounds prepared by
Hallopeau 537 shows the presence of hexites and pentites in some simple
salts :
5 K 2 5 (NH 4 ) 2 24 W0 3 22 H 2 0,
3 (NH 4 ) 2 3 Na 2 O 16 W0 3 22 H 2 0,
4 (NH 4 ) 2 Na 2 12 W0 3 14 H 2 O,
2 Na 2 3 (NH 4 ) 2 O 12 W0 3 15 H 2 0,
3 (NH 4 ) 2 3 Na 2 12 W0 3 22 H 2 0,
5K 2 -^WO.-llH.O,
Na 2 10 W0 3 21 H 2 0, etc.
4. A number of oxygen-free salts have properties confirmatory of
a hexitic or pentitic structure. Thus, the formulae CsCl 4 I, RbClJ,
KC1 4 I, LiCl 4 I, etc., indicate the presence of pentite compounds. The
formulae KI 3 , CsBr 3 , CsClBr 2 , RbCl 2 I, etc., should probably be doubled
and are then characteristic of hexites. Bredig 538 has discovered that
in the compound KI 3 or, more correctly, K 2 I 6 the group I 6 behaves
like an independent ion, and is reminiscent of Tammann's investiga-
tions on the hexa- and penta-acids.
It is thus possible that free halogen acids, H 2 X 6 (X=C1, Br, I),
may exist. The great solubility of chlorine in highly concentrated
solutions of HC1 led Berthelot 539 to the conclusion that, under such
conditions, the compound HC1 3 or H 2 C1 6 is formed in a manner
analogous to the production of K 2 I 6 by the solution of iodine in
potassium oxide. That a chemical compound is formed in this manner
has been conclusively shown by the work of Le Blanc and Noyes.
. The H.P. Theory and the Carbon Compounds
It may appear to be somewhat late to attempt to apply the H.P.
theory to the carbon compounds in general, although the classical
researches of Berzelius, Liebig, Kolbe and others 540 were made by
men who sought for laws applicable to organic chemistry in those
which applied to inorganic compounds. Nevertheless, a few facts
may be pointed out which indicate that such an application of the
H.P. theory is not without value.
Just as the aluminosilicates are converted into kaolin and may be
produced from kaolin, so may the carbon compounds be converted
into carbonic acid or may be formed from it. For instance, it is well
known that plants take carbonic acid from the air and convert it into
oxalic acid and the various kinds of sugar ; from these the animal
fats and other complex organic compounds are formed. Oxalic acid
is also a common product of the oxidation of both simple and complex
CARBON COMPOUNDS 271
organic bodies. Thus, it is produced in varying amounts by suitably
treating various carbo-hydrates, fatty acids, oils and glycerin : all the
complex carbon compounds which can be oxidised by nitric acid.
Oxalic acid, like all inorganic acids, forms, according to Rosen-
heim 541 , complex acids with other inorganic acids, hexites or pen-
tites being produced under suitable conditions. A hexitic structure
of oxalic acid is also found in a series of other compounds as in the
cobalt oxalates mentioned on p. 256.
It is also important to note that carbonic acid can also form
complexes with phosphoric acid, these complexes playing a large part
in the formation of the bony framework of the animal organisms.
According to Hoppe-Seyler (vide Scheffs "Handbuch d. Zahnheilk."
1909, 1, 362) the compound 10 CaO C0 2 3 P 2 O is contained in the
dentine and enamel of natural teeth. To this basic carbo-phosphoric
calcium salt the following structural formula may be assigned :
Ca 3 Ca 3
P
v ,
II
Ca 3
NX
Ca 3
Thus, the chief constituent of dentine and of natural dental enamel
has a chemical constitution similar to the ^-complexes (p. 76), which
are, as a rule, more stable than the a-complexes. This view of the
structure of dentine and enamel makes it easier to understand the far
higher resistance of the latter to acids than is possessed by calcium
phosphate, and explains the strong combination of the carbonic acid
and lime in the dentine. Without some such structural formula these
properties are extremely puzzling.
When these facts, together with the figure 6 for the carbon
atoms in the general formulae for the sugars n(C 6 H 12 O 6 ) (n- 1)H 2 O
and the genetic relationship between oxalic acid and the sugars are
considered, the thought naturally arises that the transformation of
oxalic acid into sugar by plants may possibly be due to both oxalic acid
and the sugars possessing cyclic structures. In an analogous manner
it is possible to explain the constitution of the sugar-like product
obtained by Buttlerow 542 from formaldehyde and calcium hydroxide.
This, according to Loew 543 , is a single compound with the formula
C 6 H 12 O 6 ; E. Fischer and F. Passmore 544 regard it as a mixture of
various aldehydic or ketonic alcohols from which a-acrose may, in
all cases, be separated. This a-acrose is, according to E. Fischer,
closely related to the natural sugars.
A possible value of the H.P. theory may lie in its application to
the formation of sugars from carbonic acid, as the assimilation of
carbonic acid by plants is the chief reason for their existence as living
organisms. The smallest observation which will assist in revealing the
272 CONSEQUENCES OF THE H.P. THEORY
secret methods by which plants effect this transformation is therefore
of great importance.
Even if the existence of a large number of hexites and pentites in
some carbon compounds may be considered doubtful, yet their presence
in certain carbon compounds is highly probable. The latter, which are
termed aromatic compounds, are well known to be different from those
compounds which are in the form of open chains.
Kekule 545 was the first to regard the aromatic compounds as
derivatives of benzene. He conceived benzene as a closed ring of
carbon atoms, the structural formula he suggested being the well-known
hexagon which has been used so largely in the study of carbon com-
pounds. This was the first hexite to appear in chemical literature.
Not only the constitution of the direct derivatives of benzene, but
those of other substances more distantly related, such as napthaline,
anthracene, phenanthrene, fluorescine and many other hydrocarbons,
together with innumerable and important derivatives, have been
studied with most useful results by means of Kekule's theory and a
greater knowledge of them has thereby been obtained.
The characteristics of the organic (carbon) pentites were first
pointed out by V. Meyer 546 in his remarkable researches on thiophenes.
It is unnecessary to point out the great value of these beginnings
of the H.P. theory in the development of organic chemistry and
for industrial chemistry generally, for this is already well known. It
is sufficient to state that Kekule's benzene theory was the scientific
foundation on which the methods of study and production of the most
wonderful colours, valuable remedies, deadly poisons, pleasant scents,
important anaesthetics, etc., have been based.
Hexite and Pentites devoid of oxygen
The H.P. theory indicates that carbon and silicon can form hexa-
and penta-radicles which contain no oxygen. In this connection the
researches of Manchot and Kieser 722 are of interest. These investiga-
tors have shown experimentally the existence of ring-compounds of
silicon with chromium and aluminium, containing 6 Si-atoms. They
consider that the behaviour of the compound Cr 2 AlSi 3 towards HF
and the consequent evolution of hydrogen shows that the molecular
weight of this substance must be at least doubled and that the 6 Si-
atoms of the compound (Cr 2 AlSi 3 ) 2 are unquestionably united to each
other. These investigators are thus the first to establish beyond all
doubt the existence of hexa-silicon ring-compounds, and their work
is an interesting confirmation of the H.P. theory.
It is also interesting to observe that in those chromo-hexites which
are devoid of oxygen, one-third of the atoms behave differently from
the others (pp. 269 and 292).
The structure of these oxygen-free compounds may be made clear
by means of the following structural formula in which the Si-atoms are
THE ARCHID HYPOTHESIS 273
directly united to other Si-atoms and chromium atoms with other
chromium atoms, the Al-atoms being indicated by dots :
A/\/\ /\/\/\/\
SilCr Or I Si | or Cr Si Si | Cr |
\/\/\/\/ \/\/\/\/
Al 4 Cr 8 Si 12 Al 4 Cr 8 Si 12
According to the H.P. theory, the molecular weight of this com-
pound is at least twice as great as Manchot and Kieser concluded from
their experiments.
When reviewing the German edition of the present work, Manchot 755
declared that the H.P. theory could not be extended beyond the chemis-
try of the silicates, but apparently did not have the above-
mentioned experiments in his mind when he wrote : " That the com-
plete neglect of this portion of the chemistry of silicon may lead to
very erroneous conclusions in regard to the silicates, the reviewer 756
has shown on a previous occasion."
Manchot here refers to his criticism that Pukall's structural
formula for kaolin, which has a double bond between the two silicon
atoms (see page 111), is not in accordance with the behaviour of kaolin
towards hydrofluoric acid : substances with united silicon atoms must
evolve hydrogen when treated with HF, whereas kaolin does not.
It is very surprising that this critic instead of considering whether
the H.P. theory of the constitution of aluminosilicates might not throw
light on his own investigations, should accuse the authors of "a
negligence which may lead to very erroneous conclusions." It appears
that he has quite overlooked the support which his own investigations
lend to the very theory which he condemns !
F. The H.P. Theory and the Constitution of the Atoms
The Archid Hypothesis.
In recent years an ever-increasing number of people have main-
tained that the atoms do not completely fill the space they occupy, but
that they possess " parts." This view has long been held by those
engaged in spectrolytic investigations, many of whom hold that the
atoms slide over each other when emitting light ; some go so far as to
say that some spectrum phenomena indicate a decomposition of the
atoms. Some physicists even speak of the ' structure ' of the atoms 547
and consider that it is by no means impossible to obtain further know-
ledge as to the internal structure of atoms, the special arrangement of
their parts and the variations in the forces of these parts.
Those who are interested in the ionisation theory also speak of the
" constituents " of the atoms, and, as the result of electrical investiga-
tions of gases, they consider that the negative electrons are really
274 CONSEQUENCES OF THE H.P. THEORY
constituents of what chemists have hitherto regarded as atoms and
that these can be separated by electrical dissociation or ionisation with
expenditure of different amounts of energy.
The hypothesis that the atoms contain " parts " has been particu-
larly confirmed by the radio-activity of some elements discovered by
H. Becquerel. According to Curie 548 , Becquerel 549 , Rutherford and
Soddy 550 , Re 551 , Stark 552 and others, radio-activity is most satis-
factorily explained by assuming atomic transmutations, i.e. the
conversion of one atom into another or into several others.
The most recent investigations with regard to the chemical nature
of the elementary atoms thus make the old hypothesis of the elements
(which is the basis of alchemy) very probable. Moreover, it can
scarcely be denied that Nature has produced her materials in accord-
ance with unitary laws. It is, therefore, of interest to endeavour to
discover the mysterious formation of the atoms from the elements.
A Hypothesis of the Constitution of the Atoms
The smallest particles of an element may conveniently be termed
archids (apx*i) ; the atoms may then be regarded as formed of archids
in a manner analogous to that in which molecules are produced by the
combination of a number of atoms. From five or six archid groups,
archid-pentites and archid-hexites are produced respectively. Two or
more archid-hexites or pentites may also combine directly or by the aid
of other archids. In this manner a-, ft- and y- " archid-complexes "
are formed in a manner similar to the atomic complexes.
The archidic radicles, like the atomic compounds, have archidic
side-chains, and these limit the reactability of the archid compounds,
viz. the atoms.
The combination of the archids occurs in accordance with archidic
valencies, as in the formation of archid-hexite or -pentite, or of
archidic radicles (hexite and pentite) and the addition and formation
of archids as side-chains. These archidic valencies differ from the
atomic valencies inasmuch as they cannot be determined by any
existing methods. By the addition of long archid chains to the radicles
or by the combination of archidic radicles with one another by means
of archids with the simultaneous addition of long archidic chains, the
archidic valencies are weakened and some must be set free, though
these weak or free valencies cannot, at present, be definitely proved to
exist.
The liberation of archidic valencies is usually accompanied by the
evolution of electrical energy (radio-activity) and, after hundreds of
years, results in a decomposition of the atoms or a transformation of
them into one or more other atoms.
If the archids are represented by dots, the structure of the atoms
may be represented, according to the new hypothesis, as follows :
THE CONSTITUTION OF THE ATOMS 275
mm mm
L ' 11
A. m_._./'\._._m ./K./i\.
Ar A, Ar Ar Ar
| A, |
m
A. B. C.
m m m in m
II III
m ____ . ---- m ,.
I'ArVAr 2 I 2 ArV Ar Ar
I I
m m
E-o
r .
m m
I I
I I
/ *\ ,/*
Ar | | Ar
\ / \
\/ \/
G.
m
I
Ar Ar Ar
I I I
.A\.A\.A\.
|3 5|5 A 3^5 . 3?
!i ele ,j, 3. ___ m ', etc. etc.
I
m
H.
The lines between the points indicate the archid valencies ; the
symbols m, m/ and m /x on the side-chains show the atomic valencies.
Thus, the atom A is monovalent, B is divalent and E is octovalent.
The Consequences of the Archid Hypothesis and the Facts
(a) The Valencies of the Atoms.
According to the structural formulae, the valencies of each of the
atoms B, C and D must be of a similar kind, those of the atoms E, F,
G and H, on the contrary, must be different. In atoms with side-chains
276 CONSEQUENCES OF THE H.P. THEORY
like E the valencies m must have a nature different from the valencies
m' ; in atoms with side-chains like F there must be three different
kinds of valencies, viz. m, m' and m".
If, in atoms of the type F, the valency m is closed by treatment
at a high temperature, m' at a medium temperature, and m" only at a
lower temperature, these atoms would appear to have " variable "
valencies and to be mono-, tri- or penta-valent. To the various positions
of the side-chains in atoms of the F type may be due the possession of
electro-positive properties by the valencies m and m' and of electro-
negative properties by the m" valencies or vice versa. Atoms with
such side-chains can only unite with a definite number of electro-
positive or electro-negative atoms or atomic groups.
From the structural formula F it may also be seen that, if the
valencies m', m, m' and m" are saturated and that one m" side-chain
is unsaturated, the atom will be capable of transformation into the tri- or
penta-valent form, according to the power of the unsaturated valency.
If the valencies m', m, m' of the atom F are strong (i.e. if they are
only affected by treatment at a high temperature) whilst the valencies
m", m" are weak (i.e. only stable at low temperatures) the atom may be
said to have three major valencies and two minor ones.
Atoms with side-chains such as H, in which part of the valency is
only stable at low temperatures, may, in the light of this explanation,
possess four minor valencies and two major ones.
The minor valencies cease to exist at other than low temperatures,
in concentrated solutions and in substances in the solid state, so that
they are usually overlooked. The authors have already (p. 228) stated
that, according to Knoblauch and Nernst, spectrum analysis affords a
very delicate means of ascertaining the constancy or otherwise of the
constitution of a substance, as any change in the absorption spectrum
of a dissolved substance indicates a change in the constitution of the
latter.
Recently Hantzsch 553 has shown, as the result of a series of experi-
mental investigations, that all changes hi the spectrum effected by
dilution are due to chemical causes and that each change in the spectrum
indicates the progress of a chemical reaction. The delicacy of spectrum
analysis is so great that the minor valencies will probably be discovered
by its aid in many cases where they are, at present, unknown.
If, in atoms with four chief and two minor valencies (formula H),
only two or three of the major valencies m' are saturated, such atoms
will have the power of saturating other m' major valencies, whence
atoms in which three major valencies are saturated must be more
active in reaction than those in which only two major valencies are
saturated. The former must be better able to pass into the tetravalent
state than the latter, as the major valencies m' are not symmetrically
saturated.
These consequences of the archid hypothesis are in agreement with
the known facts and experimental results.
THE ARCHID HYPOTHESIS 277
In addition to atoms of constant valency, such as those of hydrogen,
the alkali metals, alkaline earth metals, etc., there are atoms with
variable valency such as those of N, As, Sb, P, Fe, Mn, etc.
For instance, in nitrogen atoms the side-chains are so arranged
that the five resultant valencies are of unequal strength ; three are
stronger than the rest. The compound NH 4 C1, for example, is unstable
at high temperatures and is decomposed in accordance with this
difference of valency-strength into NH 3 +HC1.
The reasons for the conclusions drawn from the structural formulae
just described are also confirmed by a study of nitrogen, as the atomic
valencies of one and the same atom have different properties, some
being electro-positive and others electro-negative. J. v. Braun 554 has
pointed out this property of nitrogen and, according to him, a penta-
valent nitrogen compound with several atoms or atomic groups is only
formed when the five radicles necessary are not of one and the same
chemical nature, but only when some possess electro-negative properties
(like atoms and atomic groups which can act like anions of acid, as
Cr, Br', I' CN', NO 2 ') and others have electro-positive properties (as
hydrogen, hydrocarbon residues and amido groups).
The correctness of this hypothesis is shown by the failure of all
attempts to produce compounds in which the above condition is not
satisfied, such as NC1 5 , N(C 2 H 5 ) 5 . In this connection a recently
discovered group of organic substances the porphyrexides is interest-
ing. These are tetravalent derivatives of nitrogen in which the nitrogen
shows a strong tendency to combine with hydrogen, and to pass into
the trivalent state. This tendency must necessarily be due to a
definite structure of the nitrogen atom.
Other atoms with variable valencies must also show an analogous
behaviour. Recently, carbon has been placed among those atoms
having a variable valency. The side-chains of some carbon atoms may
be regarded as occupying positions represented by formulae E (octo*
valent) and H (hexavalent) the carbon being then considered as
possessing four major and two minor valencies.
If only two or three of the four side-chains are saturated, un-
saturated compounds must be formed, as already explained, whence
those with three saturated valencies must have a stronger tendency
to be transformed into the tetravalent state than those with two
valencies. Gomberg 555 has obtained compounds with trivalent carbon,
and Nef 556 has prepared others with divalent carbon. In compounds
in which only two valencies are in use, the carbon shows a much less
tendency to pass into the trivalent state than in those in which three
carbon valencies are saturated. Thus, whilst triphenylmethyl
C(C 6 H5) 3 , which was first prepared by Gomberg, can only be isolated
with difficulty on account of its enormous power of reaction, compounds
containing divalent carbon may readily be produced. These latter are
powerful reagents, but are far less readily converted into compounds
in which the carbon has four valencies.
278 CONSEQUENCES OF THE H.P. THEORY
The view that carbon may have more than four valencies does not
agree with van't Hoff's hypothesis that the affinities of carbon act as
though they were the lines connecting the centre of a regular tetra-
hedron with the four corners. According to this hypothesis, the
carbon atom has a maximum of four valencies and no minor valencies.
This is, however, in direct opposition to the proved existence of minor
valencies apart from the four major valencies.
The physical isomeric properties of the " asymmetric " carbon
atom (i.e. the one to which four different atoms or atomic groups are
attached), such as optical isomerism, can be explained by means of the
new theory (p. 312 et sqq.).
Schafer's studies in connection with spectrum analysis 557 have
provided new data respecting the minor valencies of carbon and some
other atoms. Thus, striking colour-changes frequently indicate the
presence of minor valencies, but they are best shown by certain
organo-metallic compounds, particularly the complex salts investigated
by Ley. The fact that many compounds of the heavy metals absorb
normally whilst others vary greatly in this respect shows, according to
Ley, that the metal in the latter case must possess minor valencies as
well as the known major ones. The metal compounds of the amio acids
and ketone acid-esters are interesting in this connection.
Schafer thinks that a further proof of the existence of minor valen-
cies is to be found in the pantochromism discovered by Hantzsch 558 ,
i.e. the power of certain colourless salts or faintly tinted acids to com-
bine with various colourless metals and form all kinds of colours.
Similarly, Schafer considers that the presence of minor valencies
is the cause of chromotropy, whereby many coloured compounds
(chiefly yellow and red) may be produced from indifferent substances
such as nitraniline, quinine and salts of polynitro-compounds.
The fact that water, alcohol, organic acids and other oxygen
compounds have a greater molecular weight at lower temperatures
than when in the gaseous state may also be best explained by the
presence of minor valencies in the oxygen atoms.
A number of facts which seem to show that oxygen may have a
higher valency than 2 have already been mentioned on page 259.
Quite recently, observations have been made in connection with some
organic compounds which appear to indicate the existence of higher
valencies in oxygen. The most probable explanation is the presence of
minor or weaker valencies of the oxygen. Amongst others who have
written about the higher valency of oxygen more particularly about
its " tetravalency " are Collie and Tickle 559 , Baeyer and Villiger 500 ,
Werner 561 , Kehrmann 562 , Gomberg 563 , Walden 564 , Walker 565 , Sackur 566 ,
and Cohen 567 .
(b) Homologous Series of Atoms.
The monovalent pentites with the structural formula A (p. 275),
the divalent archid-hexite radicle B, etc., can combine with n new
THE ARCHID HYPOTHESIS 279
*
archid-hexites or pentites, or m archid-hexites and m' archid-pentites
analogously to the atomic compounds, whereby a whole series of mono-
valent or divalent atoms are produced, as these new atoms only
contain one or two side-chains. In this manner homologous series *
may be formed which bear some resemblance to the homologous
series in organic chemistry.
As there is a limit to the possible number of archid-hexites and
-pentites, the weight of the atoms (atomic weight) of each homologous
series must approach a definite limit.
Such homologous series of atoms are actually known, e.g. the
halogen series, the alkali metals, the alkaline earth metals, etc. If
these are arranged according to their atomic weights, the following
series are obtained :
F = 18.90 Cl = 35.18 Br = 79.36 I = 125.90
Na = 22.88 K = 38.68 Rb = 84.80 Cs = 132.00
Mg = 24.18 Ca = 39.80 Sr = 86.94 Ba = 136.40
The differences between successive members of each series are :
16.28 44.18 46.54
15.80 46.12 47.20
15.62 47.14 49.46
The difference between consecutive atomic weights is constant,
like that between members of other homologous series ; in this case it
is either 16 or 16x3.
(c) The Causes of Radio-activity and the work of the Alchemists.
The radio-activity of some elements with high atomic weights,
such as radium, uranium and thorium, is readily explicable in the light
of the new hypotheses regarding the structure of the atoms. Assum-
ing that these atoms have a structure analogous to that of the H-
atoms, previously mentioned, i.e. that they are definitely y-archid-
complexes, their radio-activity may be readily explained as being due
to their peculiar constitution. The property these atoms possess of
radiating electrical energy is due to their structure.
From this it follows that only atoms with high atomic weights can
be radio-active. This is actually the case.
The impossibility of increasing the radio-activity of the archid
combination by existing methods of treatment indicates that enormous
amounts of energy must be stored up in these compounds. Soddy 568
has published some interesting information on this point in a lecture
* When the members of a series of compounds are similar in constitution and
chemical properties, but with the physical properties undergoing a gradual and regular
variation as the molecular weight increases, the series is termed homologous, and the
several members are said to be homologues of one another. There are many homo-
logous series, especially among organic compounds. A. B. S.
280 CONSEQUENCES OF THE H.P. THEORY
on " The Present State of Radio- Activity," in which the following
words are particularly important :
" Radium evolves for every gram weight a hundred calories of heat
per hour, and since in a year only one thousandth part changes, it
follows that the total energy evolved in the complete disintegration
of a gram of radium must be enormous. It is roughly about a million
times that given out by a similar weight of coal burning. If the thirty
milligrams of radium exhibited were all to disintegrate suddenly, the
effect produced would equal the explosion of about a hundredweight of
dynamite. Uranium in its complete disintegration produced radium,
and hence the amount of energy evolved must be as much greater than
in the case of radium as the whole is greater than the part. If we could
artificially accelerate the rate at which radium or uranium disinte-
grates, we should on the one hand have achieved transmutation of a
heavier element into lighter ones, and on the other hand have rendered
available for use a new supply of energy a million times more powerful
than any source at present known. The argument I have already
stated shows that if we succeed in artificially transmuting uranium
there is little doubt that the same means would be applicable to the
other elements. Hence the supply of energy would be inexhaustible.
But let us see what the old attempt of the alchemist involved. When
he was concerned with building up a heavy element like gold from a
lighter like silver, he was attempting a most profitless task. Frankly,
even if it could be done, it would be impossible for it to pay. The
energy absorbed would cost far more than the value of the gold
produced. The energy of some hundreds of tons of coal would have to
be put into an ounce of silver to turn it into gold. Energy possesses a
market value no less than gold, as all who have to pay electricity bills
realise. So we may dismiss this case. But where he was attempting to
produce gold out of a heavier element like lead, the enterprise, if it
had succeeded at all, would have been successful beyond the dreams
of avarice. Not only would he have got the gold from lead, but also
a store of energy would have been released in the change of far more
intrinsic and commercial value than the gold. Not suspecting this,
perhaps it was providential for him that he failed, or he might have
realised the fate of the mythical chemist who discovered a new explo-
sive the secret of which never transpired because the chemist and his
laboratory disappeared simultaneously with the discovery. Actually, the
alchemist in trying with his puny appliances to transmute lead into
gold was attempting a task no less hopeless than that of a man attempt-
ing to destroy a battleship with a percussion cap. Even if sufficiently
potent means are ever to hand to effect the transmutation of lead
into gold, it is important to bear in mind that the gold would be a
mere by-product, the energy rendered available would be the real
gold-mine."
THE ARCHID HYPOTHESIS 281
(d) Radio-activity as a Constitutional Property of the Atoms.
As radio-activity is due, according to the new hypothesis, to the
structure of the atoms, it must also be quite independent of the
chemical combination of the radio-active atoms with atoms of other
kinds, as well as independent of the physical condition of the radio-
active material, and must be impossible to prepare radio-active atoms
artificially by either synthetical or analytical methods. The facts are
fully in agreement with this consequence of the theory.
(e) The Transmutation of the Atoms.
From the authors' hypothesis it follows that it must be possible
to convert one element A into another element B or to decompose one
" element " into others.
This consequence of the theory has been proved by Sir William
Ramsay's discovery that helium can be produced from radium and
radium from uranium.
Section IV
The Extension of the H.P. Theory into a Stereo-chemical Theory,
and the Combination of the latter with the Modern Theory of
the Structure of Crystals
(a) Critical Examination of Existing Stereo-chemical Theories
"VTEITHER the H.P. theory in the form in which it is presented on
JJi pages 30-38 nor any existing theories dealing with structural
chemistry can be regarded as satisfactory, as they do not take into
account the fact that the atoms are divisible.*
The weakness of existing theories of structural chemistry has long
been known and van't Hoff 569 was the first to suggest the importance of
representing molecules by spatial diagrams.
Le Bel 570 , quite independently, published a hypothesis concerning
the spatial structure of atoms, but it received only scant attention at
the time ; those who took the most interest in it were the very men who
endeavoured to disprove it experimentally.
J. Wislicenus 571 made both the above hypotheses the basis of a
new series of experimental investigations.
This theory of spatial structure, which also deals with asymmetric
* Although the word * ' atom ' ' really means " indivisible ' ' its present use in chemistry
may be conveniently retained, the word " archid " (p. 274) being used to indicate
the smaller constituents. A. B. S.
282 EXISTING STEREO-CHEMICAL THEORIES
carbon atoms, has been supported by numerous and important
results. It is also a noteworthy fact that all optically active organic
substances, so far as their constitution is known, contain one or more
asymmetric carbon atoms.
Similar speculations have proved very fruitful in the investigations
on the sugars carried out by E. Fischer 572 .
The work of Ad. Baeyer 573 on the isomerism of the hydrated
phthallic acids also deserves special attention in this connection.
In addition to these theories various cases of isomerism of the
nitrogen compounds have been examined in connection with their
spatial relationships. The investigations of Werner and Hantzsch 574 ,
Goldschmidt 575 and others are important in this respect.
E. v. Meyer 576 considers that the deductions from observations
have been pushed as far as or even farther than is strictly legitimate.
As he rightly remarks, 577 the greatest disadvantage of the existing
stereo-chemical theories * is that they are only applicable to special
cases and are not on a sufficiently broad basis. They form a convenient
means of explaining a number of cases of isomerism, but cannot be
applied to a general stereo-chemistry in the true sense of the words, to
show the relationship between crystalline form and chemical com-
position, or to explain the various optical, thermal, electrical and other
physical properties of crystals. These latter have been the subject of
investigations by a number of mineralogists, including Schrauf 578 ,
Fock 579 , Becke 580 and others.
Schrauf considers that the atoms have definite axial positions in the
molecules and that these form the basis of crystalline form. Schrauf 's
suggestions have not proved very fruitful and, according to Arzruni 581 ,
who has criticised them, the principles and methods adopted by
Schrauf are erroneous for this purpose.
Fock sought for a relationship between crystalline form and
chemical composition in a combination of the results of modern stereo-
chemistry and general crystallography. According to him, it is a
positive fact that the affinities of the atoms do not merely have a
definite value, but operate in a definite direction. " Crystallography
teaches that the existence of a crystal is due to its general properties
varying with the direction.
" The conception of direction is of different significance in the
formation of crystals and in the chaining of the atoms, and leads to
the thought that simple relationships may exist between the directions
of the crystals."
P. Groth 582 states : " Crystals are usually characterised in their
physical relationship by their being anisotropic, i.e. that none of their
properties vary in intensity with the direction of the crystal in
accordance with definite laws."
The simplest and most natural relationship which may be ascer-
* For further information on stereo -chemistry see No. 577 in Appendix.
FOCK'S AND BECKE'S THEORIES 283
tained from Fock's work is that the directions of the affinities in a
" crystal molecule " reach the same symmetry as that of the crystal
itself.
By " crystal molecule " Fock understands one of the molecules in
the crystal, which produces an aggregate from the chemical molecules.
The difference between a chemical molecule which may be in the
form of a gas or solution and a crystal molecule which is in a solid
state is shown, according to this writer, by the following facts :
1 . Fluid or dissolved substances are chemically active ; crystalline
substances are never so.
2. Bases, acids and salts in a fluid state are electrolytes, but lose
this property on crystallisation.
3. During crystallisation many substances take up " water of
crystallisation."
4. Some crystals are optically active, but this property seldom
remains when they are dissolved.
If the existence of large, independent atomic complexes in the
crystalline state crystal molecules is assumed, the foregoing relation-
ships are, according to Fock, capable of a simple explanation.
As Fock, in his stereo- chemical theory, knew of no plausible
hypothesis by means of which the minimum molecular weight in the
solid state could be explained, he could not bring his ideas correct
as they are to a proper conclusion, and his stereo theory has therefore
proved to be no more fruitful than that of Schrauf .
Whether a polymerisation of gas-molecules occurs when a gas passes
into the fluid state, depends on the number of chemical molecules in a
single crystal molecule. P. Groth 583 distinguishes between chemical
and crystal molecules and, according to him, there is a number of
facts which indicate that a crystal molecule is composed of a smaller or
larger number of chemical molecules. Crystals thus correspond to the
polymerised state as compared with the gaseous condition of single
chemical molecules. Groth calls attention to Voigt's experiments on
the elasticity of rock-salt, according to which the molecules of NaCl
have a slightly different action in different directions a behaviour
which is incompatible with the view that the crystal molecule of rock-
salt consists of one atom of chlorine and one atom of sodium.
Other writers, as S. Hunt, consider that calcite and quartz are
aggregates consisting of 584CaC0 3 and 948Si0 2 respectively. A. E.
Tutton considers that the molecular weight of the smallest crystals
(crystal molecules) is either identical with that of the chemical molecule
or that the crystal molecule does not consist of more than 1 to 5
chemical molecules. M. Bullouin concludes that crystal molecules
may contain 4 to 5 chemical molecules. M. Herz 757 is of the opinion
that the available experimental evidence is in favour of the existence
of substances with the same molecular weights in the solid as in the
gaseous state and of others which are polymerised.
Many attempts have been made to determine the molecular weights
284 EXISTING STEREO-CHEMICAL THEORIES
of substances in the solid state by J. L. Vogt 758 , Doelter and Vucnik 759 .
All these endeavoured to determine the molecular weight of fused
silicates by the aid of van't Hoff's formula :
m 0.0198 T*
In this formula m represents the total number of grammes of silicate
dissolved in 100 g. of the solvent, M the molecular weight of the silicate,
T the absolute temperature, q the latent heat of fusion for 1 g. of the
solvent and t the depression of the melting point. This method still
leaves undetermined the question as to whether the crystal molecule
has the same molecular weight as the substance in a fused or dissolved
state.
Vogt sought to determine the molecular weights of diopsite,
olivine and anorthite in this manner and concluded that they con-
formed to the following formulae :
CaO MgO 2 SiO 2 (Diopsite)
2 MgO - SiO, (Olivine)
CaO Al a O 3 2 SiO, (Anorthite) ;
in other words, that there is no aggregation of molecules in these
substances. These determinations of molecular weights have been
determined in the same manner by Doelter and M. Vucnik 759 , but
these investigators reached entirely different conclusions and were of
the opinion that the application of the van't Hoff formula to fused
silicates is not free from objection, on account of the few determinations
of q which have been made. The determinations of T are only reliable
between 20 and 30. It is not, therefore, surprising that Doelter and
Vucnik found that the results obtained by this method disagreed with
the formulae in eight cases out of nine.
Doelter has not expressed any doubt as to the solid silicates being
polymerised compounds, and he has, indeed, pointed out that if the
van't Hoff formula is retained the results obtained from it agree much
more closely with multiple than with single formulae. According
to Doelter, an extensive polymerisation occurs when aluminous
silicates pass into the solid state, as is shown by the great heat of
crystallisation.
Van't Hoff 761 has expressed the opinion that the solid state is not
characterised by the formation of a complex molecular structure, but
that in solid solutions the facts appear to show that the molecules are
of the simplest possible constitution and not greater than twice the
molecular weight ordinarily stated. This view is based on studies of
isomorphous mix-crystals which it is assumed are in the state of solid
solutions. Positive proof of the non-polymerisation of the molecules
in solid solutions has not yet been published ; on the contrary, many
facts are quite opposed to this view.
Becke 584 has criticised Fock's theory in a manner which demands
MOLECULAR WEIGHTS OF CRYSTALS 285
further investigation. According to him, in endeavouring to explain
what relationship exists between crystalline form and chemical com-
position, special attention must be paid to symmetry as this is the
most obvious factor common to both stereo-chemistry and crystallo-
graphy. In Fock's theory this is not the case.
Becke's 585 attempt to explain stereo-chemically the cause of the
hemihedrism * of calcspar and magnesite and of the tetrahedrism t
of dolomite and ankerite is of special value. He started with the
Bravais-Sohncke theory of crystalline structure, but instead of
extensionless points he imagines symmetrical, corporeal molecules or
molecular groups as forming a kind of lattice-work. Nevertheless,
F. Becke has only been able to apply his partially developed ideas to
a few cases, and as he has suggested no hypothesis to explain the mini-
mum molecular w r eight in the solid state, his ideas do not admit of
general application. According to L. Brauns 586 , the method adopted
by Becke in attempting to ascertain the relative position of the atoms
in space may result in representing symmetry in the form of a stereo-
chemical formula.
(b) The Modern Theory of Crystalline Structure and the Possibility of
its Combination with Structural Chemical Theories
The work of Fock and Becke in connection with the formulation of a
stereo-chemical theory would probably have been crowned with quite
different results if the leading structural chemical theories were in as
complete agreement with the available experimental material as is the
case with the H.P. theory, or if the existing stereo-chemical theories
had been placed on a broader basis. Hence it seemed worth while to
endeavour to convert the H.P. theory into a general stereo-chemical
theory and to combine it with the results of crystallography. This
would appear to be the best method of solving the problem as to the
relationship between crystalline form and chemical composition.
The fact that a series of physical properties of crystals shows a
definite arrangement in the smallest particles, has stimulated a number
of investigators such as Bravais 587 , Frankenheim 588 , and Sohncke 589 to
attempt to find the laws connecting the theoretical spatial relations of
observed crystalline forms to the corresponding symmetries.
If the limiting faces of crystals are conceived as lying in three
axes which meet in a point but are not in a single plane, the crystalline
forms of any substance may as is well known be expressed in terms
of the lengths of these axes and of the angles between them. It is
also supposed that the smallest particles of which crystals are com-
posed lie along the same axes in accordance with definite laws, thus
* Hemihedrism is the formation of half the number of faces possessed by the com-
plete forms of crystals of the same series.
t Tetrahedrism occurs when a crystal has only one quarter of the number of
faces possessed by the primary form.
286
THE STEREO-HEXITE-PENTITE THEORY
forming the various crystal forms. The generally accepted explanation
of crystalline structure originated in this manner.
If this theory of crystalline structure is to be combined with a
structural chemical theory, atoms or groups of atoms must, clearly,
be conceived in place of the formless points. These points then become
the centres of gravity of the various atoms or atomic groups. The
place in which these " points " are found is their average plane of
equilibrium, as the atoms and molecules are, as a result of their heat-
content, in a state of constant, oscillatory motion.
None of the ordinary structural chemical theories can be combined
in a simple manner with the general theory of crystalline structure.
This combination is possible, however, as soon as the H.P. theory is
extended into a stereo-chemical one.
(c) Stereo-hexites and Stereo-pentites. or a Stereo-chemical Theory
In a geometrical double pyramid of the form P :
C
the two bases of the pyramids are identical.
In this bi-pyramid P, CF is represented by (7, AD by A and BE by B,
the axes of which cut each other in 0. The lines OA, OB and OC are
represented by a, b and c and the angles COB, COD and BOD by a,
ft and y. The axes CF, AD and BE are termed chemical axes, the
ratio a : b : c is termed the " chemical parameter ratio " and the angles
a, /3 and y are termed the angles of the chemical axes.
In a given hexite, such as the compound 6 Si0 2 , the atomic groups
THE POSITION OF THE ATOMS IN SPACE
287
Si0 2 may be arranged at each of the six corners of the double pyramid
P. The valencies between the Si0 2 molecules are partly in the direc-
tion of the diagonals of the hexagon, i.e. in the direction of the chemical
axes, and partly in the direction of the edges of the double pyramid.
It is clear that in a hexagon only a portion of the possible valencies
can be represented :
C
B
E
D
F
If the atomic groups of a pentite radicle 5 Si0 2 are supposed to be
distributed in space, this must be doubled and a double pyramid P'
described in which the bases ABDE and A'B'D'E' do not coincide,
but are parallel to each other, though the distance between them is
infinitely small. At the corners of this pyramid (P'), which possess a
common chemical axis CF which cuts the other parallel chemical axes
AD, BE and A'D', B'E' in the points and O', the atomic groups of
two pentites are found.
The straight lines OA, O'A', and OB, O'B' are each respectively
288
THE STEREO-HEXITE-PENTITE THEORY
equal, and may be represented by a and b. The straight line OC is
equal to O'F and may be represented by c. The pentites thus have a
chemical parameter ratio a : b : c and the angles of their chemical axes
are analogous to those in the hexites a, /3 and y.
A compound of the composition 6A1 2 3 - 12Si0 2 may be repre-
sented diagrammatically by
| Si | Al | Al | Si
or
B
B
E
D B
E
F
i.e. the atomic groups in a molecule consisting of several hexites may
be conceived as analogous to those of a hexite divided in space. The
following facts should be observed :
1. All the atomic groups (A1 2 O 3 and Si0 2 ) marked C and F in the
compound in question are found on the axis CF, whereby each four
Al 2 O 3 -groups, as shown by the structural formula, must lie near to
each other, two pairs of SiO 2 -groups, on the contrary, are further apart
from each other.
2. All the atomic groups (A1 2 3 and SiO 2 ) marked A and D are on
the axis AD whereby the A1 2 O 3 - and SiO 2 -groups are situated precisely
the same as those on the axis CF.
3. The atomic groups marked B and E are distributed along the
axis BE in an analogous manner as in 1 and 2.
4. Each six atomic groups either Si0 2 or A1 2 O 3 of the com-
pound are bound by valency forces to their position in space, as is
shown by the structural formula : special valency forces between the
Si- and the Al-radicles are also in operation, as may be seen from the
structural formula. With such an arrangement in space of the hexite
units, it must clearly occur that the distances between the atoms of
the two Al-hexites and of the two Si-hexites in the compound are
unequal. Nevertheless, the difference in the distances between the
atoms or atomic groups of the various Al- and Si-hexites is so extremely
small that the different Al- and Si-hexites in the compound may be
regarded as fully analogous.
5. A study of the aluminosilicates and allied chemical compounds
shows that side-chains (basic, constitutional, water of crystallisation,
etc.) may be attached in the direction of the axes CF, AD and BE.
6. If atoms or atomic groups occur at the point O (Fig. P), i.e.
THE STRUCTURE OF CRYSTALS 289
in the point at which the three chemical axes cut each other, and are
combined by valency forces with two, or n, hexites or pentites, the
/#- and y-complexes are formed (pp. 76 and 241).
7. The chemical parameter ratio a : b : c and the size of the angles
a, /3 and y form the chemical constants and depend upon the size of the
valency forces between the atomic groups.
(d) The Hexite-Pentite Law
The valency forces between the hexite- and pentite-units and
the radicles themselves (the hexites and pentites) of various sub-
stances are very variable ; in many compounds they are so feeble
that the existence of the hexite-pentite law has naturally been over-
looked until the present.
It is highly probable that very many compounds (both simple and
complex) of widely different elements, such as carbon, silicon, alu-
minium, iron, chromium, manganese, the halogens, nitrogen, oxygen,
etc., exist in the form of hexites and pentites or in combinations of
these as has already been shown in the present work. This implies
that this arrangement of the atoms is neither a mere coincidence nor a
property of only a few substances, but of matter generally, and on this
the hexite-pentite law is based and has proved to be of great value in
stereo-chemistry .
The hexite and pentite form is not characteristic of only a few
compounds (aluminosilicates, silico-molybdates, metal-ammonias, etc.)
but of matter generally. Each chemical compound in the solid state
is composed of hexites or pentites or combinations of them, the atoms
or atomic groups being arranged in space in the manner indicated.
In this manner major and minor valencies occur.
(e) The Combination of the Stereo-Hexite-Pentite Theory and the Modem
Theory of the Structure of Crystals
The stereo-hexite-pentite theory mentioned above, and for the
sake of brevity termed the " S.H.P. theory," may easily be combined
with the theory of crystalline structure published by Bravais, Franken-
heim and Sohncke, by substituting the units of hexites and pentites
for the formless " points " in the latter theory.
Frankenheim 590 , in his theory of the structure of crystals, has
regarded these points as molecules from which the crystals form.
Sohncke 591 , in his theory of the atomic construction of matter, also
used the word " point " as meaning " molecule." Sohncke sought to
prove by a priori arguments that if the atomic construction of matter
is the cause of the structure of crystals, only the present known systems
of crystals can exist, no others being possible.
The hexite and pentite units are not equidistant from each other,
as different affinities exist between them, especially if the substance
under consideration is composed of units of different natures. The
290 CONSEQUENCES OF STEREO-HEXITE-PENTITE LAW
distances between the various units, and particularly the differences
in these distances, are so extremely small that they may be regarded as
equidistant. If it is assumed that all the " molecular lines " AD, BE
and CF, on which the hexite and pentite units are distributed, are in
parallel groups (i.e. all the AD lines are parallel to all the AB lines
and so on) and that the "molecular planes" ABDE and A'B'D'E'
are parallel to each other, the so-called " network " and " regular
system of points," i.e. the theory of crystalline structure, follows. 592
Limits of space prevent a more detailed description of the generally
accepted theory of the structure of crystals ; this can be obtained
from the published literature on the subject. It may, however, be
noted that this theory is generally accepted because it is in full agree-
ment with numerous properties of crystals. Thus it was found, as a
result of this theory, 593 that altogether 14 kinds of parallelopipedonal
arrangements are geometrically possible and that only seven classes of
crystals can exist which can be distinguished by their symmetry. This
result is in agreement with experience. The seven different arrange-
ments in space of the molecules show the same symmetrical ratios,
as the seven classes of crystals show in regard to cohesion.
It may be inferred a priori that, as this theory of crystalline
structure does not postulate any bonds (affinity forces) between the
units of the crystal, i.e. between the atoms or atomic groups, and pays
no regard to the nature of these units, it cannot explain many of the
constitutional properties of crystals. Thus, according to the " network
theory " all crystals which crystallise regularly must be optically
iso tropic, yet such crystals are known which are optically diaxial. i.e.
anisotropic. This theory also fails to explain other properties of
crystals which are probably of a constitutional nature, such as the
difference in behaviour of a crystal in two different positions such as
is shown by its solution and change of temperature under the action of
an electric current, and by the existence of two crystals built in
opposite ways and polarising circularly in opposite directions. Sohncke
endeavoured to explain this last property crystallographically by
means of new hypotheses.
As previously explained, it is possible to combine the stereo-hexite-
pentite theory with the modern theory of the structure of crystals. It
is by no means improbable that the weaknesses in the modern theory
of the structure of crystals may be overcome by its combination with
the S.H.P. theory. To ascertain this it is now necessary to see how
the facts agree with the S.H.P. theory.
(/) The Stereo-Hexite-Pentite Theory and the Facts
A. Di- and Poly-morphism and Hauy's Law
It follows from the theory that a given compound such as CaCOj
may exist in either the hexite or pentite form if it is in the solid state.
The minimum molecular weight of this substance when in the solid
DI- AND POLY-MORPHISM 291
state may therefore correspond to (CaC0 3 ) 6 or (CaC0 3 ) 10 , or if both
hexite and pentite radicles exist in the same molecule, other compounds,
such as (CaC0 3 ) 16 , (CaCO 3 ) 22 , etc., are possible. The actual existence
of simple acids and salts in the form of hexites and pentites has been
shown in a number of cases in the chapter on " The H.P. Theory and
the Constitution of Simple Acids " (p. 268). In the following formulae,
which may lead to a theoretical minimum of molecular weight, it will
be found that simple salts may consist of hexites and pentites and
their combinations :
In this connection the composition of the following borates 594 is
interesting :
Boronatrocalcite Na a O 2 CaO 5 B 2 3 12 H 8
Ascharite 6 MgO 3 B 2 3 2 H 2
Pandermite 2 CaO 3 B 2 O 3 3 H 2 O
Colemanite 2 CaO 3 B 2 3 5 H 2 O
Franklandite Na 2 CaO 3 B 2 3 7 H 8
Hydroboracite Mgo CaO 3 B 2 3 6 H 2 O
Larderellite 2 (NH 4 ) 2 8 B 2 O 3 8 H 2 O
Kaliborite K 2 O 4 MgO 11 B 2 3 12 H 2
The minimum molecular weight of some phosphates, arsenates and
vanadates may be found from the composition of the minerals of the
apatite group : 595
f9CaO-3P 2 5 -CaFl 2
Apatite ^ 9 CaO 3 P 2 O 5 CaCl 2
[9CaO-3P 2 5 -Ca(Cl,Fl) 2
Pyromorphite 9 PbO 3 P 2 5 CaCl a
Polyspharite 9 R"O 3 P 2 O 5 CaCl 2 (R"=Pb, Ca)
Mimetesite 9 PbO 3 As 2 O 5 PbCl 2
Kampylite 9 PbO 3 RjO, PbCl 2 (R V =P, As)
Vanadinite 9 PbO 3 V 2 6 - PbCl 2
Endlichite 9 PbO 3 Rj0 5 PbCl 2 (R v =As, Vd)
Hexites and pentites may also be formed from the molecules Si0 2 ,
TiO 2 , Zr0 2 , Fe 2 O 3 , A1 2 3 and from the atoms S, Se, P, C, etc. All
these substances, when in the form of hexites or pentites, have,
nevertheless, the empirical formulae Si0 2 , Ti0 2 , etc. Hence such
hexites and pentites must be distinguished from each other by means of
their crystalline form, hardness, specific gravity, behaviour towards
reagents, etc. In a certain sense it may be stated that the substances
CaCO 3 , Si0 2 , TiO 2 , etc. are di- or poly-morphous ; in reality they form
chemically different substances.
This consequence of the theory may be fully and completely proved
by the facts. From the large amount of published information
respecting polymorphous substances 596 the following may be quoted :
Calcium carbonate (" CaCO 3 ") : hexagonal-rhombohedric as calcite
(calcspar), 597 rhombic as aragonite. 598
Strontium carbonate (" SrC0 3 ") : dimorphous. 599
Silica (" Si0 2 ") : hexagonal-trapezohedric-tetratohedric as quartz,
292 CONSEQUENCES OF STEREO-HEXITE-PENTITE THEORY
hexagonal as a-tridymite, 601 rhombic as /3-tridymite. Von Lasaulx 602
and Schuster 603 have regarded /6-tridymite as triclinic ; Mallard 604 , on
the contrary, has shown that /3-tridymite crystallises rhombically and
Arzruni 605 and Groth 606 agree with him. Silica also crystallises regularly
as a-cristobalite 607 and tetragonally as jS-cristobalite. 608
. Titanic oxide (" Ti0 2 ") : tetragonal as rutile, 609 tetragonal as anas-
tase, 610 rhombic as brookite 611 or arkansite and as edisonite. 612 Haute-
feuille 613 has prepared anastase artificially at 860, brookite between
860 and 1000 and rutile at a higher temperature.
Svlphur (" S ") : rhombic, 614 a-monoclinic, 615 /3-monoclinic, 618
y-monoclinic (?), 617 hexagonal 618 and as "black sulphur." 619
Ferric Sulphide (" FeS 2 ") : regular pentagonal hemihedric as
pyrite, 620 rhombic as marcasite. 621
An interesting light is thrown by the S.H.P. theory on the cause of
the dimorphism of the compounds with the empirical formula FeS 2 .
These sulphides may be compared with oxygen compounds from
which the oxygen has been removed. For instance, the following
compounds, with the ratio B : S = 1 : 2 are theoretically possible :
(a) 1 J R"0 3 R 2 '"0, 15 SO,
(b) 3 R 2 '"0 3 12 SO,
(c) 3R"0 6 SO,
If the oxygen is struck out and Fe" is substituted for R" and Fe'" for
R'", the following compounds will be produced :
(a) 1 J Fe" 3 Fe/" 15 S = 7.5 FeS 2
(b) 3 Fe/" 12 S = 6 FeS 2
(c) 3 Fe" 6 S = 3 FeS 2
In other words, three different compounds with the empirical formula
FeS 2 are possible. In the first, one-fifth of the iron must be present
in the ferrous state, the remainder being ferric ; in the second all the
iron is in the ferric state, and in the third compound the whole of the
iron is in the ferrous state.
According to Brown 622 , only one-fifth of the iron in pyrite is in the
ferrous state, whilst in marcasite it is all in this state, i.e. the structural
formula a is that of pyrites, and c is that of marcasite. The b form of
FeS 2 is not, at present, known. Brown assigns to pyrite the following
improbable formula :
Fe
I I
F Fe Fe Fe
^\ /\ /\
S S S SS S S S
Other metals whose compounds occur in " ous " and " ic " states
such as cobalt, nickel, etc. must form analogous compounds with the
DI- AND POLY-MORPHISM 293
general formula RS 2 . In short, compounds with the general formula
RS 2 must be di- or poly-morphous.
This treatment of the sulphides leads to new ideas as to their
constitution, and it would be interesting, did space permit, to calculate
the formulae from the analyses of such compounds and to study their
properties in the light of this theory.
The simple elements Se, P, As, C, Sn, Zn, Fe, Ir, Pd, Ag, etc., occur
in various forms, as do also the compounds: (NH 4 ) 2 SiFl 6 , K 2 SnFl 8 ,
ZnS, HgS, FeS 2 , Ag 3 SbS 3} Fe 2 3 , Sb 2 O 3 , As 2 3 , NH 4 NO 3 , KN0 3 ,
LiN0 3 , Al 2 3 -Si0 2 , Na 2 0-Al 2 3 -3SiO 2 , Na 2 A1 2 3 4Si0 2 ,
K 2 A1 2 3 2 Si0 2 , CaO A1 2 3 2 SiO 2 , etc.
According to the S.H.P. theory each chemical compound in the
solid state must have its own definite a : b : c ratio and its own a, ft and
y angles ; i.e. it must have its own crystalline form. According to this
theory it is improbable that a single substance can change its crystal-
line form. This agrees in a remarkable way with the law stated by
the well-known mineralogist Hauy 623 in 1801, to the effect that " one
and the same substance, in a chemical sense, can occur in only one
form."
Berthollet 624 opposed Hauy's view and suggested that the forms of
crystals are accidental and are independent of their chemical com-
position. In support of this he referred to the two minerals aragonite
and calcite, which have both the same chemical composition (CaC0 3 ),
yet differ in crystalline form. Hauy next suggested that the difference
in the crystalline form of these two minerals might be due to the
presence of strontium in aragonite, though he failed to find strontium
in some aragonites, and was eventually obliged to abandon this
suggestion. In spite of opposition, Hauy refused to abandon his
" law " and maintained that the calcspar-aragonite problem must be
capable of some other explanation. Since 1821, however, Hauy's law
has been neglected on account of the discovery, in that year, by
Mitscherlich 625 of two forms of sodium phosphate H 2 NaP0 4 H 2 0.
Mitscherlich 626 held that any substance elementary or compound
can occur in two different crystalline forms. This view, which was
based on the occurrence of two sodium phosphates with the formula
H 2 NaPO 4 - H 2 O and of various elements in several forms, is clearly
incorrect, as de facto these are chemically different compounds, all
of which possess the same empirical formula.
It was only towards the close of the nineteenth century that a
number of investigators concluded that Hauy's law is correct. Thus,
Geuther 627 endeavoured to find the cause of the dimorphism of CaCO 3
in the existence of a " di-carbonic acid " H 4 C 2 6 and a " mono -carbonic
acid " H 2 C0 3 ; he assigned to calcite and aragonite the following
structural formulae :
Calcite.
294 CONSEQUENCES OF STEREO-HEXITE-PENTITE THEORY
nd "
Aragonite.
The credit for an explanation of di- or poly-morphism by means
of an assumption which agrees with the S.H.P. theory is due to
O. Lehmann 628 . This is based on numerous experiments. He concluded
that the chemical molecules within the physical molecule are combined
with each other even though loosely ; and that different modifications
of a polymeric substance are really different substances.
As the result of his experiments, Lehmann was led to a " re-
discovery " of Hauy's law which he stated in the following terms :
1. No substance has more than one crystalline form. If two
substances have different crystalline forms they are different substances
chemically, no matter whether they are atomic or molecular compounds.
2. No substance has more than one state of aggregation. The so-
called " three states " of aggregation of some substances really repre-
sent three chemically different substances.
B. Isomorphism in the light of the S.H.P. Theory
Substances which are chemically related and those having an
analogous constitution must clearly be related in their crystalline
form. Such a connection between the crystalline form and chemical
composition may be inferred from the S.H.P. theory, but its existence
was discovered as early as 1819 by Mitscherlich 629 . Whilst examining
phosphates and arsenates Mitscherlich observed that the salts of both
phosphoric and arsenic acids frequently have the same form ; he
concluded that the chemical and crystalline forms are interdependent
and proposed the term " isomorphism " for this phenomenon.
From the S.H.P. theory it also follows that isomorphous compounds
have similar, but not absolutely identical chemical and geometrical
constants (a : b : c and a, /3, y). As the geometrical constants depend
on the valency forces between the units and these vary with different
units, the geometrical constants of analogously constituted substances
which contain somewhat different constituents must clearly show
certain differences. Hence, if the substances have not precisely the
same composition they cannot be regarded as of identical crystalline
form even though they are apparently quite isomorphous. Groth 630
has shown that, with more accurate instruments, the angles of crystals
of isomorphous substances are found to be very nearly, but not abso-
lutely, equal to each other.
The isomorphism discovered by Mitscherlich was found to occur in
all mineral groups, and such minerals are therefore arranged into
groups of crystallographically related substances. Amongst the most
important of these are the widely distributed minerals of the felspar
group, which have a remarkable resemblance to each other in their
crystalline form and other physical characteristics. Schuster's 631
ISOMORPHISM 295
investigations have shown that in a large number of felspars (plagio-
clases) the optical properties show these substances to be capable of
arrangement in a definite series.
Under the name " tourmaline " are grouped a number of minerals
which, with the instruments available, appear to agree completely in
their crystalline form and are, therefore, regarded as isomorphous.
Mica, clintonite, etc., form similar groups. Chemists and mineralogists
have been very energetic in endeavouring to explain the isomorphism
of such minerals in terms of chemical structure, but so far they have
found no generally satisfactory solution to this problem. Thus,
Rammelsberg 632 , as early as 1850, pointed out a relationship between
the monoclinic orthoclase and the triclinic minerals albite, oligoclase,
labradorite and anorthite. According to him these minerals closely
resemble each other in their geometrical form and do not differ from
each other more than do other isomorphous substances. They also
show a great similarity in their physical properties, but chemically
they show such differences that " chemists consider that a separation
is essential." On another occasion Rammelsberg 633 pointed out the
similarity of the tourmalines crystallographically, though, according
to him, they are quite unrelated chemically. In his opinion, the
tourmalines consist of silicates of varying degrees of saturation which
are combined in different ways and yet are isomorphous, i.e. they are
of very similar form.
In order to explain the relationship between the crystalline form
and the chemical composition of minerals of the felspar group, Tscher-
mak assumed that the felspars were isomorphous mixtures of two
silicates albite and anorthite to which he gave the following formula :
Albite NaAlSiSi 2 8
Anorthite . . . .CaAlAlSi 2 8
All triclinic felspars are, according to Tschermak, simply mixtures
of albite and anorthite in all imaginable proportions, so that a con-
tinuous series is possible. Although this felspar theory has proved of
great value for the systematic study of analyses of the felspars, it has
been powerfully opposed from several sides. As a matter of fact,
there is always some K, Mg, and ferrous and ferric iron in felspars which
do not occur in the mixtures ; i.e the felspars cannot contain these
substances if they are simply mixtures of albite and anorthite. After
prolonged discussion, extending over some years, Tschermak's theory
is now accepted by most mineralogists, particularly since Schuster 634
has shown that the plagioclases may be made to form a series based on
their optical properties and that for each composition of the limiting
members there is a definite optical behaviour which is reminiscent of
either albite or anorthite. 635
As the miscibility of albite and anorthite which are not analogous
in their chemical composition appears plausible from a chemical
point of view, attempts have been made in other directions to find
296 CONSEQUENCES OF STEREO-HEXITE-PENTITE THEORY
structural formulae for the mixed members of the felspars albite and
anorthite so that they appear to have a chemical as well as a crystallo-
graphic relationship. For instance, Clarke 636 has suggested the follow-
ing formulae :
/[Si,OJ ss Na 8 /[Si0 4 ] = Ca Ca = [Si0 4 ] x
AlAsiaOe] 33 Al Alf-[Si0 4 ] = Al Al ^ [Si0 4 HAl
\[Si,0 8 ] ss Al \[SiO J 33 Al Al ss [SiO J/
Albite. Anorthite.
Here he clearly assumes the possibility of an isomorphous replace-
ment of the tetravalent groups (Si0 4 ) and (Si 3 8 ). Groth 637 , on the
contrary, suggests the folio whig formulae for the same substances :
Q . Q .
Si\ _Al/\Si = "NoAl 0-A1 =
\O/ \
o o \o
1/0 Na I /o Ca
S S Sl ^o
Albite. Anorthite.
Attempts have also been made to explain the relationship between
the crystalline form and the chemical composition of the tourmalines
on the assumption that hypothetical members of the series exist.
Jannasch 638 has given the following simple formula for the " isomor-
phous mixture series ' ' :
Si Si
O O 0\ /O O O O
R R R | RR R
This does not agree with all the ratios of Si0 2 : B 2 O 3 actually
found in tourmalines. Clarke 639 , on the contrary, assumes the following
hypothetical members for the tourmaline series which are analogously
constituted ; these approach more closely to the actual facts :
I. II.
/Si0 4 = R s /Si0 4 SB MgH
AU_Si0 4 ss Al Alf^iO 4 ss MgH
\Si0 4 = Al B0 2 \SiO 4 = Al B0 2
I I
Al B0 3 = NaH Al B0 3 = NaH
I I
/Si0 4 = Al B0 2 /SiO 4 = Al B0 2
Alf-Si0 4 33 Al Al^-Si0 4 = Al
\Si0 4 33 Al \Si0 4 33 Al
ISOMORPHISM
297
III.
/Si0 4 = MgH
Alf-Si0 4 = MgH
\Si0 4 = Al B0 2
Al B0 3 = NaH
/Si0 4 = Al B0 2
Al^-Si0 4 = MgH
\Si0 4 35 Al
IV.
/Si0 4 ss MgH
Si0 4 s= MgH
Si0 4 = Al B0 2
Al B0 3 = NaH
/Si0 4 = Al B0 2
Al^-Si0 4 = MgH
\Si0 4 3= MgH
It is interesting to see what is the genetic relationship between all
the members of the felspar groups, both crystallographically and
physically, in the light of the S.H.P. theory. The calculation of the
formulae of a large number of analyses of the felspar group (see
Appendix) shows that they may be regarded as salts of the following
acids :
I II
. /
<j3i R ! Si
I I
I I
\/\/\_
Si R Si Si | R Si
B.
C.
D. (a)
D. (6)
i.e. A. 8 H 2 O 5 A1 2 O 3 22 SiO 2
B. 7 H 2 O 5 A1 2 O 3 24 SiO 2
C. 9 H 2 6 A1 2 O 3 20 Si0 2
D. 12 H 2 6 A1 2 3 24 Si0 2
Two isomeric compounds D are shown ; isomers of the other
hydrates are clearly possible.
As has already been shown, each of these types can produce a
298 CONSEQUENCES OF STEREO-HEX ITE-PENTITE THEORY
whole series of hydrates. Strictly speaking, the formulated felspars of
these different types are salts of various hydrates.
The hydrates here mentioned are, in a certain sense, the maximal
hydrates of the felspars of these types, with a maximum proportion of
" water of constitution " or of acid hydroxyls.
From this representation of the structure of the felspars the
following inferences which are in agreement with previous experi-
ments may be drawn :
1. There is a genetic relationship between the various members of
the series, both physically and chemically, i.e. there is a similarity in
their crystallographic, optical (see Schuster) and other physical
properties.
2. The proportion of potassium, magnesium and iron (the last
named in various states of oxidation) in some felspars is appreciable.
3. The maximum proportion of base -f water of constitution in
some felspars is explicable ; e.g. the presence in salt 50 of the A type
of 6 MO - 2 H 2 O ; the presence of 7 MO 5 H 2 O in No. 145 of type D
and of 9 MO 3 H 2 in No. 146 of the same type (see Appendix).
4. These structural formulae also provide an explanation how it is
that if the content of base is divided as in formula a (C axis) a different
system will be produced than would occur if the base were in the
positions shown in b (i.e. nearer the A and B axes) ; i.e. the formation of
monoclinic and triclinic felspars may be readily understood. The
formula b is that relating to the triclinic felspars.
The general crystalline form of a large number of compounds, such
as those of type a, is explicable by means of their common kernel or
core.
Analogous relationships are also observable in the minerals of the
tourmaline group (see Appendix).
It is interesting to note that Retgers 640 had previously suggested
that the isomorphism of the members of various silicate groups may be
completely explained by means of a large, common kernel or core.
" If we regard them as containing such a molecular core, it is at once
clear that the secondary atoms may be regarded as chemically analo-
gous. No matter whether the molecules which adhere to the large core
are small, like H 2 0, CaO or NH 3 , or whether they contain 6 or 7
molecules aq., the chief fact is that the common core reveals itself
clearly in the crystalline form."
These opinions on the constitutions of the felspars, tourmalines,
etc., were not without influence, for even simple compounds of which
the analyses lead to simple formulae have been regarded by many
writers as though they were mixtures, i.e. as composed of substances
mixed in capricious proportions and not combined in stoichiometrical
quantities. Others have regarded substances as " isomorphous
mixtures " even when they have shown them to be composed in
definite stoichiometrical proportions. As an instance of this the
" mix-crystals " of sulphurous salts investigated by Fock 641 may be
ISOMORPHISM
299
mentioned, particularly the ammonium salts (NH 4 ) 2 S 2 5 1JH 2 0,
and the salts with the general formula R"O S 2 5 J H 2 (where
R"=Zn, Cd, Fe, Ni, Co and Mn) which Fock has examined crystallo-
graphically. In spite of the fact that these " mix-crystals " contain
their various constituents in stoichiometrical proportions, Fock
regarded them as " isomorphous mixtures."
The following salts were obtained by Fock :
I.
1.
4
(NH
4 ) 2
ZnO
5
S
2 o
5
2
4
(NH
4/ 2^-^
FeO
5
S
2 o
5
3.
4
(NH
4 ) 2
NiO
5
s
2 o
5
4
4
(NH
4 ) 2 O
CoO.
5
s
2 o
5
5.
4
(NH
4/ 2^-'
MnO
5
s
2 o
5
II.
6.
3
(NH
4 ) 2 O
2CdO
5
s
2 o
5
III.
7.
16
(NH
4/ 2^-^
6
FeO
22
s
2 o
5
IV.
8.
18
(NH 4 ) 2
4
ZnO
22
s
2 o
5
On re-calculating Fock's figures the following Table is obtained :
Compound
(NH 4 ),O
per cent.
HO
per cent.
(NH 4 ) 2 S 2
1J H Z
per cent.
BSjO,
1JH.O
per cent.
Total
Mol.-
ratio
NH 4 Zn-Salt
(a) Tabular crystals
18.47
6.39
79.19
19.90
99.09
4 1
18.64
6.44
79.93
20.07
100.00
(b) Prismatic crystals .
18.82
5.82
80.71
18.12
98.83
9 2
19.02
5.92
81.57
18.43
100.00
(NH 4 ) Cd-Salt . .
14.34
16.40
61.50
38.36
99.86
3 2
13.97
17.15
59.89
40.11
100.00
NH 4 Fe-Salt
(a) Crystal from the solution
16.81
8.12
72.09
27.43
99.52
8 3
1 FeO : 1 (NH 4 ) 2 O .
17.11
7.88
73.36
26.64
100.00
(b) Crystal from the solution
18.73
5.89
80.32
19.90
100.22
4 1
1 FeO : 4 (NH 4 ) 2 O .
18.77
5.77
80.51
19.49
100.00
NH 4 -Ni-Salt
18.64
5.74
79.94
18.86
99.00
4 1
18.73
5.97
80.34
19.66
100.00
NH 4 - Co-Salt ....
18.69
5.73
80.15
18.86
99.01
4 1
18.73
5.97
80.34
19.66
100.00
NH 4 -Mn-Salt ....
18.41
5.63
78.95
19.23
98.18
4 1
18.79
5.69
80.58
19.42
100.00
The molecular ratios shown above differ slightly from Fock's ; he
obtained a series corresponding chiefly to 4 (NH 4 ) 2 R"O 5 S 2 O 5 .
According to him the geometrical ratios of these salts are :
Compound
a : b : c
NH 4
Zn Salt
2.0597
1
.2042
90 52'
NH 4
Cd Salt
2.1299
1
.2263
90 49'
NH 4
Fe Salt
2.0564
1
.1907
90 51'
NH 4
Ni Salt
2.0643
1
.2077
90 56'
NH 4
Co Salt
2.0594
1
.2045
90 54'
NH 4
mi
Mn Salt
n
t
2.1289
1
:
1.2173
90 19'
5 1 A
These figures do not indicate " isomorphous mixtures," but
definite chemical compounds in which may clearly be seen the charac-
teristic which is so often observed in pentites, viz. that one-fifth of
the units behave differently from the remainder.
300 CONSEQUENCES OF STEREO-HEXITE-PENTITE THEORY
Rammelsberg 642 has also shown that the components of " iso-
morphous mixtures " have a relatively simple relationship to each
other ; from this he concluded that they must be regarded as molecular
compounds with a simple and rational molecular ratio.
The influence of Tschermak's theory of the constitution of some
felspars has been very great and some chemists and mineralogists have
even used it to explain the crystallographic relationship between the
members of a series of other complex silicates. In this way, the
minerals of the scapolite group with its end-members consisting of
mejonite Ca 4 AlaSi 6 2 5 and marialite Na 4 Al 3 Si 9 24 Cl ; 643 the amphibole
group with actinolite (Mg. Fe) 3 CaSi 4 Oi 2 and syntagmatite (R" 3 R'" 2 -
Si 3 12 ) 644 as end metals, the clintonite, mica, orthochlorite and other
groups have been regarded as isomorphous or morphotropic 645
mixtures. No one appears to have been troubled by the thought
that many of the so-called mix-crystals of this series are still un-
known.
Rammelsberg 646 sharply protested against this generalisation of
Tschermak's theory with which he did not agree, but he was unable to
convince many people of the truth of his protest. It is clear that, if the
Tschermak theory were correct, it would be of general application and
would not apply to merely a single group of minerals, 647 - 648 as is found
to be the case. The great difficulty in the way of accepting the theory
that these substances are isomorphous mixtures is to be found in some
facts which this theory cannot explain and which are in direct con-
tradiction to it. Thus, Retgers 649 endeavoured to produce mix-
crystals from the salts KH 2 P0 4 and NH 4 H 2 P0 4 , and according to this
theory he should have obtained an " unbroken series of mixtures."
As a matter of fact, he was only able to obtain " mixtures " containing
100 to 80 per cent, of potassium salt to to 20 per cent, of the ammonium
salt, and 20 to per cent, of the former to 80 to 100 per cent, of the
latter. He could not obtain any intermediate compound containing
75 to 25 per cent, of the potassium salt and 25 to 75 per cent, of the
ammonium salt. In endeavouring to prepare mix-crystals of KC10 3
and T1C10 3 the same investigator 650 again failed to obtain a continuous
series. The crystals produced contained either to 36-3 or 97*93 to 100
molecular per cents of the first salt. Between these limits of 36-3
and 97- 93 there was a gap of nearly 62 molecular per cents. H.
Schultze 651 in preparing mix-crystals of PbMo0 4 and PbCr0 4 has
found that these only unite in certain definite proportions.
Negative results have also been obtained by several other investi-
gators such as Wyrouboff 652 with (NH 4 ) 2 S0 4 and (NH 4 ) 2 Cr0 4 ,
Topsoe 653 with BeS0 4 4 H 2 O and BeSe0 4 - 4 H 2 0. No explanation
of these facts, which are in direct opposition to the theory of isomor-
phous mixed crystals, has yet been found. Yet these facts are not
merely explicable by, but are direct consequences of the H.P. theory
when the following are taken into consideration :
1. Tammann's chemical and physio-chemical investigations have
ISOMORPHISM 301
shown that, in accordance with the H.P. theory, the OH-groups in the
hydrates
/ /|!N \
I \X I
1 11
(a) (b) ^c)
3 H 2 3 P 2 6 5 H 2 5 P 2 5 5 H 2 8 P 2 O 6
behave differently ; in a J, in b i, and in c f behave differently from
the remainder (see pp. 268 and 269). For this reason Tammann was
only able to obtain from the hydrate a the salts Na 2 O 2 K 2 O 3 P 2 5
and K 2 2 Na 2 3 P 2 5 , and could not prepare J Na 2 2|- K 2
3 P 2 O 5 and & K 2 O 2 J Na 2 O - 3 P 2 5 in this manner.
Further, in these alkali-salts of the hydrate o, only J of the base
conducts positive electricity and K 4 (PO 3 ) 6 passes off as an anion.
In the compound (NH 4 ) 2 4 (NH 4 ) 2 O 5 P 2 O 5 , J of the base
behaves differently from the remainder (p. 269) both chemically and
physio-chemically. Thus, only of the (NH 4 ) 2 O can be replaced by a
base, the compounds (NH 4 ) 2 O 4R^O - 5P 2 O 5 (R'=Na, Li) being
formed ; only ^ of the base atoms conduct electricity. From the
composition 3 R"0 2 Na 2 O - 8 P 2 O 5 (R"=Mg, Ca, Mn) it may be
seen that in the hydrate c, f of the base behave differently from the
rest.
2. The minerals of the epidote group have the general formula :
2 H 2 8 CaO 6 R 2 "'0 3 12 Si0 2 (R"' = Al, Fe),
and the structural formula :
In the R-hexites, J of the R-atoms must clearly behave differently
from the others. As a matter of fact, the end-members of this mixed
series (see Appendix) are :
I I
''
Si Al Al Si
:J| i ii
2 H 2 8 CaO 5 A1 2 3 Fe 2 3 12 Si0 2
and
II
= | Si | Fe | Fe | Si |_
II I " II
2 H 2 8 CaO 4 Fe 2 3 2 A1 2 O 3 12 Si0 2
Members with 5.5 A1 2 3 0-5 Fe 2 O 3 or 5 Fe 2 3 A1 2 3 are unknown.
302 CONSEQUENCES OF STEREO-HEXITE-PENTITE THEORY
These facts lead to the conclusion that, in many cases, the pro-
duction of a continuous series of mixtures without any gaps is chemi-
cally impossible. In this way the experimental results obtained by
Retgers, Schultze, Wyrouboff, Topsoe and others may not only be
explained, but can actually be predicted from the H.P. theory. For
instance, Schultze's experiments on the production of mix-crystals from
PbMoO 4 and PbCrO 4 lead to the result shown in the following Table :
Constituents
Mol. %
Mols.
Mol. %
Mols.
Mol. %
Mols.
Crystalline
Colour
PbMoO 4 and
PbCrO 4
74
12
66
4
58
3
Y tetragonal
red
yellow
26
4
34
2
42
2
PbMoO 4 and
PbCrO 4
27
6
10
2
I monoclinic
73
16
90
18
Schultze thus obtained two series of salts which may be distinguished
by their crystalline form and colour, viz :
I.
II.
1.
2.
3.
4.
5.
16PbO
6PbO
5PbO
22PbO
20PbO
12 Mo0 3
4Mo0 3
3Mo0 3
6Mo0 3
2Mo0 3
4Cr0 8
2Cr0 3
2Cr0 3
16 CrO,
18 CrO,
The difference in the crystalline form and the colour of the crystals
obtained from a mixture of PbMo0 4 and PbCr0 4 can be explained.
These properties are closely related to the chemical constitution of
these substances : the tetragonal form and red colour are character-
istic of hexites and pentites in molybdenum compounds in which this
metal is partly replaced by Cr, and the monoclinic form and yellow
colour are natural to chromium hexites and pentites in which part of
the metal has been replaced by Mo. There is also another good reason
why Schultze could not obtain a continuous series of mixtures from
lead molybdate and chromate, viz. in Mo- and Cr-hexites and pentites
one portion of the atoms behaves differently from the others on substitu-
tion. This behaviour is clearly shown in the compounds obtained by
Schultze.
The present fashion for considering that " isomorphous mixtures "
are not chemical compounds is partly due to the influence of Ber-
th ollet 654 , who, starting with the idea that chemical reactions depend
on the masses present, reached the conclusion that in a compound
consisting of two or more atoms the extent to which the reaction
proceeds will depend on the number of atoms available, provided that
no special conditions interfere with the mass-action. 655 From this
conclusion, Berthollet argued that substances usually enter into
combination in variable quantities according to the conditions under
which the reaction occurs.
Proust opposed this view of Berthollet's and the difference between
ISOMORPHISM 303
them was eventually ended by the definite proof of the constancy of
the combinations. It appeared, however, as if Nature had produced
both " privileged " (combined in stoichiometrical proportions) and
"unprivileged" compounds (isomorphous mixtures which are not
combined in definite proportions and obey the mass-law of Berth ollet).
This is not the case ; on the contrary, Nature has formed all definite
compounds including the so-called " mixtures " according to one
and the same law.
The following observations, made by John Hunter, with regard
to the harmony and obedience to definite laws which are always found
in Nature are well worth quoting here :
" How often we stumble against what we think are irregularities in
Nature ! How often we fancy that the chain is broken just because we
cannot see each link in the chain and because the incompleteness of
our knowledge prevents our seeing the symmetry of the whole ! When-
ever it is given to a man to see harmony where previously only discord
was apparent, or to find a relationship where formerly it was only
guessed at but could not be proved, then, in my opinion, is it the
urgent duty of such an one to show the harmony he sees in natural
phenomena. He should do this for many reasons, not the least
important of which is that the discovery of such harmony gives us all
courage to tread the path of Truth. The discovery of new harmony,
however small, lifts for a moment the shadow which ordinarily over-
hangs the Truth and hides it from our gaze."
These golden words of so great a scientist often recur to the minds
of the authors of the present volume, when they realise that, at last,
it has been permitted to them to remove completely the artificial
division set up by Proust, more than a century ago, when he divided
matter into "combinations" and "dissolutions," the former including
definite chemical " compounds " and the latter molecular " combina-
tions " in which the proportions appeared to be so irregular as to be
the sport of chance, i.e. substances which do not appear to obey the
law of constant proportions.
Soon after Proust had set up this artificial division (i.e. his system-
atic classification of matter into compounds and " mixtures "), Ber-
thollet opposed it and asked the following pertinent questions :
"Wherein shall we seek the reason why the ' compounds ' are formed
by the uniting of their constituents in constant proportions, whilst in
4 combinations ' the ratios are variable and apparently due to
chance ? Is the force which effects the union of a metal with sulphur
or oxygen different from that which forms more complex substances
out of these simpler compounds ? "
From the nature of these two questions it is clear that Berthollet
was fully convinced of the essential unity of the natural law involved.
There is an old philosophical dictum natura nonfacit saltum, quoted by
Darwin in introducing his Theory of Descent, in respect of the Harmony
which pervades the Cosmos, about which Newton wrote in so illumin-
S04 CONSEQUENCES OF STEREO-HEXITE-PENTITE THEORY
ating a manner, and regarded by Berthollet, in his classical " Essai de
statique chimie," as applying with equal truth to the world of atoms.
This idea was so firmly fixed in the mind of Berthollet that he did not
hesitate to oppose Proust's dualistic conception and to insist on the
unity of the force of chemical attraction. At the same time, it is only
fair to state that Proust himself recognised something of the truth in
Berthollet's contention when he wrote : " I do not wish to press this
matter unduly lest I lose my way in a place which is not too brightly
illuminated by facts. The forces which produce both kinds of com-
pounds may or may not be the same, but it is at least true that the re-
sults are so different that they must not be grouped indiscriminately, even
though Nature itself has placed only an indefinite line between them."
Since it has been shown in innumerable cases that the law of
constant proportions which Proust applied to only a limited number
of substances is capable of indefinite extension since Dalton's
discovery of the law of multiple proportions, the statement of Ber-
thollet quoted above becomes increasingly important and efforts
should be made with increasing earnestness to establish the general
application of the Proust-Dalton law. Even if this cannot yet be
accomplished because of the many substances, such as glass, colloids,
etc., which are regarded as solid solutions, it does not prove exceptions
to natural laws, for no such exceptions can exist ; it is merely the
incompleteness of chemical theory which prevents the natural laws
involved from being properly understood or defined so far as these
apparent exceptions are concerned.
It is certainly surprising that none of the critics have pointed out
this advantage of the H.P. theory, and it is even more remarkable
that Allen and Shepherd should consider it a drawback of the theory.
Thus, they state in their review of the German edition of this work: 737
" An important fact in this connection has been . . . completely
overlooked. We are now in possession of many facts which show that
it is never wise to assume that silicates are chemical compounds. For
instance, to take a well-known example, the felspars are solid solutions
and any theory of structure to be complete must show the permanency
which is characteristic of the properties of true compounds as distinct
from the maxima and minima of mere groupings." These critics
further state that: "The authors never distinguish, and this is most
important, between purely chemical changes and changes of an
entirely physical nature."
The reply to these statements is that there is no need specially to
distinguish between chemical compounds and the so-called isomorphous
mixtures or solid solutions, as the distinction is perfectly clear ! It
would also have been much better if the critics had quoted at least a
few of the " many facts which show that it is never wise to assume
that silicates are chemical compounds," so that the precise value of
this statement of theirs might be ascertained. As only the felspars are
mentioned, any criticism must, for the moment, be restricted to these.
INFLUENCE OF SIDE-CHAINS ON CRYSTALLINE FORM 305
Now, on studying the structural formulae of the felspars (p. 297)
carefully, it is easy to see that almost without exception they are
referable to one type. These formulae also show how various sub-
stances in other groups of siliceous compounds can be formed from
the felspars or vice versd ; they indicate the physical relationship of all
these compounds with reference to crystalline form, optical properties,
specific gravity, etc. On the other hand, the assumption that felspars
are " solid solutions " explains none of these things. How can Allen
and Shepherd explain in the light of then* theory of solid solution the
properties of felspars which are described in paragraphs numbered 2,
3 and 4 on page 298 ? For what reasons should the felspars be treated
in a different manner from other silicates and not regarded as definite
chemical compounds ? Is the force which, in the case of certain
silicates, forms definite chemical compounds, different from that which
forms the so-called " solid solutions " from simple silicates ?
Many fights between chemical dualism and monism have occurred
in the past and the victory has always been completely in favour of
monism. Sooner or later, the dualistic conception of the constitution
of compounds, which was published by Proust more than a century
since, will go the way of all other dualistic theories.
C. The Dependence of the Geometrical Constants on the Side-chains
It has been repeatedly shown in previous pages (cf. p. 216) that
the addition of bases, " water of constitution " or " water of crystal-
lisation," in the form of side-chains to hexites or pentites weakens the
bond between the units forming the hexites or pentites, whilst their
removal or splitting off strengthens the bonds. In other words, by
adding bases in the form of side-chains, part of the valencies in the
ring or core is destroyed. According to the S.H.P. theory, this must
influence the geometrical constants a : b : c and a, ft and y. Crystallo-
graphic experiments, previously made, are in agreement with this
consequence of the theory.
The influence of the " water of crystallisation " on the crystalline
form of a compound has long been recognised ; thus, the metallic sul-
phates with 5 H 2 O are known to differ in form from those with 7 H 2 0.
In this connection a series of uranium-acetates prepared by Rammels-
berg 656 are interesting. These have the general formula :
Ac
U I "aq.,
I , /r
ArN'r
or
r
Ac
U
aq.
r (r= J RO)
A. B.
306 CONSEQUENCES OF STEREO-HEXITE-PENTTTE THEORY
3 RO 6 U0 3 9 (CH 3 CO) 2 aq. 3 RO 6 U0 3 9 (CH 3 CO) 2 aq.
R = Mg, Zn, Ni, Co, Cd, Ca, Sr, (NH 4 ) 2 , K t> Ag 2 .
Of the possible compounds of this series, Rammelsberg prepared
the following :
a :b : c
1. 3 MgO 6 UO. 9 (CH 3 CO) 2 12 H rhombic 0.7468 : 1 : 0.5082
3MnO -6U0 8 -9(CH 3 CO) 2 0-12H 0.7536:1:0.4957
II. 3 MgO -6U0 8 -9(CH 3 CO) 2 0- 7H 0.8946:1:0.9924
3ZnO -6U0 8 -9(CH 3 CO) 2 0- 7H 0.8749:1:0.9493
3 NiO 6 UO 3 9 (CH 3 CO) 2 7 H 0.8670 : 1 : 0.9500
3CoO -6U0 3 -9(CH 3 CO) 2 0- 7H 0.8756:1:0.9484
III. 3MnO 6UO i -9(CH,CO),0- 6 H! 0.6330:1:0.3942
3CdO -6U0 8 -9(CH 3 CO) 2 0- 6H 0.6289:1:0.3904
IV. 3CaO -6U0 8 -9(CH 3 CO) 2 0- 6H 0.9798:1:0.3865
3SrO -6U0 3 -9(CH 3 CO) 2 0- 6H 1:0.3887
V. 3 (NH 4 ) 2 6 U0 3 9 (CH 3 CO) 2 1 : 0.4708
3 K 2 O 6 U0 3 9 (CH 3 CO) 2 O 1 : 1.2830
3Ag 2 O -6U0 3 -9(CH 3 CO) 2 1:1:5385
The results of crystallographic investigations of these urano-
acetates are in remarkable agreement with the S.H.P. theory.
The theoretical possibility of two series (A and B) of these urano-
acetates is confirmed by the existence of two series of compounds
(III and IV) with 6 H and with a different a : b : c ratio.
If the series I and II are compared it will be seen that on the loss
of 5 H the c-axis is largely increased, being, in fact, almost doubled.
A specially interesting example of the change in the geometrical
constants effected by adding or subtracting side-chains is found in the
humite series studied by Penfield and Howe, to which attention has
been drawn by P. Groth 657 , who assigns to them the folio whig structural
formulae :
Prolektite [SiO J Mg [Mg(F. OH)],
Chondrodite [Si0 4 ] 2 Mg 3 [Mg(F. OH)] 2
Humite [Si0 4 ] 3 Mg 5 [Mg(F. OH)],
Clinohumite [SiOJ 4 Mg 7 [Mg(F. OH)],
From the composition of these minerals it follows that each member
of the series differs from the previous one by Si0 4 Mg 2 . The addition
of this group always effects a definite change in the c-axis whilst the
parameter a : b remains practically unchanged.
The geometrical constants of these compounds are :
Prolektite Monocl. prism. 1.0803
Chondrodite 1.0863
Humite Rhomb, bipyr. 1.0802
Clinohumite Monocl. prism. 1.0803
3 x 0.6287 90 0'
5 x 0.6289 90 0'
7 X 0.6291
9 x 0.6288 90 0'
INFLUENCE OF SIDE-CHAINS ON CRYSTALLINE FORM 307
There is here a surprising regularity which may be expressed in the
form of a " law " : the c-axes of these minerals are in the ratio of
3:5:7:9.
According to the S.H.P. theory, and assuming the fluorine to be
replaceable by OH, the formulae of these compounds are :
Prolektite 18 MgO 6 SiO a 6 H 2
Chondrodite 15 MgO - 6 SiO 2 3 H 2 O
Humite 14 MgO 6 Si0 2 2 H 2 O
Clinohumite 13 MgO - 6 Si0 2 1 J H 2 (approx.)
The structural formulae of these compounds will then be :
3 1J 1
A A
oo po_/\_oo QO_/\_OO QO.
Si
aq,
00 00 '"* 00 00 * 00
3 ==Z 3 ='=3 3 = ! =
" ,.!
Si
Si
II I! II II
3 1J 1 J
Prolektite. Chondrodite. Humite. Clinohuniite.
In the compounds of the above series, the addition to or separation of
MgO only occurs in the direction of the c-axis. It is, therefore, clear
why only the c-axis undergoes a regular change, the ratio a : b re-
maining practically constant.
Of special interest are the topical parameters suggested by W.
Muthmann 763 and F. Becke 764 for comparing the chemical and crystallo-
graphic properties of substances. These topical parameters are a
combination of the crystallographic parameter with the molecular
volume ; they are derived from the spatial relations of the substances
concerned and show the relative distances of the molecules from each
other.
W. Muthmann has determined the topical axial ratios of the
following salts, to which he assigns the formulae :
KH 2 P0 4
(NH 4 )H 2 P0 4
KH 2 As0 4
NH 4 H 2 As0 4
and considers that the OK- or ONH 4 -groups, the residual atom and
the OH-groups are attached to the P atoms symmetrically in the chief
plane of symmetry.
J. H. van't HofF 65 endeavoured to explain the data obtained by
W. Muthmann by means of the following structural formula :
K
HO P OH
O
308 CONSEQUENCES OF STEREO-HEXITE-PENTITE THEORY
in which the vertical line represents the main axis c. The substitution
of NH 4 for K increases the length of this axis, whilst the substitution
of As for P effects changes in the dimension in every direction. This
formula of van't Hoff's does not permit the data obtained by Muth-
mann to be predicted, nor does it show any relationship between
analogous phenomena.
In accordance with the H.P. theory, Muthmann 's formulae should
be multiplied by 6, so as to give :
A. (KH 2 P0 4 ) 6 = 3 K 2 6 H 2 3 P 2 5
B. (NH 4 H 2 PO 4 ) 6 = 3 (MH 4 ) 2 6 H 2 3 P 2 O 6
C. (KH 2 As0 4 ) 6 = 3 K 2 6 H 2 3 As 2 5
D. (NH 4 H 2 As0 4 ) 6 = 3 (NH 4 ) 2 6 H 2 3 As 2 5
In each case the formula represents the minimum molecular weights.
The structural formulae of the salts should be as follows : R represent-
ing K or NH 4 , the bonds with dots indicate OK-groups and the bonds
without dots the OH-groups.
X
\/
3 R 2 6 H 2 3 X 2 5
This structural formula permits the following predictions to be
made : 1. The space between the molecules must increase or dimi-
nish in the same or almost the same proportion in all directions within
the crystal, if P as a whole is replaced in the ring by As or, conversely,
As by P, as the bond between the vertical and the horizontal axes is
influenced in the same manner. 2. The space between the molecules
can only change in the direction of a single axis, viz. the vertical or
main axis, if, in a phospho- or arseno-salt, potassium is replaced by
ammonium or vice versd, as these atoms are attached in the direction
of the vertical axis.
It is remarkable how fully the investigations of Muthmann confirm
the consequences of the S.H.P. theory.
According to Muthmann the space between the molecules is
increased in all directions in the crystal in almost exact proportion, if
the phosphorus in the phospho-salts mentioned above is replaced by
arsenic. The increase is practically the same with ammonium and
potassium, but if the potassium atom in potassium phosphate or
arsenate is replaced by an ammonium atom, the centres of gravity of
the units composing the crystal become more widely separated solely in
the direction of the main axis.
STRUCTURAL FORMULA OF BENZENE
309
The Structural Formula of Benzene according to the S.H.P. Theory
From a study of the crystalline form of the benzene derivatives,
P. Groth 659 has discovered " laws " which are reminiscent of the humite,
phosphate and arsenate series previously described. The crystallo-
graphic investigation of a series of benzene derivatives has shown that
there are certain atoms and atomic groups which replace hydrogen in
benzene and its derivatives whilst only slightly altering the crystalline
form, so that the form of the new substance may be compared with the
original one. The change is of such a nature that, e.g. in rhombic sub-
stances, the ratio of two parameters (a : b) remains almost constant (with
the small difference which all isomorphous bodies show, as is the case
with the humite series), whilst only the third axis the c-axis
undergoes a notable change in value. The atomic groups OH and N0 2
act in this manner. It is probable that the substitution of a hydrogen
atom by these groups in benzene and its derivatives occurs in the
direction of the c-axis . An energetic reaction accompanies the substitu-
tion of a hydrogen atom in benzene and its derivatives by Cl, Br and
CH 3 which systematically changes the crystalline system into a less
regular one. This may be due to substitution in the direction of the
a- or 6-axis and not in that of the c-axis.
A large number of other examples might be given to show that the
addition of side-chains to (or their separation from) the molecule results
in a change in the geometrical constants of crystalline substances.
In connection with the foregoing arguments a few words respecting
the structure of benzene according to the S.H.P. theory are of
interest.
The structural formula of benzene * deduced from the S.H.P.
theory resembles the " diagonal formula " of Glaus 660 , viz. :
H C
H C
C H
C H
but one fact deserves prominence : according to the S.H.P. theory
the six hydrogen atoms in benzene do not all behave alike, J of them
(on the c-axis) acting differently from the rest (on the a- and 6-axes).
This consequence of the S.H.P. theory agrees with Groth's discovery
* The reader who wishes to refresh his memory will find an excellent statement of
the ordinary theories of the constitution of benzene in " Organic Chemistry," by W. H.
Perkin and E. Stanley Kipping, and in most text-books on organic chemistry. A. B. S.
S10 CONSEQUENCES OF STEREO-HEXITE-PENTITE THEORY
that if the hydrogen atoms on the c-axis are substituted only these
are changed, whereas substitution of the hydrogen atoms in the a- and b-
axes is accompanied by a notable change in the system of crystallisa-
tion. If, on the contrary, all the hydrogen atoms in benzene are
assumed to be alike, Groth's discovery becomes inexplicable.
There is a more direct proof that one-third of the hydrogen or
carbon in benzene behaves differently from the rest in chemical
reactions, viz. the results of the investigations of Stohmann 661 and his
associates on the heat of combustion of the aromatic compounds and
their hydration products. These showed that the heat- values change
continually in the decomposition of di-hydro compounds, whilst the
increase in energy on the entrance of the first two hydrogen atoms in
the benzene ring is notably greater ; i.e. one-third of the carbons in
benzene behave differently from the rest.
That Kekule's formula for benzene needs modification is also clear
from the following : Ladenburg 662 was the first to point out that
Kekule's formula
CH
CH"' .YJH
CH
v
CH
CH
implies the existence of at least four bi-substitution products. 663 Of
these, three are the derivatives at the points (1, 2), (1, 3) and (1, 4),
including the assumed symmetry of the positions (1, 3) and (1, 5).
There is also at least one series of derivatives in the position (1, 6),
as this position is notably different from the position (1, 2) on account
of the double bond between the carbon atoms in the position (1, 6).
Glaus 664 therefore suggested the following formula for benzene :
CH
CH
\3
CH
CH
He argued from this that there are two kinds of valencies in benzene,
viz. (a) those in compounds produced from the periphery of the
hexagon, and (b) those formed from the diagonals of the hexagon.
From this structural formula which resembles that suggested for
benzene by the S.H.P. theory the existence of only three di-
substitution products of benzene is explained, and this number is that
actually found by experiment.
Another formula which represents the structural formula of benzene
STRUCTURAL FORMULA OF BENZENE 811
in a manner very similar to the S.H.P. theory is the centric formula
devised by Armstrong 665 and v. Baeyer 666 :
H
H C
H C
C H
C H
which is really a modification of Claus' formula. Von Baeyer has also
proposed a centric formula with spatial representation.
Ladenburg's prism formula
H
H C
H C
C H
C H
was one of the first stereo-chemical formulae for benzene. Other stereo-
chemical formulae have been devised by R. Meyer 668 , Thomsen 669 ,
Sachse 670 , Schmidt 671 , Vaubel 672 , Hermann 673 , Diamant 674 , etc.
It has frequently been pointed out in the foregoing pages that the
bond between the units of hexite and pentite radicles is weakened by
the addition of side-chains (see p. 216, etc.). From this it follows
that benzene and its derivatives must be more stable than hydro-
benzene and the hydro-derivatives of benzene. This consequence of
the theory is confirmed by the facts. The hydro-derivatives of benzene
have been shown by the investigations of v. Baeyer to differ consider-
ably from those which are not hydrated. For instance, di- and tetra-
hydro-derivatives were shown to have a marked olefine character.
Thus, phthalic acid is completely resistant to potassium permanganate
solution, but the di-hydrophthalic acids are oxidised by it. The
benzene nucleus is not sensitive to hydrobromic acid and oxidising
agents, but this resistance does not exist in the hydro-benzenes.
The stability of benzene which has been proved experimentally
is in direct contradiction to Kekule's formula. 675
That a close relationship exists between compounds of the aliphatic
312 CONSEQUENCES OF STEREO-HEXITE-PENTITE THEORY
and aromatic series (c/. p. 270), as may be inferred from the S.H.P.
theory, has been proved by the work of Schiff 676 , Lessen and Zander 677 ,
Horstmann 678 and Briihl 679 . From this it must be seen that the
formation of hydro-derivatives of olefinic and aromatic compounds is
analogous.
D. The Optical Properties of Crystals and the S.H.P. Theory
The physical properties of crystals are well known 680 to bear a
very close relationship to their morphological characters. Light,
heat and electricity operate in complete agreement in crystals, and
the crystal systems arrange themselves in the same manner. This may
be used as an argument in favour of grouping according to the optical,
thermic, magnetic and other properties of crystals. Hence, if the
optical properties of a crystal are known, it may be stated that each
geometrical plane of symmetry of a crystal is also a physical one and
that two crystallographic equivalent directions have also a physical
relationship.*
There are, however, exceptions to this rule : some crystals, for
instance, are regular and their physical properties indicate no isotropic
construction. In this connection the optical characters of crystals
are frequently curious. An interesting example of this is found in the
alum crystals : as substances which crystallise regularly they should be
optically isotropic, but Brewster 681 showed in 1816 that the alums
have a double refraction. Biot 682 , who has still further studied these
characteristics of the alums, confirms this view; The double refraction
of the alums has also been studied by Reusch 683 , E. Mallard 684 , F.
Klocke 685 , Brauns 686 and other observers. Several explanations have
been offered to account for their abnormal behaviour. The ordinary
theory of crystalline structure neither affords an explanation nor does
it give anything whereon one may be founded. Mallard 687 endeavoured
to explain the anomaly crystallographically by assuming a special
structure of the alum crystals, and regarded them as consisting of
several individuals of lower symmetry than that of the whole crystal.
Although several mineralogists have expressed their sympathy with
this view, others, such as F. Klocke 688 , disagree with it. Klocke
considered that the optical anomalies of the alums are due to a " state
of tension," but he regards the question as still open.
No less interesting is the cause of the rotation of the plane of
polarised light shown by some crystals ; there is ample reason for re-
ferring this to the chemical constitution of the crystals. This hypo-
* Von Federow has recently prepared a Table, comprising no less than 10,000
substances, the crystals of which have been adequately measured by skilled crystallo-
graphers. By means of this Table, von Federow declares it is possible to identify any
substance included in it when the crystals have been properly measured. The Table
is not available for general use, but in the hands of Prof. Federow it has proved very
successful. A brief account of Federow's theory is given in Tutton's " Crystallography
and Practical Crystal Measurement" (Macmillan). A. B. S.
OPTICAL PROPERTIES OF CRYSTALS
thesis is confirmed by the enantiomorphism of the circular polarising
substances.
[Enantiomorphous crystals are those which have the same relation to each other
as an object has to its mirror-image, as will be seen by holding the sketch of crystal I
before a mirror, when the darkened faces, a, 6, will appear as in the sketch in crystal II
viewed directly, and vice versa.}
I. U.
Enantiomorphous Crystals.
As early as 1848, Pasteur 689 , in studying optically active tartaric acid
and the optically inactive racemic acid, discovered this relationship
between crystalline form and optical activity. Groth also regards
optical activity as entirely due to the structure of the smallest particles
of circular polarising crystals. He considers that if this optical
property is characteristic of the crystal molecule itself, the solution
must be saturated in order to produce optical rotation; as, unless the
particles in solution have a complexity comparable to that of the
crystalline molecules, no separation of the substance in a crystalline
state can possibly occur. With many substances, however, this is not
the case ; for instance, solutions of sodium chlorate show no optical
rotation, but only those crystals whose forms are such that they are
mirror-images of each other.
An apparently complete proof of this view is found in the interesting
observation of Reusch 690 on the production of circular polarisation in
mica plates. According to Reusch, if a large number (12-36) of
uniform thin plates of bi-axial mica are laid one above another so that
the plane of the (vertical) optical axis of each plate is turned to the
right through an angle of 120 with respect to the plate below it, this
combination of plates turns the plane of polarisation of a vertical
beam of light to the right, the combination behaving, in a polarisation
apparatus, in a manner similar to a plate of dextro-rotatory quartz cut
vertically to the axis. If the mica plates are turned through an angle
of 120 in the opposite direction, the combination is laevo-rotatory.
Pasteur's discovery respecting the crystalline forms of optically
active tartaric acid and the inactive racemic acid, the fact that some
substances only show circular polarisation effects when in the solid
state, and the property of the mica sheets discovered by Reusch, all
show that there is undoubtedly a relationship existing between optical
activity and the structure of crystals, though it has not yet been
proved that optical activity is entirely produced by the peculiar struc-
314 CONSEQUENCES OF STEREO-HEXITE-PENTITE THEORY
ture of such crystals. The fact, pointed out by Groth, that some
substances only rotate the plane of polarisation when in the solid
form, is not a complete proof, as on entering into solution equivalent
amounts of laevo- and dextro-rotatory substances may be formed and
so make the solution inactive. As a matter of fact, Groth has found
that a solution of NaC10 3 in which laevo- and dextro-rotatory crystals
of this substance are dissolved, can deposit both laevo- and dextro-
rotatory crystals.
If the optical activity is entirely conditioned by the peculiar crystal-
line form of some substances, enantiomorphous crystals, such as the
regular tetrahedric or trapezoidal hemihedric substances, should
necessarily have the power of circular polarisation. This is not the
case. For instance, L. Wulff 691 has shown that lead, barium and
strontium nitrates, in spite of the regular tetrahedric form of their
crystals, i.e. their enantiomorphous constitution, have no effect on
the plane of polarisation either in the solid or dissolved state. A
further series of substances whose crystalline form is that of the
trapezoidal hemihedric substances did not show any optical activity
when examined by WulfL This fact implies that the cause of the
property of circular polarisation must be dependent on the chemical
constitution of the crystal nuclei, quite apart from the physical
structure of the crystal ; optically active substances must not only be
enantiomorphous, but must have a definite chemical structure. For
instance, lead, barium and strontium nitrates are truly enantiomor-
phous, but they do not possess the structure of optically active sub-
stances and they are, therefore, optically inactive. Hence it is neces-
sary to enquire what chemical structure is essential to render enantio-
morphous substances optically active.
It is probable that the optical anomalies of some regularly crystal-
lisable substances are of a constitutional nature, and if the chemical
factors, such as those which cause the optical abnormalities of the
alums, could be discovered, it is not improbable that these factors
would be the causes of circular polarisation.
The following facts show that chemical structure has an undoubted
influence on the optical properties of crystals :
Mallard, in his studies of the zeolites, has observed that, on pro-
longed heating, these slowly change their optical properties in con-
sequence of the steady loss of their water of crystallisation, i.e. by
changes in the side-chains, until finally the crystal has the properties
of the anhydrous substance. This condition continues if a re-
absorption of water is prevented, as by embedding in Canada balsam ;
but if the temperature reached has not been excessive and the crystal
is allowed to cool in moist air it will regain its water almost completely,
and, simultaneously with this, its optical properties. In this way
Mallard has found a direct proof for the dependence of the optical
characters on the chemical constitution.
In the case of circularising substances, it is noteworthy that Le
OPTICAL PROPERTIES OF CRYSTALS 315
Bel 692 and van't Hoff 693 discovered, almost simultaneously, the fact
that all organic compounds which rotate the plane of polarisation of
light contain asymmetric carbon atoms, i.e. carbon atoms in which
each of the four valencies is saturated with a different group of atoms.
As it has been observed that all organic substances which are optically
active contain one or more asymmetric carbon atoms, it appears
probable that the source of optical anomalies and of circular polarisa-
tion may be due to this asymmetry or to an asymmetrical substitution
of the side-chains or of the hexite and pentite in some substances.
From this it follows that a potash alum of the structural formula
-A A/
= I S I Al I S
3 K 2 12 H 2 - 3 A1 2 0, 12 SO, 10 H
will have a normal optical behaviour, i.e. it must be isotropic. If,
however, part of the potassium is replaced by sodium, lithium or a
similar metal, or if part of the aluminium is replaced by Fe'", Cr"',
Mn'", etc., or if part of the sulphur is replaced asymmetrically by
selenium, the crystalline form remaining unchanged, i.e. regular, these
substances will be optically aniso tropic.
In an analogous manner the source of circular polarisation may be
considered as due to the chemical structure of enantiomorphous
substances.
It is not surprising that Brauns 694 has shown experimentally that,
as a matter of fact, the pure alums are optically isotropic, but the
mixed ones are double refracting, i.e. anisotropic. According to
Brauns, all crystals of pure potash-alumina-alum and ammonia-
alumina-alum are optically isotropic, but those crystals which are
produced from solutions of the mixed substances are optically different
and show a double refraction. Crystals obtained from a solution
containing equal weights of ammonia- and potash-alum show, according
to Brauns, a very strong double refraction, are full of irregular cracks,
and, on removing them from the solution, they fall to pieces. On
representing the structure of such an alum by
the NH 4 -groups being marked + and the potassium atoms its
asymmetric structure is clear and the abnormal optical behaviour
of this alum, the irregular cracks in it, and the falling to pieces of the
crystals on removing them from the solution are rendered explicable.
316 CONSEQUENCES OF STEREO-HEXITE-PENTITE THEORY
It is noteworthy that Brauns has observed faint circular polarisa-
tion phenomena, in consequence of which it is highly probable that
such asymmetric substitution is the cause of the optical activity of a
number of enantiomorphous substances. As a matter of fact, the
micas from which Reusch built his optically active compounds are
silicates in which both the side-chains and the aluminium hexites and
pentites are composed of different constituents which are often
asymmetrically arranged in the molecule (see " Micas " in Appendix).
Some substances, such as quartz, are optically active and, without
exception, possess enantiomorphous crystalline forms. Their structural
formulae, as derived from ultimate analyses and other studies, must be
asymmetric if this theory of circular polarisation is correct and of
general application.
The Bravais-Frankenheim theory of crystalline structure does not
indicate the enantiomorphous forms. Sohncke sought for the source
of optical rotation of some crystals and of the appearance of these in
enantiomorphous forms in an inner structure of the same, which is
similar to Reusch J s mica arrangement. The theory of crystalline
structure may be enlarged in this direction. The optically active
crystals consist, according to him, of step-like lamellae which are
optically bi-axial and do not show double refraction in the axis of
rotation, but show circular polarisation effects.
The S.H.P. theory may also be enlarged in the same sense. The
units may be so arranged that a series of double pyramids (see P and
P', pp. 286 and 287) P, P', P", P'" . . . with the surfaces ABDE,
A'B'D'E', A"B"D"E" ... are produced. These double pyramids
P, P', P" . . . have axes AD, ATX, A" D" . . . BE, B'E', B"E" . . .
arid are so placed that each of their axes in the base forms an angle of
120 in the direction of the movement of the hands of a clock, or
vice versa with the corresponding axes of the next base, i.e. AD with
A'D', A'D' with A"D", A"D" with A'"D'". In the first case dextro-,
and in the second laevo-rotatory crystals are produced, provided that
the crystals are also chemically asymmetric.
The S.H.P. theory thus provides a single explanation for the cause
of circular polarisation in both organic and inorganic compounds.
E. The Dependence of the Geometrical Constants on the Temperature
The bonds between the nuclei of the radicles (i.e. the hexites and
pentites) and between the radicles and the side-chains are loosened by
the addition of bases, water of constitution and of crystallisation and
on raising the temperature. Hence, on altering the temperature the
geometric constants must be influenced, as they have a close relation-
ship to the valency-forces. The consequence of the theory is also
confirmed by the facts.
Mitscherlich 695 , G. Rose 696 , F. de Filippi 697 , Frankenheim 698 and
others have shown that when aragonite is heated to a suitable
MOLECULAR VOLUMES
317
temperature it is converted into calcspar. Hauy 699 has also observed
that on heating aragonite to a dull red heat it falls to powder, and
Haidinger 700 represented this process as a conversion of aragonite
into calcspar. G. Rose 701 has shown that calcite and also aragonite are
formed from warm solutions of CaC0 3 and that, at higher temperatures,
only calcite is formed. C. Klein 702 has made the interesting observa-
tion that a plate cut from aragonite in a direction vertical to the
principal axis becomes optically monoaxial and has a negative double
refraction when heated, i.e. the plate assumes the characteristic
properties of calcspar when warmed.
The changes of the crystalline forms of substances on raising their
temperature has been observed in numerous cases by O. Lehmann 703 ,
who has examined two groups of polymerised substances, of which :
1. The members of one group are converted, with absorption of
heat, into another modification ; on cooling, the original form (en-
antio tropic modification) is reproduced and heat is evolved.
2. The members of the other group are stable and labile modifica-
tions which differ from the enantiotropic substances and are not
converted into other forms on alteration of the temperature.
F. Molecular Volumes and the S.H.P. Theory
It follows from the S.H.P. theory that the molecular volumes of
analogously constituted substances cannot be identical, as the affinities
between the various nuclei must differ from each other.
An interesting confirmation of this consequence of the theory is
found in the results of investigations of the molecular volumes of a
series of alums by O. Petterson 704 , which are shown in the following
Table :
Sulphate Alums
Mol.
Vols.
Selenate Alums
Mol.
Vols.
Differ,
between
Vols.
KiH 4 (S-Al-.)
10 H
541.6
K 6 H 24 (Se-Al-Se)
10 H
568.0
26.4
(NH 4 )OHJ 4 (S-A1-S) -
10 H
552.2
(NH 4 )H 4 (Se-Al-Se)
10 H
578.6
26.4
Rb 8 H 4 (S-Al-S)
10 H
551.0
Rb<jH|j 4 (Se-Al-Se)
10 H
576.2
25.2
Cs 6 H 4 (S-Al.S)
10 H
569.2
Cs 6 H 4 (Se-Al-Se)
10 H
595.6
26.4
Kj>H 24 (S-(>S)
10 H
542.2
KH 24 (Se-Al-Se)
10 H
571.0
28.8
(NH 4 ) 6 H| 4 (S-Cr-S)
RbgH 4 (S-Cr-S)
10 H
10 &
553.6
554.6
(NH 4 ) 6 Ho 4 (Se-Al.Se)
RbH 4 (Se-Al-Se)
10 Bt
10 H
577.4
576.8
23.8
22.2
T1H 24 (S-(>S)
10 H
554.2
TlH 2 4 (Se-Al-Se) r
10 H
576.6
22.4
From this Table it may be seen that not only are the molecular
volumes of different alums not identical, but that there is a striking
regularity in the difference in the molecular volumes caused by the
substitution of selenium for sulphur.
Summary and Conclusions
IN the foregoing pages an attempt has been made to obtain a glance at
the structure of the silicon compounds . After a critical examination
of existing theories which have been proposed for the representation of
the structure of the aluminosilicates and the silicates generally, it has
been found that the conception of the aluminosilicates as complex
acids or salts of complex acids agrees best with the facts. The
reactions of the aluminosilicates can only be understood if both
alumina and silica are regarded as playing similar roles in the silicates,
i.e. the roles of acids. A number of properties appear, however, to
contradict the theory of the aluminosilicates as complex compounds,
and this conception does not enable any systematic arrangement to
be made of all the aluminosilicates in spite of the undoubted genetic
relationship between them.
It is very surprising that scarcely any of the critics of the German
edition of this work have paid any attention to the main thesis that
the silicates, or more correctly the aluminosilicates, should be classed
with the complex acids. Yet it is stated quite definitely on page 30 :
" It is, however, not improbable that these objections (i.e. to the sixth
hypothesis) are only apparent, and that they would be completely
overcome if the manner in which the atoms in the anhydrides of the
aluminosilicates are bound to each other were known. By the use of a
suitable hypothesis for the structure of these anhydrides a confirmation
of this statement may be found. The authors of this present volume
have actually formulated such a hypothesis, and its nature and the
conclusions to be drawn from it form the subject-matter of the following
pages."
On page 62 it is stated that: "The conclusion has already (see pp.
22 and 26) been reached that, of all the theories devised for showing
the constitution of the aluminosilicates, the one which agrees best
with the facts is that which assumes that these compounds are complex
acids and the corresponding salts."
On page 63 it is stated that : "The conception of the alumino-
silicates as complex acids thus agrees excellently with the experi-
mental results."
On pages 79-102 it is shown that the molybdenum and tungsten
complexes, i.e. the complex acids and their salts, are par excellence true
analogues of the aluminosilicates and agree perfectly with structural
formulae which are fully analogous to those used for the alumino-
silicates.
318
SUMMARY 319
The foregoing quotations, and the present work as a whole, show
clearly that, quite apart from the hexite-pentite theory, the view that
aluminosilicates are complex acids and salts is the foundation on which
a knowledge of the constitution of these substances must be based.
Yet this fact, as already remarked, does not appear to have been
noticed by a single critic. Thus, in a review by J. J. P. 766 it is stated
that : "The conception of hexite and pentite radicles (ring-compounds
with 5 or 6 Al- or Si-atoms and a number of 0-atoms) is the foundation
of a systematic study of the silicates."
Stremme 767 commences with the view that the hexite-pentite
theory is the sole foundation of the present volume, and then reaches
the remarkable conclusion that the chief difficulty in mineral chemistry
the explanation of the extraordinarily great variations in the com-
position of the silicates becomes " playfully easy," "it is only
necessary to introduce new hexite and pentite groups into existing
combinations." He then stated that : " In not a single case is it shown
that even one silicate must necessarily contain a hexite or pentite
group."
In reply to this criticism, which completely overlooks the complex
nature of the aluminosilicates, it may be well to remark that the H.P.
structural formulae of the aluminosilicates have been devised in
accordance with definite rules, and in no case have " new hexites or
pentites " been introduced in a haphazard manner. The proof that
the aluminosilicates have the constitution indicated by the H.P.
theory (i.e. that they contain hexites or pentites of silicon and
aluminium which are arranged in accordance with definite laws) has
been published in the customary scientific manner, as everyone who will
read it impartially must admit. The theoretically possible formulae
were first set down, and the consequences deducible from them were
then compared with the available experimental evidence. Stremme
terms this " not proved," and his contention might be sound if the
experimental evidence did not agree with the logical conclusions from
the theory. As a matter of fact, the agreement is remarkably close.
If Stremme or any other critic can find a better method of testing a
theory than the one adopted in the present volume, he would render
an inestimable service to mankind if he would publish it.
The method adopted by this critic to show the " worthlessness "
of the H.P. theory could be easily used to upset the most firmly-
established theories. For example, on what foundations are the atomic
theory, the benzene theory and the theory of dissociation based ?
Surely they have been accepted as the result of entirely analogous
methods of argument to those used in the present volume !
C. H. Desch 736 has overlooked the fact that the main foundation of
this exposition of the constitution of aluminosilicates is the fact of
their complex nature, inasmuch as he states that " the felspars, the
hardening of cements, the hydra tion of zeolites . . . are dealt with
exclusively from a structural chemical point of view."
320 SUMMARY
A further criticism of Desch's views will be found on reference to
the Name Index.
Allen and Shepherd 737 also appear to have completely overlooked
the fact that the complex nature of the aluminosilicates is the essential
basis of the constitution attributed to them by the authors of the H.P.
theory,. and it appears strange to them that the structure of the complex
compounds of tungsten, vanadium and molybdenum should also be
described in the present volume. It is, nevertheless, very remarkable
that Allen and Shepherd have overlooked this fact, or even that they
could overlook it, as they specifically refer to "an excellent review of
previous theories of the structure of silicates and a proof of their
insufficiency " contained in the present work. Yet in this review it
is clearly shown that the starting point of any theory of alumino-
silicates must be based on their complex nature. It is the neglect of
this which leads Allen and Shepherd to oppose the application of
the new theory to Portland cements. If they had only seen that the
aluminosilicates are complex acids or the corresponding salts, they
must have realised the a priori probability of the existence of highly
basic calcium aluminosilicates, i.e. they must have reached a concep-
tion of the constitution of Portland cements which agrees with the one
herein published. If a theory shows the possible existence of these
substances, and all their properties agree with the structural formulae
which are based on the theory, there is no reason to doubt the correct-
ness of the constitutions thus formulated.
Manchot 775 , alone of all the critics, refers to the complex nature of
the aluminosilicates. From his statement "It is in any case worth
consideration whether it can be proved that among the silicates as in
other branches of chemistry the number 6 plays so special a part "
it follows that he considers that the new theory cannot in any way be
regarded as properly supported by facts. This critic should, however,
state, at the earliest opportunity, how large must be the mass of facts
in support of a theory before he would consider that theory established.
If his attitude in his own researches may be regarded as satisfactory
to himself, he will doubtless be interested to refer to an investigation he
made in 1905 into the constitution of silicides and published in the
"Annalen der Chemie," 1905, 3J$, 356-363. In this instance this
investigator did not hesitate to state that these compounds form
hexites, notwithstanding that he had only a single fact upon which to
rely for his conclusion, viz. the behaviour of these substances towards
hydrofluoric acid. Yet when he comes to review the German edition
of the present work, he considers that the innumerable facts and the
whole mass of available experimental evidence are not sufficient to
establish the hexite formation of the silicates ! The number and
importance of these facts and the manner in which this critic uses his
own experimental results in criticising the constitutional formulae of
the silicates quietly passing over in silence those which may happen to
agree with the theory he is criticising is highly significant (see p. 273).
SUMMARY 321
The H.P. theory is the first one enabling structural formulae to be
devised in agreement with the conception of the aluminosilicates as
complex compounds, which is free from the drawbacks of the
earlier theories, is capable of being used in the systematic arrange-
ment of all the silicates and also enables a series of properties
of the aluminosilicates to be predicted a priori, which have, so
far as they have been investigated experimentally, been fully con-
firmed.
Thus the structural formulae of the silicates devised by means of
the H.P. theory have led to the remarkable prediction that all the
aluminium and silicon atoms in the aluminosilicates will not behave
exactly alike when examined chemically and physio-chemically, and
that atoms occupying certain positions in the molecule will behave
differently from the rest. This consequence of the theory is fully
confirmed by the available experimental material, and particularly
by the work of Thugutt, Silber and others.
The agreement between the minimum molecular weights which
may be inferred from the H.P. theory and those found experimentally
is also important, particularly as regards the results obtained by
Thugutt on a series of aluminosilicates such as orthoclase, nepheline,
and the sodalites.
Considerable importance also attaches to that consequence of the
H.P. theory which states that chemical compounds may contain
various kinds of combined water " water of constitution " and
" water of crystallisation " the first being acid- water and the second
basic-water, and to the agreement of this consequence with the
facts ascertained experimentally such as Clarke's studies of the
zeolites.
The H.P. theory is not only applicable to the representation of the
structure of the aluminosilicates, but to the complex acids generally.
According to the investigations of Gibbs, Blomstrand, Pechard,
Parmentier, Kehrmann, Friedheim and others, complex acids are
produced by the union of one acid with another, e.g. of molybdic
acid with vanadic, phosphoric, antimonic or arsenic acid; and of
aluminic acid with phosphoric, vanadic, molybdic, sulphuric or
tungstic acid. By means of the H.P. theory the structure of all the
various complex acids and their salts can be shown on a priori grounds.
This theory also shows that a genetic relationship must exist between
the various complex acids of the same class, e.g. between all the
aluminosilicates, all the aluminophosphates, all the aluminosulphates,
and between all the salts of the complex acids of the same class. As a
matter of fact, such a relationship does exist, as may be seen on
examination of the available experimental results.
It is specially important to observe the fact that the addition of a
basic or other side-chain weakens the bonds of the nucleus, and that
the most stable types of the complex acids are those in which the ratio
of the acid-forming atoms is 1 : 1 ; thus, the most stable aluminosilicates
322 SUMMARY
are those with a ratio of A1 2 3 : Si0 2 =l : 2 ; the most stable vanado-
tungstates are those in which V 2 5 : WO 3 =1 : 2.
The H.P. theory is also of value in ascertaining the constitution of
several aluminosilicates of great technical importance, such as clays,
ultramarines, Portland cements, slag cements, porcelain cements, etc.
The clays are of great technical value because they are a raw material
used in the production of pottery, cement, ultramarines, etc., and
they are also of great theoretical importance because they constitute
some of the various aluminosilicic acids whose existence may be inferred
from the H.P. theory. The behaviour of clays towards strong acids
(the so-called " rational analysis "), the cause of the plasticity of clays
and the changes which occur on burning may all be explained by
means of the H.P. theory. Innumerable investigations have been
made in order to ascertain the constitution of the ultramarines. The
H.P. theory supplies a hypothesis from which the structure of the
whole of the theoretically possible substances of the ultramarine class
may be derived ; a large number of these compounds are already
known to exist. On the other hand, no ultramarines have yet been
found which, according to the theory, are theoretically impossible
(such as those in which A1 2 3 : Si0 2 = 1:6). The ultramarine theory,
based on the more general H.P. theory, is in entire agreement with the
experimental results of the valuable work of Hoffmann, Heumann,
Philipp, Szilasi, Gmelin and others. The experimental work of
Guckelberger on the minimum molecular weight of some ultra-
marines is in remarkable agreement with the H.P. theory and is fully
confirmatory of the theoretical inferences from it.
Innumerable attempts have also been made to ascertain the
structure of Portland, slag, porcelain and other silicate cements and
especially to explain the reactions which occur during the hardening
of these cements. These and other problems find a clear and simple
solution when once the structure of the silicates has been ascertained
by means of a suitable theory. As a matter of fact, the H.P.
theory has led to conceptions of the structure of cements which
not only agree with experimental observations, but also permit
of very full prognostications in regard to the possibility of solving
the great problem of the use of cement in sea-water and coastal
masonry.
The new H.P. theory has proved to be of special value in ascertain-
ing the structure of the porcelain (dental) cements, i.e. those compounds
which are both theoretically and practically important on account of
their extended use in dentistry.
The poisonous action of some of these cements has been studied,
and the H.P. theory shows which portion of these cements has a toxic
action and it indicates how their poisonous nature may be destroyed
and the cements rendered quite harmless. To solve this obviously
physiological chemical problem it is necessary to study the toxines
generally in order to ascertain the nature of their actions and the
SUMMARY 323
causes of the poisoning. Ehrlich's theory of the toxines on the one
hand and the H.P. theory on the other combine to solve the problem
of the poisonous nature of many porcelain cements and show clearly
which of the available cements are toxic, or at least risky, and which
are harmless.
The aluminosilicates, generally speaking, cannot be satisfactorily
studied because of their great resistance to reagents, few of the ordinary
methods of investigation being available. Yet, by means of the H.P.
theory, it is possible to produce a theory of such general application
that, with the aid of modern methods of investigation, the constitution
of all the silicates may be ascertained. For instance, the results of
physical and chemical researches on the silico-molybdates by
W. Asch are in complete agreement with the H.P. theory. This
agreement between the facts and theory is very striking in the
case of the alums and chromo-sulphuric acids which have been
specially studied in a chemico-physical manner by Recoura and
Whitney.
There can be no doubt that Nature has formed all substances
according to monistic laws. Hence the probability of the H.P. theory
being extended so as to make it applicable as a general chemical
theory.
An attempt thus to enlarge the scope of the H.P. theory, though
made on only a small scale, has led to a new theory of acids, new views
on the constitution of solutions and new views of the structure of
carbon compounds.
The H.P. theory itself does not take cognisance of the fact that
atoms exist in space; consequently it required extension and com-
bination with the modern theory of the structure of crystals in order
to convert it into a general stereo-chemical theory. This has been accom-
plished to the extent that, by means of the " hexite-pentite law "
(p. 289), the stereo-hexite-pentite theory (abbreviated to " S.H.P."
theory) is capable of development into a general theory of chemical
compounds. The S.H.P. theory has proved to be of great value ; it
helps to explain many puzzling properties of crystals, confirms Hauy's
law of relationship between crystalline form and chemical composition,
permits the prediction of isomers of chemically allied substances
(Mitscherlich) and solves the problem of the structure of the so-
called isomorphous mixtures. Thus, the H.P. theory may be compared
to a bridge between the realms of organic and inorganic chemistry,
and the S.H.P. theory to an indivisible bond between chemistry and
the allied sciences of physics and crystallography.
The S.H.P. theory appears to be particularly valuable when
it is compared with existing theories of the constitution of
chemical compounds. It is then seen that many modern theories
are, in a sense, only portions of the new theory and may be inferred
from it.
In a review of the German edition of the present work by Stremme 767
324 SUMMARY
the following remark occurs : "In short, an attempt is made to
develop a Chemistry of Silicon corresponding to that of Carbon such
as has so frequently been attempted by others." As a matter of fact,
the view that Nature forms substances in accordance with monistic
laws, permits many applications of the results of the study of organic
compounds (including their structural formulae) to inorganic substances.
The critic must therefore ascertain what beneficial results (if any) have
resulted from the present investigation and whether previous investiga-
tions are completely analogous to it. He is compelled to deny the
analogy if he compares the results of this investigation with previous
ones. In order to show this more clearly, two investigations of the
relationship between the compounds of silicon and carbon, both of
great importance to a study of the structure of silicates, may here be
critically examined, viz. that of A. Safarik 768 and that of W. Ver-
nadsky 769 .
A. Safarik has endeavoured to find a complete analogy between
silicates and organic compounds and has assumed that the silicates are
open or closed ring-compounds such as are found in the aliphatic and
aromatic compounds of carbon. This analogy between silicon and
carbon, the former being a constituent of the inorganic crust of the
earth and the latter the foundation of all organic nature, " thus
assumes a new and deeper significance." In addition to this
analogy there is, according to Safarik, a difference between the
compounds of silicon and carbon inasmuch as in the silicates silicon
is bound to silicon through oxygen and the polyvalent metals, whilst
in the organic compounds there is a direct bond between carbon and
carbon.
A glance at Safarik's formula shows at once that it differs greatly
from those derived from the H.P. theory. The necessary explanatory
support is lacking for Safafik's theory of the silicates, and for this
reason it cannot be applied to the silicates as a whole. An important
disadvantage of his structural formula is due to the fact that
it is not based on any natural law and that it contains a dualism,
the origin of which may be found in the present dualistic con-
ception of organic chemistry, viz. the division of organic compounds
into an aliphatic and an aromatic series. The result is that
this theory, notwithstanding its derivation from organic chemistry,
has not led Safaf* ik very far. The poor result which he has obtained
in applying organic theories to inorganic compounds caused Safaf ik to
make the following remarks : " The most natural means of bringing
inorganic chemistry into unison with the fundamental theories of the
present time is that which has led to such remarkably successful
results in organic chemistry ; each single element must be examined
in such a manner as has been the case with carbon or, as Erlenmeyer
so pregnantly observed, we must have as many chemistries as there
SUMMARY 325
are elements. To attempt this work would be to commence a task of
incredible magnitude."
From these words it is clear how little satisfaction Safarik obtained
from his researches, and the authors of the present volume are equally
unable to accept the view that the problems of the structure of chemical
compounds can ever be solved by simply studying the elements in a
systematic manner. They incline more to the opinion that if the
present conception of the structure of organic compounds cannot be
applied to inorganic substances, then this very inapplicability is the
best proof that the generally accepted theory of organic structures is
not so devoid of objection that it cannot, with advantage, be modified.
The possibility or otherwise of applying a theory which appears to be
satisfactory for one element to others is one of the best tests of the
value of such a theory.
W. Vernadsky has also endeavoured to devise structural formulae
for silicates which bear some resemblance to those of organic chemistry.
He assumed the existence of two radicles in aluminosilicates : one
with an open or chlorite ring and the other with a closed or cyclic
chain (mica ring). The constitution of these rings is shown by the
following formulae :
OH OH
/\ /\
O O
Si 0=Si Si=0
4 A
\/ \/
Al Al
Chlorite Ring. Mica Ring.
According to Vernadsky these rings remain unaltered in most
chemical reactions, this property being highly characteristic of the
aluminosilicates. The compounds with a mica ring are, according
to this investigator, much more strongly characterised than minerals
with a chlorite ring.
As the durability of the rings is characteristic of cyclic chemical
compounds, and experience in organic chemistry shows that this
durability is exceptionally high in heterocyclic compounds, Vernadsky
considered that it might be assumed that minerals containing
mica contain heterocyclic rings, i.e. rings composed of several
elements.
Vernadsky has had no specially satisfactory results from this
326 SUMMARY
theory because, as he himself admits, it is necessary to limit the applica-
tion of the theory to the simplest and best known compounds, and
because he persistently adheres to an entirely unnecessary dualism,
inasmuch as he divides silicates into two groups : one containing those
which are undoubtedly chemical compounds and the other comprising
the so-called physical combinations. Vernadsky's theory is thus
inapplicable as a general theory of silicates and also as a monistic
chemical theory of general application.
This short statement with regard to important attempts to apply
the theories current in organic chemistry to the elucidation of in-
organic structures must suffice to show that there is no parallel
between such an application of existing theories and the H.P. theory
developed in the present volume. Hence, before the H.P. theory can be
discarded or regarded as of no importance, those who criticise it must
disprove the statements made and must show that a still larger number
of facts can be fairly used in support of a new theory which, so far as
those concerned with the writing and translation of the present volume
are aware, has not yet been published. The ineffectiveness of all the
noteworthy existing theories has, it is believed, been conclusively
shown in the foregoing pages.
The H.P. theory leads by quite different means from those hitherto
used to the " benzene-ring theory " which has proved so advantage-
ous in studying the constitution and properties of carbon compounds.
It is scarcely necessary to state that Werner's co-ordination law is, in
some respects, a part of the S.H.P. theory. If a=6=c=l and
a=|8=y=90 , this produces Werner's octohedron, to the corners of
which are attached the molecules of various metal ammonias and
allied substances. It is a strong confirmation of the S.H.P. theory
that Werner's co-ordination law has solved a number of puzzling
problems in connection with the metal ammonias and allied substances,
that its inferences have been fully confirmed by experiment, and that
Werner's theory has proved of value in the development of a system-
atic arrangement of the compounds concerned.
Arrhenius' "Dissociation Hypothesis." van't Hoff's "Theory of
Solutions," and the Kinetic Theory of Gases are all, in a certain
sense, capable of being regarded as consequences of the S.H.P.
theory.
It is particularly important to note that, by the combination of the
S.H.P. theory with the modern theory of the structure of crystals, a
great step towards the object of all investigation has been made, and
some approach has been effected to the time when it will be possible
to show the true relationship between crystalline form and chemical
composition. This object will, clearly, be attained as soon as it is
possible to ascertain the exact relationship between the geometrical
constants (a : b : c and a, /3 and y) and the chemical constants, and to
predict both from the structural formula.
De Bois-Reymond 705 has no doubt that these problems will be
SUMMARY 327
solved as soon as structural chemistry and crystallography unite, and
he has written the following : " We see, in imagination, Structural
Chemistry reaching out her hand to Crystallography ; we see the
atoms with their measured valencies filling spaces of definite
shapes, and forming the tools employed in building crystals."
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Reagents used for proving the presence of free lime in clinker are, I. Water: Winkler,
Chem. Centralbl. 1858, 482 ; Le Chatelier, Bull, de la soc. chim. 41, 377 ; Levoir,
Rec. des trav. chim. des Pays-Bas. 1886, 59 ; Zulkowsky, Chem. Ind. 1901, 290 ;
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332 BIBLIOGRAPHY
841, 1229 ; Hauenschild, Tonind.-Ztg. 1895, 239 ; Zulkowsky, Tonind.-Ztg. 1898,
285 ; 4. Lime-water: Laudrin, Compt. rend. 96, 156, 379, 841, 1229 ; Le Chatelier,
Bull, de la soc. chim. 41, 377 ; 5. Sodium Carbonate : Feichtinger, Bayer. Kunst- u.
Gewerbebl. 1858, 69 ; Schott, Dingl. Polyt. Journ. 202, 434 ; 6. Potassium Carbonate :
Oddou. Manselle, Gaz. ital. 25, 101 ; Feichtinger, Bayer. Kunst- u. Gewerbebl. 1858,
69 ; 7. Ammonium Carbonate : Feichtinger, ibid. ; 8. Ammonium Chloride : Knapp,
Dingl. Polyt. Journ. 265, 184 ; Tomei, Tonind.-Ztg. 1895, 177, Hauenschild, Tonind.
Ztg. 1895, 239 ; Wormser, Tonind.-Ztg. 1900 ; 9. Ammonium Hydroxide : Tomei,
Tonind.-Ztg. 1895, 177 ; 10. Ammonium Acetate : Tomei, ibid. ; 11. Ammonium
Oxalate : Wormser, Tonind.-Ztg. 1900 ; 12. Sodium Hydroxide : Hardt, Tonind.-Ztg.
1900, 1674 ; 13. Magnesium Chloride : Knapp, Dingl. Polyt. Journ. 265, 184 ;
14. Calcium Chloride : Levoir, Rec. des trav. chim. des Pays-Bas 1885, 55 ;
15. Sulphuretted Hydrogen : Steuer, Tonind.-Ztg. 1899, 1604 ; 16. HCl in Alkalies :
Feichtinger, Dingl. Polyt. Journ. 174, 437 ; 17. Iodine and Bromine in Alkalies :
Hardt, Dingl. Polyt. Journ. 175, 208 ; 18. NH^Cl in Alkalies : Michel, Journ.
f. prakt. Chem. 33, 548; 19. NH^NO 3 in Alkalies: Winkler, Dingl. Polyt.
Journ. J75, 208 ; 20. Mg(NO s ) 2 in Alkalies : Zulkowsky, Zeitschr. d. niederosterreich.
Ingenieurvereins 1863 ; 21. AIC1 5 in Alkalies : Wormser u. Spanjer, Tonind.-Ztg.
1899, 1785 ; 22. Water-glass : Heldt, Journ. f. prakt. Chem. 94, 129 ; 23. Glycerin :
Hardt, Tonind.-Ztg. 1900, 1674 ; 24. Sugar solution : Heldt, Journ. f. prakt. Chem.
94, 129 ; Levoir, Rec. des trav. chim. des Pays-Bas 1886, 59 ; Parsons, Deutsche
Topfer- u. Ziegler-Ztg. 1888, 585 ; Masson, Journ. Amer. Chem. Soc. 16, 733 ; Rebbufat,
Tonind.-Ztg. 1899, 782, 823, 883, 900 ; 25. Ox-blood : Mason, Journ. Amer. Chem.
Soc. 16, 733. 279, Sehuliatschenko, Dingl. Polyt. Journ. 194, 355. 280, Michaelis,
Tonind.-Ztg. 1900, 860. 281, Jordis u. Kanter, Zeitschr. f. angew. Chem. 1903, 462-8,
485-92 ; Hardt, Tonind.-Ztg. 1900, 1674. 282, Jordis u. Kanter, I. c. 283, Heldt,
Studien iiber die Zemente, Journ. f. prakt. Chem. 1865, 207. 284, Sehuliatschenko,
Tonind.-Ztg. 1901, 25, 1050, 1053. 284a, The cause of setting is said to be the formation
of aluminates, and that of hardening to be the production of certain silicates, by Michel,
Journ. f. prakt. Chem. 1886, 33, 548 ; A. Meyer, Bull. Boucarest 1901, Nr. 6. On harden-
ing, the following silicates are formed : 1. CaO SiO 2 H 2 O according to Le Chatelier,
Bull, de la soc. chim. 1885, 42, 82 ; Jex, Tonind.-Ztg. 1900, 1856-1919 ; A. Meyer,
Bull. Boucarest 1901, Nr. 6 ; Zulkowski, Broschiire 1901 ; 2. 4 CaO 3 SiO 2 H 2 O
according to Laudrin, Compt. rend. 1883, 96, 156, 379, 841, 1229 ; 3. 5 CaO 3 SiO 2
H 2 O according to Michaelis, Journ. f. prakt. Chem. 100, 257,-303 ; 4. 3 CaO 2 SiO a
H 2 O according to Michaelis, Verhandl. d. Vereins zur Bef order, d. Gewerbefl. 1896,
317 ; 5. 2 CaO SiO 2 H 2 O according to Rebbufat, Tonind.-Ztg. 1899, 782, 823,
853, 1900 ; A. Meyer, Bull. Boucarest 1901, Nr. 6 ; Erdmenger, Chem.-Ztg. 1893,
982 ; 6. 3 CaO SiO 2 H 2 O according to Rivot & Chatoney, Compt. rend. 1856,
153, 302, 785 ; 7. SiO 2 H 2 O according to Kuhlmann, Compt. rend., Mai 1841 ; 8.
The formation of calcium hydrosilicates was assumed by Berthier, Ann. chim. et phys.
22, 62 ; Fremy, Compt. rend. 60, 993 ; Lieven, Archiv. f . d. Naturk. v. Livland, Estland,
u. Kurland 1864, 4, 45 ; Michaelis, Topfer- u. Ziegler-Zgt. 1880, 194 ; 9. A mixture of
basic, neutral and acid silicates was assumed by Heldt, Journ. f. prakt. Chem. 1865,
94, 124-61 ; 10. The formation of silicates without any statement as to their formulae was
assumed by Vicat & John, Ann. chim. et phys. 5, 387 ; Feichtinger, Bayer. Kunst-
u. Gewerbebl. 1858, 69 ; Winkler, Chem. Centralbl. 1858, 482 et seq. 284b, Jordis. u.
Kanter, Zeitschr. f. angew. Chem. 1903, 462-8, 485-92. 285, Le Chatelier, Compt.
rend. 94, 867 ; Bull, de la soc. chim. 41, 377 ; 42, 82. 286, Newberry, Tonind.-Ztg.
1898, 879. 287, Kosmann. Tonind.-Ztg. 1902, 1895 ; 1895, 237. 288, Jex, Tonind.-
Ztg. 1886, 1919 ; 1900, 1856. 289, Erdmenger, Tonind.-Ztg. 1879, Nr. 1, 19, 20, 49 ;
Chem.-Ztg. 1893, 982 ; Dingl. Polyt. Journ. 218, 507. 290, Hardt, Tonind.-Ztg. 1900,
1674. 291, Schonaich-Carolath, Chem. Centralbl. 1866, 1062. 292, Schott, Dingl.
Polyt. Journ. 202, 434. 293, Zsigmondy, Chem. Centralbl. 94, 1064. 294, Meyer-
Mahlstatt, Protok. d. Vereins d. Portlandzem.-Fabr. 1901. 295, Rohland, Zur Frage
iiber die Konstitut. d. Portlandzem., Zeitschr. f. Baumaterialienkunde, Nr. 6, 1901,
20. For further information on Constitution of Clinkers see Fremy, Compt. rend.
60, 993 ; Sehuliatschenko, Dingl. Polyt. Journ. 194, 355 ; Michel, Journ. f. prakt.
Chem. 93, 548 ; TSrnebohm, Kongr. d. internation. Verb. f. Materialpr., Stockholm
1897 ; Rebbufat, Gaz. chim. ital. 28, Teil II ; Zulkowski, Chem. Ind. 1901, 290 ; Leduc,
Sur la Dissociation des produits hydraul., Sept. 1901 ; Rivot u. Chatoney, Compt.
rend. 153, 302, 785; A. Meyer, Bull. Boucar. 1901, Nr. 6; Tonind.-Ztg. 1902, 1895;
Ludwig, Tonind.-Ztg. 1901, 2084; Richardson, Tonind.-Ztg. 1902,. 1928; Michaelia,
Versamml. d. Vereins d. Portlandzem.-Fabr. 1903 ; Winkler, Journ. f. prakt. Chem.
67, 444 ; Dingl. Polyt. Journ. 775, 208 ; Heldt, Journ. f. prakt. Chem. 94, 129, 202-37 ;
BIBLIOGRAPHY 333
Laudrin, Compt. rend. 96, 156, 379, 841, 1229 ; Foy, Ann. ind. 1887, 90. 296, Le
Chatelier, Compt. rend. 94, 867. 297, Tornebohm, Kongr. des internation. Verb. f.
Materialienpr., Stockholm 1897. 298, Richardson, Baumaterialienk, 1903, Heft 11,
150 ; Tonind.-Ztg. 1903, Nr. 58. For further information on the use of the microscope in
the study of the constitution of Portland cement see W. Michaelis, Der ErhartungsprozeB
der kalkhaltigen hydraul. Bindemittel, Dresden 1909, also Keisermann, Der Port-
landzement, seine Hydratbildung und Konstitution, Kolloidchemische Beihefte. Bd.
I, 1910, Keisermann endeavoured to ascertain the constitution of Portland cement by
microscopical crystallographic methods with the aid of aniline dyes as selective staining
agents. He concluded that clinker is probably a conglomerate of dicalcium silicate and
tricalcuim aluminate in the proportion of 4 (2 CaO SiO 2 ) + 3 CaO A1 2 O 3 . Keisermann
(1. c.) and O. Schmidt (Der Portlandzement, Stuttgart 1906, 29) state that there are now
in existence about 28 theories of the constitution and hydratisation of cements. 299, Schott,
1. c. 300, Zulkowski, Zur Erhartungstheorie d. natiirl. u. kunstl. hydraul. Kalkes,
Berlin 1898, 45 ; Sonderabdr. a. d. Zeitschr. Chem. Ind. 1898. 301, Lunge, Tonind.-
Ztg. 1900, 763-5 ; Zeitschr. f. angew. Chem. 1900, 409. 302, Schott, I. c. 303, Michaelis,
Die hydraulischen Mfirtel 1869, 193. 303a, Theories of the process of burning have been
published by Knipp (On burning the cohesion of the silica is reduced), Osterr. Zeitschr.
f. Berg- u. Hiittenwesen 1865, Nr. 40 u. 41 ; Mann (Burning draws the smallest particles
close together), Tonind.-Ztg. 1877, Nr. 26 u. 30; Michaelis (Burning produces a state of
physical tension in the molecule), Journal f. prakt. Chem. 100, 257-303 ; Erdmenger
(E. considered this state of tension to be partly chemical), Tonind.-Ztg. 1878, 232, 250,
259, 378. Theories respecting the cause of " dead-burned " cement have been published
by : Fremy, Pettenkofer, Schonaich-Carolath who attributed it to the formation of a
silicate, Chem. Centralbl. 1866, 1062 ; Vicat and many others attribute it to the production
of a fluid (molten) material, Ann. chim. et phys. 1820 ; Michaelis has shown by experi-
ments, that Vicat's view is erroneous, Tonind.-Ztg. 1892, 124, 403 ; Schuliatschenko
attributed this phenomenon to physical causes, Chem. News 1869, 190 ; Hewett to an
allotropic modification of normal cement, Tonid.-Ztg. 1899, 211 et seq. 303b, The follow-
ing papers have been published on slag cements : Eisner, Dingl. Polyt. Journ. 106, 32 ;
Ott, ibid. 208, 57 ; Huck, Polyt. Centralbl. 1870, 778 ; Pelouze and Fremy, Berg-
u. Hiittenm. Ztg. 1872, 335 ; Bodner, ibid. 1874, 262 ; Wood, ibid. 1878, 432 ; Bosse,
Tonind.-Ztg. 1885, Nr. 41 ; 1886, Nr. 9 ; Manske, Zeitschr. d. Vereins d. Ing. 1885,
921 ; Herrmann, Deutsche Topfer- u. Zeigler-Ztg. 1886, Nr. 5 ; Schumann, Deutsche
Bauztg. 1886, 4 ; Tonind.-Ztg. 1886, Nr. 5 ; Farinaux, Tonind.-Ztg. 1886, Nr. 18-20 ;
Stahl u. Eisen 1886, Nr. 1 ; Ausfiihrl. iiber Schlackenz. nach Tetmajer in Tonind.-Ztg.
1885, Nr. 36 ; 1886, Nr. 22 and Deutsche Topfer- u. Ziegler-Ztg. 1887, Nr. 26 ; Knapp,
Dingl. Polyt. Journ. 265, 184 et seq. 304, Jantzen, Tonind.-Ztg. 1903, Nr. 32. 305,
Lunge, I. c.
305a, Theories of hardening : i. Physical reactions (crystallisations) the cause of
setting, according to Wolters, Dingl. Polyt. Journ. 1874, 214, 392 ; Le Chatelier, Bull,
de la soc. chim. 1885, 42, 82 ; Tonind.-Ztg. 1892, 1032 ; Levoir, Rec. des trav. chim.
des Pays-Bas 1886, 59 ; Erdmenger, Chem.-Ztg. 1893, 982 ; Rebbufat, Tonind.-Ztg.
1899, 782, 823, 853, 900. 2. The solidification or coagulation of the colloids produced on
mixing the cement with water is the cause of setting according to Hauerschild, Wochenschr.
d. niederosterr. Gew. -Vereins 1881, 271. 3. Erdmenger has suggested that the dis-
integrated lime forces the gelatinous material, produced by the action of water, into the
pores or voids and so causes the hardening of the mass, Tonind.-Ztg. 1881, 782, 823, 883,
900. 4. Hardening is attributed to drying by Heldt, Journ. f. prakt. Chem. 1865, 94,
124-61 ; Erdmenger, Tonind.-Ztg. 1880, Nr. 1, 42. 305b, A hydration of the com-
pounds occurring in clinker is said to occur, by Fuchs, Gesammelte Schriften, Miinchen
1829, 113 ; Knau6, Wiirttemb. Gewerbeblatt 1855, Nr. 4 ; Rivot u. Chatoney, Compt.
rend. 153, 302, 785 ; Schuliatschenko, Chem. News 1869, 190 ; Knapp. Dingl. Polyt.
Journ. 1887, 265, 184 ; Perrodil, Dingl. Polyt. Journ. 1885, 255, 76 ; Le Chatelier,
Bull, de la soc. chim. 1885, 42, 82 ; Zulkowsky, I. c. 300, Knapp, Dingl. Polyt. Journ.
1871, 202, 524. 307, cf. Knapp, ibid. p. 573. 308, ibid. p. 518. 309, Richter, Zur Konstit.
der Portlandz. Tonind.-Ztg. 1903, Nr. 120. 310, Michaelis, Die hydraul. M6rtel, p. 577.
311, Winkler, Journ. f. prakt. Chem. 1856, 67, 444. 312, Winkler, I.e. 313, Heldt,
Journ. f. prakt. Chem. 1865, 94, 129. 314, Fuchs, I. c. 277. 315, Zulkowski, tfber den
Wahren Grund der Erhartung der hydraulischen Bindemittel, Chem. Ind. 1898, 99 ;
(see also 31 la). 316, Von Teicheck, Chem. Ind. 1901, 445. 317, Zulkowsky, Chem.
Ind. 1901, 372. 318, Zulkowsky, Chem. Ind. 1898, 101. 319, Feichtinger, Dingl.
Polyt. Journ. 1859, 40-61, 108-18. 319a, "Dber die quantitative Bestimmung des
freien Kalkhydrats im erharteten Zement N. Ljamin, Tonind.-Ztg. 1899, 230 ; Schuliats-
chenko, Uber das Calciumhydrat in dem erharteten Portlandzement, Verhandl.
334 BIBLIOGRAPHY
d. Vereins Deutsch. Portlandzem.-Fabr. 1899 of 23. and 24. Febr. ; Jahresber.
d. chem. Techn. 1898, 44, 727. 320, Michaelis, 1. c. 321, Feichtinger, I. c.
322, Ostwald, Rigasche Ind.-Ztg. 1883 ; Fischer, Handb. d. Technol. 1893, 829
et seq. The development of heat by cement during hardening has also been shown by
Hardt u. Meyer, Tonind.-Ztg. 1895 ; Hardt, Tonind.-Ztg. 1901, 1157. 323, Feich-
tinger, Dingl. Polyt. Journ. 1859, 57. 324, Feichtinger, ibid. 40-61, 108-18. 325,
Schott, Studien iiber den Portlandzement, Dingl. Polyt. Journ. 1871, 202, 436-40.
326, Schott, I. c. 327, Fremy, Compt. rend. 67, 1205. 328, Zulkowsky, Sonderabdr.
1898, 49. 329, Schott, I.e. 330, Schuliatschenko, Ber. der Meerwasserkommiss.,
Tonind.-Ztg. 1903, 1227. 331, Memoires ayant trait aux proprietes des cimenta, Paris
1890. 332, Michaelis, Tonind.-Ztg. 1892, 115 ; Deutsche Topfer- u. Ziegler-Ztg. 1896,
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APPENDIX
CALCULATION OF FORMULAE FROM THE RESULTS
OF LEMBERG'S EXPERIMENTS *
A. Production of a series of Sodalites with the general formula
m Na 2 (6 A1 2 3 12 Si0 2 ) m' Salt n H 2
or the formula
Na 12 (Si Al Al Si) m'2 n H 2
(a) The following compound
(6 Na 2 6 A1 2 3 12 Si0 2 ) 4 NaCl 4 H 2
=Na 12 (Si Al Al S A i) 4 NaCl 4 H 2 O
is the final product of the action of a 20 per cent, solution of caustic soda
saturated with sodium chloride on the following silicates :
6 H 2 6 A1 2 3 12 Si0 2 6 H 2 (Kaolin from Karlsbad)
= H 12 (Si Al A Si) 6 H 2
6 Na 2 6 A1 2 3 12 Si0 2 (Elaolite from Brevig)
= Na 12 (Si Al Al Si)
6 Na 2 6 A1 2 3 18 Si0 2 12 H 2 (Brevicite from Brevig)
= Na 12 (Si Al Si Al S A i) 12 H 2
3 Na 2 3 A1 2 3 12 Si0 2 6 H 2 (Analcime from Fassthal)
= Na 6 (Si Al Si) 6 H 2
3 K 2 3 A1 2 3 12 Si0 2 (Leucitefrom Vesuvius)
= K 6 (S A i Al Si)
3 K 2 3 A1 2 3 18 Si0 2 (Orthoclase from Striegau)
the reagent and silicate being treated at various temperatures (100, 180 to
190 C.) for various periods ranging from 74 hours to six months.
Theory.
4
4f
4g
4c
4d
4a
3Na 2
18.51
19.02
18.65
19.35
19.04
18.53
18.57
3A1 2 3
30.45
31.63
31.81
31.61
30.70
30.84
30.73
6SiO 2
35.82
35.14
36.32
36.66
36.02
36.42
36.78
2 NaCl
11.64
10.71
11.22
11.32
10.22
10.22
10.23
2H 2
3.58
2.61
0.94
1.14
3.60
3.13
3.25
CaO
0.30
0.63
0.14
0.49
0.25
100.00 99.41 99.57 100.08 99.72 99.63 99.81
* * Zeitschr. d. Deutsch. geol. Gesellsch. 1876-85.
2 Cf. pages 60, 61 and 140 of this volume.
Cf. Lemberg, 1. c. 1883, p. 582.
340
LEMBERG'S EXPERIMENTS 341
(b) After two months' action, at 100, of 15 and 12 per cent, solutions of
caustic potash saturated with potassium chloride on the silicates *
3 K 2 - 3 A1 2 3 12 Si0 2 (Leucite from Vesuvius) = K 6 (S A i Al Si)
/ >A
3 K 2 O 3 A1 2 O 3 18 Si0 2 (Orthoclase from Striegau) = K 6 I Al Si I
V W
LEMBERG obtained the sodalite
(6 K 2 6 A1 2 3 12 Si0 2 ) 2 KC1 8 H 2
= K 12 (Si Al Al Si) 2 KC1 8 H 2 0.
Theory.
6c
6a
3K 2 O
25.77
24.72
23.84
3A1 2 3
27.96
27.47
27.10
6Si0 2
32.89
32.31
32.26
KC1
6.80
7.34
7.00
4H 2
6.58
7.80
8.22
CaO
0.30
100.00 99.94 99.42
(c) The silicates f
6 H 2 6 A1 2 3 12 Si0 2 6 H 2 O (Kaolin from Karlsbad)
= H ]2 (Si - Al Al Si) 6 H 2
6 Na 2 6 A1 2 3 18 Si0 2 12 H 2 (Brevicite from Brevig)
= Na 12 (S A i - Al Si - Al Si) 12 H 2 O
3 Na 2 3 A1 2 3 12 Si0 2 6 H 2 (Analcime from Fassthal)
= Na 6 (Si Al Si) 6 H 2
3 K 2 3 A1 2 3 12 Si0 2 (Leucite from Vesuvius)
= K 6 (Sl Al S A i)
3 Na 2 3 A1 2 3 18 Si0 2 (Albite from Viesch)
= Na e
3 K 2 3 A1 2 3 18 Si0 2 (Orthoclase from Striegau)
* Lemberg, 1. c. 1883, p. 587.
t Lemberg, I. c. 1883, pp. 579, 580.
342 LEMBERG'S EXPERIMENTS
If a 20 per cent, solution of caustic soda, saturated with sodium sulphate,
is used at various temperatures (100, 180-190) for different periods (74
hours to six months) only the following sodalite is formed :
(6 Na 2 6 A1 2 3 12 Si0 2 ) 2 Na 2 S0 4 6 H 2
= Na 12 (Si - Al Al Si) 2 Na 2 S0 4 6 H 2 0.
Theory.
3
3f
3a
3b
38
3c
3d
3Na 2
17.75
17.96
17.75
17.72
17.77
17.39
17.11
18.53
3A1 2 3
29.20
30.00
30.24
29.44
29.55
29.66
29.01
30.04
6Si0 2
34.35
34.31
34.03
14.78
34.29
35.14
35.27
34.74
Na 2 S0 4
13.55
11.82
13.22
12.65
11.80
12.63
11.21
9.33
3H 2
5.15
5.70
5.02
5.35
5.89
4.90
6.25
5.88
CaO
0.35
0.40
0.20
0.20
100.00 100.14 100.26 99.94 99.70 99.72 99.05 98.72
(d) Three to five grammes of the following silicates : *
6 H 2 6 A1 2 3 12 Si0 2 6 H 2 (Kaolin from Karlsbad)
= H 12 (Si Al Al Si) 6 H 2
6 Na 2 6 A1 2 3 12 Si0 2 (Elaolite from Brevig)
= Na 12 (Si Al Al Si)
3 Na 2 3 A1 2 3 12 Si0 2 6 H 2 (Analcime from Fassthal)
= Na 6 (Si M - Si) 6 H 2
3 K 2 3 A1 2 3 12 Si0 2 (Leucite from Vesuvius)
= K 6 (Si - Al Si)
3 Na 2 3 A1 2 3 18 Si0 2 (Albite from Viesch)
= Na,( Al^Si)
V \0i/
were mixed with 40 g. of the sodium silicate Na 2 Si0 2 8 H 2 0, which
had been melted in its own water of crystallisation and the mixture heated
at 200 for 100 hours in a digester. The excess of sodium silicate was then
washed out with cold water. An analysis of the residue corresponded to the
compound
(6 Na 2 6 A1 2 3 12 Si0 2 ) 2 Na 2 Si0 3 8 H 2
= Na 12 (Si Al Al - S A i) 2 Na 2 Si0 3 8 H 2 O.
Theory.
3
3c
3e
3f
3g
4
Na 2
23.
71
22.
61
23
.30
23.34
21.
03
21.70
3
A1 2 3
29.
27
29
,31
28
.69
29.16
29.
60
29.25
7
Si0 2
40.
15
40,
,30
39
.43
40.15
40.
52
40.84
4
H 2
6.
87
6
,68
6
.88
6.38
7.
49
6.94
CaO
.90
100.00 98.90 99.20 99.03 98.64 99.73
* Lemberg, I. c. 1885, pp. 961, 962.
LEMBERG'S EXPERIMENTS 343
(e) The silicates
6 H 2 6 A1 2 3 12 Si0 2 6 H 2 O (Kaolin from Karlsbad)
= H M (Si Al - Al Si) 6 H 2
3 Na 2 3 A1 2 3 12 Si0 2 6 H 2 O (Analcime from Fassthal)
= Na e - (Si - Al Si) 6 H 2 O
3 K 2 3 A1 2 3 12 Si0 2 (Leucite from Vesuvius)
= K 6 (S A i Al Si)
were treated with a 15-20 per cent, solution of caustic soda saturated with
sodium carbonate at various temperatures (100, 180-190) and for different
periods ranging from 74 hours to six months.* Analyses of the products gave
the following formula :
3 (6 Na 2 O 6 A1 2 3 12 Si0 2 ) 4 Na 2 C0 3 30 H 2
= {Na 12 (Si - Al - AJ Si)} 3 ' 4 Na 2 C0 3 30 H 2 0.
Theory.
5
5b
5c
9Na 2
18.38
18.23
17.17
18.13
9 A1 2 2
30.22
30.84
29.18
29.47
18 Si0 2
35.55
34.82
35.50
35.27
2 Na 2 OC 3
6.96
7.13
6.96
6.58
15H 2
8.89
8.68
9.40
9.18
CaO
0.30
0.10
0.40
100.00 100.00 98.84 99.03
B. A Series of Changes in Aluminosilicates based on Lemberg's
Experiments.
(a) The action of caustic soda solution of various concentrations (30 per
cent, and 56 per cent.) at 100 for various periods ranging from 72 hours to
14 days on the following silicates :
(1) 3 Na 2 3 A1 2 3 12 Si0 2 6 H 2 (Analcime from Fassthal)
= Na 6 (Si Al S A i) 6 H 2 0f
(2) 6 Na 2 6 A1 2 3 12 Si0 2 (Elaolite from Brevig)
= Na 12 (Si Al Al Si)J
(3) 6 H 2 6 A1 2 3 12 SiO 2 6 H 2 (Kaolin from Karlsbad)
= H ]2 (Si Al Al - Si) - 6 H 2
gave the following results :
From Compound 1 was obtained the substance :
6 Na 2 6 A1 2 3 12 Si0 2 15 H 2 = Na 32 (S A i Al A! Si) 15 H 2
from Compound 2 the substance :
8 Na 2 6 A1 2 O 3 12 Si0 2 7 H 2 O = Na 16 (Si Al Al Si) 7 H 2
* Lemberg, I. c. 1883, pp. 583-4.
t Lemberg, 1. c. 1883, p. 579, Expt. 2.
j Lemberg, L c. 1885, pp. 960-1, Expts. 2c. and 2d.
Lemberg, L c. 1883, p. 579, Expt. 1 ; I.e. 1885, p. 960, Expt. 2b.
344 LEMBERG'S EXPERIMENTS
and from Compound 3 the silicates :
6 Na 2 6 A1 2 3 12 Si0 2 15 H 2 = Na 12 (Si Al Al Si) 15 H 2
8 Na 2 6 A1 2 3 12 Si0 2 7 H 2 = Na 16 (Si Al Al Si) 7 H 2
Theory.
1
2
6Na 2
6A1 2 3
18.84
31.01
18.30
31.13
18.87
31.35
12 Si0 2
15H 2
36.47
13.68
36.52
14.59
36.28
13.39
100.00
100.54
99.89
Theory.
2b
2c
2d
8Na 2
25.38
26.05
25.29
24.99
6A1 2 3
31.32
31.42
31.05
31.16
12 Si0 2
7H 2
CaO
36.85
6.45
36.25
6.87
36.63
5.71
1.08
36.12
6.36
1.02
100.00 100.59 99.76 99.65
(b) On treating the silicates :
(1) 6 Na 2 6 A1 2 3 12 Si0 2 (Elaolite from Brevig)
= Na 12 (Si Al - M Si)*
(2) 3 Na 2 3 A1 2 3 12 Si0 2 6 H 2 (Analcime from Fassthal)
= Na 6 (Sl Al Si) 6 H 2 f
(3) 3 K 2 3 A1 2 3 18 Si0 2 (Orthoclase from Striegau)
in the state of a molten glass with aqueous solutions of sodium silicate,
Na 2 O 2 2 Si0 2 aq. of suitable concentration, at various temperatures
(100, 200-210) for various periods (78 hours to five months) the following
substance
(3 Na 2 - 3 A1 2 3 15 Si0 2 7J H 2 0) 2
\ \Sv
15H 2
was produced from Compounds 1 and 2, and the compound
3 Na 2 3 A1 2 3 12 Si0 2 6 H 2 = Na 6 (S A i Al Si) 6 H 2
from the silicate 3.
* Lemberg, 1. c. 1883, p. 608, Expts. 35 and 36.
t Lemberg, I. c. 1885, pp. 992-3, Expts. 42 and 43.
J Lemberg, I. c. 1885, pp. 993-4, Expt. 47.
LEMBERG'S EXPERIMENTS
345
Theory.
35
36
42
43
3Na 2 O
12.18
12.80
12.64
12.90
12.27
3 A1 2 O 3
20.04
20.95
20.64
20.54
19.35
15 SiO 2
58.94
57.10
57.67
57.78
59.35
7JH 2
8.84
8.68
8.79
8.78
9.03
0.47
0.30
100.00
100.00
100.04
100.00
100.00
Theory.
47
3Na 2 O
14.09
14.01
3 A1 2 3
23.20
22.80
12 Si0 2
54.54
54.36
6H 2
8.17
8.53
100.00 99.70
(c) The silicate
3 Na 2 3 A1 2 3 15 SiO 2 7J H 2 *
formed from the analcime from Fassthal, after a three weeks' treatment with
potassium chloride solution at 100 and a further treatment] for 100 hours
at 200, gave the compound
(3 K 2 3 A1 2 O 3 15 Si0 2 1 J H 2 0) 2
3H 2 Of
Theory.
42a
43a
3 K 2 18.62
19.05
18.64
3A1 2 3 20.19
20.79
20.25
15 Si0 2 59.40
58.92
59.90
1 J H 2 1.79
1.24
1.21
100.00 100.00 100.00
(d) The behaviours towards acids of the following silicates :
(1) 0,5 Na 2 O 2,5 CaO - 3 A1 2 3 18 Si0 2 17 H 2 (Stilbite from
Berufjord) *
NaCa 2 ,
2'5
i -17H 2 Ot
Si
(2) 0,5 Na 2 2,5 CaO 3 A1 2 O 3 18 Si0 2 H 2 (Desmine from Farsern)
Si
= NaCa 2 , 5 AlSi - 20 H 2
(3) 0,5 K 2 2 Na 2 O 2,5 CaO 5 A1 2 O 3 18_Si0 2 -^8H 2 (See-
bachite from Richmond) = KNa 5 Ca 2 , 5 (Si- M Si Al - Si) -28 H 2 0|f
* Lemberg, 1. c. 1885, p. 992, Expts. 42 and 43.
f Lemberg, /. c. 1885, pp. 992-3, Expts. 42a and 43a.
J Lemberg, Z. c. 1885, pp. 987-8.
Lemberg, I. c. 1885, pp. 989, 990, 993.
|| Lemberg, I. c. 1885, pp. 972, 977-8.
346
LEMBERG'S EXPERIMENTS
(4) 0.5 K 2 2.5 Na 2 2 CaO 5 A1 2 0<
lite from Acireale)= KNa 5 Ca 2 (Si Al Si
18 SiO 2
Al Si) 28
28H 2
(Hersche-
H 2 0,* and their
derivatives are shown in the following Tables I, II, III and IV, in which
V = Lemberg's Experiment Number.
S = The silicates used.
A = The salt solutions employed.
Z = The duration of the experiments.
T = The Temperature.
P = The Products obtained.
Table I
V.
8.
A.
Z.
T
P.
39 a
0.5 NajO'2.5 CaO'3 A1,O, )
18 SKV17 H 2 O I
KC1 solution
1.5 Mths.
100
3 K 2 O'3 AlsOa'18 Si0 2 '13 H 2
39 b
3 K 2 O'3 A1 2 O 3 '18 SiO 2 '13 H 2 O
Naa
14 Days
100*
3 Na 2 0'3 A1 2 O 8 -18 SiO 2 '16 H 2 O
39 c
3 Na 2 O'3 A1 2 O 3 '18 SiO 2 '16 H 2 O
Nad
1355 Hrs.
210-220
3 Na 2 0-3 AljOj'18 Si0 2 '8 H 2 O
39 d
3 Na 2 0'3 Al a O 3 '18 SiO a '16 H 2 O
(Na 2 0- Si0 2 +NaCl) .,
75Hrs.
195-205
3 Na 2 0'3 A1 2 3 '18 SiO 2 '8 H 2 O
39 g
3 Na a 0'3 Al a 3 '18 Si0 2 '16 H 2 O
(Borax+NaCl)
78 Hrs.
200-210
3 Na 2 0'3 A1 2 O S '18 Si0 2 '8 H 2 O
39 h
3 Na a O'3 A1 2 O 3 -18 SiO a '16 H 2 O
(Borax +NaCl)
78 Hrs.
200-210
3 Na 2 O'3 AI 2 3 '18 Si0 2 '8 H 2 O
39k
3 Na a O'3 AI a O 3 '18 SiO a '16 H 2 O
(Na 2 HP0 4 +NaCl) ,.
74 Hrs.
220
3 Na 2 O'3 A1 2 O S '18 Si0 2 '8 H 2 O
39 e
3 Na a 0'3 A1 2 3 '18 Si0 2 '8 H 2 O
Ka ..
75 Hrs.
200
3 K 2 O'3 A1 2 3 18 SiO 2 'H 2 O
391
3 Na 2 O'3 AljO 8 -18 Si0 2 '8 H 2 O
KC1
78 Hrs.
210-215
3 K 2 O'3 A1 2 O 3 -18 Si0 2 'H 2 O
391
3 Na 2 O'3 A1 2 O 3 '18 SiO 2 '8 H 2 O
KC1 .,
79 Hrs.
210
3 K 2 O-3 AI 2 O,'18 Si0 2 'H 2 O
39 f
3 K 2 0'3 Al 2 Oa'18 SiO^'HsO
NaCl
6 Days
100
3 Na 2 O'3 A1 2 O,'18 Si0 2 '8 H 2 O
Theory.
39
0.5 Na 2
1.66
1.40
2.5 CaO
7.53
7.43
3 A1 2 3
16.26
16.48
18 SiO 2
58.09
57.97
17 H 2
16.46
16.20
K 2
0.52
100.00 100.00
Analyses
Theory.
39a
3K 2
14.82
14.30
3 A1 2 3
18 SiO 2
16.09
56.78
16.34
57.21
13H 2 O
12.31
12.85
Theory.
39b
3Na 2
10.00
8.89
3 A1 2 3
16.45
16.72
18 Si0 2
58.07
58.14
16H 2
15.48
15.47
CaO
0.78
100.00 100.70
100.00 100.00
Lemberg, I. c. 1885, pp. 976, 979.
LEMBERG'S EXPERIMENTS
547
Theory.
39c
39d
39g
39h
39k
39f
3Na 2
10
.84
10
.61
10
.94
11.
27
11.07
10.74
10.81
3A1 2 3
17
.84
17
.56
17
.99
17.
74
17.56
18.21
17.71
18 Si0 2
62
.94
62
.56
62
.54
62.
22
62.68
62.32
62.87
8H 2
8
.38
9
.27
8
.53
8.
77
8.69
8.73
8.61
100.00 100.00 100.00 100.00 100.00 100.00 100.00
Theory.
39e
39i
391
3 Na 2 16.73
16.66
16.87
16.63
3 A1 2 3 18.10
18.15
18.00
18.72
18 SiO 2 64.09
64.27
63.89
63.41
H 2 O 1.08
0.92
1.24
1.24
100.00 100.00 100.00 100.00
The experiments shown in Table I indicate a replacement of the mono-
and di-valent elements and a variation of the water in compounds of the
type
Table II
V.
S.
A.
z.
T.
P.
40 a
0.5 Na 2 O'2.5 CaO'3 A1 2 8 '18 Si0 2 '20 H 2 O
KC1 sol.
1 Month
100
3 K,O'3 A1 2 0,'18 Si0 2 '13 H 2
40 b
3 K 2 0'3 A1 2 S '18 SiOj'13 H 2 O
NaCl ..
14 Days
100
3 Na 2 0'3 A1 2 O,'18 Si0 2 '16 H 2
40 c
3 Na 2 O-3 A1 2 O 2 '18 Si0 2 '16 H 2
NaCl ,.
1029 Hrs.
210-220
3 Na 2 O'3 A1 2 O S '18 Si0 2 '8 H 2
40 d
3 Na 2 O'3 A1 2 8 '18 Si0 2 '16 H 2
(Na 2 0-2SiO,+NaCl) ..
74 Hrs.
220
3 Na 2 0-3 A1 2 S '18 SiO 2 '8H 2 O
40 f
3 Na 2 O'3 A1 2 3 '18 Si0 2 '16 H 2 O
(Borax +NaCl) ,.
186 Hrs.
210-220
3 Na 2 O'3 A1 2 3 '18 Si0 2 '8 H 2 O
40 e
3 Na 2 O'3 A1 2 S -18 Si0 2 '8 H 2 O
KC1 ..
79 Hrs.
210"
3 K 2 O'3 A1 2 O S '18 SiO 2 -H 2 O
40 g
3 Na 2 0-3 A1 2 8 '18 Si0 2 '8 H 2 O
KC1 ..
79 Hrs.
210-220
3 K 2 O'3 A1 2 O 3 '18 Si0 2 'H 2 O
44
0.5 Na 2 0'2.5 CaO'3 A1 2 0,'18 Si0 2 '20 H 2 O
20%Na 2 CO, ,.
15 Mnths.
100
3 Na 2 0'3 A1 2 S '15 SiO 2 '7i H 2 O
44 a
3 Na 2 0'3 A1 2 8 '15 Si0 2 '7i H 2 O
Ka ,.
100 Hrs.
200"
3 K 2 O'3 A1 2 S '15 SiO 2 'li H 2
45
0.5 Na 2 O'2.5 CaO'3 AJ 2 S '18 Si0 2 '20 H 2 O
25%Na 2 0'Si0 2 ,.
2 Mnths.
100
3 Na 2 0'3 A1 2 8 '12 Si0 2 '6 H 2 O
45 a
3 Na 2 O'3 A1 2 8 '12 SiO 2 '6 H 2 O
Ka ..
3 Weeks
100
3 K 2 O'3 AI 2 0,'12 Si0 2 'H 2 O
Analyses
Theory.
40
0.5 Na 2 1.60
0.91
2.5 CaO 7.31
7.60
3 A1 2 O 3 15.96
16.18
18 Si0 2 56.36
56.62
20 H 2 O 18.77
18.63
K 2
0.24
100.00 100.18
348
LEMBERG'S EXPERIMENTS
Theory. 40a
3 K 2 14.82 14.42
3 A1 2 3 16.09 15.83
18 SiO 2 56.78 56.81
13 H 2 O 12.31 12.94
Theory. 40b
3 Na 2 O 10.00 9.74
3 A1 2 3 16.45 16.35
18 SiO 2 58.07 57.09
16 ELO 15.48 16.82
100.00 100.00
100.00 100.00
Theory.
40c
40d
40f
3 Na 2
10.84
10.63
11.12
11.46
3A1 2 3
17.84
17.62
17.83
17.73
18 Si0 2
62.94
62.48
62.08
61.87
8H 2
8.38
9.27
8.97
8.94
100.00 100.00 100.00 100.00
Theory.
40e
40g
3K 2
16.73
17.18
17.11
3A1 2 3
18.10
18.51
18.39
16 SiO 2
64.09
62.77
62.95
H 2
1.08
1.54
1.55
Theory.
44
3Na 2
3 A1 2 3
15 Si0 2
12.18
20.04
58.94
11.84
19.79
59.93
7iH 2
8.84
8.44
100.00 100.00 100.00
100.00 100.00
Theory.
44a
3K 2
18.62
18.19
3A1 2 3
20.19
20.21
15 SiO 2
59.40
60.90
liH 2
1.79
0.70
100.00 100.00
Theory.
45
3Na 2 O
14.09
13.72
3A1 2 3
23.20
22.14
12 Si0 2
54.54
55.26
6H 2
8.17
8.88
100.00
100.00
Theory.
45a
3K 2
21.26
20.78
3 A1 2 3
12 Si0 2
H 2
23.09
54.30
1.35
22.54
55.53
1.15
100.00 100.00
From the results shown in Table II it will be seen that there occur :
1. A substitution of the mono- and di-valent elements of compounds
of the type
and a substitution of mono-valent elements in compounds of the types
Si)
(S\
Al^-Si I and R 6 (Si Al * &
X Si/
LEMBERG'S EXPERIMENTS
2. A conversion of the compounds of the type
349
l Si
into those of the types
R 6 AlSi and R 6 (Si Al Si)
3. A change in the water-content is observable in some cases.
Table III.
V.
S.
A.
Z.
T.
P.
26 a
0.5 K 2 0'2 NajO'2.5 CaO'5 A1 2 0, \
18 SiO 2 '28 H 2 O /
KC1 Solution
2 Mtbs.
100
5 K 2 O'5 AlaOj'18 Si0 2 '24 H 2
26 b
0.5 K 2 0'2 Na 2 O-2.5 CaO'5 A1 2 0, \
18 SiOj'28 H 2 O /
(8%K a CO+15%Ka) ..
70Hrs.
200-210
5 K 2 O'5 A1 2 O,'18 SiOj'24 H 2
26 c
5 K 2 O'5 A1,O S '18 SiO 2 '24 H 2 O
NaCl ,.
20 Days
100
5 Na,0'5 A1 2 3 '18 Si0 2 '27 H 2 O
26 d
26 f
26 e
5 K 2 O'5 A1 2 O 8 '18 SiO 2 '24 H 2 O
5 K 2 O'5 A1 2 O,'18 SiO 2 -24 H 2 O
5 Na,0'5 A1 2 O,'18 SiOj'10 H 2 O
(15%NaCl+5%Na 2 CO,)..
(15% NaQ+5% Na 2 CO) ,.
KC1
150 Hrs.
150 Hrs.
100 Hrs.
200-210
200-210
200-215
5 Na 2 O'5 A1 2 S '18 Si0 2 '10 H 2 O
5 Na 2 O'5 A1 2 O,'18 SiO 2 '10 H 2
5 K 2 O'5 A1 2 0,'18 SiO 2 'H 2 O
26 g
5 Na 2 O'5 A1 2 0,'18 SiOj'10 H 2 O
KC1 ,.
100 Hrs.
210
5K 2 0-5Al 2 0,'18Si0 2 -H 2
Theory.
26
0.5 K 2
2Na 2
2.5 CaO
1.94
5.09
5.78
2.00
4.92
5.89
5 A1 2 3
18 Si0 2
21.04
44.54
21.66
44.30
28H 2
21.61
21.23
Analyses
Theory.
26a
26b
5K 2
18.87
18.85
18.65
5 A1 2 3
20.48
20.43
20.49
18Si0 2
43.35
43.75
44.21
24H 2
17.30
16.96
16.65
100.00 99.99 100.00
100.00 100.00
Theory.
26c
5 Na 2
5 A1 2 3
18 SiO 2
27H 2
12.98
21.44
45.23
20.35
12.89
21.27
45.44
20.40
100.00
100.00
Theory.
26d
26f
5Na 2
14.91
14.98
14.98
5A1 2 3
24.52
24.68
24.33
18 Si0 2
51.92
51.59
52.05
10H 2 O
8.65
8.75
8.64
100.00 100.00 100.00
Theory.
26e
26g
5 K 2 22.62
21.86
21.64
5 A1 2 O 3 24.54
25.87
25.31
18 Si0 2 51.97
51.70
52.49
H 2 0.87
0.57
0.56
100.00 100.00 100.00
350
LEMBERG'S EXPERIMENTS
Table IV
V.
S.
A.
Z.
T.
P.
27 a
0.5 K,O'2.5 Na 2 O'2 CaO'5 A10 S \
18 SiOj'28 H a O f
KC1 Solution
1 Mth.
100"
5 K,O'5 Al 2 0a'18 Si0 2 '24 H0
27 b
0.5 KjO'2.5 Na,O'2 CaO'5 A1 2 S )
18 SiOj'28 H 2 O f
(15%KC1+8%K 2 C0 3 ) ..
150 Hrs.
210-220
5 K 2 O'5 A1 2 2 -18 SiOt'16 H 2 O
27 c
5 KjO'o A1 2 3 '18 SKV24 H 2 O
NaCl .,
18 Days
100
5 Na 2 0-5 A1 2 O S '18 Si0 2 '27 H 2 O
27 d
5 Na 2 O'5 A1 2 O 3 '18 SiO 2 '27 H 2 O
(15%NaCl+5%Na 2 C0 3 )
170 Hrs.
210-220
5 Na 2 0'5 Al 2 O s -18Si0 2 '10H 2 O
27 e
5 Na 2 O'5 A1 2 3 '18 SiO 2 '10 H 2 O
KC1 ..
75 Hrs.
200-210
5 K 2 O'5 A1 2 3 '18 SiO 2 'H 2 O
27 f
5 K 2 0'5 A1 2 3 '18 Si0 2 'H 2 O
NaCl ,.
10 Days
100"
5 Na 2 O'5 A1 2 S '18 SiO,'10 H 2
Analyses
Theory.
27
0.5 K 2 O
1.94
1.27
2.5 Na 2
2CaO
6.40
4.55
6.76
5.05
5A1 2 3
18 SiO 2
28H 2 O
21.03
44.49
21.59
21.27
44.12
21.57
Theory.
27a
5K 2
18.87
18.67
5 A1 2 3
20.48
20.41
18 Si0 2
43.35
44.08
24H 2
17.30
16.84
100.00 100.00
100.00 100.04
Theory.
27b
5K 2
20.02
19.55
5A1 2 3
21.72
21.96
18 Si0 2
45.99
46.34
16H 2 O
12.27
12.15
100.00
100.00
Theory.
27d
27f
5Na 2
14.91
14.97
14.86
5 A1 2 3
24.52
24.52
24.44
18 SiO 2
51.92
51.96
52.16
10H 2 O
8.65
8.55
8.54
Theory.
27c
5Na 2
12.88
12.50
5 A1 2 3
21.44
21.28
18 Si0 2
45.33
45.68
27H 2
20.35
20.54
100.00
100.00
Theory.
27e
5K 2
22.62
21.57
5 A1 2 3
18 Si0 2
24.54
51.97
25.20
52.74
H 2
0.87
0.49
100.00 100.00 100.00
100.00 100.00
From the results given in Tables III and IV there is clearly a substitution
of the mono- and di-valent elements in the type
R 10 (Si AT Si Al Si)
and in one case (Table IV, No. 27d) a change in the water-content,
(e) The formation of compounds of the type *
5.5 R 2 6 A1 2 O 3 16 Si0 2 = R u (Si Al Si Al Si).
On treating two molecules of K 2 O Si0 2 with one molecule of H 2 K 2 O
A1 2 3 LEMBERG obtained the substance
0.5 Na 2 5 K 2 6 A1 2 O 3 16 Si0 2 = NaK 10 "(Si Al Si Al Si) f
* Lemberg, I. c. 1876, pp. 574-5.
t Expt: 1, L c. p. 574.
LEMBERG'S EXPERIMENTS
351
On treating this silicate for a further period of 7 or 18 days at the ordinary
temperature with variable quantities of solutions of sodium chloride,
potassium chloride, etc.,* LEMBERG obtained compounds whose analyses
corresponded to the general formula
5.5 R 2 6 A1 2 3 16 SiO 2 = R u (Si Al Si Al Si)
16 Si0 2 (Expt. 2b)
16 Si0 2 (Expts. la, Ig, 2a, 2c)
16Si0 2 (Expts, lb, If, 2d)
16 SiO 2 (Expts. Ic, le)
16Si0 2 (Expt. Id)
16 Si0 2 (Expt: 2)
16 Si0 2 (Expt. 4b)
16 Si0 2 (Expts. 4a, 4c)
16 Si0 2 (Expt. 4d)
16Si0 2 (Expt. 4)
16 Si0 2 (Expts. 3a, 3b, 3c)
16 Si0 2 (Expt. 3d)
16 Si0 2 (Expt. 3).
Na 2
4.5 K 2
6 A1 2 3
2Na 2
3.5 K 2
6 A1 2 3
2.5 Na 2
3K 2
6A1 2 3 -
3Na 2 O
2.5 K 2 O
6 A1 2 3
3.5 Na 2 O
2K 2
6 A1 2 O 3
5Na 2 O
0.5 K 2 O
6 A1 2 3
1.5 K 2
4 MgO
6 A1 2 3 -
2K 2
3.5 MgO
6 A1 2 3
2.5 K 2 O
3 MgO
6 A1 2 3
3K 2
2.5 MgO
6 A1 2 3
1.5 K 2 O
4 CaO
6 A1 2 3
2K 2 O
3.5 CaO
6 A1 2 3
2.25 K 2
3.25 CaO
6 A1 2 3 -
Theory.
1
0.5 Na 2 O
1.50
1.83
5K 2
22.67
22.75
6A1 2 3
29.52
29.38
16 Si0 2
46.31
46.04
100.00 100.00
Theory.
2b
Na 2
3.02
2.55
4.5 K 2 O
20.56
21.21
6A1 2 3
29.75
30.60
16 Si0 2
46.67
45.64
100.00 100.00
Theory.
la
Ig
2a
2c
2Na 2
3.5 K 2
6.12
16.25
6.41
16.00
6.67
15.40
5.98
16.37
5.91
16.79
6A1 2 3
16 Si0 2
30.22
47,41
29.99
47.60
29.88
48.05
30.40
47.25
30.30
47.00
100.00 100.00 100.00 100.00 100.00
Theory.
lb
If
2d
2.5 Na 2
7.72
7.54
7.52
7.54
3K 2
14.04
14.12
14.03
14.71
6A1 2 3
30.46
29.74
30.00
30.00
16 Si0 2
47.78
48.60
48.45
47.75
100.00 100.00 100.00 100.00
* In the cases mentioned the salt solutions were of a definite concentration. The
salts were: NaCl-, KC1-, MgCl a -, CaCl a -, (NaCl+KCl)-, (MgCl 2 -f-KCl)-, (CaCl a +KCl).
352
LEMBERG'S EXPERIMENTS
Theory.
Ic
le
Theory.
Id
3
2.5
6
16
Na 2 O
K 2
A1 2 3
Si0 2
9.33
11.79
30.71
48.17
8.97
11.89
30.12
49.02
8.78
12.10
30.13
48.99
3.5 Na 2 10
2 K 2 9
6 A1 2 3 30.
16 Si0 2 48.
.97
.57
96
50
11.19
8.95
30.29
49.57
100.00
100.00
100.00
100.00
100.00
Theory.
2
Theory.
4b
5
0.5
6
16
Na 2
K 2 O
A1 2 3
Si0 2
16.07
2.43
31.73
49.77
15.60
3.21
31.20
49.99
1.5 K 2 7.
4 MgO 8.
6 A1 2 3 32,
16 Si0 2 51,
52
54
68
26
7.94
8.33
32.29
51.44
100.00
100.00
100
.00
100.00
Theory.
4a
4c
Theory.
4d
2
3.5
6
16
K 2 O
MgO
A1 2 3
Si0 2
9.89
7.36
32.22
50.53
10.03
6.97
31.72
51.28
10.01
7.03
31.60
51.36
2.5 K 2 12.
3 MgO 6.
6 A1 2 3 31,
16 Si0 2 49.
19
23
76
82
11.59
6.37
31.69
50.35
100.00
100.00
100.00
100.
00
100.00
Theory.
4
3 K 2
2.5 MgO
6 A1 2 3
14.43
5.12
31.32
13.72
4.94
31.80
16 Si0 2
49.13
49.19
100.00
99.65
Theory.
3a
3b 3o
1.5
K 2 O
7.28
7.75
6.42 7.32
4
CaO
11.57
11.07
12.14 10.99
6
16
A1 2 3
Si0 2
31.60
49.55
30.91
50.27
31.20 31.00
50.24 50.79
100.00
100.00
100.00 100.10
Theory.
3d
Theory.
3
2
3.5
K 2
CaO
9.61
10.02
8.81
10.10
2.25 K 2 10.
3.25 CaO 9.
76
26
10.87
9.22
6
16
A1 2 3
Si0 2
31.29
49.08
31.03
50.06
6 A1 2 3 31.
16 SiO 2 48.
13
85
30.64
49.23
100.00 100.00
100.00 99.96
THE TOPAZ GROUP
353
The Topaz Group
The following analyses of the Topazes conform to compounds of the type
Al - Si Al = 6 A1 2 3 6 SiO 2
and to the following formulae :
(a) SieAluO* F1 8 ,
(b) Si 6 Al 12 25 . 5 Fl 9 ,
(c) Si 6 Al 12 25 F1 10 ,
(d) SieAl^O^gFl^,
(e) Si 6 Al 12 24 F1 12 .
SiOj
A1 2 3
Fl
Total
Source
Analyst
(a) Si 6 Al 12 26 Fl 8 .
Theory
33.97
57.74
14.34
106.05
I
34.24
57.45
14.99
107.37
Schneckenstein
Berzelius 1 *
XII
34.36
57.74
15.02
107.12
Finbo
Berzelius 2
XXII
34.01
58.38
15.06
107.45
Brazil
Berzelius 3
(b) Si 6 Al 12 25 . 5 Fl 9 .
Theory
33.62
57.14
15.97
106.73
XXIV
33.73
57.39
16.12
107.24
Brazil
Rammelsberg 4
XXV
33.15
57.01
16.04
106.20
Pikes Peak
Hillebrand 6
(c) Si 6 Al 12 25 Fl 10 .
Theory
33.25
56.55
17.56
107.36
IV
33.35
56.53
17.69
107.57
Altenberg
Klemm 8
V
33.23
56.20
17.37
106.80
Altenberg
Klemm 7
VI
33.38
56.32
17.26
106.96
Altenberg
Klemm 8
XIV
33.72
56.10
17.20
107.02
Finbo
Klemm 9
XV
33.57
56.30
17.00
106.87
Finbo
Klemm 10
XVI
33.64
56.24
17.12
107.00
Finbo
Klemm 11
XVIII
33.68
56.36
17.11
107.15
Miask
Klemm 18
XIX
33.19
56.72
17.09
107.00
Miask
Klemm 13
XXI
33.24
57.02
17.64
108.73
Tasmania
Sommerland 1 '
(d) Si 6 Al 12 24 . 5 Fl n .
Theory
32.93
55.97
19.12
108.02
III
33.53
56.54
18.62
108.69
Schneckenstein
Rammelsberg 15
X
32.28
55.86
18.28
106.42
Zinnwald
Rammelsberg 1 '
XI
XX
33.27
33.56
56.76
56.28
18.54
18.30
108.67
106.14
Schlaggenwald
Adun-Tschilon
Rammelsberg 17
Rammelsberg x 8
* References to the Literature are given on p. 438 et eeq.
2 A
354
THE EPIDOTES
The Epidotes
The following analyses of the Epidotes conform to compounds of the type
Si Al Al Si = 6 A1 2 3 12 Si0 2
or to the general formula :
4
H 2 0-
(a)
(b)
(c)
(d)
(e)
(f)
(g)
(h)
(i)
16
4
4
4
4
4
4
4
4
4
CaO
H 2
H 2
H 2
H 2 O
H 2
H 2
H 2
H 2
H 2
2 (6 R 2
- 16 CaO
16 CaO
16 CaO
16 CaO
16 CaO
16 CaO
16 CaO
16 CaO
16 CaO
3 12 Si0 2 )
2 Fe 2 3
2.25 Fe 2 3
2.5 Fe 2 O 3 -
2.75 Fe 2 O 3
3Fe 2 3 -
3.25 Fe 2 3
3.5 Fe 2 3
3.75 Fe 2 3
4 Fe 2 3
(12 R 2 3 =
10 A1 2 3
9.75 A1 2 3
9.5 A1 2 3
9.25 A1 2 O 3
9A1 2 3 -
8.75 A1 2 3
8.5 A1 2 O 3
8.25 A1 2 3
8 A1 2 3
mFe 2 3 nAl 2 3 ).
24 SiO 2 .
24Si0 2 .
24Si0 2 .
24 Si0 2 .
24Si0 2 .
24 SiO 2 .
24Si0 2 .
24 Si0 2 .
24Si0 2 .
Si0 2
A1 2 0,
Fe a O s
CaO
H a O
FeO
Total
Source
Analyst
(a) 4 H 2 16 CaO 2 Fe 2 3 10 A1 2 O 3 24 Si0 2 .
Theory
38.44
27.21
8.54
23.90
1.91
100.00
III
39.18
26.52
8.21
23.89
2.20
100.00
Zoptau
Nanke 1 *
XVI
38.42
26.62
8.72
23.66
2.46
99.88
Sustenhorn
Stockar-Escher 2
XVII
38.43
26.18
8.77
24.13
2.46
99.97
Sustenhorn
Stockar-Escher 3
XX
37.66
27.36
8.90
23.90
2.33
100.15
Caverdiras
Stockar-Escher*
XXI
38.08
27.74
8.27
23.53
2.04
99.66
Maggiatal
Stockar-Escher 5
XXII
38.28
27.53
8.66
22.87
2.41
99.75
Formarzatal?
Stockar-Escher 6
XLIV
37.92
27.90
9.10
22.81
2.02
99.75
Pargas
Wilk 7
(b) 4 H 2 16 CaO 2.25 Fe 2 O 3 9.75 A1 2 3 24 Si0 2 .
Theory
38.28
26.43
9.57
23.81
1.91
100.00
XIV
37.96
26.35
9.71
23.77
2.02
99.81
Guttannen
Stockar-Escher 8
XV
38.13
26.42
9.74
23.30
2.02
99.61
Guttannen
Stockar-Escher 9
XXXIV
37.87
24.72
9.96
23.10
2.82
0.36
100.14a
Mainland
Heddle 10
(c) 4 H 2 O 16 CaO 2.5 Fe 2 O 3 9.5 A1 2 O 3 24 Si0 2 .
Theory
38.13
25.65
10.59
23.72
1.91
100.00
XIII
38.99
25.75
9.99
23.76
2.05
0.61 MgO
100.16
Guttannen
Scheerer 11
XLI
38.84
25.45
10.88
22.62
2.41
100.20
Arendal
Richter 12
(d) 4 H 2 O 16 CaO 2.75 Fe 2 3 9.25 A1 2 3 24 Si0 2 .
Theory
38.00
24.90
11.60
23.62
1.88
100.00
_ i _
LIII
37.47
24.09
10.60
22.19
2.24
2.81
99.40
Achtenskoi Hermann 1 3
LIX
38.20
24.62
12.20
21.59
2.16
0.57 MnO
99.846
Rowe, Mass. JA. G. Dana 14
(e) 4 H 2 16 CaO 3 Fe 2 3 9 A1 2 3 24 Si0 2 .
Theory
37.84
24.12
12.61
23.54
1.89
100.00
VIII
38.60
23.08
12.34
24.17
1.88
0.95
101.02
Sulzbachtal
Mauthner 15
IX
36.90
24.36
12.40
23.54
2.01
0.72
lOO.OOe
Sulzbachtal
Laspeyres 18
XXXII
38.26
24.75
11.07
23.63
2.26
0.56
100.53
Quenast
Renard 17
XXXVII
37.32
22.85
11.56
22.13
2.93
1.86
99.32d
Arendal
Hermann 18
a Inch 0.54 MnO 0.77 MgO.
6 Inol. 0.07 MnO.
* For references see p. 438.
c. Inch 0.13 MgO 0.37 Alkalies.
d Incl. 0.77 MgO.
THE GRANITES
355
SiO,
A1.0,
Fe 2 8
CaO
HO
FeO
Total
Source
Analyst
(f) 4 H 2 O 16 CaO 3.25 Fe 2 O 3 8.75 A1 2 O 3 24 Si0 2 .
Theory
37.70
23.37
13.601 23.45
1.881
100.00
IV
38.37
22.09
13.77 22.90
2.11
99.24
Sulzbachtal
v. Drasche 19
VI
37.83
23.43
13.3l| 23.47
2.06| 0.48
100.58
Sulzbachtal
Ludwig 80
(g) 4 H 2 16 CaO - 3.5 Fe 2 O 3 8.5 A1 2 O 3 24 Si0 2 .
Theory
37.55
22.61
14.60
23.36
1.88
100.00
V
XXX
LVIII
37.83
36.71
37.04
22.63
22.61
22.99
14.02
14.47
14.19
23.27
23.67
24.09
2.05
1.92
2.16
0.93
0.62
100.73
100.00
100.47
Sulzbachtal
"Bourg d'Osians"
Hereroland
Ludwig 21
Laspeyres 22
Wulf 23
(h) 4 H 2 16 CaO 3.75 Fe 2 3 8.25 A1 2 O 3 24 Si0 2 .
Theory
37.40
21.861 15,59
23.28
1.87
100.00
VII
37.11
21.90| 16,00
23.19
2.03
100.23
Sulzbachtal
Rammelsberg 24
(i) 4 H 2 16 CaO 4 Fe 2 O 3 8 A1 2 3 24 Si0 2 .
Theory
37.27
21.11 16.56 23.1911.87
__
100.00 _
XXIII
37.65
20.64
16.50
22.32 2.06
0.49MnO
100.12
Traversella
Scheerer 25
XXVIII
XXIX
XXXVII
XL
37.56
37.35
38.76
37.59
20.78
22.02
20.36
20.73
16.49
15.67
16.35
16.57
22.70
22.54i
23.71
22.64
2.09
2.35
2.00
2.11
0.29 MgO
0.44 MgO
0.41 MgO
99.91
99.93
101.67
100.05
"Bourg d'Osians"
"Bourg d'Osians"
Arendal
Arendal
Scheerer 26
Stockar-Escher 27
Rammelsberg 2 8
Scheerer* 9
The Granite Group
A number of Granites examined by K. H. Schneer may be expressed by
the general formula :
18 RO 6 R 2 3 18 Si0 2 and 16 RO 6 R 2 3 16 Si0 2
as may be ascertained from the following Table :
% Molecules
No.
CaO
FeO
MnO
A1.0,
Fe 2 0,
SiO a
H,0 || CaO
FeO
MnO
A1.0,
Fe,0,|siO,|H,O
Theory
33.25
1.22
6.92
21.72
36.89
1
33.59
1.17
7.44
20.94
36.56
17.5
0.5
2
4
18
Theory
32.12
1.82
0.60
6.88
21.59
36.68
0.31
2
32.36
1.91
0.48
7.35
21.58
36.33
0.48
17
0.75
0.25
2
4
18
0.5
Theory
32.12
2.43
6.88
21.59
36.68
0.30
3
31.51
2.88
7.07
22.51
35.97
0.25
17
1
2
4
18
0.5
Theory
33.52
1.25
0.61
12.39
13.88
37.73
0.62
4
33.55
1.68
0.28
11.99
14.79
37.53
0.48
17.25
0.5
0.25
3.5
2.5
18
1
Theory
34.22
1.25
13.36
12.57
37.96
0.64
5
34.01
1.71
0.54
13.29
13.01
37.52
0.53
17.5
0.5
3.75
2.25
18
1
Theory
32.46
3.85
16.37
8.56
38.76
6
31.98
4.46
0.57
16.29
8.73
37.96
0.22
16.25
1.75
4.5
1.5
18
Theory
32.05
2.74
13.72
14.60
36.89
7
32.73
2.54
13.73
14.03
37.18
15
1
3.75
2.25
16
356
THE MESOLITES
The
The following analyses of the
(a) S Al - Si Al S = 6 A1 2 3 15 Si0 2 ,
(b) Si Al Si Al Si = 6 A1 2 3 16 Si0 2 ,
(a) Mesolites of the type
Sf Al Si Al Si = 6 A1 2 3 15 Si0 2 ,
Source
Analyst
1
9 MO
2(6A1 2 O 3 -
15 SiO 2 )
36H 2 O
9MO = 3Na 2
6CaO
Antrimolite
Bengune
Thomson
2
11 MO
2 (6 A1 2 O 3
15SiO 2 )
26H 2 O
HMO = 5Na 2 O
6CaO
Eisenach
Luedecke
(b) Mesolites of the type
Si -Al - Si Al Si = 6 A1 2 3 16 Si0 2
Source
Analyst
3
10 MO - 2 (6 A1 2 O 3 16 SiO 2 ) 30 H 2 O
10MO=4Na 2 O-6CaO
Sandy Cove, N.S.
Marsh
4
11 MO 2 (6 A1 2 O 3 16 SiO 2 ) 40 H 2 O
HMO = 5Na 2 O-6CaO
Caranja Isle
Thomson
5
12 MO 2 (6 A1 2 O 3 16 SiO 2 ) 24 H 2 O
12MO = 4Na 2 O-8CaO
Harringtonite
Thomson
(c) Mesolites of the type
Si Al Si Al - Si = 6 A1 2 3 17 Si0 2
Source
Analyst
6
9 MO 2 (6 A1 2 O 3 17 SiO 2 ) 32 H 2 O
9 MO = 2 Na 2 O 7 CaO Iceland
Fuchs & Gehlen
7
11 MO 2 (6 A1 2 O 3 17 SiO 2 ) 30H 2 O
1 1 MO = 4 Na 2 O 7 CaO Iceland
Breidenstein
(d) Mesolites of the type
Si Al Si Al Si = 6 A1 2 3 18 Si0 2
1
Source
Analyst
8
12 MO- 2(6 A1 2 O 3 - 18 SiO 2 ) 30H 2 O
12MO = 4 Na 2 O 8 CaO
Niederkirchen
Riegel
9
10
11
12
13
99 99 99
99 99 99
99 99 99
99 99 99
99 9
99 9
99 9
99 9
99 9
Tirol
Antrimolite /
Bengune \
Skye
Skye
Fuchs & Gehlen
Heddle
Heddle
Heddle
Heddle
THE MESOLITES
357
Mesolites
Mesolites conform to the following types :
(c) Si Al Si Al Si = 6 A1 2 3
(d) Si Ai S*i Al Si = 6 A1 2 3
or the general formula
m MO 2 (6 A1 2 3 15 Si0 2 ) n H 2 0.
17 SiO,
18 SiO,
SiO,
Al,0,
CaO
Na,0
H,0
MgO
Total
Theory
VII
42.92
43.47
29.18
30.26
8.01
7.50
4.43
4.10*
15.46
15.32
0.19 FeO
100.00
100.94
Theory
II
43.50
43.83
29.57
29.04
8.12
7.84
7.49
7.80
11.31
11.75
z
100.00
100.26
or the general formula
m MO 2 (6 A1 2 3 16 Si0 2 )
nHoO.
Si0 2
A1,0 S
CaO
Na a O
H,0
MgO
Total
Theory
XXXII
44.98
45.39
28.68
28.09
7.87
7.55
5.81
5.28
12.66
12.71
0.49 K 2 O
100.00
99.51
Theory
XXXIX
42.58
42.70
27.14
27.50
7.45
7.61
6.87
7.00
15.96
14.71
100.00
99.52
Theory
XI
44.95
44.84
28.65
28.48
11.21
10.68
5.80
5.56
10.11
10.28
100.00
99.84
or the general formula
m MO 2 (6 R 2 3 17 Si0 2 )
nHoO.
SiO,
Al,0 8
CaO
Na,0 | H,0
MgO
Total
Theory
XXVI
46.83
46.58
28.10
27.57
9.00
9.10
2.84
3.64
13.83
13.17
0.03
100.00
100.14
Theory
XXIII
45.90
45.78
27.54
27.53
8.82
9.00
5.58
5.03
12.15
12.30
0.31 K,O
100.00
100.13
or the general formula
m MO 2 (6 A1 2 3 18 SiO 2 ) n H 2 O.
SiO,
Al,0,
CaO
Na,0
H,0
MgO
Total
Theory
V
VIII
IX
XIII
XIV
46.76
46.65
46.04
47.07
45.98
46.70
46.72
26.49
27.40
27.00
26.23
26.18
26.62
26.70
9.70
9.26
9.61
9.88
10.78
9.08
8.90
5.37
4.91
5.20
4.89
4.54
5.39
5.40
11.68
12.00
12.36
12.24
13.00
12.83
12.92
100.00
100.22
100.21
100.31
100.48
100.63
100.64
* Determined by Thomson as K a O.
358
THE CLINTONITES
Source
Analyst
12MO2(6A1 2 O S -18 SiO 2 )-30H 2 O
12MO = 4Na 2 O-8CaO
14
Skye
Heddle
15
NaalsjO
Berzelius
16
NaalsjS
Heddle
17
Naalsjo
Fuchs and Gehlen
18
Naalsjo
Durscher
19
StromO
E. E. Schmid
20
Berufjord
S. v. Waltershausen
21
Iceland
Fuchs and Gehlen
22
Iceland
Fuchs and Gehlen
23
Iceland
E. E. Schmid
24
Iceland
Lemberg
25
Port George, N.S.
How
26
Port George, N.S.
How
27
Cape Blomidon
Marsh
28
Atacama, Chili
Darapsky
29
14MO2(6 Al 2 O 8 -18SiO 2 H4H 2 O
14MO = 3Na 2 0-llCaO
Fritz Island, Pa.
Sadtler
The
The following analyses of the minerals of the
= 5R,O a - 6Si0 2 ,
12 Si0 2 ,
6 Si0 2 ,
12 Si0 2 ,
Si = 6 R,0 a 16 Si0 2 ,
18 Si0 2 .
A.
B.
C.
D.
E.
F.
R
R
R
R
Si
Si
&
si-
Si-
Si-
R.
R.
R
Si
R
Si
Si
Si
R
R
R
-R
2 ^3
= 5R 2 3
= 6 R 2 3
- 6 R 2 3
6R 2 3
6R 0,
A. Compounds of the type
R . Si R = 5 R 2 3 6 Si0 2
j
Source
Analyst
1
12M02 (5 Al 2 3 -6Si0 2 )-12H 2
12MO = 8FeO -4MgO
St. Marcel
Kobell
2
13MO-2 (5 Al 2 O 3 -6 SiO 2 )-9 H 2 O
13MO = 10FeO-2.5 MgO-0.5 MnO
Leeds, Canada
Hunt
B. Compounds of the type
R si Si R = 5 R 2 3 12 Si0 2
Source
Analyst
3 13MO-2(5 Al 2 O 3 -12SiO 2 )-llH 2 o| 13MO = 9.25FeO3.75 MgO St. Marcel Damour
THE CLINTONITE GROUP 359
SiO,
Al,0,
CaO
Na 2 O
H,0
MgO
Total
Theory
46.76
26.49
9.70
5.37
11.68
100.00
XV
46.26
26.48
10.00
4.98
13.04
100.76
XVII
46.80
26.50
9.87
5.40
12.30
100.87
XVIII 46.80
26.46
9.08
5.14
12.28
99.76
XIX 47.00
26.13
9.35
5.47
12.25
100.20
XX
47.50
26.10
9.15
4.57
12.80
100.12
XXI
47.40
27.05
9.16
4.69
12.69
0.06
101.05
XXII
46.41
26.24
9.68
4.46
13.76
0.01
100.97
XXIV
46.78
25.66
10.06
4.79
12.31
99.60
XXV
47.46
25.35
10.04
4.87
12.41
100.13
XXVII
47.13
26.52
10.36
4.50
12.59
101.12
XXVIII
45.96
26.69
9.48
5.09
12.78
100.00
XXIX
46.66
26.48
9.63
4.83
12.25
99.85
XXX
46.71
26.68
9.55
5.68
11.42
100.04
XXXI
45.89
27.55
9.13
5.09
12.79
0.48 K 2
100.93
XXXVI
46.74
25.99
9.11
5.23
12.41
99.48
Theory
43.39
24.59
12.37
3.73
15.92
_
100.00
XXXIII
43.29
25.02
12.15
3.40
16.01
99.87
Glintonite Group *
Clintonite group conform to the following types :
G. Sl
= 7.5 R0 6 Si0
23
H. R Si R S A i R = 8 R 2 3 12 Si0 2 ,
Jk
J. SI^-R = 9R 2 3 - 6Si0 2 ,
X R
K. R Si R Si R = 9 R 2 3 12 Si0 2 .
or the general formula
m MO 2 (5 R 2 3 6 Si0 2 ) n H 2 0.
SiO,
A1 2 0,
Fe,0,
FeO
MnO
MgO
CaO
H,O Total
Theory
IX
26.74
25.75
37.89
37.50
~
21.40
21.00
z
5.94
6.20
-
8.03
7.80
100.00
98.25
Theory
XXXI
26.12
26.30
36.99
37.10
~
26.11
25.92
1.28
0.93
3.62
3.66
-
5.88
6.10
100.00
100.01
or the general formula
m MO 2 (5 R 2 3 12.Si0 2 ) n H 2 0.
SiO,
A1 2 8
Fe 2 0,
FeO
MnO
MgO
CaO
H 2
* Known in Germany as the Sprodglimmer or "brittle micas."
Total
Theory
XI
26.23 37.27
25.50 38.13
24.27
23.58
5.11
5.19
7.22
6.90
100.00
99.30
360
THE CLINTONITE GROUP
C. Compounds of the type
R- Si R = 6R 2 3 6Si0 2
Source
4
10 MO 2(6 B 2 O 3 6 SiO 2 ) - 10 H 2 O
10MO = 7FeO-3MgO
12 R 2 3 = 8.75 A1 2 3 3.25 Fe 2 O 3
Kossoibrod.
5
6
11 MO 2(6 R 2 3 6 Si0 2 ) 10 H 2 O
11 MO 2(6 R 2 O 3 6 Si0 2 ) 10 H 2 O
11 MO = 5 MgO 5.5 FeO 0.5 CaO
12 R 2 3 = 11.25 A1 2 3 0.75 Fe 2 O 3
11 MO = 4.75 MgO 0.25 MnO 5.5 FeO
0.5 CaO 12 R 2 O 3 = 11.5 A1 2 O 3 0.5 Fe 2 O 3
St. Marcel
Shetland
7
11 MO - 2(6 A1 2 3 6 Si0 2 )- 12 H 2 O
HMO = llFeO
St. Marcel.
8
12MO-2(6Al 2 3 -6Si0 2 )
12MO = 12FeO
Kossoibrod.
9
12 MO 2(6 A1 2 O 3 6 SiO 2 )- 10 H 2 O
12 MO = 1 1.5 FeO 0.5 H 2 O
Gumuch-Dagh
10
11
12 MO 2(6 A1 2 O 3 - 6 SiO 2 ) 10 H 2 O
12 MO 2(6 A1 2 O 3 - 6 SiO 2 ) - 12 H 2 O
12 MO = 10.5 FeO 1.5 MgO
12 MO = 7.75 FeO 4.25 MgO
Grippe, He de
Groix
Zermatt.
12
12 MO 2(6 A1 2 O 3 - 6 SiO 2 ) 12 H 2 O
12 MO = 9.75 FeO 2.25 MgO
Pregratten.
13
13 MO 2(6 A1 2 O 3 - 6 SiO 2 ) 12 H 2 O
13 MO = 11.75 FeO 0.75 MgO 0.25 MnO
0.25 CaO
Gumuch-Dagh.
14
13 MO - 2(6 A1 2 3 - 6 SiO 2 ) 12 H 2 O
13 MO = 11. 75 FeO -0.75 MgO -0.25 MnO
0.25 CaO
Gumuch-Dagh.
15
13 MO 2(6 A1 2 O 3 - 6 SiO 3 ) 12 H 2 O
13 MO = 7.5 FeO 0.5 MnO 5 MgO
Shetland.
16
15 MO - 2(6 A1 2 O 3 - 6 SiO 2 ) 11 H 2 O
15MO = 12FeO-3MgO
Kossoibrod.
D. Compounds of the type
R Si Si R =6 R 2 3 12 Si0 2
Source
Analyst
17
18
10MO-2(6R 2 O 3 *12SiO 2 )-
19MO-2(6Al 2 3 -12SiO 2 )
8H 2
14H 2
10 MO = 6 FeO 3 MnO 0.5 MgO
0.5 CaO 12 R 2 O 3 =11 A1 2 O 3 1 Fe 2 O 3
19 MO = 15.5 FeO 3.5 MnO
Lierneux
Natic,Rh.
Island
Renard
Jackson
E. Compounds of the type
Si Al Si Al- Si = 6 A1 2 3 16 Si0 2
Source
Analyst
19 13MO-2(6Al 2 O 3 -16SiO 2 )-12H 2 O 13 MO = 12.5 FeO 0.5 MgO
Venasque
Damour
THE CLINTONITE GROUP
361
or the general formula
m MO 2 (6 R 2 3 6 Si0 2 ) n H 2 0.
Analyst
| Si0 8
A1 2 8
Fe a 3
FeO
MnO
MgO
CaO
H,0
Total
Hermann
Theory
XXVI
24.52
24.54
30.39
30.72
17.71
17.28
17.17
17.30
,
4.08
3.75
6.13
6.38
100.00
99.97
Suida
Theory
X
25.79
26.03
41.11
42.33
4.29
4.09
14.19
14.32
__
7.16
7.30
1.00
0.35
6.46
6.56
100.00
100.98
Heddle
Theory
XXI
25.91
25.36
42.21
41.74
2.87
3.90
14.05
13.93
0.64
0.92
6.84
6.82
1.00
0.90
6.48
6.57
100.00
100.14
Delesse
Theory
VIII
24.39
24.10
41.47
40.71
~
26.83
27.10
z
~
7.31
7.24
100.00
99.15
Erdmann
Theory
XXIV
25.64
24.96
43.59
43.83
~
30.77
31.21
~
~
~
100.00
100.00
Smith
Theory
XXVIII
24.41
24.10
41.50
39.80
27.69
27.55
0.30
(K 2 O+Na 2 O)
6.40
6.50
100.00
98.25
Renard
Theory
XIII
24.59
24.90
41.78
40.36
25.45
26.17
___
2.05
2.54
-
6.13
6.23
100.00
100.23
Damour
Theory
VI
24.93
24.40
42.38
42.80
19.33
19.17
5.88
6.17
7.48
6.90
100.00
99.44
A. Sipocz
Theory
IV
24.39
24.90
41.46
40.99
0.55
23.78
24.28
3.05
3.33
7.32
7.82
100.00
101.87
L. Smith
Theory
XXIX
23.47
23.94
39.90
39.52
27.58
28.05
0.58
0.52
0.98
0.80
0.46
0.45
7.03
7.08
100.00
100.36
L. Smith
Theory
XXX
23.47
23.20
39.90
40.21
27.58
27.25
0.58
0.98
0.95
0.46
0.83
7.03
6.97
100.00
99.41
Heddle
Theory
XX
24.53
24.47
41.70
41.34
0.38
18.40
18.52
1.21
0.91
6.81
6.80
0.30
7.35
6.98
100.00
99.70
Kobell
Theory
XXVII
23.03
23.01
39.15
40.26
27.64
27.40
3.84
3.97
6.34
6.34
100.00
100.98
or the general formula
m MO 2 (6 R 2 3 12 Si0 2 ) n H 2 0.
SiO,
A1 2 3
Fe 2 8
FeO
MnO | MgO
CaO
H 2
Total
Theory
XVIII
40.52
40.55
31.58
30.80
4.50
3.82
11.99
12.46
5.99
6.51
0.57
0.45
0.79
1.29
4.06
4.12
100.00
100.00
Theory
XXXII
33.64
33.20
28.59
29.00
26.07
25.93
5.81
6.00
0.24
__
5.89
5.60
100.00
99.97
or the general formula
m MO 2 (6 R 2 O 3 16 Si0 2 ) n H 2 0.
SiO,
A1 2 0,
Fe 2 0,
FeO
MnO
MgO
CaO
H 2
Total
Theory
XII
44.87
44.79
28.60
29.71
21.03
20.75
0.46
0.62
5.04 1 100.00
4.93 1 100.80
THE CLINTONITE GROUP
F. Compounds of the type
Si ft Si ft Si = 6 R 2 3 18 Si0 2
Source
Analyst
20
17 MO2(6 A1 2 O 8 -18 SiO 2 )-16 H 2 O
17MO = 11.5FeO-5.5MnO
Ottre
Damour
21
17 MO2(6 A1 2 O 8 -18 SiO 2 )-16 H 2 O
17 MO- 11.5 FeO - 5.5 MnO
Ottrf
Damour
G. Compounds of the type
i R = 7.5R 2 O
X R
6Si0
Source
Analyst
22 29 M02(7.5 R 2 O 3 -6 SiO 2 )
12H 2
= 19.75MgO-8.25CaO-lFeO
15R 2 3 =14.5Al 2 3 -0.5Fe 2 3 I
Manzoni
Sipocz
H. Compounds of the type
R Si R Si R = 8 R 2 3 12 Si0 2
Source Analyst
23
24
12MO-2(8R 2 O 3 -12SiO 2 )
12H 2
24 MO-2(8 A1 2 O 8 -12 SiO 2 )
14H 2 O
12MO = 10FeO-2MgO
16R 2 O 3 =llAl 2 3 -5Fe 2 8
24 MO = 24 FeO
Natic, Rh.
Island
Natic, Rh.
Island
Hermann
Whitney
J. Compounds of the type
Source
Analyst
25
26
30MO-2(9R 2 O 3 -6SiO 2 )
6H 2
30MO-2(9R 2 O 3 -6 SiO 8 )
6H 2
30MO = 21.5MgO-8.5CaO
18 R 2 O 3 =17.5 A1 2 O 3 -0.5 Fe 2 O 8
30 MO = 21. 5 MgO-8.5 CaO
18R 2 O 3 = 17.5Al 2 O 3 -0.5Fe 2 O 3
Ural
Ural
G. Wagner
O. Schieffer-
deeker
K. Compounds of the type
R Si 6 Si R = 9 R 2 3 12 Si0 2
Source
Analyst
27
28
29
20 MO-2(9 A1 2 O 3 -12 SiO 2 )
24H 2
22 MO-2(9 A1 2 O 3 -12 SiO 2 )
16H 2 O
25MO-2(9Al 2 O 3 -12SiO 2 )
20 H a O
20 MO = 15.5 FeO-3.5 MgO
0.5 MnO 0.5 CaO
22 MO = 21 FeO- 1 MgO
25 MO = 19.5 FeO 5.5 MgO
Kaisersberg
Hetzschen
Kossoibrod
v. Foullon
Schroder
Bonsdorff
THE CLINTONITE GROUP
or the general formula
m MO 2 (6 R 2 3 18 Si0 2 ) n H 2 O.
363
SiO,
A1,0 S
Fe,0,
FeO
MnO
Mgo
CaO
H,O
Total
Theory
XIV
44.16
43.52
25.04
23.89
__
16.93
16.81
7.98
8.03
___
5.89
5.63
100.00
97.88
Theory
XV
44.16
43.34
25.04
24.63
16.93
16.72
7.98
8.18
z
5.63
5.66
100.00
98.53
or the general formula
m MO 2 (7.5 R 2 O 3 6 SiO 2 ) n H 2 0.
SiO,
A1|0 S
Fe,0,
FeO
MnO
MgO
CaO
H,0
Total
Theory
11*
18.95
18.75
38.94
39.10
2.10
3.24
1.89
1.62
20.80
20.46
12.16
12.14
5.16
5.35
100.00
100.66
or the general formula
m MO 2 (8 R 2 3 12 Si0 2 ) n H 2 O.
SiO,
Al,0,
Fe,0,
FeO
MnO
MgO
CaO
H,0
Total
Theory
XXXIV
32.89
32.68
25.63
26.38
18.28
18.95
16.45
16.17
1.82
1.32
4.93
4.50
100.00
100.00
Theory
XXXIII
28.51
28.27
32.30
32.16
~
34.20
33.72
0.13
4.99
5.00
100.00
99.28
or the general formula
m MO 2 (9 R 2 3 6 Si0 2 ) n H 2 O.
SiO,
Al,0 3
Fe,0,
FeO
MnO
MgO
CaO
H,0
Total
Theory
17.87
44.30
1.99
21.35
11.81
2.68
100.00
Vllf
17.42
44.18
3.53
20.61
11.95
2.61
100.30
Theory
17.87
44.30
1.99
21.35
11.81
2.68
100.00
Vlllf
17.70
43.60
2.90
20.90
11.50
2.50
99.10
or the general formula
m MO 2 (9 R 2 3 12 Si0 2 ) n H 2 O.
SiO,
Al,0,
Fe,0,
FeO MnO
MgO
CaO
H,O
Total
Theory
28.64
36.52
22.20
0.71
2.78
0.56
8.59
100.00
II
28.48
36.86
21.88
0.97
2.80
0.59
8.09
100.36
Theory
28.15
35.89
29.55
0.78
5.63
100.00
I *
28.04
36.19
29.79
1.25
0.20
5.88
100.35
Theory
27.38
34.91
26.69
4.18
6.84
100.00
XXII
27.48
35.57
27.05
0.30
4.29
6.95
101.64
* Brandisite t Xanthophyllite
364
THE MICA GROUP
The
The following analyses of the minerals of the
A. Si R Si = 3 R 2 3 10 SiO 2 ,
B. Si - R Si = 3 R 2 3 12 Si0 2 ,
/Si
C. R-Si = 3 R 2 3 15 Si0 2 ,
D. R-Si = 3 R 2 O 3 18 Si0 2 ,
x s A i
E. R-Si-R = 5R
X Si
A
x s A i
R-Si-R = 5R 2 3 - 6Si0 2 ,
A. Mica of the type
Si R - Si = 3 R 2 3 10 Si0 2
Source
20 MO
2(3R 2 3 -
6H 2 O
10 Si0 2 )
20 MO
6 R 2 3
= 16.5 MgO
= 4.5A1 2 O 3 -
3.5 K 2 O
1.5Fe 2 O 3
Biotite
Chester,
Mass.
B. Mica of the type
S A i R Si = 3 R 2 3 12 Si0 2
Source
6MO-2(3R 2 3 -12Si0 2 )
28MO-2(3R 2 O 3 -12SiO 2 )
6H 2
32 MO 2 (3 A1 2 O 3 12 SiO 2 )
2H 2 O
6MO=1.5FeO-2MgO-2K 2 0-0.5Na 2 O
6R 2 3 =5A1 2 3 -1V 2 3
28 MO = 23 MgO 2 FeO 3 K 2 O
6R 2 O 3 = 5.5 A1 2 O 3 0.5 Fe 2 O 3
32 MO = 26.5 MgO 2.5 K 2 O 3 Na 2 O
Roscoe-
lite
Biotite
Colorado
Moravicza
Edwards,
N.S.
C. Mica of the type
/SI
R~Si = 3R 2 3 - 15Si0 2
X Si
Source
115 MO 2 (3 R 2 O 3 15 SiO 2 )
20 H 2
15 MO = 15 MgO
6 R 2 O 3 = 3.5 Fe 2 O 3 2.5 A1 2 O 3
Biotite
Vermont
D. Mica of the type
A
R; Si = 3 R 2 3 18 Si0 2
Source
39 MO
47 MO
2(3R 2 3 -18Si0 2 )
6H 2
2 (3 A1 2 O 3 18 SiO.)
1H 2 O
39 MO = 32 MgO- 7 K 2 O
6 R 2 O 3 = 3 A1 2 O 3 3 Fe 2 O 3
47MO = 3 FeO 17 MnO 21 MgO
3 CaO 3 K 2
Biotite
Herschenberg
Pajoberg
THE MICA GROUP
365
Mica Group
Mica group conform to the following types :
F. Si R R Si
= 5 R 2 3
12 Si0 2 ,
G. Si -R Si R Si
- 5 R 2 3
18 Si0 2 ,
H. R - Si R
= 6 R 2 3
6Si0 2 ,
J. Si R - R Si
= 6 R 2 3
10 Si0 2 ,
K. S A i R R Si
= 6 R 2 3
12 Si0 2 ,
L. Si R Si R Si
= 6 R 2 3 16 Si0 2 ,
M. Si R Si R Si
= 6 R 2 3
18 Si0 2 ,
N. R Si R Si R
= 9 R 2 O 3 12 Si0 2 ,
0. Si R Si R Si R
T = 9 R 2 S
20 Si0 2 .
of the general formula
m MO 2 (3 R 2 3 10 Si0 2
) n H 2 0.
Analyst SiO 8
A1 2 0, Fe,0 8
FeO CaO MgO K 2 O
Na 2 O H 2 O Total
Pisani Theory 39.95
15.28 7.99
21.97 10.95
3.86 100.00
CLXX 39.55
15.95 7.80
22.25 10.35
4.10 100.00
or the general formula
m MO 2 (3 R 2 3
12 Si0 2 ) n H 2 O.
Analyst
SiO s
Al,0 8
Fe 2 0,
FeO
CaO
MgO
K,0
Na 2
H 2
Total
Genth
Theory-
57.43
56.74
20.34
19.62
6.00V 2 3
7.78V 2 3
4.31
3.84
3.19
2.63
7.50
8.11
1.23
0.94
100.00
99.66
Rumpf
Theory
XLIV
40.73
40.16
15.87
15.79
2.26
2.53
4.07
4.12
~
26.03
26.15
7.98
7.64
0.37
3.06
3.58
100.00
100.34
Crawe
Theory
CLI
40.35
40.36
17.15
16.45
29.70
29.55
6.58
7.23
5.21
4.94
1.01
0.95
100.00
99.48
or the general formula
m MO 2 (3 R 2 3 15 Si0 2 )
nH 2 0.
Analyst
Si0 2
AljO 8 j Fe 2 O 3
FeO
CaO
MgO
K a O
Na 2
H 2 O
Total
Thomson
Theory
CLXXII
50.34
49.08
7.13
7.28
15.67
16.12
16.79
16.96
10.07
10.28
100.00
99.72
or the general formula
m MO 2 (3 R 2 3 18 Si0 2 ) n H 2 0.
Analyst
SiO a
A1.0,
Fe 2 8
FeO
CaO
MgO
K 2 O
NajO
H S O
Total
Bromeis
Theory
XXIII
43.27
42.89
1 6.13
6.09
9.62
10.59
25.64
25.09
13.18
13.15
0.36
2.16
2.30
100.00
100.47
Igelstrom
Theory
CX
38.63
38.50
10.94
11.00
3.86
3.78
3.00
3.20
15.01
15.01
5.04
5.51
21.58MnO
21.40MnO
1.94
1.60
100.00
100.00
366
THE MICA GROUP
E. Micas of the type
R -Si R = 5R 2 3 -6Si0 2
1
Source
8
6.5 MO
2 (5 A1 2 3
6H 2
6 SiO 2 )
6.5MO = 4.5CaO
1.5 FeO -0.5 MgO
Margarite
Peekskill
F. Micas of the type
Si R R Si = 5 R 2 3 12 Si0 2
Source
9
3 MO
2 (5 A1 2 3
12 SiO 2 )
3 MO = 1 FeO 0.5 MgO 1.5 K 2 O
Pinitoid
Weinheim
9H 2
10
5 MO
2(5A1 2 3
12 SiO 2 )
5 MO = 1 MgO- 1.5K 2 O-2.5Na 2 O
Friebenreuth
9H 2
11
6 MO
2 (5 A1 2 3
12 SiO 2 )
6 MO = 2 MgO 3.5 K 2 O 0.5 Na 2 O
Muscovite
Unionville,
8H 2 O
Pensylv.
12
6 MO
2 (5 R 2 O 3
12 SiO 2 )
6 MO = 1 MgO 0.5 CaO 3.5 K 2 O
Pinitoid
Gleichinger
11 H 2
1 Na 2 O 10 R 2 O 3 =9.5 A1 2 O 3 0.5Fe 2 O 3
Fels
13
7 MO
2 (5 A1 2 O 3
12 Si0 2 )
7 MO =4 FeO 0.5 MgO 2 K 2 O
Chemnitz
7H 2
0.5 Na 2 O
14
20 MO
. 2 (5 R 2 O 3
12 SiO 2 )
20 MO = 9.5 FeO 6.5 MgO 1.5 CaO
Biotite
Adamello
2.5Na 2 O 10R 2 O 3 =6 A1 2 O 3 4Fe 2 O 3
15
22 MO
2 (5 R 2 3
12 SiO 2 )
22 MO = 21 MgO 1 FeO
?>
Westchester
48 H 2 O
10 R 2 O 3 = 8 A1 2 O 3 2 Fe 2 O 3
16
23 MO
2 (5 R 2 O 3
12 SiO 2 )
23 MO = 22 MgO 1 FeO
M
Westchester
50 H 2 O
10R 2 3 = 8A1 2 3 - 2Fe 2 3
17
24 MO
2 (5 R 2 O 3
12 SiO 2 )
24 MO = 23 MgO 0.5 FeO 0.5 NiO
M
Culsagee
44 H 2
10 R 2 O 3 = 8.5 A1 2 O 3 1.5 Fe 2 O 3
Mine
G. Micas of the type
Si R Si R"- Sf = 5 R 2 3 18 Si0 2
Source
18
4MO-
2(5A1 2 3 -
18 SiO 2 )
4 MO = 1 FeO 0.5 MgO 2 K 2 O
Hygro-
Rheinpfalz
20H 2 O
0.5Na 2
philite
19
7 MO-
2 (5 R 2 O 3
18 SiO 2 )
7 MO = 1 MnO 1 MgO 5K 2 O
Muscovite
Heidelberg
6H 2
10 R 2 O 3 = 9.5 A1 2 O 3 0.5 Fe 2 O 3
20
8 MO-
2(5R 2 3 -
18 SiO 2 )
8 MO = 5.5 MgO 0.5 CaO 2 K 2 O
Gongylite
Yli-Kitka-
12H 2 O
10R 2 O 3 =8.5A1 2 O 3 - 1.5Fe 2 O 3
jarvi
21
25 MO-
2(5R 2 3 -
18 SiO 2 )
25MO = 12.5FeO-5CaO-0.5MgO-4.5K,O
Biotite
Brevik
4H 2
2.5 Na 2 O
10R 2 3 = 7Fe 2 3 -3Al 2 3
22
34 MO-
2 (5 R 2 3
18SiO 2 )
34 MO =25 MgO 4 FeO 5K 2 O
Karosulik
12H 2
10R 2 3 =8.5 A1 2 3 - 1.5Fe 2 3
23
40 MO-
2(5R 2 3 -
18 SiO 2 )
40 MO = 11.5 FeO 23 MgO 5 K 2 O
M
Tschebarkul
2H 2 O
0.5 Na 2 O
10R 2 O 3 = 8Al 2 3 -2Fe 2 O 3
24
50 MO -
2 (5 A1 2 O 3
34H 2
18 SiO 2 )
50 MO = 41.5 MgO 8.5 FeO
Milbury
THE MICA GROUP
or the general formula
m MO 2 (5 R 2 3 6 Si0 2 ) n H 2 0.
367
Analyst
Si0 2 A1 4 3 Fe a 3 FeO
CaO
MgO K a O Na z O H,0 Total
Chatard
Theory
XVIII
32.32
32.73
45.78
46.58
4.84
5.12
11.32
11.04
0.90
1.00
4.84 | 100.00
4.49 1100.96
or the general formula
m MO 2 (5 R 2 3 12 Si0 2 ) n H 2 0.
Analyst
Si0 2
A1 2 3
Fe a 3
FeO
CaO
MgO
K 8
Na a O
H a O | Total
Cohen
Theory
III
50.44
50.82
35.72
35.93
~
2.53
2.92
~
0.70
0.41
4.93
4.13
0.08
5.67
5.68
100.00
99.99
v. Ammon
Theory
IV
48.68
49.08
34.49
34.75
~
z
~
1.33
0.85
4.78
5.40
5.24
5.30
5.48
5.35
100.00
100.73
Chatard
Theory
C
47.30
46.60
33.50
32.39
2.54
~
~
2.63
2.01
10.81
10.39
1.02
0.54
4.73
4.81
100.00
99.28
Hilger
Knop
Theory
V
Theory
45.92
45.24
46.26
47.77
30.90
29.96
32.76
32.65
2.55
3.16
0.32P 2 5
9.25
8.94
0.89
1.44
1.27
1.15
0.64
0.49
10.17
10.13
6.04
5.86
1.98
2.15
0.99
1.50
6.32
6.24
4.06
4.19
100.00
99.79
100.00
101.00
Baltzer
Theory
LIII
36.41
36.43
15.47
14.40
16.19
16.71
17.30
17.40
2.12
1.66
6.57
6.87
5.94
5.54
0.03
100.00
99.04
Konig
Theory
CXXXVIII
33.22
33.35
18.81
17.78
7.38
7.32
1.66
2.11
19.01
19.26
__
___
19.92
19.87
100.00
99.69
Konig
Theory
CXL
32.52
33.03
18.43
17.38
7.23
7.41
1.63
1.44
-
19.87
20.16
20.32
20.90
100.00
100.32
Chatard
Theory
CXXXII
33.24
34.00
20.01
20.36
5.54
4.91
0.82
0.42
21.23
21.71
0.86NiO
0.57N1O
18.30
18.50
100.00
100.47
or the general formula
m MO 2 (5 R 2 3 18 Si0 2 ) . n H 2 0.
Analyst
Si0 2
Al a 8
Fe 2 3
FeO
CaO
MgO
K 8
Na,0
H,0
Total
Sch wager
Theory
II
56.08
56.64
26.49
26.68
1.87
1.68
0.22
0.52
0.29
4.88
5.33
0.80
0.64
9.36
9.13
100.00
100.73
Knop
Theory
55.41
56.37
24.86
24.22
2.05
2.09
1.82MnO
2.5 MnO
~
1.03
0.83
12.06
12.61
0.03
2.77
2.41
100.00
101.06
Thoreld
Theory
55.11
55.22
22.12
21.80
6.12
4.80
0.32MnO
0.72
0.77
5.62
5.90
4.80
4.46
0.45
5.51
5.77
100.00
99.49
Muller
Theory
XCIX
39.59
39.38
5.60
6.65
20.53
19.89
16.50
16.43
5.13
5.47
0.73
0.56
7.75
7.86
2.84
2.81
1.33
1.39
100.00
100.44
Kobell
Theory
CLXXVII
41.21
41.00
16.55
16.88
4.58
4.50
5.49
5.05
19.08
18.86
8.97
8.76
4.12
4.30
100.00
99.35
Zellner
Theory
cxx
38.72
38.49
14.63
14.43
5.73
5.44
14.85
14.75
,
16.50
16.35
8.42
8.12
0.50
0.53
0.65
0.89
100.00
99.00
Crossley
Theory
CLXXI
35.62
35.74
16.82
16.42
10.09
10.02
27.38
27.44
10.09
10.30
100.00
99.92
368
THE MICA GROUP
H. Micas of the type
R Si R = 6 R0, 6 SiO
Source
25
1MO-
2(6A1 2 O 3 -
6 SiO 2 )
2H 2 O
1 MO = 0.25 MgO 0.25 K 2 O
0.25 Na 2 0- 0.25 H 2
Lesleyite
26
2 MO-
2(6A1 2 O 8
6 SiO 2 )
5H 2
2 MO = 1.75 K 2 O-0.25 H 2 O
N
27
6MO-
2(6R 2 3 -
6 SiO 2 )
7H 2
6MO = 5CaO- 1 Na 2 O
12 R 2 O 3 = 11.75 Al 2 O 3 -0.25Fe 2 O 3
Margarite
Nikaria
J. Micas of the type
Si R R Si = 6 R 2 3 10 Si0 2
Source
28
29 4 MO 2 (6 A1 2 O 3 10 SiO 2 ) . 10 H 2 O
30
31
4 MO 2(6 A1 2 O 3 10 SiO 2 ) 10 H 2 O
4 MO 2 (6 A1 2 3 10 Si0 2 ) 10 H 2 O
4 MO 2 (6 A1 2 O 3 10 SiO 2 ) 10 H 2 O
4 MO = 0.5 CaO 0.5 MgO -1K 2 O
2 Na 2 O
4 MO =0.5 CaO 0.5 MgO 1K 2 O
. 2 Na 2 O
4 MO=0.5 CaO 0.5 MgO 1K 2 O
2Na 2
4 MO=0.5 CaO 0.5 MgO 1K 2 O
2Na,0
Muscovite
Ebendaher
K. Micas of the type
Si R R Si = 6 R 2 2 12 SiO,
Source
32
33
4 MO 2 (6 R 2 O 3 12 SiO 2 )
4 MO 2 (6 A1 2 3 12 SiO 2 ) 8 H 2 O
4MO = 4K 2 O
12 R 2 O 3 = 9.5 Al 2 O 3 -2.5Fe 2 O 3
4 MO =0.5 CaO 0.5MgO-3Na 2 O
Micarelle
Paragonite
M. Campione
34
>
4MO = lK 2 O-3Na 2 O
n
M. Campione
35
4 MO 2 (6 A1 2 O 3 12 SiO 2 ) 9 H 2 O
4 MO = 3.5 K 2 O 0.5 Na 2 O
Muscovite
Unionville
30
>
4 MO = 3.5 K 2 O 0.5 Na 2 O
n
"
37
> >
4 MO = 3.5 K 2 O 0.5 Na 2 O
Wiesenthal
38
4 MO = 0.5 K 2 O 3.5 Na 2 O
Paragonite
Borgofrance
30
4 MO =0.5 K 2 O 3.5 Na 2 O
n
Colle Blasier
40
> >
4 MO = 0.5MgO-3K 2 O-0.5Na 2 O
Muscovite
Culsagee
Mine
41
4 MO 2 (6 A1 2 3 12 SiO 2 ) 10^,0
4MO = 4K 2 O
Vallee de
1'Evel
42
5 MO 2(6 A1 2 O 3 12 SiO 2 ) 8 H 2 O
5MO = 0.5MgO-0.5CaO-0.5FeO
3 K 2 O 0.5 Na 2 O
Bengal
THE MICA GROUP
of the general formula
m MO 2 (6 R 2 3 6 Si0 2 )
nH 2 0.
Analyst
Si0 2
A1 2 3
Fe 2 3
FeO
CaO
MgO
K 8
Na 2
H 2
Total
Genth
Theory
35.42
60.19
0.51
0.76
1.13
1.99
100.00
XI
35.68
60.29
0.72
0.29
0.41
0.96
1.78
100,13
Sharpless
Theory
32.69
55.56
7.46
4.29
100.00
V
33.59
55.41
7.43
4.30
100.73
Smith
Theory
29.65
49.39
1.65
11.55
2.55
5.19
100.00
IX
30.22
49.67
1.33
11.57
Trace
2.31
5.12
100.22
or the general formula
m MO 2 (6 R 2 3 10 Si0 2 ) n H 2 0.
Analyst
Si0 2
A1 2 8
Fe 2 0,
FeO
CaO
MgO
K 8
NaaO
H,0
Total
Smith & Brush
Theory
CII
41.82
40.29
42.65
43.00
1.30
0.98
1.01
0.69
0.62
3.27
3.94
4.32
5.16
6.27
5.00
100.00
100.32
Theory
cm
41.82
39.64
42.65
42.40
1.60
~
0.98
1.00
0.69
0.70
3.27
3.94
4.32
5.16
6.27
5.08
100.00
99.52
>
Theory
CIV
41.82
40.21
42.65
41.40
1.30
~
0.98
1.11
0.69
0.70
3.27
3.25
4.32
4.26
6.27
6.23
100.00
99.21
Theory
CV
41.82
40.96
42.65
41.40
1.30
~
0.98
1.11
0.69
0.70
3.27
3.25
4.32
4.26
6.27
6.23
100.00
99.21
or the general formula
m MO 2 (6 R 2 3 12 Si0 2 ) n H 2 0.
Analyst
SiO 2
A1 2 3
Fe 2 O s
FeO
CaO
MgO
K 2 O
Na,0
H 2
Total
Massalin
Theory
45.21
30.42
12.56
11.81
_
_
100.00
I
45.00
30.00
12.60
12.40
100.00
Rammelsberg
Theory
47.34
40.24
0.92
0.66
6.11
4.73
100.00
II
46.81
40.06
Trace
1.26
0.65
Trace
6.40
4.82
100.00
Lemberg
Theory
46.65
39.64
3.04
6.01
4.66
100.00
IV
46.17
40.29
3.09
5.53
4.92
100.00
Genth
Theory
45.21
38.42
10.32
0.97
5.08
100.00
XCVII
45.86
37.61
0.59
0.31
0.55
10.40
0.80
4.74
100.90
Konig
Theory
45.21
38.42
10.32
0.97
5.08
100.00
XCVIII
45.73
37.10
1.30
0.34
10.50
0.88
4.48
100.33
Sauer
Theory
45.21
38.42
10.32
0.97
5.08
100.00
XVIII
45.71
38.64
9.53
0.90
5.17
100.00
Cossa
Theory
46.61
39.61
1.52
7.02
5.24
100.00
VII
46.67
39.02
2.01
1.36
6.37
4.91
100.34
Theory
46.61
39.61
1.52
7.02
5.24
100.00
VIII
46.68
39.88
1.06
0.84
6.91
5.08
100.45
K6nig
Theory
45.69
38.75
0.63
8.92
0.98
5.13
100.00
XC
45.62
35.93
2.93 =
1.87A1 2 3
0.34
9.40
0.71
4.93
99.86
Delesse
Theory
44.72
38.01
11.68
5.95
100.00
XLVIII
45.22
37.85
Trace
11.20
5.25
99.52
Blau
Theory
44.93
38.19
1.12
0.87
0.62
8.80
0.96
4.49
100.00
LXXXI
45.57
36.72
0.95
1.28
0.21
0.38
8.81
0.62
5.05
99.93
2 B
370
THE MICA GROUP
Source
5 MO 2(6 A1 2 O 3 12 SiO 2 ) 8 H 2 O
7 MO 2(6 A1 2 O 3 12 Si0 3 ) 12 H 2 O
= 0.5MgO-0.5CaO-0.5FeO
3 K 2 O-0.5 Na 2 O
= 4K 2 O-lMgO
12 R 2 O 3 =11 A1 2 O 3 -1 Fe 2 O 3
= 0.5CaO-2.5MgO-3.5K 2 O
0.5 Na 2 O
Muscovite
East Indies
Horrsjoberg
Maryland
Si
Si
L. Micas of the type
R Si = 6 R 2 O 3 16 SiO 2
Source
46
4 MO 2(6 A1 2 O 3
16SiO 2 )
4 MO = 0.5 FeO 3 K 2 O 0.5 Na 2 O
Killinite
Branchville
8H 2 O
47
5MO-2(6A1 2 O 3 -
16 Si0 2 )
5 MO = 1.5 FeO 1 CaO 0.5 Li 2 O
,,
Killiney
8H 2 O
2K 2
Hill
48
5 MO 2(6 R 2 O 3 -
9H 2
16 SiO 2 )
5 MO = 1 MgO 2 K 2 - 2 Na 2 O
12 R 2 O 3 = 10 A1 2 O 3 2 Fe 2 O 3
Muscovite
Oravicza
49
6MO-2(6R 2 O 3 -
16 SiO 2 )
6 MO = 0.5 MgO 5.5 K 2 O
tf
Striegau
10H 2
12R 2 O 3 =lFe 2 3 'llAl 2 3
50
6 MO 2(6 A1 2 O 3
22 H 2
16SiO 2 )
6 MO = 1.5 FeO 0.5 CaO 1 MgO
3K 2
Killinite
Killiney
Hill
51
6MO-2(6A1 2 O 3 -
16SiO 2 )
6MO = 1.5FeO 1.1 MnO 0.5 CaO
t
>
22 H 2
0.5 MgO- 2.5 K 2
52
7 MO 2(6 A1 2 3
10H 2
16 SiO 2 )
7 MO =0.5 FeO 2.5 MgO - 4 K 2 O
Muscovite
Grube Him-
melsfiirst
53
7 MO 2(6 A1 2 O 3
16 SiO 2 )
7 MO = 1.5 FeO 0.5 CaO 2 MgO
Hygro-
20 H 2 O
2 K 2 O 1 Na 2 O
philite
54
8 MO 2(6 A1 2 O 3
16 SiO 2 )
8 MO = 2 FeO 1 CaO 0.5 MgO
n
20 H 2 O
- 0.25 K 2 O - 1 Na 2 O
55
12MO-2(6A1 2 O 3 -
16SiO 2 )
12 MO = 1 CaO 3.5 MgO 4.5 K 2 O
Paragonite
Fenestrelle
-6H 2 O
3Na 2
56
26MO-2(6R 2 O 3 -
16SiO 2 )
26 MO =0.5 CaO 18.5 MgO 7 K 2 O
Biotite
Zillerthal
3H 2
12R 2 O 3 =8Al 2 3 -4Fe 2 O 3
57
27 MO 2(6 R 2 O 3 -
16 SiO 2 )
27 MO = 1 FeO 0.5 CaO 25.5 MgO
West-
40H 2 O
12 R 2 3 =8.5 A1 2 3 - 3.5 Fe 2 O 3
chester
58
29MO-2(6R 2 3 -
16 SiO 2 )
29 MO = 1.5 FeO - 27.5 MgO
,,
60 H 2 O
12R 2 3 =9Al 2 3 -3Fe 2 O 3
59
30MO-2(6R 2 O 3 -
16 SiO 2 )
30 MO = 1 1 FeO -12.5 MgO 5 K 2 O
>
Renchthal
6H 2
1.5Na 2 - 12 R 2 3 =10 A1 2 O 3 2 Fe 2 O 3
60
30MO-2(6A1 2 3 -
16 SiO 2 )
30 MO = 21.5 FeO - 8.5 MgO
>
Monroe
28 H 2
61
32MO-2(6R 2 O 3 -
16 SiO 2 )
32 MO=31.5 MgO 0.5 FeO
M
Calsagee
32H 2
12 R 2 3 = 10 A1 2 O 3 - 2 Fe 2 O 3
Mine
62
32MO-2(6R 2 O 3 -
16 SiO a )
32 MO =31. 5 MgO 0.5 FeO
JM
64H 2
12 R 2 O 3 = 10 AI 2 O 3 2 Fe 2 O 3
63
34MO-2(6R 2 3 -
16SiO 2 )
34 MO = 33.5 MgO 0.5 FeO
ft
60$ 2
12 R 2 O 3 = 10 A1 2 O 3 2 Fe 2 O 3
64
35 MO 2(6 Al a O 3
16 Si0 2 )
35MO = 21.5FeO-lCaO-11.5MgO
Rio de
34 H 2
1K 2
Janeiro
THE MICA GROUP
371
Analyst
SiO,
Al,0,
Fe,0, | FeO | CaO
MgO
K,0
Na,O
H,0
Total
Sipocz
Theory
LXXXII
44.93
45.71
38.19
36.57
1.19
1.12
1.07
0.87
0.46
0.62
0.71
8.80
9.22
0.96
0.70
4.49
4.83
100.00
100.67
Igelstrom
Theory
LXXIII
43.88
43.41
34.18
35.17
4.87
4.62
.
1.22
1.40
11.46
10.90
~
4.39
4.50
100.00
100.00
Chatard
Theory
XCIII
42.75
42.21
36.35
34.55
1.03
2.03Cr 2 O 3
0.83
0.47
2.96
3.13
9.77
9.16
0.92
0.82
6.42
6.77
100.00
100.17
or the general formula
m MO 2 (6 R 2 3 - 16 Si0 2 ) n H 2 0.
Analyst
SiO,
Al,0,
Fe a 3 | FeO
CaO
MgO
K,0
Na,0
H,0
Total
Dewey
Theory
52.79
33.65
0.99
7.76
0.86
3.95
100.00
VII
53.47
32.36
0.79
0.42
0.17
0.72 MnO
7.68
0.44
4.07
100.16
Mallet
Theory
52.53
33.49
2.95
1.53
5.14
0.42 Li 2 O
3.94
100.00
III
52.89
33.24
3.27
1.45
4.94
0.46 Li 2 O
3.67
99.92
Kjerulf
Theory
50.88
27.03
8.47
1.06
4.98
3.29
4.29
100.00
XXIV
50.88
26.69
8.48
1.19
4.52
2.72
4.19
98.67
Riepe
Theory
48.99
28.62
4.08
0.52
13.20
4.59
100.00
XIX
49.27
28.69
2.89
0.42
13.91
4.77
99.95
Lehunt
Theory
48.03
30.62
?2.70
0.70
1.00
7.05
9.90
100.00
I
49.08
30.60
2.27
0.68
1.08
6.72
10.00
100.43
Blythe
Theory
47.98
30.59
1.77MnO
2.69
0.70
0.50
5.88
9.89
100.00
II
47.93
31.04
1.26MnO
2.33
0.72
0.46
6.06
10.00
99.80
Scheerer
Theory
50.05
31.91
___
0.94
__
2.61
9.80
4.69
100.00
XV
47.84
29.98
2.91
1.12
0.05
2.02
9.48
1.72 TiO a
4.40
99.52
Killing
Theory
48.36
30.81
2.72
0.71
2.02
4.73
1.56
9.07
100.00
IV
48.60
32.82
2.76
0.84
2.37
4.08
1.32
8.83
101.62
Laspeyres
Theory
47.28
30.14
3.54
1.38
1.47
5.79
1.53
8.87
100.00
I
48.42
32.06
3.26
1.15
1.72
5.67
1.36
9.02
102.66
Cossa
Theory
47.33
30.17
1.38
3.45
10.43
4.58
2.66
100.00
IX
47.96
31.03
1.07
3.42
10.44
4.08
2.41
100.41
Varren-
Theory
39.54
16.81
13.17
__
0.58
15.24
13.55
1.11
100.00
trapp
XLVI
39.85
16.07
13.21
0.42
15.60
13.68
1.17
100.00
Brush
Theory
37.02
16.72
10.80
1.39
0.54
19.65
13.88
100.00
CXXXVII
37.10
17.57
10.54
1.26
0.56
19.65
0.43
13.76
100.87
Chatard
Theory
34.25
16.37
8.56
1.93
__
19.62
19.27
100.00
CXXXIX
34.40
16.63
8.00
2.11
19.30
19.03
99.47
Killing
Theory
36.73
19.52
6.12
15.23
_ _
9.57
8.99
1.77
2.07
100.00
VI
37.67
18.79
6.48
15.28
9.72
8.93
1-92
2.33
101.12
Pisani
Theory
34.69
22.11
27.96
__
6.14
9.10
100.00
CLXIV
34.98
21.88
28.44
6.24
9.22
100.76
Cooke
Theory
37.42
19.87
6.23
0.70
__
24.55
11.33
100.00
CXXXIII
37.58
19.73
5.95
0.58
25.13
11.09
100.06
Chatard
Theory
33.64
17.88
5.59
0.63
_
22.08
20.18
100.00
CXXXI
33.77
17.56
5.61
0.50
22.48
20.30
100.22
Konig
Theory
33.59
17.85
5.60
0.63
_ _
23.45
18.88
100.00
cxxx
33.93
17.38
5.42
0.50
23.43
0.35 NiO
19.17
100.18
C.v.Hauer
Theory
32.47
20.70
26.17
0.95
7.77
1.59
10.35
100.00
cxxv
32.33
20.47
,26.25
0.85
7.75
2.02
10.33
100.00
372
THE MICA GROUP
M. Micas of the type
Si R Si R Si = 6 R 2 3 18 Si0 2
Source
65
5 MO
2(6R 2 3 -
18SiO 2 )
5 MO = 0.5 CaO 4.5 K 2 O
Micarelle
3H 2
12 R 2 3 = 9.5 Al 2 3 -2 Fe 2 O 3 -0.5 Mn 2 O 3
66
6 MO
2(6 A1 2 O 3
18 SiO 2 )
6 M0 = 2 FeO 1.5 MgO 2 K 2 O
Killinite
Killiney
18H 2
0.5 Na 2
Hill
67
6 MO
2(6 A1 2 O 3
18SiO 2 )
6 M0 = 1.5 FeO 1 MgO 3 K 2 O
n
Dalkey
19H 2 O
0.5 Na 2 O
68
7 MO
2(6 A1 2 O 3
18SiO 2 )
7 MO=0.5 FeO 3.5 MgO 3 K 2 O
Muscovite
Tamsweg
10H 2 O
69
26 MO
2(6 R 2 O 3
18Si0 2 )
26 MO = 12 FeO 5.5 CaO- 5 K 2 O
Biotite
Brevik
4H 2 O
3.5 Na 2 O; 12 R 2 O 3 = 9.5 Al 2 O 3 -2.5Fe 2 O 3
70
29 MO
2(6R 2 3 -
18 SiO 2 )
29 MO = 23.5 MgO 4.5 K 2 O 1 Na 2 O
M
Laacher
12 R 2 O 3 = 8.5 A1 2 O 3 3.5 Fe 2 O 3
See
71
36 MO
2(6R 2 O 3 -
18 SiO 2 )
36 MO = 35.5 MgO 0.5 FeO
Magnet
86H 2
12 R 2 O 3 =9.5 A1 2 O 3 2.5 Fe 2 O 3
72
37 MO
2(6A1 2 3 -
18SiO 2 )
37 MO = 15.5 FeO 2 MnO 19.5 MgO
Prefiburg
12H 2
73
39 MO
2(6R 2 3 -
18Si0 2 )
39 M0 = 33 MgO 1 CaO 5 K 2 O
M
Vesuvius
2H 2
12 R 2 O 3 = 9 A1 2 O 3 3 Fe 2 O 3
N. Micas of the type
R Si R Si R = 9 R 2 3 12 Si0 2
1
Source
74
12MO-
2(9 A1 2 O 3
12H 2
12 SiO 2 )
12 M0 = 2 FeO 0.5 MnO 9.5 CaO
Margarite
Tokowaja
75
76
29 MO-
29 MO-
2(9 R 2 3
10H 2 O
2(9R 2 3
10H 2 O
12 SiO 2 )
12 Si0 2 )
29 MO = 1 .5 FeO 21 MgO 1.5 K 2 O
5 Na 2 O ; 18 R 2 O 3 = 17.5 Al 2 O 3 -0.5Fe 2 O 3
29 MO = 1.5 FeO 21 MgO 1.5 K 2 O
. 5 Na 2 O ; 18 R 2 O 3 = 17.5 A1 2 O 3 -0.5 Fe 2 O 3
Willcoxite
Shooting
Creek
Cullakenee
Mine
0. Micas of the type
Si R * Si R Si R Si = 9 R 2 3 20 Si0 2
1
Source
77
4MO-
2(9 R 2 O 3
24H 2
20 SiO 2 )
4 MO = 0.5 FeO 0.5 MgO 2.5 K 2 O
0.5 CaO; 18 R 2 O 3 = 17.5 Al 2 O 3 -0.5Fe 2 O 3
Hygro-
philite
Nil St.
Vincent
78
6MO-
2(9 R 2 3
18H 2 O
20 Si0 2 )
6MO = 5.5K 2 O-0.5H 2 O
18R 2 3 = 17Al 2 3 -lFe 2 3
Lesleyite
79
7MO-
2(9A1 2 3 -
20 SiO 2 )
7 MO = 2.5 CaO 3 MgO 1.5 K 2 O
Muscovite
Dobrawa
15 H 2
80
8MO-
2(9R 2 3 -
16H 2
20 SiO 2 )
8MO = lMgO-7K 2 O
18 R 2 O 3 = 16 A1 2 O 3 2 Fe 2 O 3
"
Mt.Leinster
Carlow
81
9MO-
2(9 R 2 O 3
20 SiO 2 )
9 MO = 1 CaO - 2 MgO 4 K 2 O 2 Na 2 O
Botriphinie
16 H 2
18 R 2 O 3 = 15.5 A1 2 O 3 2.5 Fe 2 O 3
82
9MO-
2(9R 2 3 -
20 Si0 2 )
9 MO = 1 CaO 2 MgO - 4 K 2 O 2 Na 2 O
n
Vanlup
16H 2
18 R 2 O 3 = 15.5 A1 2 O 3 2.5 Fe 2 O 8
83
9 MO
2(9 R 2 8
20 SiO 2 )
9 MO = 3 MgO 5 K 2 O 1 Na 2 O
t
St. Etienne
12H 2 O
18 R 2 O 3 = 17 A1 2 O 3 1 Fe 2 O 3
THE MICA GROUP
373
or the general formula
m MO 2 (6 R 2 3 18 Si0 2 )
nH,0.
Analyst
SiOj
AljOa
Fe 2 0,
FeO
CaO
MgO
K,0
Na,0
H,0
Total
Ficinus
Galbraith
Theory
II
Theory
IV
53.56
54.60
52.28
50.45
24.03
23.60
29.63
30.13
7
8
.93
.60
1.96Mn 2 O 3
1.60Mn 2 O 3
3.48
3.53
0.69
0.80
1.45
1.09
10.49
11.20
4.55
4.81
0.75
0.95
1.34
1.20
7.84
7.58
100.00
101.60
100.00
98.54
Theory
V
51.59
50.11
29.23
29.37
2.58
2.23
0.34
0.95
1.03
6.73
6.71
0.74
0.60
8.18
8.03
100.00
98.42
Kobell
Theory
XXXIII
53
52
.71
.52
30.43
30.88
0.89
0.80
3.48
3.82
7.02
6.38
~
4.47
4.60
100.00
99.00
Miiller
Theory
C
36.82
36.08
4
4
.32
.99
25.92
25.98
14.73
14.28
5.25
5.43
8.02
7.96
3.69
3.68
1.22
1.31
100.00
99.71
Bromeis
Theory
XXII
43
43
27
02
17
16
.37
.85
11
11
.22
.63
18.83
19.11
8.07
8.60
1.24
1.16
z
100.00
100.36
Konig
Theory
cxxxv
33
33
06
28
14.84
14.88
6.12
6.36
0.55
0.57
21.74
21.52
23.69
23.90
100.00
100.51
C.v.Hauer
Theory
XLV
38
38
26
13
21
21
82
60
19.77
19.92
13.81
13.76
2.51 MnO
2.61 MnO
3.83
3.98
100.00
100.00
Bromeis
Theory
LIV
39.71
39.75
16.88
15.99
8
8
82
29
1.02
0.87
24.26
24.49
8.64
8.78
=
0.67
0.75
100.00
98.92
or the general formula
m MO 2 (9 R 2 3 12 Si0 2 )
nH 2
0.
Analyst
SiO,
A1 2 0,
Fe,O, FeO
CaO
MgO KjO
Na,O
H,0
Total
Jewrechow
Theory
XV
34.26
34.02
43.68
43.33
3.42
3.02
12.67
13.11
0.84 MnO
1.05 MnO
5.13
5.34
100.00
99.87
Kdnig
Theory
I
29.48
28.96
36.56
37.49
1.64 2.22
1.26 2.46
17.20 2.88 (
17.35 2.46 (
3.34
5.73
3.68
4.00
100.00
100.69
M
Theory
II
29.48
29.50
36.56
37.56
1.64 2.22
1.40 2.42
-
17.20 2.88 <
17.20 2.42 (
3.34
5.24
3.68
3.32
100.00
100.02
or the general formula
m MO 2 (9 R 2 3 20 Si0 2 ) n H 2 0.
Analyst
SiO a
A1 2 3
Fe 2 8
FeO
CaO
MgO
K,0
Na,O
H,0
Total
Renard
Theory
III
47.33
47.02
35.19
34.82
1.58
2.57
1.41
0.68
0.55
0.20
0.79
0.52
4.63
4.60
0.18
8.52
8.35
100.00
98.94
Roepper
Theory
VIII
46.66
47.02
33.71
33.27
3.11
2.84
z
~
10.05
9.97
~
6.47
6.71
100.00
99.79
Boricky
Theory
XXX
48.91
48.74
37.42
37.96
z
2.85
2.63
2.44
2.41
2.87
3.07
5.51
5.45
100.00
100.26
Haughton
Theory
LVIII
44.96
44.64
30.57
30.18
5.99
6.35
0.75
0.72
12.33
12.40
5.40
5.32
100.00
99.61
Heddle
Theory
LI
45.24
45.10
29.80
29.90
7.54
7.87
0.03 MnO
1.06
0.62
1.51
0.72
7.09
7.84
2.34
2.56
5.43
5.51
100.00
100.15
Theory
LIV
45.24
45.43
29.80
29.65
7.54
8.33
0.02 MnO
1.06
0.79
1.51
1.70
7.09
6.94
2.34
2.27
5.43
5.29
100.00
100.42
Delesse
Theory
XLVII
46.67
46.23
33.71
33.03
3.12
3.48
__
__
1.94
2.10
9.14
8.87
1.21
1.45
4.21
4.12
100.00
99.28
374
THE SCAPOLITE GROUP
Source
84
85
86
10 MO 2(9 R 2 O 3 20 SiO 2 )
4H 2
14 MO 2(9 A1 2 O 3 20 SiO 2 )
11 H 2 O
14MO-2(9AI 2 O 3 -20SiO) 2
11H 2 O
10 MO =4 K 2 O 3.5 Na 2 O 2.5 MgO
18 R 2 O 3 =17.5 A1 2 3 0.5 Fe 2 O 3
14 MO = 1 .5 FeO 2 BaO 0.5 CaO
4 MgO 4.5 K 2 O 1.5 Na 2 O
14 MO = 1.5 FeO - 2 BaO 0.5 CaO
4MgO-4.5K 2 O-1.5Na 2 O
Muscovite
Zillertal
Pfitschtal
New Formulae for the
The following analyses of the minerals
A. Si R Si =3 R 2 3 10 SiO
B. Si - R Si =3 R 2 3 - 12 Si0 2 ,
/Si
C. R^Si - 3 R 2 3 - 15 Si0 2 ,
Vi
D. R Si - Si R =5 R 2 3 12 Si0 2 ,
E. Si R Si R S A i = 5 R 2 3 18 Si0 2 ,
A. Scapolites of the type
Si & Si = 3 R 2 3 10 Si0 2
Source
Analyst
l
6 MO 2(3 R 2 O 3 10 SiO 2 )
6 MO = 3 MgO 2.5 K 2 O 0.5 H 2 O
Algerite
Crossley
6H 2 O
6 R 2 O 3 =5.75 A1 2 O 3 0.25 Fe 2 O 3
Franklin N.J.
2
9 MO 2(3 A1 2 O 3 10 SiO 2 )
9 MO = 4.25 CaO 4.25 Na 2 O 0.5 H 2 O
St. Lawrence
Rammels-
2H 2 O
Co., N.S.
berg
3
9MO-2(3Al 2 O 3 -10SiO 2 )
9 MO = 5.75 CaO 2.75 Na 2 O
Arendal
Wolff
0.5H 2
- 0.25 MgO - 0.25 K 2 O
4
9MO-2(3Al 2 O 3 -10SiO 2 )
9 MO = 6 CaO 2.25 Na 2 O 0.25 K 2 O
Arendal
D amour
4H 2 O
0.5H 2 O
5
HMO-2(3Al 2 O 3 -10SiO 2 )
11 MO = 7.75 CaO 1.5 Na 2 O
Mais j 6
G. v. Rath
2.5H 2 O
0.25 K 2 O- 1.5 MgO
6
12 MO 8(3 R 2 O 3 10 SiO 2 )
40 H 2 O 4 CaCO 3
12MO = 10K 2 O-2MgO
24 R 2 3 = 23 A1 2 O 3 1 Fe 2 O 3
Algerite
Franklin N.J.
Hunt
7
23 MO 8(3 A1 2 O 3 10 SiO 2 )
23 MO = 12 CaO 10 Na 2 O 1 K 2 O
Gulsj6
Hermann
- 2 H 2 O 3 CaCO 3
8
22 MO 8(3 A1 2 O 3 10 SiO 2 )
22 MO = 12 MgO 10 K 2 O
Algerite
Crossley
26H 2 0-4CaC0 3 )
24 R 2 3 = 23 A1 2 3 - 1 Fe 2 O 3
Franklin N.J.
9
36 MO 8(3 A1 2 O 3 10 SiO 2 )
36 MO = 22 CaO 9 Na 2 O 2 K 2 O
Mais j 5
G. v. Rath
12H 2 O-lCaCO 3
3 MgO
10
30 MO 8(3 A1 2 O 3 10 SiO 2 )
30 MO = 20 CaO 10 Na 2 O
Kupfermine
Lacroix
2H 2 O-1 CaS0 4
THE ORTHOCHLORITE GROUP
375
Analyst
SiOj
AlaO,
Fe 2 0,
FeO
CaO
MgO
K a O
Na,0
H,0
Total
Schafhautl
Theory
XXXVI
47.72
47.05
35.49
34.90
1.59
1.50
___
1.98
1.95
7.47
7.96
4.32
4.07
1.43
1.45
100.00
98.88
Rammels-
berg
Theory
XL
43.39
43.09
33.19
32.79
5.51 BaO
5.91 BaO
1.95
1.85
0.56
0.23
2.88
2.90
7.28
7.61
1.68
1.42
3.56
4.26
100.00
100.35
Rammels-
berg
Theory
XLI
43.39
42.90
33.19
32.40
5.51 BaO
5.82 BaO
1.95
2.40
0.56
0.80
2.88
2.87
7.28
7,47
1.68
1.73
3.56
3.02
100.00
99.41
Scapolito Group
of this group conform to the following formulae :
F. Si R . Si Si R Si =5 R 2 3 22 Si0 2 ,
G. R Si Si R
H. Si R Si R Si
J. Si R Si R Si
K. Si R S A i Si R Si
L. Si R Si R Si R Si = 9 R 2 3 20 Si0 2 .
or the general formulae
(a) m MO 2 (3 R 2 3 10 Si0 2 ) n H 2 0,
(b) m MO 8 (3 R 2 3 10 Si0 2 ) n H 2 p CaC0 3 (or p CaS0 4 ).
= 6 R 2 3 12 Si0 2 ,
= 6 R 2 3 16 Si0 2 ,
= 6 R 2 3 18 Si0 2 ,
= 6 R 2 3 22 Si0 2 ,
SiO a
Al,0,
Fe.0,
FeO | MgO
CaO
K 8 O
Na z O
H a O
NaCl
CaCO,
CO,
a
Total
Theory
LXXXIa
52.21
52.00
25.52
25.42
1.74
1.54
-
5.22
5.39
10.22
10.38
5.09
5.27
100.00
100.00
Theory
XCII
50.88
50.73
25.95
25.40
-
~
10.09
10.24
11.17
11.09
1.91
1.96
___
0.09
100.00
99.60
Theory
XXX
51.14
50.91
26.07
25.81
0.75
0.43
0.58
13.75
13.34
1.00
0.85
7.26
7.09
0.38
0.41
__
100.00
99.74
Theory
XXXVI
50.17
50.30
25.58
25.08
14.05
14.08
0.98
1.01
5.83
5.98
3.39
3.25
.
100.00
99.70
Theory
XLII
48.63
47.24
24.81
24.69
Trace
2.43
2.18
17.59
16.84
0.95
0.85
3.77
3.55
1.82
1.72
___
100.00
98.07
Theory
LXXX
50.81
49.82
24.84
24.91
1.69
1.85
0.85
1.15
2.37
2.20
9.95
10.21
Trace
7.57
1.86
1.74
100.00
99.45
Theory
XLV
53.52
52.94
27.29
27.64
0.30
0.25 MnO
9.36
9.10
1.05
0.54
6.91
6.89
0.40
0.66
1.47
1.50
100.00
99.72
Theory
LXXXI
50.03
49-96
24.45
24.41
1.68
1.48
5.00
5.18
___
9.80
9.97
_
4.87
5.06
4.17
4.21
100.00
100.27
Theory
XLI
49.68
49.36
25.33
25.33
__
1.24
1.05
12.75
12.47
1.95
1.51
5.77
5.81
2.24
2.42
1.04
1.35
100.00
99.35
Theory
CXV
52.41
52.62
26.72
26.42
Trace
z
~
12.84
13.11
0.45
6.77
6.62
0.39
0.43
0.87 SO 3
0.79 SO 8
__
__
0.10
100.00
100.54
376
THE SCAPOLITE GROUP
B. Scapolites of the type
-R-S A i = 3R 2 3 -12Si0 2
Source
Analyst
11
9 MO
2(3 A1 2 O 3
12 SiO 2 )
9 MO =4.25 CaO 4.25 Na 2 O 0.5 K 2 O
Mizzonite
Rath
12
13
9 MO
15 MO
2(3 A1 2 O 3
1H 2 O
4(3 A1O 3
3NaCl
12SiO 2 )
12 SiO 2 )
9 MO=4.25 CaO 1.75 K 2 O 1.5 Na 2 O
1 MgO 0.5 H 2 O
15 MO = 9 CaO 5.5 Na 2 O 0.5 K 2 O
Dipyre from
Pouzac
St.Lawrence
Co., N.S.
H. Schulz
Lemberg
C. Scapolites of the type
/s
R Si = 3 R 2 3 15 Si0 2
14
15
Source
Analyst
8 MO
10 MO
2(3 Al 2 a
2(3 A1 2 2
4H 2 O
15 SiO 2 )
15 SiO 2 )
8 MO =4.5Na 2 O - 2.5 CaO 0.5 MgO
0.5 K 2 O
10 MO =5.5 MgO 3 K 2 O 0.75 FeO
0.25 Na 2 O 0.5 CaO
Marialite,
Pianura
Couseranite,
Pouzac
G. v. Rath
Pisani
D. Scapolites of the type
R"- Si - Si - RT= 5 R 2 3 12 Si0 2
Source
Analyst
16
10MO-2(5A1 2 3 -
12 SiO 2 )
10 MO = 10 CaO
Stansvik
Lagus
Olckonen
17
10MO-2(5A1 2 3 -
2H 2
12 Si0 2 )
10MO=9CaO-lNa 2 O
Clay Co., N.C.
Berkley
18
11MO-2(5A1 2 O 3 -
2H 2
12 SiO 2 )
HMO = 10CaO-0.5K 2 O
0.5 Na 2 O
Pargas
Wolff
19
11MO-2(5A1 2 3 -
17H 2
12 SiO 2 )
HMO = 4MgO-3CaO
3 K 2 O 1 Na 2 O
Wilsonite
Bathurst, Canada
Selkmann
20
12MO-2(5A1 2 O 3 -
12 SiO 2 )
12 MO = 12 CaO
Stansvik
Lagus
Olckonen
21
14MO-2(5A1 2 O 3 -
12 SiO 2 )
14MO = 12CaO-1.5Na 2 O
0.5 K 2 O
Ersbyite, Pargas
N. Norden-
skiold
22
15MO-2(5A1 2 O 3 -
12 SiO 2 )
15MO = 13CaO-2Na 2 O
Baikalsee
Hermann
23
15MO-2(5A1 2 O 3 -
12 SiO 2 )
15 MO = 13 CaO -1 MgO
0.5 K 2 O 0.5 Na 2 O
Mejonite from
Vesuvius
G. v. Rath
24
18MO-2(5A1 2 O 3 -
14H 2
12SiO 2 )
18 MO = 15.5 CaO 2.5 MgO
10R 2 O 3 = 8.5Al 2 O 3 -1.5Fe 2 O 3
Atheriastite,
Arendal
Berlin
THE SCAPOLITE GROUP
377
or the general formulae
(a) m MO 2 (3 R 2 3 12 SiO 2 ) n H 2 0,
(b) m MO 4 (3 R 2 3 12 Si0 2 ) n NaCl.
SiO,
Al,0,
Fe 2 s
FeO
MgO
CaO
K,0
Na,0
H,0
NaCl
CaCO,
CO,
ci
Total
Theory
XVI
55.38
54.70
23.52
23.80
z
0.22
9.15
8.77
1.82
2.14
10.13
9.83
0.13
~
~
-
100.00
99.59
Theory
XXIII
55.08
53.97
23.41
23.68
z
-^
1.53
1.40
9.10
8.76
6.29
6.43
3.56
3.55
1.03
0.98
~
~
-
-
100.00
98.77
Theory
XCIV
55.69
55.04
23.67
23.62
z
-
~
9.75
9.38
0.91
0.73
6.59
6.29
0.28
3.39
3.69
~
-
~
100.00
99.03
or the general formula
m MO 2 (3 R 2 3 15 Si0 2 ) n H 2 0.
SiO,
Al,0,
Fe,0,
FeO
MgO
CaO
K,0
Na,O
H,0
NaCl
CaCO,
CO,
Cl
Total
Theory
XVIII
62.11
62.72
21.12
21.82
z
z
0.69
0.31
4.83
4.62
1.62
1.15
9.63
9.37
Z
z
100.00
100.00
Theory
XXV
58.37
58,33
19.85
20.20
-
1.75
1.90
7.14
7.20
0.90
0.99
9.15
8.82
0.50
0.76
2.34
2.35
~
-
-
100.00
100.55
or the general formula
m MO 2 (5 R 2 3 12 Si0 2 ) n H 2 0.
SiO,
Al,0,
Fe 2 0,
FeO
MgO
CaO
K,0
Na 2
H a O
NaCl
CaC0 3
CO,
Cl
Total
Theory
LXVHI
47.68
47.60
33.77
33.50
-
-
z
18.55
17.20
~
__
___
100.00
98.30
Theory
LXXVIII
47.03
47.54
33.31
34.03
-
-
16.46
17.23
2.02
1.82
1.18
1.02
100.00
101.64
Theory
LIX
45.95
45.10
32.55
32.76
-
17.87
17.84
1.50
0.68
0.99
0.76
1.14
1.04
100.00
98.18
Theory
CXIII
41.88
41.26
29.66
30.31
-
4.66
4.20
4.89
5.34
8.20
7.43
1.80
1.97
8.91
8.83
100.00
99.34
Theory
LXIX
45.98
45.60
32.56
32.60
-
21.46
23.40
z
z
100.00
101.60
Theory
LVII
44.02
44.26
31.17
30.37
-
0.15
20.54
20.17
1.43
1.15
2.84
2.75
100.00
98.85
Theory
LXXVa
43.48
43.35
30.80
30.52
0.95
~
21.98
21.59
z
3.74
3.74
__
100.00
100.15
Theory
XIII
43.56
42.55
30.85
30.89
0.41
1.21
0.83
22.02
21.41
1.42
0.93
0.94
1.25
__
100.00
98.46
Theory
XXXVIII
38.23
38.00
23.02
24.10
6.37
5-60
-
2.65
2.80
23.04
22.64
6.69
6.95
___
_
100.00
100.09
378
THE SCAPOLITE GROUP
E. Scapolites of the type
Si R Si R Si = 5 R 2 3 18 Si0 2
Source Analyst
25
HMO
2(5R 2 O 3 -
18SiO 2 )
H MO = 9 CaO 4.5 Na 2 O 0.5 K 2 O
Mais j 6 SipOcz
26
HMO
2(5R 2 O 3 -
18 SiO 2 )
14 MO = 6 CaO 3 K 2 O 3 MgO-1 Na 2 O
Tiree F. Heddle
HH 2
. 1 FeO ; 10 R 2 O 3 =9 A1 2 O 3 1 Fe 2 O 3
27
32 MO
2(5A1 2 O 3
18SiO 2 )
32MO = 31CaO-lMgO
Storgard Norden-
10H 2
skiold
28
8 MO
2(5 R 2 O 3
18SiO 2 )
8 M0=3.5 K 2 2.5 CaO 2 MgO
Bolton, G. v. Rath
10H 2 O-3CaCO 3 )
10 R 2 O 3 =9.5 A1 2 O 3 0.5 Fe 2 O 3
Mass.
F. Scapolites of the type
Si R S A i Si R Si = 5 R 2 3 22 Si0 2
Source
Analyst
29
12 MO
2(5R 2 O 8 -
22 SiO 2 )
12 MO = 6.5 Na 2 O 5 CaO 0.5 MgO
Coquimbo
Jannetaz
10H 2 O
10R 2 3 =9Al 2 O 3 -lFe 2 3
30
15 MO
2(5Al 2 O a
22SiO 2 )
15 MO = 3 MgO 6 CaO 6 Na 2 O
Bamle
Vogt
G. Scapolites of the type
R Si Si R = 6 R 2 3 12 Si0 2
Source
Analyst
31
11 MO
2(6A1 2 O 8 -
12SiO 2 )
HMO = llCaO
Helsingfors
Wilk
32
11 MO
2(6A1 2 O 8 -
12SiO 2 )
HMO = llCaO
Pargas
Norden-
2H 2
skiold
H. Scapolites of the type
Si R Si R Si = 6 R 2 3 16 Si0 2
Source
Analyst
33
9 MO
2(6R 2 S
16SiO 2 )
9 MO = 6 CaO 3 Na 2 O 12 R 2 O 3
Petteby
Hartwall
2H 2
= 11.5Al 2 O 3 -0.5Fe 2 O 3
34
10 MO
2(6A1 2 3
16SiO 2 )
10 MO = 4.5 MgO 4 K 2 O 1 CaO
Bathurst,
Hunt
12H 2 O
0.5Na 2
Canada
35
13 MO
2(6R 2 3 -
16 SiO 2 )
13 MO = 10.5 CaO 1.5 Na 2 O-0.5 K 2 O
Diana,Lewis
Hermann
0.5H 2 O; 12R 2 O 3 =--11.5Al 2 O 3 -0.5Fe 2 O 3
Co., N.S.
36
13 MO
2(6A1 2 3
16SiO 2 )
13MO = llCaO-2Na 2 O
Ersby
Hartwall
1H 2
Herdberg
37
HMO
2(6 A1 2 O 3
16SiO 2 )
14 MO = 5 CaO 4 MgO 4 K 2 O
Bathurst,
Hunt
21 H 2
1 Na 2
Canada
38
17 MO
2(6A1 2 3
16 SiO 2
17 MO = 14.5 CaO 2 Na 2 O 0.5 K 2 O
Laacher See
Rath
1H 2
39
18 MO
2(6 R 2 O 3
16 SiO 2 )
18 MO = 15.5 CaO 1.5 Na 2 O 1 MgO
Bolton,
G. v. Rath
3H 2 O
1 2 R 2 O 3 = 1 1 A1 2 O 3 1 Fe 2 O 3
Mass.
THE SCAPOLITE GROUP
379
or the general formulae
(a) m MO 2 (5 R 2 3 18 Si0 2 ) n H 2 0,
(b) m MO 2 (5 R 2 3 18 SiO 2 ) n H 2 0. p CaC0 3 .
Si0 2
Al,0,
Fe,0,
FeO
MgO
CaO
K 8
Na,O
H,0
Nad
CaCO,
CO,
Cl
Total
Theory
XLIII
53.86
52.48
25.44
25.56
-
0.39
___
12.57
12.44
1.17
0.79
6.96
6.52
0.61
0.58 SO 3
0.14
0.27
100.00
99.78
Theory
XXIX
49.52
48.92
21.05
22.10
3.67
3.16
1.65
1.51
2.75
2.77
7.70
7.75
6.47
6.06
1.42
1.28
5.77
5.69
0.54 MnO
100.00
99.78
Theory
LV
42.06
41.25
19.86
20.36
z
0.78
0.54
33.80
33.58
z
~
3.50
3.32
100.00
99.05
Theory
CVI
50.97
49.99
22.87
23.01
1.89
1.64
-
1.89
1.73
3.30
3.35
7.76
7.09
0.35
4.25
4.23
7.07
7.80
___
100.00
99.19
or the general formula
m MO 2 (5 R 2 3 22 Si0 2 ) n H 2 O.
SiO 2
Al,0,
Fe,0,
FeO
MgO
CaO
K,0
Na,O
H,0
NaCl
CaCO,
CO,
Cl
Total
Theory
LXXVII
57.38
57.40
19.95
19.60
3.48
3.40
0.43
0.40
6.09
6.20
Trace
8.76
8.80
3.91
3.41
__
___
100.00
99.21
Theory
XXXIX
58.82
59.66
22.73
22.65
2.67
2.60
7.49
7.32
-
8.29
8.13
~
z
-
100.00
100.36
or the general formula
m MO 2 (6 R 2 3 12 Si0 2 )
nH 2 0.
SiO,
Al,0,
Fe,0,
FeO
MgO
CaO | K a O
Na 2
H 2
NaCl
CaCO,
CO,
Cl
Total
Theory
LXX
43.90
43.63
37.32
36.93
-
~
~
18.78
18.37
-
~
-
-
-
100.00
98.93
Theory
LIII
43.43
43.83
36.91
35.43
-
-
~
18.57
18.96
z
-
1.09
1.03
-
100.00
99.25
or the general formula
m MO 2 (6 R 2 3 16 SiO 2 ) n H 2 0.
SiO,
Al,0,
Fe 2 O
FeO
MgO
CaO
K a O
Na 2 o| H a O
NaCl
CaCO,
CO,
Cl
Total
Theory
LXVII
51.46
51.34
31.44
32.27
2.15
1.91
9.01
9.33
-
4.98
5.12
0.96
1.00
100.00
100.97
Theory
CXII
47.97
47.60
30.58
31.20
~
z
4.50
4.19
1.40
0.95
9.39
9.30
0.77
0.88
5.39
5.43
z
z
z
z
100.00
99.55
Theory
LXXXVI
49.10
47.94
30.00
30.02
2.05
2.60
0.26 MnO
z
15.04
14.41
1.20
0.73
2.38
2.20
0.22
0.31
___
z
z
100.00
98.47
Theory
LXV
49.20
48.87
31.37
31.05
__
15.79
15.94
3.18
3.25
0.46
0.61
__
z
z
100.00
99.62
Theory
CXI
43.64
43.55
27.82
27.94
0.20
3.63
3.81
6.36
6.50
8.55
8.37
1.41
1.45
8.59
8.61
___
z
100.00
100.43
Theory
46.32
45.13
29.53
29.83
-
0.13
19.59
18.98
1.14
1.40
2.99
2.73
0.43
0.41
100.00
98.61
Theory
CV
45.09
44.40
26.35
25.52
3.76
3.79
0.94
1.01
20.39
20.18
0.51
2.18
2.09
1.29
1.24
-
100.00
98.74
380
THE SCAPOLITE GROUP
J. Scapolites of the type
R Si R Si = 6 R 2 3 18 Si0 2
Source
Analyst
40
2MO-2(6A1 2 O 3 -18S10 2 )
2 MO = 1.5 Na 2 O 0.5 H 2 O
St. Lawrence
Rammels-
6H 2
Co., N.S.
berg
41
3 MO 2(6 A1 2 O 3 18 SiO 2 )
3 MO = 1 CaO 1 Na 2 O 0.5 MgO
Bolton,
Hermann
2H 2 O
0.5 K 2 O
Mass.
42
14 MO 2(6 A1 2 O 3 18 SiO 2 )
1H 2
14 MO = 10 CaO 2.5 Na 2 O 0.5 FeO
0.5 K 2 O 0.5 MgO
Boxborough
Becke
43
14MO-2(6Al 2 O 3 -18SiO 2 )
14 MO -8 CaO 3.5 MgO 2 Na 2 O
Glaukolite
Berge-
4H 2
0.5 K 2 O
Baikalsee
mann
44
14MO-2(6Al 2 3 -18Si0 2 )
14 MO = 8.5 CaO 2.5 MgO 2 Na 2 O
tt
Giwar-
4H 2
0.5 MnO 0.5 K 2 O
towsky
45
15MO-2(6Al 2 3 -18SiO 2 )
15MO = llCaO-4Na 2
Obernzell
Fuchs
2H 2
bei Passau
46
17 MO 2(6 A1 2 O 3 18 SiO 2 )
17 MO = 12 CaO 3 Na 2 O 1.5 MgO
Bolton,
Wolff
2H 2 O
0.5 K 2 O
Mass.
47
18MO-2(6R 2 3 -18Si0 2 )
18MO = 13.5CaO-3.5Na 2 O- 1 MgO
Hirvensalo
M
2H 2
12 R 2 3 =11.5Al 2 3 -0.5Fe 2 O 3
48
18MO-2(6Al 2 3 -18SiO 2 )
18 MO = 14 CaO 3.5 Na 2 O 0.5 MgO
Drothem
Berg
4H 2
49
18 MO 2(6 A1 2 O 3 18 SiO 2 )
18 MO = 15.5 CaO 2.5 Na 2 O
Bolton,
Thomson
13H 2
Mass.
50
19 MO 2(6 A1 2 O 3 18 SiO 2 )
19 MO = 14.5 CaO 2.5 Na 2 O
Bucks
Leeds
4H 2
- 1.5 MgO 0.5 K 2
Co., Pa.
51
19 MO 2(6 A1 2 O 3 18 SiO 2 )
19 M0 = ll CaO 4 MgO 2 Na 2 O
Perth,
Hunt
7H 2
2K 2
Canada
52
20MO-2(6R 2 O 3 -18SiO 2 )
20MO = 14CaO-6Na 2
Bolton,
Wurtz
12 R 2 O 3 = 11.5 A1 2 O 3 0.5 Fe 2 O 3
Mass.
53
20MO-2(6R 2 O 3 -18SiO 2 )
20 MO = 14 CaO 5.5 Na 2 O 0.5 K 2 O
Arendal
G. v. Rath
1H 2 O
12 R 2 O 3 = 11.5 A1 2 O 3 0.5 Fe 2 O 3
54
22MO-2(6R 2 O 3 -18SiO 2 )
22 MO = 18 CaO 2 Na 2 O 1.5 MgO
Bolton,
M
2H 2
0.5 K 2 O ; 12 R 2 O 3 =11A1 2 O 3 - 1 Fe 2 O 3
Mass.
55
HMO-2(6R 2 3 -18Si0 2 )
1 1 MO = 10 CaO 0.5 MgO 0.5 K 2 O
Hesselkulla
Hermann
3 Na 2 C0 3
12 R,O, = 11.25 A1 2 O 3 0.75 Fe 2 O 3
56
12MO-2(6Al 2 3 -18SiO 2 )
12 MO = 12 CaO
Obernzell
Fuchs
-6 Had
bei Passau
57
15 MO 2(6 A1 2 O 3 18 SiO 2 )
15 MO = 12 CaO 2.5 Na 2 O - 0.5 K 2 O
Ersby
Lemberg
2H 2 O-lNaCl
THE SCAPOLITE GROUP
381
or the general formulse
(a) m MO 2 (6 R 2 3 18 Si0 2 ) n H 2 0,
(b) m MO 2 (6 R 2 3 18 Si0 2 ) p Na 2 C0 3 (or p
Nad).
Si0 2
A1 Z 8
Fe 2 0,
FeO
MgO
CaO
K 2
Na 2
H 2
NaCl
CaC0 8
CO,
Cl
Total
Theory
XCIII
60.10
59.29
34.05
34.78
z
0.07
0.11
2.59
2.31
3.26
3.31
Z
-
0.20
100.00
100.07
Theory
cm
52.56
51.68
29.79
29.30
z
0.49
0.78
13.63
13.51
1.14
0.94
1.61
1.46
0.88
0.82
0.15MnO
z
-
z
100.00
99.80
Theory
CVIII
51.19
50.53
29.00
29.31
0.85
0.49
0.47
0.46
13.27
13.37
1.11
1.23
3.68
3.91
0.43
0.54
~
-
0.21
100.00
100.05
Theory
LXXII
51.25
50.58
29.03
27.60
0.86Mn 2 O 3
0.10
3.32
3.72
10.63
10.27
1.11
1.27
2.94
2.97
1.72
1.73
100.00
99.11
Theory
LXXIII
50.96
50.49
28.88
28.12
0.40 FeO
0.84MnO
0.60 MnO
2.36
2.68
11.23
11.31
1.10
1.00
2.93
3.10
1.70
1.79
100.00
99.49
Theory
II
50.42
49.30
28.57
27.90
z
z
z
14.38
14.42
~
5.79
5.46
0.84
0.90
-
z
z
100.00
97.98
Theory
C
49.26
48.79
27.92
28.16
0.32
~
1.37
1.29
15.33
15.02
1.07
0.54
4.24
4.52
0.81
0.74
-
z
z
100.00
99.38
Theory
LII
48.41
48.15
26.29
25.38
1.79
1.48
z
0.90
0.84
16.94
16.63
0.12
4.86
4.91
0.81
0.85
-
z
z
100.00
98.36
Theory
XLVII
48.25
46.35
27.34
26.34
0.32
-
0.45
0.54
17.51
17.00
0.32
4.85
4.71
1.60
1.60
0.99 ResU
-
100.00
98.17
Theory
XCIX
46.54
46.30
26.37
26.48
~
-
18.71
18.64
3.34
3.64
5.04
5.04
~ m
z
z
100.00
100.08
Theory
LXXXV
47.68
47.47
27.02
27.51
1.32
1.20
17.93
17.59
1.04
1.40
3.42
3.05
1.59
1.48
z
z
100.00
99.70
Theory
CX
46.97
46.30
26.62
26.20
3.48
3.63
13.39
12.88
4.08
4.30
2.70
2.88
2.76
2.80
z
100.00
98.99
Theory
CI
47.29
47.67
25.66
25.75
i.75
2.26
-
z
17.16
17.31
8.14
7.76
z
z
-
-
100.00
100.75
Theory
XXXII
46.93
46.82
25.48
26.12
1.74
1.39
0.26
17.03
17.23
1.02
0.97
7.41
6.88
0.39
0.33
z
z
-
z
100.00
100.00
Theory
CIV
45.79
45.57
23.79
23.65
3.39
3.38
1.27
1.23
21.37
20.81
1.00
0.63
2.63
2.46
0.76
0.78
-
-
-
z
100.00
98.51
Theory
L
49.40
49.49
26.25
26.06
2.74
2.65
0.25 MnO
0.46
0.36
12.81
12.89
1.07
0.80
4.25
4.50
z
-
-
3.02
3.00
100.00
100.00
Theory
III
49.01
49.42
27.78
27.50
z
z
15.25
15.25
7.96
7.83
-
100.00
100.00
Theory
LXIII
49.62
49.30
28.12
26.99
15.44
15.59
1.08
0.69
3.56
3.48
0.83
0.66
1.35
1.35
z
-
100.00
98.06
382
THE SCAPOLITE GROUP
K. Scapolites of the type
Si R Si Si R Si = 6 R 2 3 22 Si0 2
Source
Analyst
58
14MO-2(6R 2 3 -22SiO 2 )
14 MO = 7.5 CaO 4 K 2 O 2.5 MgO
Bolton, Mass.
G. v. Rath
12 H 2
12 R 2 O 3 =11.5 A1 2 O 3 - 0.5 Fe 2 O 3
59
18MO-2(6Al 2 O 3 -22SiO a )
18 M0 = 9 CaO 7 Na 2 O - 1 K 2 O
St. Lawrence
4H a O
IMgO
Co., N.S.
60
20 MO 2 (6 A1 2 O 3 22 SiO 2 )
20 MO = 10 Na 2 O 9 CaO 1 K 2 O
Monzoni
Kiepen-
heuer
61
20 MO 2 (6 A1 2 O 3 22 SiO 2 )
20 MO = 7.5 Na 2 O 7 CaO 3.5 MgO
Dipyre,Breno
Salomon
4H 2 O
1 K 2 1 H 2 O
62
14 MO 2 (6 A1 2 O 3 22 SiO 2 )
2NaCl
14 MO = 10 CaO 3 Na 2 O 1 K 2 O
Steinhag
Wittstein
63
14MO-2(6Al a O 3 -22SiO 2 )
14 MO = 8.5 CaO - 0.5 K 2 O 5 Na 2 O
French Creek,
Genth
4H 2 O-3CaCO 3
Pa.
64
15MO-2(6Al 2 3 -22SiO 2 )
2H 2 O-2NaCl
15 MO = 8.5 CaO 6.5 Na 2 O
Pargas
Rammels-
berg
65
15MO-2(6Al a 3 -22SiO 2 )
2H 2 O-2NaCl
15 MO = 9 CaO 4 Na 2 O 2 K 2 O
"
66
15 MO.- 2 (6 A1 2 O 3 22 SiO 2 )
15 MO = 9.5 CaO 4.5 Na 2 O 1 K 2 O
St. Lawrence
n
4 NaCl
Co., N.Y.
L. Scapolites of the type
-R-Si = 9 R 2 3 20 Si0 2
Source
Analyst
67
68
16MO-2(9Al 2 3 -20Si0 2 )
18 H 2
24MO-2(9Al a O 3 -20SiO 2 )
16 MO =9 CaO - 4 Na 2 O 1.5 MgO
1.5K 2 O
24 MO = 20.5 CaO - 2.5 Na 2 O 1 FeO
Saleix, Ariege
Vesuvius
Grandeau
Gmelin
69
70
26 MO 2 (9 R 2 O 3 20 SiO 2 )
6H 2 O
22 MO 2 (9 A1 2 O 3 20 SiO 2 )
4 CaCO 3
26 MO = 21 CaO- 5 K 2 O
18 R 2 3 = 15 A1 2 O 3 3 Fe 2 O 3
22 MO = 19.5 CaO - 2.5 Na a O
Bolton, Mass.
Vesuvius
Muir
Gmelin
THE SCAPOLITE GROUP
383
or the general formulae
(a) m MO 2 (6 R 2 3 22 Si0 2 ) n H 2 0,
(b) m MO 2 (6 R 2 O 3 22 Si0 2 ) n H 2 p
NaCl (or p CaC0 3 ).
SiOj
AI,0,
Fe 2 0,
FeO
MgO
CaO
K,0
Na 2
H a O
NaCl
CaCOa
CO, | Cl | Total
Theory
CVIa
52.75
52.20
23.42
24.03
1.60
1.71
z
2.00
1.80
8.39
8.06
7.51
7.40
0.37
4.33
4.43
z
z
100.00
100.00
Theory
LXXXIX
52.72
52.25
24.44
23.97
Trace
~
0.80
0.78
10.06
9.86
1.88
1.73
8.67
8.70
1.43
1.20
z
100.00
98.49
Theory
VII
51.95
52.19
24.08
23.54
~
~
~
9.92
9.61
1.85
2.11
12.20
12.65
z
z
-
z
100.00
100.10
Theory
VIII
52.71
52.74
24.44
23.98
0.40
~
2.79
2.77
7.83
7.43
1.88
1.86
9.28
9.00
1.07
1.18
z
-
100.00
99.36
Theory
VI
54.76
54.87
25.39
25.32
z
~
~
11.62
11.63
1.95
1.50
3.86
3.86
z
2.42
2.15
-
100.00
99.33
Theory
LXXXIV
52.08
52.30
24.15
23.68
0.58
0.05
12.70
12.36
0.93
0.77
6.11
6.29
1.42
1.50
-
2.61
2.63
100.00
100.16
Theory
LXI
54.04
53.32
24.91
24.67
~
~
9.69
9.84
9.46
9.12
0.73
0.73
-
-
1.48
1.73
100.31*
99.41
Theory
LXII
53.43
53.32
24.60
24.08
-
~
10.13
9.60
3.78
3.93
6.23
6.31
0.72
0.71
1.43
1.71
100.32*
99.66
Theory
XCI
52.93
52.90
24.38
24.95
-
-
10.59
10.54
1.87
1.53
8.03
8.10
2.83
2.33
101.63*
100.35
or the general formulse
(a) m MO 2 (9 R 2 3 20 Si0 2 ) n H 2 0,
(b) m MO 2 (9 R 2 3 - 20 Si0 2 ) n CaCO,
SiO,
A1,O 3
Fe,0 s
FeO
MgO
CaO
K,0
Na,O
H,0
NaCl
CaCO,
CO,
a
Total
Theory
XXVII
43.54
44.08
33.50
32.85
z
z
1.09
1.18
9.14
9.17
2.56
2.68
4.49
4.43
5.88
6.20
100.00
100.59
Theory
X
42.78
43.80
32.72
32.85
z
1.28
1.07
z
20.46
20.64
2.76
2.57
z
z
100.00
100.93
Theory
XCVIII
38.94
37.81
24.83
25.10
7.78
7.89
z
19.07
18.34
7.63
7.30
1.75
1.50
z
z
z
z
100.00
97.94
Theory
IX
40.80
40.80
31.21
30.60
-
22.37
22.10
z
2.63
2.40
z
-
2.99
3.10
z
100.00
100.00
* The excess above 100.00 in the Theory-Total in Nos. 64, 65 and 66 is due to the oxygen -
equivalent of the chlorine being included in the figures in the Na 2 column. A. B. S.
384
THE ORTHOCHLORITE GROUP
The
The following analyses of the minerals
A. Si R Si =3 R 2 3 10 SiO
B. Si R Si
^x sl
C. Rf-Si
= 3 R 2 3 12 SiO
2>
2>
3 R 2 3 15 Si0 2 ,
D.
Ni
E. R - Si
F. Si-R
R
R
= 3 R 2 3 18 Si0 25
= 5 R 2 3 6 Si0 2 ,
Si = 5 R 2 3 12 Si0 2 ,
A. Orthochlorites of the type
Si R Si = 3 R 2 3 10 Si0 2
Source
22 MO 2 (3 A1 2 3 10 SiO 2 )
16 H 2
31MO-2(3R 2 3 -10Si0 2 )
26 H 2 O
32 MO 2 (3 R 2 O 3 10 SiO 2 )
24H 2
34 MO 2 (3 A1 2 O 3 10 SiO 2 )
26 H 2
43MO-2(3R 2 O 3 -10Si0 2 )
8H 2 O
22 MO = 12.5 FeO 7 MgO 1 CaO
0.5 MnO 0.5 K 2 O 0.5 Na 2 O
31 MO = 27 MgO 3.5 FeO 0.5 CaO ;
6R 2 3 = 5Al 2 3 -lFe 2 3
32 MO = 30 MgO -2 FeO;
6 R 2 O 3 =5.5 A1 2 O 3 0.5 Fe 2 O 3
34 MO = 31 MgO -3 FeO
43 MO = 40.5 MgO 2.5 FeO ;
6 R 2 O 3 =5 A1 2 O 3 1 Cr 2 O 3
Ortho-
chlorite
Delessite
Orthochlorite
(Clinochlorite)
Orthochlorite
M
Bishops Hill
St. Cyrus,
Scotland
Kupferberg
Zillertal
Webster,
N.C.
B. Orthochlorites of the types
Si R Si = 3 R 2 3 12 Si0 2
Source
6
25 MO-
2 (3 R 2 3 -
12 Si0 2 )
25 MO = 25 MgO
Lennilite
Petham,
- *
22H 2 O
6R 2 3 = 5Al 2 3 -lFe 2 O 3
Mass.
7
33 MO-
2 (3 R 2 3
12Si0 2 )
33 MO = 19MgO-6FeO-7CaO-lK 2 O
Orthochlorite
Corry-
28H 2
6 R 2 O 3 = 5.5 A1 2 O 3 0.5 Fe 2 O 3
(Pennine)
charmaig
8
33 MO-
2 (3 R 2 O 3
12 Si0 2 )
33 M0 = 31 MgO 1 FeO 1 CaO
Orthochlorite
Bissersk
28H 2 O
6 R 2 O 3 = 5.5 A1 2 O 3 0.5 Cr 2 O 3
9
36 MO-
2 (3 A1 2 3 -
12 SiO 2 )
36 MO = 31.5 MgO 1.5 FeO-1.5 K 2 O
w
Tilly Foster
24H 2
!Na 2 O-0.5Li 2 O
Mine, N.Y.
10
38 MO
2 (3 R 2 3
12 SiO 2 )
38 MO = 37 MgO -1 FeO
>
Itkul Sea
28H 2
6 R 2 O 3 = 4.5 A1 2 O 3 1.5 Cr 2 O 3
11
38 MO-
2 (3 R 2 O 3
12 Si0 2 )
38 MO = 38 MgO
M
Calumet
38H 2 O
6 R 2 O 3 = 5.5 A1 2 O 3 0.5 Fe 2 O 3
Falls, Can.
12
39 MO-
2 (3 R 2 3
12 SiO 2 )
39 MO = 39 MgO
>
Texas, Pa.
.
30H 2
6 R 2 O 3 =4.5 A1 2 O 3 -0.5 Fe 2 O 3 - 1 Cr 2 O 3
THE ORTHOCHLORITE GROUP
Orthochlorite Group
of the orthochlorite group conform to the following types :
385
G. Si R Si R Si
H. Si R Si
J. R-Si-R
JA.. fel * -LV * _tv
Si R Si =
m
L. Si R R Si
M. Si R Si R Si
N. Si-R-iSi-R-Si =
0. R Si R S A i R
P. R S A i R Si - R
5R 2 3
18 Si0 2 ,
5R 2 3
22Si0 2 ,
6R 2 3
6Si0 2 ,
6R 2 3
10 Si0 2 ,
6R 2 3
12 Si0 2 ,
6R 2 3
16 SiO a ,
6R 2 3
18 Si0 2 ,
8R 2 3
12 SiO 2 ,
9 R 2 a
12 SiO*
or the general formula
m MO 2 (3 R 2 3 10 Si0 2 ) n H 2 0.
Analyst
Si0 2
A1 2 8
Fe 2 3
Cr z 3
FeO
MnO
CaO
MgO
K,0
Na 2 O
H 2
Total
Heddle
Theory
LXIX
34.89
35.41
17.79
18.08
0.48
z
26.16
26.47
1.03
0.61
1.34
1.01
8.14
8.77
1.37
0.98
0.90
0.52
8.38
8.03
100.00
100.36
Theory
V
32.45
32.69
13.79
13.44
4.33
4.40
6.81
6.62
z
0.76
0.86
29.20
28.77
z
12.66
13.25
100.00
100.03
Kobell
Theory
III
33.17
33.49
15.51
15.37
2.23
2.30
0.55
3.98
4.25
33.17
32.94
11.94
11.50
100.00
100.40
Briiel
Theory
XXIII
32.12
31.47
16.38
16.67
~
5.78
5.97
0.11
33.19
32.56
12.53
12.43
100.00
99.21
Genth
Theory
CLX
31.53
31.45
13.40
13.08
3.99
4.16
4.74
4.88
0.17
42.56
43.10
0.06
0.16 NiO
3.78
3.29
100.00
100.35
or the general formula
m MO 2 (3 R 2 3 12 Si0 2 ) n H 2 0.
Analyst
SiO a
A1 2 3
Fe 2 s
Cr 2 8
FeO
MnO
CaO
MgO
K,0
NajO
H 2
Total
Gooch
Theory
III
41.07
41.27
14.55
15.19
4.56
4.14
28.53
28.25
11.09
11.32
100.00
100.17
Heddle
Theory
LXII
33.78
34.31
13.16
13.64
1.88
0.36
z
10.13
10.31
0.23
9.19
8.97
17.83
18.14
2.20
1.36
0.13
11.83
12.41
100.00
99.76
Hartwall
Theory
CXI
36.83
37.00
14.36
14.20
1.94
1.00
1.84
1.50
1.43
1.50
30.69
31.50
z
12.91
13.00
100.00
99.70
Schlaepfer
Theory
CXXVII
35.38
36.18
15.04
14.34
0.28
z
2.65
2.88
0.38 Li 2 O
0.42 Li 2
30.95
31.26
3.46
3.09
1.52
1.99
10.62
10.31
100.00
100.75
Hermann
Theory
CXIII
34.42
34.64
10.97
10.50
5.46
5.50
1.72
2.00
~
35.38
35.47
12,05
12.03
100.00
100.14
Hunt
Theory
CXVIII
33.61
33.28
13.09
13.30
1.87
1.92
-
-
35.47
35.50
-
15.96
16.00
100.00
100.00
Smith und
Brush
Theory
CXLIV
34.03
33.26
10.84
10.69
1.89
1.96
3.60
4.78
36.87
35.93
-
0.35
12.77
12.64
100.00
99.61
2 c
386
THE ORTHOCHLORITE GROUP
Source
13
39 MO 2 (3 R 2 O 3
30 H 2 O
12Si0 2 )
39 MO = 39 MgO
6 R 2 O 3 = 4.5 A1 2 O 3 -0.5 Fe 2 O 3 - !Cr 2 O 3
Orthochlorite
Texas, Pa.
14
39 MO 2 (3 R 2 O 3
32H 2
12SiO a )
39 MO = 37 MgO -2 FeO
6 R 2 O 3 =5.5 A1 2 O 3 -0.5 Fe 2 O 3
Zillertal
15
39 MO 2 (3 R 2 O 3
- 32 H 2 O
-12Si0 2 )
39 MO = 37 MgO -2 FeO
6 R 2 O 3 = 5.5 A1 2 O 3 0.5 Fe,O 3
"
16
39 MO 2 (3 R 2 O 3
32 H 2 O
12 SiO 2 )
39 MO = 37 MgO -2 FeO
6 R 2 O 3 = 5.5 A1 2 O 3 0.5 Fe 2 O 3
NaBfeld
17
39 MO 2 (3 R 2 3
32 H 2
12 SiO 2 )
39 MO = 37 MgO -2 FeO
6 R 2 O 3 = 5.5 A1 2 O 3 0.5 Fe 2 O 3
99
Zermatt
18
39MO-2(3R 2 3
32 H 2
12Si0 2 )
39 MO = 37 MgO -2 FeO
6 R 2 O 3 =5.5 A1 2 O 3 0.5 Fe 2 O 3
99
'
19
39 MO 2 (3 R 2 3
32 H 2
12Si0 2 )
39 MO = 37 MgO -2 FeO
6 R 2 3 =5.5 A1 2 3 0.5 Fe 2 O 3
99
20
40 MO 2 (3 A1 2 O 3
30 H 2 O
12 SiO 2 )
40 MO = 37 MgO -3 FeO
Binnenthal
21
40 MO - 2 (3 A1 2 O 3
30 H 2 O
12SiO 2 )
99
99
Zermatt
22
40 MO 2 (3 A1 2 3
30 H 2
12 SiO 2 )
99 99
99
23
40MO-2(3A1 2 O 3
30 H 2
12 SiO 2 )
99 99 99
99
24
40 MO 2 (3 R 2 O 3
30H 2
12 SiO a )
40 MO = 38.5 MgO 1.5 MnO
6 R 2 O 3 = 5.5 A1 2 3 0.5 Fe 2 O 3
9*
Pojsberg
25
43 MO 2 (3 A1 2 O 3
30 H 2 O
12Si0 2 )
43 MO = 25.5 MgO 17.5 FeO
Diabantite
Landes-
freude
26
45 MO 2 (3 R 2 O 3
30H 2 O
12SiO 2 )
45 MO = 36MgO-7FeO-l MnO-lNa 2 O
6 R 2 O 3 = 5 A1 2 O 3 - 1 Fe 2 O 3
Orthochlorite
Sealpay
C. Orthochlorites of the type
/Si
R^-Si = 3 R 2 3 15 Si0 2
Source
27
32 MO 2 (3 A1 2 O 3 15 SiO 2 ) 42 H 2 O
32MO = 29MgO-3FeO
Orthochlorite
North
Burgess, Can.
28
32 MO 2 (3 R 2 O 3 15 SiO 2 ) 54 H 2 O
32 MO = 32 MgO
99
Culsagee
6R 2 O 3 = 5Al 2 O 3 -lFe 2 O 3
Mine, N.C.
29
99 99 99 99
32 MO = 32 MgO
99
99
6R 2 3 =5Al 2 3 -lFe 2 3
30
39 MO 2 (3 A1 2 3 15 SiO 2 ) 20 H 2 O
39 MO = 32 MgO -7 FeO
99
Traversella
31
48 MO 2 (3 A1 2 3 15 SiO 2 ) 38 H 2 O
48 MO = 44 MgO
99
Beautyhill
2 FeO 1 CaO - 1 MnO
32
53 MO 2 (3 A1 2 3 15 SiO 2 ) 36 H 2 O
53 MO =47 MgO -6 FeO
99
Zermatt
33
99 99
99
'
THE ORTHOCHLORITE GROUP
387
Analyst
SiO,
A1 2 0,
Fe a O,
Cr,O s
FeO
MnO
CaO
MgO
K,0
Na,0
H,0
Total
Smith and
Theory
34.03
10.84
1.89
3.60
36.87
12.77
100.00
Brush
CXLV
33.30
10.50
1.60
4.67
36.08
0.35 Alk
13.25
99.75
Rumpf
Theory
33.60
13.10
1.83
3.36
34.57
13.48
100.00
XXIV
34.24
12.64
1.64
3.35
0.30
34.86
14.44
101.15
Ludwig
Theory
XXV
33.83
12.95
2.25
3.02
34.94
13.11
100.10
Telek
Theory
XXI
33.44
13.72
3.40
3.26
32.99
12.71
99.52
Schlaepfer
Theory
XLVII
34.06
11.75
1.92
0.69
2.78
33.90
0.39
2.45
13.08
101.02
v. Fellenberg
Theory
XLIV
33.12
13.25
1.52
0.60
4.69
34.04
12.87
100.09
v. Hamm
Theory
XLVI
33.71
12.55
2.74
3.40
0.66
34.70
12.27
100.03
Marignac
Theory
33.58
14.27
5.04
34.52
12.59
100.00
XLVIII
33.95
13.46
0.24
6.12
33.71
12.52
100.00
Theory
XXXVIII
33.36
13.24
0.20
5.93
34.21
12.80
99.74
Theory
33.58
14.27
5.04
34.52
12.59
100.00
XXXIX
33.40
13.41
0.15
5.73
34.57
12.74
100.00
Wartha
Theory
XLIII
32.51
14.55
4.96
34.01
14.07
100.10
Hamberg
Theory
33.73
13.14
1.87
2.53
__
36.08
12.65
100.00
LXXXVIII
33.71
13.80
1.64
2.28
35.88
13.11
100.75
Liebe
Theory
29.56
12.57
25.86
20.94
11.08
100.00
II
29.37
12.00
25.63
0.33
21.01
11.27
99.28
Heddle
Theory
30.40
10.77
3.38
10.60
1.50
30.40
1.52
11.43
100.00
LXI
30.41
11.58
2.34
10.71
1.19
30.63
0.01
1.31
11.74
99.92
or the general formula
m MO 2 (3 R 2 3 15 Si0 2 ) n H 2 0.
Analyst
SiO,
Al,0 3
Fe 2 0,
Cr z 3
FeO
MnO
CaO
MgO
K,O
Na z O
H a O
Total
Hunt
Theory
39.61
13.47
4.75
25.53
16.64
100.00
cxx
39.30
14.25
4.41
25.73
16.93
100.62
Chatard
Theory
38.12
10.80
3.38
27.12
20.58
100.00
CLVIII
38.29
11.41
1.95
0.32
0.25(Ni, Cop
26.40
21.25
99.87
Clarke &
Theory
38.12
10.80
3.38
27.12
20.58
100.00
Schneider
CLIX
38.13
11.22
2.28
0.18
0.48 NiO
27.39
20.47
100.15
Marignac
Theory
39.51
13.44
11.06
28.09
7.90
100.00
LIV
39.81
12.56
11.10
28.41
7.79
99.67
Heddle
Theory
35.11
11.94
2.81
1.38
1.09
34.33
13.34
100.00
LXV
34.73
12.44
2.68
1.17
1.60
34.10
13.10
99.82
Max
Theory
33.51
11.39
8.01
35.00
12.09
100.00
Donnell
XL
33.64
10.64
8.83
34.95
12.40
100.46
Merz
Theory
XLI
33.26
11.69
7.20
35.18
12.18
99.51
388
THE ORTHOCHLORITE GROUP
D. Orthochlorites of the type
Rr-S A i = 3 R 2 3 18 Si0 2
X Si
Source
34
46 MO
2(3A1 2 O 3
18SiO 2 )-
22H 2 O
46 MO =39 MgO -7 FeO
Orthochlorite
Traversella
35
36
48 MO
50 MO
2(3A1 2 3
2(3A1 2 3
18 SiO 2 ) -
18S10,)-
24H 2 O
26H 2 O
48MO=35MgO-6FeO-3CaO
3 Na 2 O 1 K 2 O
50MO=40MgO-10FeO
Hillswick
Traversella
37
38
50 MO
59 MO
2(3A1 2 3
2(3A1 2 3
18SiO 2 )-
18 SiO 2 )
46H 2
64H 2 O
50 MO = 42 MgO -8 FeO
59 MO = 32.5 MgO-26.5FeO
>
Diabantite
North Elms-
ley, Can.
Holletal
39
63 MO
2(3A1 2 3
18 SiO 2 )
44H 2 O
63 MO = 53 MgO -10 FeO
Orthochlorite
Zermatt
40
ft
j> ?
>
E. Orthochlorites of the type
R S A i R = 5 R 2 3 6 Si0 2
Source
41
24 MO 2 (5 A1 2 O 3 6 SiO 2 20 H 2 O
24MO = 16.5MgO-7.5FeO
Orthochlorite
Chester,
Mass.
F. Orthochlorites of the type
Si R R Si = 5 R 2 3 12 Si0 2
Source
42
12MO-2(5R 2 3 -12SiO 2 )
28H 2
12 MO = 8MgO-2.5CaO-lMnO-0.5K 8
10 R 2 O 3 =6.5 A1 2 O 3 3.5 Fe 2 O 3
Hullite
Kinkell
43
22MO-2(5Al 2 3 -12Si0 2
24H 2
22 MO = 21 MgO 0.5 CaO 0.5 FeO
Orthochlorite
Markirch
44
29MO-2(5R 2 3 -12SiO 2
38 H 2
29MO = 29FeO
10 R 2 O 3 = 9 A1 2 O 3 1 Fe 2 O 3
Chamosite
Schmiedefeld
45
33MO-2(5R 2 O 3 -12SiO 2 )
32H 2
33 MO = 17.5 MgO- 11 FeO 4.5 CaO
10R 2 3 = 7Al 2 3 -3Fe 2 3
Chloropite
Chloropitschiefer
von Koditz
46
34MO-2(5R 2 O 3 -12SiO 2 )
34 H 2 O
34 MO = 20.5 MgO 12.5 FeO 1 CaO
10 R 2 O 3 = 8,5 A1 2 O 3 1.5 Fe 2 O 3
Delessite
Friedrichsroda
47
36 MO-2(5 Al 2 O 3 -12SiO 2 )
36 H 2 O
36 MO = 33 FeO 3 MgO
Chamosite
Chrustenic
48
38 MO-2(5 Al 2 O 3 -12SiO 2 )
32H 2
38 MO = 35 MgO -3 FeO
Orthochlorite
Newlin, Pa.
49
40MO-2(5R 2 O 3 -12SiO 2 )
32 H 2 O
40 MO = 40 MgO
10 R 2 O 3 = 8.5 A1 2 O 3 1.5 Fe 2 O 3
?>
Alatal
50
40MO-2(5R 2 3 -12Si0 2 )
32H 2 O
40 MO = 40 MgO
10 R 2 O = 8.5 A1 2 O 3 1.5 Fe 2 O 3
Achmatowsk
THE ORTHOCHLORITE GROUP
389
or the general formula
m MO 2 (3 R 2 O 3 18 Si0 2 ) n H 2 0.
Analyst.
SiO a
Al 2 o s
Fe a Oi 1 Cr 2 0j | FeO
MnO
CaO
MgO
K0
Na,0
H,0
Total
Marignac
Theory
LV
41.28
41.34
11.70
11.42
~
~
9.63
10.09
29.82
29.67
~
7.57
7.66
100.00
100.18
Heddle
Theory
LXXVIII
39.39
39.81
11.16
11.43
~
~
7.88
7.97
0.26
3.06
2.80
25.53
25.65
1.71
1.20
3.39
3.15
7.88
7.91
100.00
100.18
Marignac
Theory
LIII
38.84
38.45
11.01
11.75
~
~
12.94
12.82
~
28.76
28.19
__
8.45
8.49
100.00
99.70
Hunt
Theory
CXIX
36.88
36.70
10.45
10.96
~
9.84
9.36
28.69
28.19
14.14
14.31
100.00
99.52
Liebe
Theory
V
30.29
29.85
8.58
9.07
~
~
26.75
26.60
18.23
17.92
16.15
15.81
100.00
99.25
Schweizer
Theory
XXXVI
33.73
33.82
9.56
9.32
~
~
11.24
11.30
-
__
33.10
33.04
__
12.37
11.50
100.00
98.98
Theory
XXXVII
33.07
9.69
11.36
32.34
12.58
99.04
or the general formula
m MO 5 (5 R 2 3 6 Si0 2 ) n H 2 0.
Analyst
Si0 2
A1.0,
Fe 2 8
Cr 2 3
FeO
MnO
CaO
MgO
K 2
Na 2
H 2
Total
Pisani
Theory
CXXIV
21.81
21.40
30.91
32.30
16.36
15.80
20.00
19.90
10.91
10.90
100.00
100.30
or the general formula
mMO 2(5R 2 3 - 12S10,
nH 2 0.
Analyst
Si0 2
A1 2 3
Fe 2 3
Cr 2 s
FeO
MnO
CaO
MgO
K 2 |Na 2 o| H 2
Total
Heddle
Theory
II
38.45
38.59
17.71
17.34
14.95
15.97
1.90
1.56
3.74
3.94
8.54
8.65
1.25
0.67
-
13.46
13.48
100.00
100.20
Delesse
Theory
37.94
38.39
26.87
26.54
0.94
0.59
z
0.74
0.67
22.13
22.16
z
-
11.38
11.65
100.00
100.00
Loretz
Theory
III
27.22
27.00
17.35
17.00
3.02
4.00
39.47
39.00
z
z
z
~
12.94
13.00
100.00
100.00
>
Theory
IV
29.07
29.06
14.41
14.04
9.69
9.27
-
15.99
15.96
5.08
5.02
14.13
13.95
11.63
11.64
100.00
98.94
Pufahl
Theory
IV
29.18
28.79
17.57
16.74
4.86
4.83
18.24
18.30
-
1.13
0.98
16.61
16.62
12.41
12.25
100.00
100.21
Boricky
Theory
VI
25.69
25.60
18.20
18.72
42.40
42.31
-
2.14
2.13
-
11.57
11.24
100.00
100.00
Leeds
Theory
CXXXVII
30.96
30.62
21.92
21.73
0.42
~
4.64
5.01
30.09
29.69
0.11Li 2 O
0.14
12.39
12.26
100.00
99.98
Marignac
Theory
L
30.49
30.01
18.36
19.11
5.08
4.81
33.88
33.15
__
12.19
12.52
100.00
99.60
'
Theory
XCI
30.49
30.27
18.36
19.85
5.08
4.42
-
-
33.88
33.13
~
12.19
12.54
100.00
100.25
390
THE SCAPOLITE GROUP
Source
51
40 MO 2(5 A1 2 O 3 12 SiO 2 )
32H 2
40 MO = 23.5 MgO 16.5 FeO
Orthochlorite
Gumuch, Dagh.
52
40 MO 2(5 A1 2 O 3 12 SiO 2 )
34H 2
40 MO = 22 MgO- 18 FeO
Sept-Lacs
53
40 MO 2(5 R 2 O 3 12 SiO 2 )
40 MO = 38 MgO -2 FeO
Jf
Borostyanko
34 H 2 O
10R 2 O 3 =9Al 2 3 -lFe 2 O 3
54
40 MO 2(5 A1 2 O 3 12 SiO 2 )
40 MO = 38 MgO -2 FeO
99
Alatal
40 H 2 O
55
40 MO 2(5 A1 2 3 12 SiO 2 )
>
>
,,
40 H 2 O
56
41 MO - 2(5 R 2 O 3 12 SiO 2 )
41 MO = 37 MgO -4 FeO
M
Montafun
34H 2
10 R 2 O 3 =9.5 A1 2 O 3 0.5 Fe 2 O 3
57
41 MO 2(5 A1 2 O 3 12 SiO 2 )
46H 2
41MO = 34FeO-5MgO- 1 CaO
1K 2
Metachlorite
Buchenberge
bei Elbingerode
58
42 MO 2(5 A1 2 O 3 12 SiO 2 )
42 MO = 38 MgO 4 FeO
Orthochlorite
Culsagee Mine,
32 H 2 O
N.C.
59
42MO-2(5Al 2 O 3 -12Si0 2 )
42MO = 41.5MgO-0.5FeO
Amity, N.Y.
34H 2
60
42MO-2(5Al 2 3 -12Si0 2 )
42 MO = 21 MgO -20 FeO
M
Foundry Run,
46H 2
- 1 Na 2
Georget, D.C.
61
46 MO 2(5 A1 2 O 3 12 SiO 2 )
46 MO = 24 MgO 22 FeO
M
St. Gotthard
28 H 2 O
62
46 MO 2(5 A1 2 O 3 12 SiO 2 )
46 MO = 33 MgO 12 FeO 1 CaO
>
Zillertal
38 H 2 O
63
47MO-2(5R 2 O 3 -12Si0 2 )
47 MO = 33.5MgO-12.5FeO-lMnO
>f
Loch Laggan
36H 2
10 R 2 O 3 = 9.5 A1 2 3 0.5 Fe 2 O 3
G. Orthochlorites of the type
Si E Si R S A i = 5 R 2 3 18 Si0 2
Source
64
42 MO
2(5 R 2 O 3
36 H 2
18 Si0 2 )
42 MO = 42 MgO
10 R 2 O 3 = 7.5 A1 2 O 3 2.5 Fe 2 O 3
Lennilite
Lenni
65
44 MO
2(5 R 2 3
34H 2
18SiO 2 )
44 MO = 37.5 MgO 3.5 FeO 3 CaO
10 R 2 O 3 = 7.5 A1 2 O 3 2.5 Fe 2 O 3 &?
Berlauite
Berlaubach
bei Budweis
66
44 MO
2(5R 2 3 -
40 H 2
18 SiO 2 )
44 MO = 28.5MgO 14 FeO 1.5 CaO
10 R 2 O 3 =7.5 A1 2 O 3 2.5 Fe 2 O 3
Euralite
Kiperjarvi
67
44 MO
2(5 R 2 3
58 H 2 O
18 SiO 3 )
44 MO = 37.5 MgO 3.5 FeO 3 CaO
10 R 2 3 = 7.5 A1 2 3 2.5 Fe 2 O 3 ., [
Berlauite
Berlaubach
bei Budweis
68
53 MO
2(5 R 2 3
48 H 2
18Si0 2 )
53 MO = 53 MgO
10 R 2 O 3 = 7 A1 2 O 3 3 Fe 2 O 3
Ortho-
chlorite
Snarum
69
54 MO
- 2(5 A1 2 3
48 H 2 O
18 SiO 2 )
54 MO = 53 MgO- 1 FeO
Ploben
70
56 MO
2(5 R 2 3
54 H 2 O
18 SiO 2 )
56 MO = 33 MgO 18 FeO 2 CaO -1 MnO
1.5Na 2 O-0.5K 2 O;10R 2 O 3 = 9Al 2 O 3 -lFe 2 O 3
Delessite
Elie, Fife-
shire
71
57 MO
2(5R 2 O 3 -
48 H 2 O
18 SiO 2 )
57 MO = 57 MgO
10 R 2 O 3 =7 A1 2 O 3 2.5 Cr 2 O 3 0.5 Fe 2 O 3
Ortho-
chlorite
Texas, Pa.
72
57 MO
2(5R 2 3 -
"-.48 H 2 O
18.Si0 8 )
57 MO = 57 MgO
10 R 2 O 3 = 7 A1 2 O 3 2.5 Cr 2 O 3 0.5 Fe 2 O 3
n
THE ORTHOCHLORITE GROUP
391
Analyst
Si0 2
A1 2 3
Fe 2 8
Cr 2 3
FeO
MnO
CaO
MgO
K 2 O
Na 2
H 2
Total
L. Smith
Theory
27.88
19.75
23.01
18.21
11.15
100.00
CXIV
27.20
18.62
23.21
17.64
10.61
97.28
Marignac
Theory
27.44
19.44
24.70
16.77
11.65
100.00
LX
27.14
19.19
24.76
16.78
11.50
99.37
Szilasi
Theory
30.04
19.15
3.34
3.00
31.71
12.76
100.00
XVI
30.45
18.96
3.70
2.21
32.20
12.79
100.31
Jannasch
Theory
29.73
21.06
2.97
31.37
14.87
100.00
LI
29.31
21.31
0.07
3.24
31.28
0.43
14.58
100.22
Theory
LII
29.59
24.82(Al 2 O 3 +FeO)
31.46
0.30
14.73
100.90
Wartha
Theory
29.57
19.91
1.64
5.91
30.41
12.56
100.00
XXXII
29.44
20.98
2.00
5.60
30.31
12.29
100.62
List
Theory
23.65
16.76
40.22
0.93
3.28
1.55
13.61
100.00
I
23.78
16.43
40.37
0.74
3.10
1.38
0.08
13.76
99.64
Genth
Theory
29.73
21.06
5.94
31.38
11.89
100.00
CLVI
29.48
22.22
0.70
5.30
0.17
30.99
0.11(]S
iCo)O
11.63
100.60
Sipocz
Theory
30.20
21.40
0.76
34.81
12.83
100.00
cxxv
30.28
22.13
1.08
34.45
12.61
100.55
Clarke
Theory
25.57
18.11
25.57
14.92
1.09
14.70
100.00
CLI
25.45
17.88
24.98
15.04
0.67
14.43
98.45
Varren-
Theory
26.14
18.52
28.76
17.43
9.15
100.00
trapp
XXXIII
25.37
18.50
28.79
17.09
8.96
98.71
Tscher-
Theory
26.69
18.91
16.02
1.04
24.47
12.87
100.00
mak
XXXI
26.30
19.80
15.10
1.00
24.40
12.40
99.00
Heddle
Theory
26.42
17.79
1.47
16.52
1.30
24.59
11.91
100.00
LXXV
26.25
19.22
1.67
16.44
1.02
24.35
11.67
100.62
or the general formula
m MO 2 (5 R 2 O 3 18 Si0 2 ) n H 2 0.
Analyst
Si0 2
A1 2 8
Fe 2 3
Cr 2 O 8
FeO
MnO
CaO
MgO
K 2
Na 2
H 2
Total
Gooch
Theory
II
38.21
38.03
13.53
12.93
7.08
7.02
0.50
29.72
29.64
11.46
11.68
100.00
99.80
Schrauf
Theory
II
36.88
37.25
13.05
13.75
6.83
6.86
~
4.31
4.02
z
2.86
2.81
25.62
25.77
10.45
9.82
100.00
100.28
Wilk
Theory
34.41
33.68
12.18
12.15
6.37
6.80
16.06
15.66
1.34
1.34
18.16
17.92
z
-
11.48
11.49
100.00
99.04
Schrauf
Theory
34.35
34.38
12.16
12.69
6.36
6.33
4.00
3.71
-
2.67
2.59
23.85
23.79
z
16.61
16.79
100.00
100.28
Rammels-
berg
v. Drasche
Theory
LXXIX
Theory
XII
34.07
34.88
34.64
34.63
11.27
12.48
16.35
17.13
7.57
5.81
1.14
1.61
33.45
34.02
34.00
33.38
13.64
13.68
13.87
13.93
100.00
100.87
100.00
100.68
Heddle
Theory
IX
30.22
30.69
12.84
12.83
2.24
1.63
18.14
18.32
0.99
1.00
1.56
1.59
18.46
18.60
0.65
0.57
1.30
1.11
13.60
13.77
100.00
100.11
Genth
Theory
CXLII
33.34
33.20
11.02
11.11
1.24
1.43
5.88
6.85
z
z
35.19
35.54
0.38 Alk
z
13.33
12.95
100.00
101.46
Dieffen-
bach
Theory
CXLVI
33.34
33.04
11.02
11.09
1.24
1.33
5.88
5.91
z
z
35.19
34.30
0.38 Alk
z
13.33
12.81
100.00
98.86
392
THE ORTHOCHLORITE GROUP
Source
73
74
75
76
77
78
79
58MO-2(5Al 2 3 -18SiO 2 )
48 H 2
60MO-2(5R 2 3 -18SiO 2 )
48H 2
61MO-2(5R 2 O 3 -18SiO 2 )
48H 2
61 MO 2(5 A1 2 O 3 18 SiO 2 )
-44H 2
63MO-2(5R 2 O 3 -18SiO 2 )
52 H 2 O
63MO-2(5R 2 3 -18Si0 2 )
52 H 2 O
65MO-2(5Al,0 3 -18SiO 2 )
44 H 2 6
58 MO = 56 MgO -2 FeO
60 MO = 54 MgO 5 FeO 1 CaO
10 R 2 O 3 = 9 A1 2 O 3 1 Fe 2 O 8
61 MO = 60 MgO- IFeO
10R 2 O 3 =5Al 2 3 -5Cr 2 3
61 MO = 55 MgO -6 FeO
63 M0 = 60 MgO 2 FeO 1 CaO
10 R 2 O 3 = 8.5 A1 2 O 3 1.5 Cr 2 O 3
63 MO = 60 MgO 2 FeO 1 CaO
10 R 2 O 3 =8.5 A1 2 O 3 - 1.5 Cr 2 O 3
65 MO = 58 MgO 5 FeO 1 CaO
0.5 K 2 O 0.5 Na 2 O
Ortho-
chlorite
Zdjar-Berg
Hillswick
Green Valley
Cal.
Zillertal
Texas, Pa.
Tilly Foster
Mine, N.Y.
H. Orthochlorites of the type
Si R Si Si R Si = 5 R 2 3 22 Si0 2
Source
80
42 MO 2(5 R 2 O 3 22 SiO 2 )
42 M0 = 33 MgO 8 FeO 1 CaO
Epichlorite
Harz
36 H 2
10R 2 O 3 = 6.5 A1 2 O 3 3.5 Fe 2 O 3
81
46 MO 2(5 Fe 2 O 3 22 SiO 2 )
46 MO = 46 FeO
Cron-
Pfibram
50 H 2 O
stedtite
82
51 MO 2(5 R 2 O 3 22 SiO 2 )
51 MO = 48.5 MgO 2.5 FeO
Lennilite
Kremze
48 H 2 O
10R 2 O 3 = 9Al 2 3 -lFe 2 8
83
52MO-2(5R 2 3 -22Si0 2 )
52MO = 44MgO-5CaO-2.5FeO-0.5 NiO
Ortho-
Texas, Pa.
52 H 2 O
10 R 2 O 3 = 8 A1 2 O 3 2 Cr 2 O 3
chlorite
84
60 MO 2(5 R 2 3 22 SiO 2 )
60 MO = 51 MgO-3 K 2 O-3 FeO-3 Na 2 O
w
Taberg
24H 2
10 R 2 O 3 = 8.5 A1 2 O 3 1.5 Fe 2 O 3
85
60 MO 2(5 R 2 O 3 22 SiO 2 )
60 MO = 32 MgO 27 FeO 1 CaO
Diabantite
Farmington
44 H 2 O
10 R 2 O 3 = 8.5 A1 2 O 3 1.5 Fe 2 O 3
Hills
86
60 MO 2(5 R 2 O 3 22 SiO 2 )
60 MO = 32 MgO - 27 FeO 1 CaO
n
n
44 H 2 O
10 R 2 O 3 = 8.5 A1 2 O 3 1.5 Fe 2 O 3
87
69 MO 2(5 R 2 3 22 SiO 2 )
69 MO = 41.5 MgO 27.5 FeO
99
Trillochtal
52 H 2
10R 2 3 =8Al 2 3 -2Fe 2 3
88
72 MO -2(5Al 2 3 -22Si0 2 )
72 MO = 47 MgO 25 FeO
99
Landes-
56 H 2
freude
89
72 MO 2(5 A1 2 O 3 22 SiO 2 )
M
56 H 2 O
90
72 MO 2(5 A1 2 O 3 22 SiO 2 )
> >
Grafenwart
56 H 2 O
91
73 MO 2(5 A1 2 O 3 22 SiO 2 )
73 MO = 66 MgO -7 FeO
Ortho-
Zermatt
54 H 2 O
chlorite
92
74 MO 2(5 R 2 O 3 22 SiO 2 )
74 MO = 66 MgO 6 CaO 2 FeO
99
Unst
64 H 2 O
10R 2 3 = 6Al 2 3 -4Cr 2 3
93
75 MO 2(5 R 2 O 3 22 SiO 2 )
75 MO = 73 MgO -2 FeO
Zermatt
58 H 2 O
10R 2 O 3 =9Al 2 3 -lFe 2 3
94
79 MO 2(5 A1 2 O 3 22 SiO 2 )
79 MO = 46.5 MgO 32.5 FeO
Diabantite
Reinsdorf
50 H 2 O
THE ORTHOCHLORITE GROUP
Analyst
Si0 2
Al a O s
Fe 2 3
CTjOs
FeO
MnO
CaO
MgO
K,0
Nao
H a o
Total
K.v.
Theory
33.60
15.87
2.24
34.85
13.44
100.00
Hauer
XIV
33.51
15.42
2.58
34.41
13.21
99.13
Heddle
Theory
32.35
13.76
2.39
5.39
0.83
32.34
12.94
100.00
LXVIII
32.55
13.95
0.97
5.28
0.16
0.79
32.78
0.48
0.06
13.17
100.19
Melville
Theory
31.92
7.54
11.25
1.06
35.46
12.77
100.00
CLXII
31.74
6.74
11.39
1.23
.
0.18
35.18
0.49 NiO
13.04
99.99
Kobell
Theory
32.71
15.44
6.54
33.32
11.99
100.00
XXII
32.68
14.57
5.97
0.28
33.11
1.02 Resid.
12.10
99.73
Pearse
Theory
31.71
12.73
3.33
2.11
1.12
35.23
13.75
100.00
CXLVII
31.31
12.84
2.98
2.46
0.82
35.02
0.45 NiO
13.20
99.08
Pearse
Theory
31.71
12.73
3.33
2.11
1.12
35.23
13.75
100.00
CXLVIII
31.86
13.75
2.15
2.31
1.27
34.90
0.22 NiO
13.98
100.44
Breiden-
Theory
31.83
15.03
5.30
0.82
34.19
0.69
0.46
11.68
100.00
baugh
CXXVI
32.33
14.56
5.29
1.04
33.74
0.87
0.54
12.02
100.39
or the general formula
m MO 2 (5 R 2 3 22 Si0 2 ) n H 2 0.
Analyst
SiOa | Al a 3
Fe a O,
CTj0 3
FeO
MnO
CaO | MgO
K a O
Na,0
H a O
Total
Rammels-
berg
Theory
I
40.85
40.88
10.26
10.96
8.66
9.72
z
8.91
8.96
-
0.87
0.68
20.43
20.00
Z
10.02
10.18
100.00
100.38
Field
Theory
IX
31.24
31.72
18.93
18.51
39.19
39.46
10.64
11.02
100.00
100.71
Schrauf
Theory
39.38
38.88
13.70
13.45
2.39
3.22
2.68
2.55
-
0.45
28.95
28.57
z
12.90
12.75
100.00
99.87
Garret
Theory
CXLIII
37.77
37.66
11.68
11.82
4.35
3.60
2.57
2.50
4.01
4.11
25.17
24.98
1.06N1O
0.67NiO
13.39
13.58
100.00
98.92
Paltauf
Theory
LXXXVI
38.24
38.04
12.56
12.62
3.48
2.53
~
3.13
2.93
0.51F1
0.48
29.55
29.45
4.09
4.17
2.69
2.73
6.26
6.25
100.00
99.71
Hawes
Theory
VIII
33.76
33.24
11.08
11.07
3.07
2.26
24.86
25.11
0.41
0.72
1.11
16.37
16.51
0.25
10.14
9.91
100.00
99.87
Theory
IX
33.76
33.68
11.08
10.84
3.07
2.86
24.86
24.33
0.38
0.72
0.73
16.37
16.52
0.33
10.14
10.02
100.00
99.69
Liebe
Theory
VI
31.61
31.25
9.77
10.03
3.83
3.47
z
23.70
23.52
-
19.83
19.73
11.21
11.37
100.00
99.37
n
Theory
III
31.63
31.69
12.22
12.22
21.56
21.26
~
22.52
22.05
z
12.07
12.47
100.00
99.69
Theory
IV
31.63
31.38
12.22
11.89
~
21.56
22.72
z
z
22.52
22.91
12.07
10.91
100.00
99.81
"
Theory
VII
31.63
31.56
12.22
12.08
~
21.56
21.61
z
22.52
22.44
12.07
11.78
100.00
99.47
Piccard
Theory
XLII
33.94
33.54
13.12
13.39
-
~
6.49
6.62
z
33.94
33.56
12.51
12.38
100.00
99.49
Heddle
Theory
LXIV
32.46
32.31
7.52
7.50
-
7.49
7.89
1.77
2.08
z
4.13
3.83
32.46
32.15
___
___
14.17
14.25
100.00
100.01
v. Fellen-
berg
Theory
XLV
33.73
33.97
11.73
11.66
2.04
2.49
1.84
1.81
37.32
37.60
13.04
13.57
100.00
101.10
Liebe
Theory
30.14
30.27
11.64
11.16
.
'
26.70
26.94
-
21.24
21.22
10.28
10.20
100.00
99.79
394
THE ORTHOCHLORITE GROUP
J. Orthochlorites of the type
R Si R = 6 R 2 3 6 SiO 2
Source
95
18 MO
2 (6 Fe 2 3
22 H 2 O
6 Si0 2 )
18 MO = 18 FeO
Cron-
stedtite
Kuttenberg
K. Orthochlorites of the type
Si R R Si = 6 R 2 3 10 Si0 2
96
Source
16MO-2(6R 2 <V10SiO 8 )
28 H 2
16 MO = 16 MgO
12 R 2 3 =9.5 A1 2 3 2.5 Fe 2 O 3
Ortho
chlorite
Unionville
97
16MO-2(6R 2 O 3 -10SiO 2 )
30 H 2 O
16MO = 16MgO
12 R 2 O 3 =8 A1 2 O 3 4 Fe 2 O 3
"
98
20MO-2(6R 2 3 -10Si0 2 )
24H 2
20 MO = 18 FeO- 1.5 MgO 0.5 CaO
12 R 2 O 3 = 8.5 A1 2 O 3 3.5 Fe 2 O 3
Aphro-
siderite
Konigshain
99
23 MO 2(6 R 2 O 3 10 SiO 2 )
26 H 2 O
23 MO = 17 MgO 5 FeO 1 K 2 O
12R 2 3 =llAl 2 3 -lFe 2 3
Ortho-
chlorite
Unionville
100
23MO-2(6R 2 O 3 -10SiO 2 )
26 H 2 O
23 MO = 17,MgO - SJFeO 1 K 2 O
12R 2 O 3 =11A1 2 O 3 - !Fe 2 O 3
>
101
26 MO 2(6 R 2 O 3 10 SiO 2 )
30 H 2 O
26 MO = 24 FeO -2 MgO
12R 2 3 = 8Al 2 3 -4Fe 2 3
Thuringite
Harper's
Ferry
102
26 MO 2(6 R 2 O 3 10 SiO 2 )
30 H 2 O
26 MO = 24 FeO -2 MgO
12R 2 3 =8Al 2 3 -4Fe 2 O 3
M
Schmiede-
feld
103
26 MO 2(6 R 2 O 3 10 SiO 2 )
30 H 2 O
26 MO = 23.5 FeO 2 MgO 0.5 Na 2 O
12R 2 3 = 8 A1 2 3 4Fe 2 3
Harper's
Ferry
104
26 MO 2(6 R 2 O 3 10 SiO 2 )
30 H 2 O
26 MO = 23.5 FeO 2 MgO 0.5 Na 2 O
12 R 2 O 3 = 8 A1 2 O 3 4 Fe 2 O 3
>
105
27 MO 2(6 Fe 2 O 3 10 SiO 2 )
24 H 2 O
27 MO = 19 FeO 7 MgO 1 MnO
Cron-
stedtite
Pfibram
106
27 MO 2(6 R 2 O 3 10 SiO 2 )
30 H 2 O
27 MO = 23.5 FeO - 2.5 MgO 1 MnO
12 R 2 O 3 = 8 A1 2 O 3 - 4 Fe 2 O 3
Thuringite
Hot
Springs
107
28 MO 2(6 R 2 O 3 10 SiO 2 )
32 H 2 O
28 MO = 28 FeO
12 R 2 O 3 =9.5 A1 2 O 3 2.5 Fe 2 O 3
Zirmsee
108
29MO-2(6Fe 2 3 -10Si0 2 )
32H 2 O
29 M0 = 20 FeO 7 MgO 2 MnO
Cron-
stedtite
Pfibram
109
29MO-2(6Fe 2 3 -10Si0 2 )
32 H 2 O
>
>
110
30MO-2(6R 2 3 -10Si0 2 )
28 H 2 O
30 MO = 23 MgO 6 FeO 1 MnO
12R 2 O 3 =10.5A1 2 O 3 - 1.5Fe 2 O 3
Klementite
Vielsalm
111
30 MO 2(6A1 2 3 10 SiO 2 )
32 H 2 O
30 MO = 27.5 FeO -1 MgO
1 Na 2 O 0.5 MnO
Daphnite
Penzance
112
30MO-2(6R 2 3 -10Si0 2 )
32 H 2 O
30 MO = 21. 5 FeO 8.5 MgO
12 R 2 O 3 =11 A1 2 O 3 1 Fe 2 O 3
Ortho-
chlorite
Diillen
113
30MO-2(6Fe 2 3 -10Si0 2 )
38 H 2
30 MO = 23 FeO 6 MgO 1 MnO
Cron-
stedtite
Pfibram
114
34 MO- 2(6 R 2 8 -10810,)
32H 2
34 MO = 22 MgO- 12 FeO
12 R 2 O 3 = 1 1 A1 2 O 3 1 Fe 2 O 3
Ortho-
chlorite
Washing-
ton, D.C.
115
36MO-2(6R 2 O 3 -10SiO 2 )
28H 2
36 MO = 15.5 MgO 16 FeO 0.5 MnO
12 R 2 O 3 = 10.5 A1 2 O 3 1.5 Fe 2 O 3
M
Steeles
Mount, N.C.
THE ORTHOCHLORITE GROUP
or the general formula
m MO 2 (6 R 2 O 3 6 Si0 2 ) n H 2 0.
395
Analyst
Si0 2
A1 2 0,
Fe 2 0,
Cr 2 0,
FeO |MnO
CaO
MgO
K a O
Na 2
H0
Total
Rosam
Theory
VI
16.62
17.34
44.32
43.05
29.92
30.27
0.16
9.14100.00
9.18100.00
or the general formula
m MO - 2 (6 R 2 3 10 Si0 2 ) n H 2 0.
Analyst
Si0 2
A1 2 S
FezOa
Cr 2 0,
FeO |MnO
CaO
MgO
K.O
Na,0
H 2
Total
Konig
Theory
CXXXIV
32.32
32.80
26.10
26.07
10.77
9.80
-
17.25
17.70
13.56
13.75
100.00
100.12
?>
Theory
CXXXIII
31.29
31.35
21.27
21.58
16.67
14.17
~
z
16.68
16.67
14.09
14.45
100.00
98.22
Woitschach
Theory
V
27.01
27.06
19.52
19.56
12.60
11.71
-
29.17
28.91
~
0.63
0.38
1.35
1.18
~
9.72
9.73
100.00
98.53
Gintl
Theory
CXXXVIII
29.38
29.89
27.47
30.87
3.92
-
8.81
9.17
~
~
16.64
17.53
2.32
2.41
0.83
11.46
11.60
100.00
102.30
Theory
CXXXIX
29.38
29.90
27.47
27.59
3.92
3.12
8.81
9.17
~
16.64
17.10
2.32
2.33
0.58
11.46
11.51
100.00
101.30
Keyser
Theory
VI
23.98
23.21
16.31
15.59
12.79
13.89
-
34.53
34.51
~
0.36
1.60
1.26
0.08
0.41
10.79
10.59
100.00
99.97
Smith
Theory
III
23.98
23.55
16.31
15.63
12.79
13.79
-
34.53
34.20
~
z
1.60
1.47
~
10.79
10.57
100.00
99.21
Theory
VII
24.01
23.58
16.32
16.85
12.80
14.33
33.85
33.20
0.09
z
1.60
1.52
0.62
0.46
10.80
10.45
100.00
100.48
95
Theory
VIII
24.01
23.52
16.32
16.08
12.80
-
33.85
32.18
~
z
1.60
1.68
~
0.62
10.80
10.48
100.00
Ludwig
Theory
V
22.76
22.21
~
36.43
37.49
-
25.96
25.28
1.35
1.20
5.31
5.23
-
~
8.19
8.27
100.00
99.68
Smith
Theory
IX
23.77
23.70
16.17
16.54
12.68
12.13
-
33.29
33.14
1.41
1.16
1.98
1.85
0.32 (K.
O,Na 2 O)
10.70
10.90
100.00
99.74
Gintl
Theory
V
23.25
22.65
18.77
18.92
7.75
8.12
-
39.06
38.49
-
~
11.17
10.78
100.00
98.96
Steinmann
Theory
I
21.59
22.45
34.55
58.85
(Fe 2 O 3 +FeO)
25.91
2.55
2.89
5.04
5.08
10.37
10.70
100.00
99.97
Kobell
Theory
II
21.59
22.45
34.55
35.35
25.91
27.11
2,55
2.89
5.04
5.08
10.37
10.70
100.00
103.58
Klement
Theory
27.04
27.13
24.13
24.70
5.41
5.84
~
9.73
9.72
1.69
1.98
-
20.73
20.52
11.36
11.35
100.00
101.24
R.v.Zeynek
Theory
23.46
23.62
23.92
22.26
38.70
38.97
0.67
0.98
0.29
0.78
1.09
0.28
1.21
1.10
11.26
11.16
100.00
99.75
v. Giimbel
Theory
V '
24.26
23.56
22.69
22.35
3.23
4.25
31.30
30.43
0.23
6.87
6.75
O.lOAlk
11.65
11.49
100.00
99.16
Janowsky
Theory
IV
20.78
21.30
33.26
32.34
28.70
29.23
1.23
1.25
4.15
4.51
__
11.88
11.90
100.00
100.53
Clarke and
Schneider
Theory
CL
24.99
25.40
23.36
22.80
3.33
2.86
~
17.99
17.77
0.25
-
18.33
19.09
-
-
12.00
12.21
100.00
100.38
Genth
Theory
CLXI
24.78
24.90
22.12
21.77
4.96
4.60
___
23.79
24.21
1.14
1.15
-
12.81
12.78
-
~
10.40
10.59
100.00
100.00
396
THE ORTHOCHLORITE GROUP
1
Source
116
36 MO 2 (6 R 2 O 3
10 SiO 2 )
36 MO = 22 MgO 14 FeO
Orthochlorite
Lude
32 H 2 O
12 R 2 O 3 =11.5Al 2 O 3 -0.5Fe 2 O 3
,,
117
36 MO 2 (6 R 2 O 3
10 SiO 2 )
36 MO = 22 MgO 14 FeO
n
32 H 2 O
12 R a O a = 11.5 A1 2 O 3 0.5 Fe 2 O 3
118
37.MO-2(6R 2 <V
10 SiO 2 )
37 MO = 25 MgO 12 FeO
M
Chester,
34 H 2 O
12 R 2 O 3 = 11.5 A1 2 O 3 0.5 Fe 2 O 3
Mass.
119
38 MO 2 (6 A1 2 3
10 SiO 2 )
38 MO = 28 MgO -10 FeO
w
32H 2
L. Orthochlorites of the type
Si R R Si = 6 R 2 3 12 Si0 2
Source
120
18MO-2(6R 2 O 3 - 12SiO 2 )
28 H 2 O
18 MO = 15 MgO 2.5 K 2 O 0.5 Na 2 O
1 2 R 2 O 3 = 9 A1 2 O 3 3 Fe 2 O 8
Ortho-
chlorite
Culsagee Mine,
N.C.
121
24 MO 2(6R 2 O 3 12 SiO 2 )
26H 2 O
24 MO = 18.5 FeO 5 MnO 0.5 CaO
12 R 2 O 3 =8.5 A1 2 O 3 - 3.5 Fe 2 O 3
Strigo-
vite
Striegau
122
25 MO 2 (6 R 2 O 3 12SiO 2 )
24 H 2 O
25 MO = 10 FeO 10.5 MgO 3.5 CaO
1 Na 2 O; 12 R 2 O 3 =8 A1 2 O 3 4 Fe 2 O 3
Chloro-
pite
Weidesgriin
123
25MO-2(6R 2 O 3 -12Si0 2 )
30 H 2 O
25 MO = 22 MgO - 2.5 FeO 0.5 CaO
12R 2 3 =7Al 2 3 -5Fe 2 O 3
Deles-
site
La Greve
bei Mielin
124
26MO-2(6R 2 O 3 -12Si0 2 )
40H 2
26 MO = 22 FeO 2 MgO - 2 CaO
12 R 2 O 3 =11.5 A1 2 O 3 0.5 Fe 2 3
Ortho-
chlorite
Striegau
125
28MO-2(6R 2 3 12 SiO 2 )
22 H 2
28 MO = 6.5 MgO 20 FeO 1 K 2 O
0.5 MnO; 12R 2 O 3 = 9 Al 2 O 3 -3Fe 2 O 3
Waldsassen
126
29MO-2(6R 2 3 -12Si0 3 )
34H 2
29 MO = 18.5 MgO 10 FeO 0.5 CaO
12 R 2 O 3 = 9.6 A1 2 O 3 2.5 Fe 2 O 3
Delassite
Planitz bei
Zwickau
127
30MO-2(6R 2 3 -12Si0 2 )
28H 2
30 MO = 17.5 FeO - 11.5MgO-0.5 K 2 O
0.5 Na 2 O; 12R 2 O 3 =7.5 Al 2 O 3 -4.5Fe 2 O 3
Chloro-
pite
Schwarzen-
bach
128
30MO-2(6R 2 3 -12Si0 2 )
30 H 2 O
30MO = 9 FeO-18.5 MgO-1 CaO-1 Na 2 O
05 K 2 O; 12 R 2 O 3 = 7 A1 2 O 3 5 Fe a O 3
H
Lippertsgriin
129
30 MO 2 (6 A1 2 O 3 12 SiO 2 )
32H 2
30 MO = 20 FeO 10 MgO
Ortho-
chlorite
Taszopatak
130
35 MO 2 (6 A1 2 O 3 12 SiO 2 )
24 H 2 O
35 MO =33.5 FeO 1.5 MgO
Aphro-
siderite
Weilburg
131
36MO-2(6R 2 O 3 - 12SiO 2 )
30 H 2 O
36 MO = 29.5 FeO 6.5 MgO
12 R 2 3 =10 A1 2 3 2 Fe 2 3
Striegau
132
36MO-2(6Al 2 3 -12Si0 2 )
40 H 2
36 MO = 30 FeO -6 MgO
Chamo-
site
Windgallen
133
38MO-2(6R 2 3 -12SiO 2 )
32 H 2
38 MO = 16 MgO -22 FeO
1 2 R 2 O 3 = 1 1 A1 2 O 3 1 Fe 2 O 3
Ortho-
chlorite
Mutters-
hausen
134
38MO-2(6R 2 3 -12SiO 2 )
32 H 2
38MO = 16MgO-22FeO
12R 2 3 = llAl 2 3 -lFe 2 3
Balduinstein
135
38MO-2(6R 2 3 -12Si0 2 )
34 H 2
38 MO = 34 MgO -4 FeO
12R 2 3 =llAL0 3 -lFe 2 O 3
Unionville,
Pa.
136
38MO-2(6Ro0 3 -12Si0 2 )
34 H 2 6
38 MO = 34 MgO -4 FeO
12R 2 3 = llAl 2 3 -lFe 2 O 3
>
137
38MO-2(6R 2 3 -12Si0 2 )
34 H 2
38 MO = 31 FeO 6.5 MgO 0.5 CaO
12 R 2 O 3 = 10 A1 2 O 3 2 Fe 2 O 3
Meta-
chlorite
Bvichenberge
b. Elbingerode
THE ORTHOCHLORITE GROUP
397
Analyst
Si0 2
A1 2 3
Fe 2 8 1 Cr 2 O,
FeO
MnO
CaO
MgO
K 2
Na a O
H 2 O
Total
Heddle
Theory
LXXIII
24.40
23.92
23.86
22.98
1.62
1.11
~
20.50
19.54
0.28
2.45
17.90
17.26
~
11.72
11.78
100.00
99.32
Theory
LXXIV
24.40
24.66
23.86
23.19
1.62
0.64
20.50
20.58
0.29
0.40
17.90
17.79
11.72
12.12
100.00
99.67
Obermayer
Theory
CXXIII
24.35
23.84
23.80
25.22
1.62
2.81
17.53
17.06
20.29
19.83
12.41
11.90
100.00
100.66
Pasani
Theory
CXXI
24.79
24.00
25.29
25.90
~
z
14.88
14.80
23.14
22.70
~
11.90
11.90
100.00
99.30
or the general formula
m MO 2 (6 R 2 3 12 Si0 2 ) n H 2 0.
Analyst
SiO, | AljOs | Fe 2 8 | Cr 2 O,
FeO
MnO
CaO
MgO
K 2
Na,0 | H 2 | Total ,
Chatard
Theory
34.32
21.81
11.41
14.26
5.58
0.74
11.98
100.00
CLVII
34.22
21.53
12.41
.12(Ni.Co)o
14.46
5.70
0.51
11.85
100.80
Websky
Theory
28.53
17.17
11.09
26.39
6.99
0.55
9.28
100.00
I
28.43
16.60
11.43
26.21
7.25
0.37
0.36
9.31
99.96
Loretz
Theory
30.46
17.26
13.54
15.24
4.16
8.89
1.31
9.14
100.00
II
30.56
16.57
13.02
15.51
4.14
8.97
0.36
1.18
1 9.08
99.39
(Delesse
Theory
31.43
15.58
17.46
3.93
0.60
19.21
11.79
100.00
I
31.07
15.47
17.54
4.07
0.46
19.14
11.55
99.30
Traube
Theory
27.75
22.61
1.54
30.52
2.15
1.54
13.89
100.00
X
27.12
22.40
2.13
30.19
2.23
1.54
13.45
99.06
v. Giimbel
Theory
27.99
19.41
9.33
27.99
0.69
5.05
1.83
7.71
100.00
IV
27.50
18.15
10.80
28.02
0.60
5.13
1.66
0.44
7.50
99.80
Delesse
Theory
29.33
19.74
8.14
14.67
0.57
15.07
12.48
100.00
III
29.45
18.25
8.17
15.12
0.45
15.32
12.57
99.33
1 Loretz
Theory
27.55
14.63
13.77
24.12
8.80
0.90
0.59
9.64
100-00
I
27.10
14.64
14.80
23.85
8.78
0.52
0.56
9.69
99.94
Theory
28.44
14.10
15.80
12.80
1.10
14.64
0.92
1.22
10.98
100.00
III
29.10
14.31
14.87
13.27
1.00
15.08
0.60
1.09
10.77
100.09
K. v. Hauer
Theory
28.35
24.10
28.35
7.87
_^_
11.33
100.00
XVII
28.02
23.84
28.60
8.09
11.45
100.00
Sandberger
Theory
25.86
21.98
43.32
1.08
7.76
100.00
I
26.45
21.25
44.24
1.06
7.74
100.74
Rammelsberg
Theory
25.24
17.88
5.61
37.24
4.56
9.47
100.00
IV
24.78
18.69
6.45
36.17
Trace
4.52
9.09
99.70
C. Schmidt
Theory
24.90
21.16
37.35
4.14
12.45
100.00
II
25.23
19.97
37.51
4.39
12.90
100.00
Erlenmeyer
Theory
26.07
20.32
2.90
28.69
11.59
10.43
100.00
VI
25.72
20.69
4.01
27.79
11.70
10.05
99.96
ff
Theory
26.07
20.32
2.90
28.69
11.59
10.43
100.00
VII
25.99
4.13
27.60
11.93
10.13
Chatard
Theory
28.68
22.35
3.13
5.75
27.90
12.19
100.00
cxxxv
29.43
22.0
I A"
5.64
28.46
12.40
99.42
Theory
28.68
22.35
3.13
5.75
27.90
12.19
100.00
CXXXVI
29.59
22.1
1.33
5.77
28.54
12.40
99.81
Zeynek
Theory
24.36
17.2
5.4
37.75
0.47
4.40
10.36
100.00
II
24.2S
17.8
4.6-J
37.85
0.57
4.26
0.09
0.30
10.19
100.04
398
THE ORTHOCHLORITE GROUP
1
Source
138
39 MO 2 (6 A1 2 O 3 12 SiO 2 )
30H 2 O
39 MO = 25 FeO- 14MgO
Ortho-
chlorite
Grabener
Wiesen
139
39MO-2(6R 2 O 3 -12SiO 2 )
34 H 2 O
39 MO = 25 MgO- 12 FeO- 1 K 2 O
1 Na 2 O; 12 R 2 O 3 = 10.5Al 2 O 3 -1.5Fe 2 O 3
Fuschertal
140
39 MO 2 (6 R 2 O 3 12 SiO 2 )
36 H 2 O
39 MO - 19 MgO 20 FeO
12 R 2 O 3 = 10.5 A1 2 O 3 1.5 Fe 2 O 3
H
Zillerthal
141
39 MO 2 (6 Fe 2 O 3 12SiO 2 )
36 H 2 O
39 MO = 31. 5 FeO -6.5 MgO- 1 MnO
Cronsted
tite
Pfibram
142
40MO-2(6R 2 3 -12Si0 2 )
36 H 2
40 MO = 19 MgO -21 FeO
1 2 R 2 O 3 = 1 1 A1 2 O 3 1 Fe 2 O 3
Ortho-
chlorite
Zillertal
143
41MO-2(6R 2 O 3 -12SiO 2 )
40 H 2
41 MO = 37 MgO -4 FeO
12 R 2 O 3 = 11.5 A1 2 O 3 0.5 Fe 2 O 3
Culsagee Mine,
N.C.
144
41MO-2(6R 2 O 3 - 12SiO 2 )
40 H 2 O
41 MO = 37 MgO -4 FeO
12 R 2 O 3 = 11.5 A1 2 O 3 0.5 Fe 2 O 3
n
M
145
41MO-2(6R 2 O 3 -12SiO 2 )
40 H 2 O
41 MO = 37 MgO -4 FeO
12 R 2 O 3 = 11.5 A1 2 O 3 0.5 Fe 2 O 3
"
146
42MO-2(6Al 2 3 -12Si0 2 )
36 H 2
42 MO = 21 FeO 19 MgO 1 K 2 O
0.5 MnO 0.5 CaO
f>
Ben Derag
147
42MO-2(6R 2 3 -12Si0 2 )
38 H 2
42 MO = 26 MgO -16 FeO
12 R 2 O 8 = 11.5 A1 2 O 3 0.5 Fe 2 O 3
H
Aacherkoppe
148
43 MO 2 (6 R 2 O 3 12SiO 2 )
34H 2
43 MO = 25 MgO -18 FeO
12 R 2 O 3 = 11.5 A1 2 O 3 0.5 Fe 2 O 3
H
St. Gotthard
149
43MO-2(6R 2 O 3 - 12SiO 2 )
34 H 2 O
43 MO = 32 MgO 10.5 FeO 0.5 MnO
12R 2 O 3 = llAl 2 3 -lFe 2 3
Portsoy
150
43MO-2(6Al 2 O 3 -12SiO 2 )
36 H 2 O
43MO = 32MgO-llFeO
Zillertal
151
43MO-2(6A1 2 O 3 -12 SiO 2 )
36 H 2 O
>
M
>
152
43 MO 2 (6 R 2 O 3 12SiO 2 )
38H 2 O
43 MO = 22 MgO 20 FeO 1 CaO
12 R 2 O 3 = 1 1.5 A1 2 O 3 0.5 Fe 2 O 3
n
Massa-
schlucht
153
43 MO 2 (6 R 2 O 3 12 SiO 2 )
40 H 2 O
43 MO = 19.5 MgO 22 FeO 1 CaO
0.5MnO;12R 2 O 3 = 11.5Al 2 O 3 -0.5Fe 2 O 3
M
Girdleness
154
44 MO 2 (6 R 2 O 3 12 SiO 2 )
30 H 2 O
44 MO = 22 MgO 22 FeO
12R 2 O 3 = 11.5Al 2 O 3 -0.5Fe 2 O 3
ZiUertal
155
44MO-2(6Al 2 3 -12Si0 2 )
34H 2
44 MO = 40 MgO -4 FeO
H
Grochau
156
46MO-2(6Al 2 O 3 -12SiO 2 )
24H 2 '
46 MO = 20.5 MgO 25.5 FeO
M
Guistberg
157
48 MO 2 (6 R 2 O 3 12 SiO 2 )
38 H 2 O
48 MO = 33 MgO 14 FeO 0.5 MnO
O.SCaO; 12R 2 O 3 =11.5 Al 2 O 3 -0.5Fe 2 O 3
n
Fethaland
158
51MO-2(6A1 2 O 3 - 12SiO 2 )
32H 2 O
51MO = 31MgO-16FeO-2CaO-lK 2 O
0.5 MnO 0.5 Na 2 O
Craig an
Lochan
M. Orthochlorites of the type
Si R S A i R Si = 6 R 2 3 16 Si0 2
Source
159
160
32 MO-
41 MO
2 (6 R 2 a
36H 2 O
2(6R 2 O a
52H 2 O
16 Si0 2 )
16Si0 2 )
32 MO = 30 MgO -2 FeO
12 R 2 O 3 = 6.5 A1 2 O 3 1 Fe 2 O 3 -4.5Cr 2 O 3
41 MO = 29.5 MgO 10 FeO 1.5 CaO
12 R a O,= 11.5 A1 2 O 3 - 0.5 Fe 2 O 3
Ortho-
chlorite
Delessite
Norrbotten
Dumbuek
THE ORTHOCHLORITE GROUP
399
Analyst
Si0 2
A1 2 3
Fe 2 0,
Cr 2 3
FeO
MnO
CaO | MgO
K,0
NajO
H,o
Total
K. v.
Theory
25.82
21.93
32.26
10.03
9.96
100.00
Hauer
XVIII
26.08
20.27
32.91
10.00
10.06
99.32
Vuylsteke
Theory
26.75
19.89
4.46
16.06
18.57
1.74
1.15
11.38
100.00
XIX
27.03
20.07
4.72
16.47
18.90
1.22
0.72
11.78
100.91
Klement
Theory
25.72
19.13
4.29
.
25.72
13.58
11.56
100.00
XXIX
25.84
19.58
4.42
25.99
13.57
11.34
100.74
D amour
Theory
21.89
29.06
34.33
1.07
3.93
9.81
100.00
III
21.39
29.08
33.52
1.01
4.02
9.76
98.78
Klement
Theory
25.52
19.89
2.84
26.80
13.46
11.49
100.00
XXX
25.84
19.58
2.13
28.05
13.57
11.34
100.51
Genth
Theory
27.79
22.64
1.55
5.56
28.56
13.90
100.00
CLIII
27.56
22.75
2.56
5.43
28.47
0.30(Mn,Ni,Co)0
13.80
100.87
Chatard
Theory
27.79
22.64
1.55
5.56
__
,
28.56
13.90
100.00
CLIV
27.28
22.11
2.50
5.43
28.38
0.41 (Mn, Ni, Co)O
14.50
100.57
Theory
27.79
22.64
1.55
5.56
28.56
13.90
100.00
CLV
27.17
22.35
2.71
5.43
27.73
0.26 (Mn, Ni, Co)O
14.36
100.00
Heddle
Theory
25.11
21.34
26.35
0.62
0.40
13.25
1.63
11.30
100.00
LXXI
24.72
21.57
0.62
26.16
0.47
0.45
12.86
1.73
0.05
10.89
99.52
Jacobs
Theory
25.86
21.07
1.43
20.68
18.68
12.28
100.00
VIII
25.53
20.49
1.68
0.08
20.85
0.15TiO 2
0.06
18.60
0.07
0.09
12.26
99.86
Rammels-
Theory
25.71
20.95
1.43
P 2 5
23.14
17.85
10.92
100.00
berg
XXXIV
25.12
22.26
1.09
23.11
17.41
10.70
99.69
Heddle
Theory
26.59
20.72
2.95
13.96
0.83
23.64
11.31
100.00
LXXVI
26.71
20.42
3.47
13.99
0.73
23.90
11.17
100.39
Kobell
Theory
26.74
22.72
14.71
23.77
12.06
100.00
XXVI
26.51
21.81
15.00
22.83
12.00
98.15
n
Theory
26.74
22.72
14.71
23.77
12.06
100.00
XXVII
27.32
20.69
15.23
0.47
24.89
12.00
100.60
Fellen-
Theory
25.03
20.39
1.39
^_
25.03
0.97
15.29
11.90
100.00
berg
XXXV
24.85
20.70
1.00
25.00
0.60
15.31
0.45 Ti0 2
12.05
99.96
Heddle
Theory
24.53
19.97
1.36
27.04
0.60
0.95
13.28
__
12.27
100.00
LXXVII
24.77
20.16
1.38
27.38
0.61
0.90
13.34
12.05
100.59
Egger
Theory
25.28
20.59
1.42
27.80
15.45
9.48
100.00
XXVIII
26.02
20.16
1.07
28.08
0.44
15.50
9.65
100.92
Bock
Theory
27.88
23.70
5.58
30.99
11.85
100.00
IX
28.20
24.56
5.27
30.94
12.15
101.12
Igelstrom
Theory
25.03
21.28
31.92
14.25
7.52
100.00
LXXXIII
25.00
20.60
32.00
14.30
7.60
99.50
Heddle
Theory
24.96
20.33
1.39
17.48
0.61
0.49
22.88
11.86
100.00
LXX
24.30
20.86
3.57
16.72
0.55
0.50
22.20
11.55
100.25
Theory
24.39
20.73
__
19.51
0.59
1.96
21.00
1.59
0.52
9.77
100.00
LXXII
24.29
21.15
0.10
18.74
0.80
1.66
21.03
1.29
0.56
10.08
99.70
or the general formula
m MO 2 (6 R 2 3 16 Si0 2 ) n H 2 0.
Analyst
SiO a
AljO,
Fe s O,
Cr a O s
FeO
MnO
CaO
MgO
K,o
Na,0
H,O
Total
Sanderson
Theory
LXXXVII
35.42
34.49
12.23
12.40
2.95
3.14
12.64
13.46
2.66
3.28
z
22.14
21.83
__
11.96
11.85
100.00
100.45
Heddle
Theory
VII
31.52
32.01
19.25
18.87
1.31
1.18
11.82
12.09
Trace
1.37
1.39
19.36
19.64
-
-
15.37
15.46
100.00
100.64
400
THE ORTHOCHLORITE GROUP
Source
161
48 MO 2 (6 A1 2 O 3 16 SiO 2 )
48 MO = 43 MgO -5 FeO
Ortho-
Brosso
32 H 2 O
chlorite
162
48MO-2(6RoO 3 -16SiO 2 )
48 MO = 48 MgO
>
Westchester,
40 H 2 6
12R 2 O 3 =10Al 2 O 3 -1.5Fe 2 O 3 -0.5Cr 2 O 3
Pa.
163
48MO-2(6R 2 O 3 -16SiO 2 )
48 MO = 48 MgO
t
40H 2
12 R 2 O 3 = 10 A1 2 O 3 -1.5 Fe 2 O 3 -0.5 Cr 2 O 3
164
49MO-2(6R 2 O 3 -16SiO 2 )
49 MO = 47 MgO -2 FeO
Zoutpansberge
46H 2
12 R 2 O 3 = 11.5 A1 2 O 3 0.5 Fe 2 O 3
165
51MO-2(6R 2 O 3 -16Si0 2 )
-40H 2
51 MO = 26 MgO 21 FeO 4 MnO
12 R 2 O 3 =9.5 A1 2 O 3 2.5 Fe 2 O 3
"
Dannemora
166
51MO-2(6R 2 O 3 -16SiO 2 )
51 M0 = 26 MgO 21 FeO 4 MnO
J?
40H 2
12 R 2 O 3 =9.5 A1 2 O 3 2.5 Fe 2 O 3
167
52 MO 2 (6 A1 2 O 3 16 SiO 2 )
52 MO = 23 MgO 29 FeO
St. Christophe
44 H 2 O
168
53 MO 2 (6 A1 2 O 3 16 SiO 2 )
53 MO = 46 MgO -7 FeO
>
Blair Athol
46 H 2 O
169
53MO-2(6R 2 3 -16Si0 2 )
53 MO=52.5 MgO 0.5 FeO
>?
Achmatowsk
- 46 H 2 O
12 R 2 O 3 = 11 A1 2 O 3 1 Fe 2 O 3
170
55 MO 2 (6 R 2 O 3 16 SiO 2 )
55 MO = 51 MgO 2 FeO 2 Na 2 O
5>
Westchester,
50H 2
12 R 2 O 3 = 11 Al 2 O 3 -0.5Fe 2 O 3 -0.5Cr 2 O 3
Pa
171
55 MO 2 (6 R 2 O 3 16 SiO 2 )
55 MO =52 MgO 2 FeO 1 CaO
>
>
40 H 2
12 R 2 O 3 = 11 Al 2 O 3 -0.5Fe 2 O 3 -0.5 Cr 2 O 3
172
55MO-2(6R 2 O 3 -16SiO 2 )
55 MO = 53 MgO -2 FeO
f
)f
48 H 2 O
12 R 2 O 3 =9 A1 2 O 3 2 Fe 2 O 3 1 Cr 2 O 3
173
56 MO 2 (6 R 2 O 3 16 SiO 2 )
56 MO = 53 MgO -3 FeO
?>
Itkul Sea
42 H 2
12 R 2 3 = 10 A1 2 3 2 Cr 2 3
174
56 MO 2 (6 A1 2 O 3 16 SiO 2 )
56 MO = 54 MgO -2 FeO
ff
Schischimsker
44H 2
Berge
175
56MO-2(6Al 2 O 3 -16Si0 2 )
56 MO =54 MgO -2 FeO
5
44H 2
176
56 MO 2 (6 A1 2 O 3 16 SiO 2 )
j>
)}
44H 2
177
58 MO 2 (6 A1 2 O 3 16 SiO 2 )
58 MO = 29 MgO-29 FeO
>
Glacier d'Ar-
40 H 2 O
gentieres
178
58 MO 2 (6 R 2 O 3 16 SiO 2 )
58 MO = 58 MgO
n
FluB Iremel
42 H 2 O
12 R 2 O 3 = 1 1 A1 2 O 3 1 Fe 2 O 3
179
61 MO 2 (6 A1 2 O 3 16 SiO 2 )
61 MO = 54 MgO 3.5 FeO 2 CaO
tt
Texas, Pa.
52 H 2 O
1.5K 2
N. Orthochlorites of the type
Si R Si R Si = 6 R 2 O 3 18 Si0 2
Source
180
181
182
18MO-
23 MO-
36 MO-
2 (6 R 2 3
42H 2 O
2 (6 R 2 3
34H 2 O
2 (6 A1 2 O 3
26H 2 O
18 SiO 2 )
18 SiO 2 )
18 SiO 2 )
18 MO = 10.5 MgO 4.5 CaO 3 FeO
12R 2 3 = 7Fe 2 3 -5Al 2 3
23MO = 21,5FeO-1.5Na 2
12 R 2 O 3 =9 Fe 2 O 3 3 A1 2 O 3
36 MO = 20 MgO -16 FeO
Hullite
Melano-
lite
Epi-
phanite
Carnmoney
Hill
Milk-Row
Quarry, Mass.
Wermland
THE ORTHOCHLORITE GROUP
401
Analyst
Si0 2
Al,o,
Fe 2 3
Cr 2
FeO
MnO
CaO
MgO
K 2
Na 2 O
H0
Total
Damour
Theory
33.10
21.10
6.21
29.64
_
9.95
100.00
LVI
33.67
20.37
6.37
29.49
10.10
100.00
Graw
Theory
32.56
17.30
4.07
1.29
32.56
12.22
100.00
CXXVIII
nri
31.34
17.47
3.85
1.69
33.44
12.60
100.39
Theory
CXXIX
32.56
31.78
22.71
32.56
33.64
__
12.22
12.60
100.00
100.73
Yvan Riesen
Theory
31.86
19.47
1.33
2.39
31.21
_
13.74
100.00
cxv
32.38
18.79
0.80
2.39
31.64
14.15
100.15
Erdmann
Theory
28.05
14.15
5.84
22.09
4.15
15.19
10.53
100.00
LXXX
27.83
14.23
5.34
22.53
3.21
15.42
0.36
0.27
10.19
99.38
Jf
Theory
28.05
14.15
5.84
22.09
4.15
15.19
10.53
100.00
LXXXI
27.89
14.30
5.96
21.21
5.43
0.43
14.42
0.17
0.23
10.30
100.34
Marignac
Theory
27.65
17.63
30.07
13.25
11.40
100.00
LIX
26.88
17.52
29.76
13.84
11.33
99.33
Heddle
Theory
30.40
19.38
7.98
29.13
13.11
100.00
LXVI
30.30
19.40
8.23
0.37
29.10
13.07
100.47
Ortraann
Theory
31.15
18.19
2.59
0.58
,
34.05
13.44
100.00
XCIV
31.31
18.34
2.10
0.77
34.25
0.06
0.17
13.33
100.33
Schlaepfer
Theory
29.96
17.52
1.25
1.18
2.25
31.85
1.94
14.05
100.00
CXXXII
30.11
18.31
1.16
1.55
2.11
0.31 Li,0
31.89
0.37
1.99
14.14
101.94
Neminar
Theory
30.98
18.11
1.29
1.23
2.32
0.90
33.56
11.61
100.00
cxxx
31.08
18.85
1.55
1.09
2.33
0.81
33.50
11.53
100.74
Clarke and
Theory
29.83
14.26
4.97
2.36
2.24
32.93
13.41
100.00
Schneider
CXXXI
29.87
14.48
5.52
1.56
1.93
33.06
0.17NIO
13.60
100.19
Hermann
Theory
30.31
16.09
4.81
3.40
33.45
11.94
100.00
CXII
30.58
15.94
4.99
3.32
33.45
12.05
100.33
Herzog N.v
Theory
30.77
19.62
2.31
__
34.61
12.69
100.00
Leuchtenberg
XCVIII
30.60
19.63
2.02
34.41
12.76
99.42
,,
Theory
30.77
19.62
2.31
34.61
12.69
100.00
XCIX
30.33
19.85
2.43
0.11
34.64
12.73
100.09
Lagorio
Theory
30.77
19.62
2.31
34.61
12.69
100.00
C
30.61
19.52
0.30
2.53
34.20
12.53
99.69
Brun
Theory
27.00
17.21
29.36
16.31
10.13
100.00
XLIX
26.60
18.02
29.67
15.85
9.98
100.12
Hermann
Theory
30.58
17.87
2.55
36.96
12.04
100.00
CX
30.80
17.27
1.37
37.08
12.30
98.82
Pearse
Theory
28.47
18.15
3.73
1.66
32.02
2-09
13.88
100.00
CXL
28.62
18.37
0.37NiO
3.73
1.45
32.13
1.97
14.02
100.00
or the general formula
m MO 2 (6 R 2 3 18 Si0 2 ) n H 2 0.
Analyst
Sio,
A1 2 0,
Fe 2 O,
Cr 2 O,
FeO
MnO
CaO
MgO
K,0
NatO
HO
Total
Hardmann
Theory
39.75
39.44
9.39
10.35
20.61
20.72
3.98
3.70
Trace
4.64
4.48
7.73
7.47
-
13.90
13.62
100.00
99.78
Wurtz
Theory
II
35.07
35.24
4.97
4.48
23.38
23.13
~
25.14
25.09
~
1.51
1.85
9.93
10.21
100.00
100.00
Igelstrom
Theory
37.22
37.10
21.09
21.13
~
19.85
20.00
Trace
13.78
14.03
8.06
7.83
100.00
100.09
2 D
402
THE ORTHOCHLORITE GROUP
Source
183
44MO-2(6R 2 3 -18Si0 2 )
42 H 2
44 MO = 44 FeO
1 2 R 2 O 3 = 10 A1 2 O 3 - 2 Fe 2 O 3
Chamo-
site
Schmiedefeld
184
48MO-2(6R 2 O 3 - 18SiO 2 )
48 H 2
48 MO = 30 MgO 17 FeO 1 MnO
12R 2 3 = 10Al 2 3 -2Fe 2 3
Ortho-
chlorite
Cape Wrath
185
48MO-2(6R 2 O 3 - 18SiO 2 )
60 H 2 O
48 MO = 34.5 MgO -11.5 FeO 2 CaO
12 R a O 8 = 11.5 A1 2 O 3 0.5 Fe 2 O 3
Deles-
site
Bowling Quarry,
Dumbarton
186
49 MO 2 (6 R 2 O 3 18SiO 2 )
- 56 H 2
49 M0 = 32.5 MgO - 15 FeO 1.5 CaO
12 R 2 3 = 10.5 A1 2 3 1.5 Fe 2 3
"
Long Craig,
Dumbarton
187
49 MO 2 (6 R 2 O 3 18SiO 2 )
44 H 2
49 MO = 48 MgO -1 FeO
12 R 2 O 3 = 11.5 A1 2 O 3 0.5 Fe 2 O 3
Ortho-
chlorite
Ckyn
188
52MO-2(6R 2 3 -18Si0 2 )
52 H 2
52 MO = 50 MgO 1 CaO 1 FeO
1 2 R 2 O 3 = 1 1 A1 2 O 3 1 Fe 2 O 3
Markich
189
54 MO 2 (6 R 2 O 3 18SiO 2 )
30H 2
54 MO = 53 MgO -1 CaO
12R 2 O 3 = 10.5A1 2 O 3 - 1.5Fe 2 O 3
H
Schischimsker
Berge
190
54 MO 2 (6 R 2 O 3 18SiO 2 )
30 H 2 O
54 MO = 53 MgO- 1 CaO
12 R 2 O 3 = 10.5 A1 2 O 3 1.5 Fe 2 O 3
"
191
57MO-2(6A1 2 O 3 - 18SiO 2 )
46H 2 O
57 MO = 53 MgO -4 FeO
"
192
68MO-2(6R 2 O 3 - 18SiO 2 )
42 H 2 6
58 MO = 50 MgO -8 CaO
12R 2 O 3 =10.5A1 2 O 3 - 1.5Fe 2 O 3
>
193
58M0 2 2(6R 2 3 -18Si0 2 )
46 H 2 O
58 MO = 58 MgO
12R 2 O 3 = 8.5A1 2 O 3 - 1 .5Fe 2 O 3 -2Cr 2 O 3
"
Ufalejsk
194
58MO-2(6R 2 3 -18Si0 2 )
46 H 2
58 MO = 58 MgO
12 R 2 3 = 8.5 A1 2 3 -1.5 Fe 2 O 3 -2 Cr 2 O 3
n
tt
195
58MO-2(6R 2 O 3 - 18SiO 2 )
46 H 2 O
58 MO = 58 MgO
12 R 2 O 3 = 8.5 A1 2 O 3 -1.5Fe 2 O 3 -2 Cr 2 O 3
"
"
196
58MO-2(6R 2 O 8 - 18SiO 2 )
46 H 2 O
58 MO = 58 MgO
12 R 2 O 3 = 8.5 A1 2 O 3 -1.5 Fe 2 O 3 -2 Cr 2 O 3
"
Bilimbajewsk
197
59MO-2(6R 2 O 3 - 18SiO 2 )
48 H 2
59 MO = 59 MgO
12R 2 3 =10Al 2 3 -2Fe 2 3
Texas, Pa.
198
59 MO 2 (6 R 2 O 3 18SiO 2 )
48 H 2
59 MO = 59 MgO
12R 2 3 = 10Al 2 3 -2Fe 2 3
Willimantic,
Conn.
199
60MO-2(6R 2 O 3 -18SiO 2 )
48 H 2 O
60 MO = 55 MgO - 4 FeO 1 CaO
12 R 2 O 3 = 11.5 A1 2 O 3 0.5 Fe 2 O 3
i>
Kariaet,
Greenland
200
62 MO 2 (6 R 2 O 3 18SiO 2 )
52 H 2 O
62 MO = 54 MgO-2 FeO-4 CaO-1 K 2 O
1 Na 2 O ; 12 R 2 O 3 = 9 Al 2 O 3 -3 Cr 2 O 3
Unst
201
62MO-2(6AU) 3 -18Si0 2 )
46 H 2 O
62 MO = 61 .5 MgO 0.5 FeO
Mauleon
202
62MO-2(6R 2 3 -18Si0 2 )
48 H 2
62 MO = 62 MgO
12R 2 3 =9Al 2 3 -3Fe 2 3
>
Achmatowsk
203
62 MO 2 (6 R 2 O 3 18SiO 2 )
48 H 2
62 MO = 62 MgO
12 R 2 O 3 = 9 A1 2 O 3 3 Fe 2 O 3
n
204
63MO-2(6Al 2 O 3 -18SiO 2 )
48 H 2
63 MO = 53 MgO 8 FeO - 2 CaO
tt
Kariaet,
Greenland
205
64 MO 2 (6 A1 2 O 3 18 SiO 2 )
48 H 2
64 MO = 60 MgO -4 FeO
"
Achmatowsk
206
64 MO 2 (6 A1 2 O 3 18SiO a )
48H 2
"
THE ORTHOCHLORITE GROUP
403
Analyst
SiO,
A1 2 S
Fe,0 3
Cr 2 3
FeO
MnO
CaO | MgQ
K a o
Na,0
H,0
Total
Loretz
Theory
29.08 13.79
4.33
42.62
10.18
100.00
IV
29.00 13.00
6.00
42.00
10.00
100.00
Heddle
Theory
31.49 14.87
4.67
17.85
1.03
17.49
12.60
100.00
LXVIII
31.03
14.85
5.73
17.42
1.00
0.36
17.42
12.48
100.29
it
Theory
31.70
17.22
1.17
12.16
1.64
20.25
15.86
100.00
VI
32.00 17.33
1.19
12.45
1.57
20.42
15.45
100.41
M
Theory
31.11 15.43
3.46
15.55
1.21
18.73
14.51
100.00
VIII
30.93
15.32
3.16
15.31
0.38
1.38
18.65
14.69
99.82
Gintl
Theory
34.85
18.93
1.29
1.16
30.97
12.78
100.00
XIII
35.31
18.28
1.26
0.83
31.61
13.26
100.55
van
Theory
33.21
17.23
2.46
1.11
0.86
30.74
14.39
100.00
Weryecke
II
32.84
17.34
3.29
1.04
0.75
30.48
14.44
100.18
Komonen
Theory
35.12
17.40
3.90
0.90
33.92
8.75
100.00
xcv
34.99
17.15
3.39
1.42
34.49
8.56
100.00
M
Theory
35.12
17.40
3.90
0.90
33.92
8.75
100.00
XCVI
34.23
16.31
3.33
1.75
35.36
8.68
99.66
Hermann
Theory
32.62
18.49
4.35
32.02
12.52
100.00
XCVII
32.35
18.00
4.37
32.29
12.50
99.51
Clarke and
Theory
32.36
16.05
3.59
.
6.71
29.96
11.33
100.00
Schneider
CI
32.27
16.05
4.26
0.28
6.21
29.75
11.47
100.29
Herzog von
Theory
32.14
12.90
3.57
4.53
34.54
12.32
100.00
Leuchtenberg
CII
33.12
13.56
2.29
4.19
35.77
12.65
101.58
)t
Theory
32.14
12.90
3.57
4.53
34.54
12.32
100.00
cm
32.35
13.29
2.00
4.19
35.04
12.62
99.49
N. v. Zinn
Theory
32.14
12.90
3.57
4.53
34.54
12.32
100.00
CIV
33.31
12.60
2.30
4.04
35.62
12.62
100.49
M
Theory
32.14
12.90
3.57
4.53
34.54
12.32
100.00
CVI
32.50
13.20
2.30
4.00
35.60
12.60
100.30
Hermann
Theory
32.13
15.15
4.76
35.10
12.86
100.00
CXLI
31.82
15.10
4.06
0.90
0.25 NiO
35.24
12.75
100.12
Burton
Theory
32.13
15.15
4.76
35.10
12.86
100.00
CXLIX
31.86
15.80
4.77
0.30
34.30
12.72
99.75
Hammer-
Theory
31.76
16.95
1.19
4.23
0.82
32.35
12.70
100.00
schlag
CXVI
30.34
16.86
1.86
4.53
0.61
31.82
0.37
12.70
99.09
Heddle
Theory
30.19
12.83
6.38
2.01
3.13
30.19
1.32
0.87
13.08
100.00
LXIII
29.89
12.93
5.97
1.96
3.54
29.93
1.16
0.97
13.27
99.62
Delesse
Theory
31.99
18.13
1.18
36.44
12.26
100.00
LVIII
32.10
18.50
0.60
36.70
12.10
100.00
Struve
Theory
31.29
13.30
6.95
35.93
12.53
100.00
XCII
31.64
13.54
5.83
0.05
36.20
12.74
100.00
Theory
31.29
13.30
6.95
___
35.93
12.53
100.00
XCIII
31.52
13.96
6.12
0.05
35.68
12.67
100.00
Janowsky
Theory
30.62
17.34
8.16
1.59
30.04
12.25
100.04
CXVII
30.32
17.90
7.71
1.28
29.88
12.28
99.37
Kobell
Theory
31.14
17.64
4.16
34.60
0.85(Resd.)
12.46
100.00
LXXXIX
31.14
17.14
3.85
0.53
34.40
12.20
100.11
Varrentrapp
Theory
31.14
17.64
4.16
34.60
0.85(Besd.)
12.46
100.00
XC
30.38
16.97
4.37
33.97
12.63
98.32
404
THE ORTHOCHLORITE GROUP
0. Orthoehlorites of the type
R Si R Si R = 8 R 9 0o 12 SiO,
Source
207
40 MO
2(8Fe 2 O 3 -
12 SiO 2 )
44 H 2 O
40 MO = 40 FeO
Cronstedtite
Cornwall
208
41 MO
-2(8A1 2 O 8 -
12SiO 2 )
40H 2 O
41 MO = 31 FeO -10 MgO
Thuringite
Lake Superior
P. Orthoehlorites of the type
R S A i R Si R = 9 R 2 3 12 Si0 2
209
210
211
212
213
214
Source
16 MO 2(9 A1 2 O 3 12 SiO 2 )
34 H 2 O
28MO-2(9R 2 O 3 -12SiO 2 )
30 H 2 O
30MO-2(9R 2 3 -12Si0 2 )
42 H 2
33MO-2(9R 2 O 3 -12SiO 2 )
36H 2
37MO-2(9Al 2 O 3 -12SiO 2 )
34H 2 O
40 MO 2(9 Fe 2 O 3 12 SiO 2 )
46H 2
16 M0 = 14 MgO 1 CaO 1 FeO
28 MO = 25 FeO -3 MgO
18R 2 3 = 15Al 2 3 -3Fe 2 3
30 MO = 28 FeO -2 MgO
18 R 2 O 3 = 7-5 Fe 2 O 3 10.5 Al
33 MO = 31 FeO -2 MgO
18R 2 3 =12Al 2 3 -6Fe 2 3
37 MO = 24 MgO 13 FeO
40 MO = 40 FeO
FeO
P 3
3
U 2 O 3
Rumpfite
Aphrosiderite
Thuringite
St. Michael
Weilburg
Schmiedefeld
3
P 3
3
Orthochlorite
Chester, Mass.
Cronstedtite
Cornwall
New Formulae for
The following analyses of the minerals
A. R Si R =5 R 2 O 3 6 Si0 2 ,
B. R S A i R Si R = 8 R 2 3 12 Si0 2 ,
A. Tourmalines of the type
R Si R = 5 R 2 3 6 Si0 2
Source
Analyst *
4 RO 4(5 R 2 O 3
6Si0 2 )
4MO = 0.5MnO- 1.5Li 2 O-l Na 2 O-0.5K 2 O
Elba
Rammelsberg
4H 2
0.5 H 2 O ; 20 R 2 O 3 =16 A1 2 O 3 4 B 2 O 3
4 RO 4(5 R 2 O 3
6 SiO 2 )
4 MO =0.5 CaO 2 Li 2 O 1.5 Na 2 O
Rumford
Riggs
9H 2
20 R 2 O 3 = 15.5 A1 2 O 3 4.5 B 2 O 3
5 MO 4(5 R 2 3
- 6 SiO 2 )
5 MO = 1 MnO-0.5 CaO-1.5 Li a O-1.5 Na 2 O
Paris
Rammelsberg
4H 2
0.5 K 2 O ; 20 R 2 O 3 = 15.5 A1 2 O 3 4.5 B 2 O 3
5 MO 4(5 R 2 O 3
5H 2
6 SiO 2 )
5 MO = 1 MnO-0.5 CaO- 1.5 MgO 1 Li 2 O
1 Na 2 ; 20 R 2 O 3 = 16 A1 2 O 3 4 B 2 O 3
Schaitauka
5 MO 4(5 R 2 O 3
6 Si0 2 )
5MO = 1.5FeO-0.5MgO-lLi 2 O- 1.5 MnO
Elba
n
5H 2
1.5 Na 2 O ; 20 R 2 O 3 = 15 Al 2 O 3 -5 B 2 O 3
5 MO 4(5 R 2 O 3
6 SiO 2 )
5 MO = 0.5 MnO-0.5 CaO-2 Li 2 O 1 Na O
Schiitten-
Scharizer
10H 2
1 K 2 ; 20 R 2 3 =15.5 A1 2 O 3 4.5 B 2 O 3
hofen
6 MO 4(5 R 2 O 3
6 SiO 2 )
6 MO = 1.5 FeO-1.5 MnO-0.5 CaO-0.5 Li 2 O
Brazil
Jannasch
7H 2 O
2 Na 2 O ; 20 R 2 O 3 = 15 A1 2 O 3 5 B 2 O 3
and Calb
6MO-4(5R 2 O 3
6 SiO 2 )
6 MO = 1 FeO 1 MnO 0.5 CaO 2 Li 2 O
H
Riggs
8H 2 O
1.5Na 8 O ; 20R 2 O 3 = 14.5 Al 2 O 3 -5.5 B 2 O 3
* See references on p. 441
THE TOURMALINE GROUP
405
or the general formula
m MO 2 (8 R 2 O 3 12 Si0 2 )
nHoO.
Analyst
1
SiO
Al,0 3
Fe t 3
Cr a 8
FeO
MnO
CaO
MgO
K,o
Na,0
H,0
Total
Flight
Penfield
and Sperry
Theory
VIII
Theory
X
18.77
18.55
22.28
22.35
25.25
25.14
33.36
32.75
37.54
38.57
35.25
34.39
6.18
6.41
10.33
10.13
11.14
11.25
100.00
100.00
100.00
99.54
or the general formula
m MO 2 (9 R 2 3 12 Si0 2 ) n H 2 O.
Analyst
SiO a
Al a o s
Fe a 3 '
Cr a Oa
FeO
MnO
CaO
MgO
K,0
Na,0
H,0
Total
Firtsch
Theory
31.48
40.12
1.57
1.22
12.23
13.38
100.00
I "
30.75
41.66
1.61
0.89
12.09
13.12
100.12
Sand-
Theory
24.36
25.89
8.13
30.45
2.03
9.14
100.00
berger
III
24.63
25.25
8.50
30.61
1.82
9.19
100.00
L. Smith
Theory
21.94
16.32
18.28
30.72
1.22
11.52
100.00
I
22.05
16.40
17.66
30.78
0.89
0.14(K 2 O'Na,O)
11.44
99.36
Kammels-
Theory
21.74
18.48
14.47
34.30
1.21
9.78
100.00
berg
II
22.35
18.39
14.86
34.34
1.25
9.81
101.00
L. Smith
Theory
24.90
31.71
16.21
16.60
10.58
100.00
CXXII
25.06
30.70
16.50
16.41
10.62
99.29
Flight
Theory
17.94
35.87
35.87
10.32
100.00
VII
17.47
36.76
36.31
0.09
10.09
100.72
the Tourmaline Group
of this group conform to the following types :
C. R Si R Si R = 9 R 2 3 12 Si0 2 .
or the general formula
m MO 4 (5 R 2 O 3 6 Si0 2 ) n H 2
SiO>
B,0,
AUG.
Fe,0,
FeO
TiO,
MnO
CaO
MgO
Li.O
Na,0
K,0
H,0
Fl
Total
Loss on
Ignition
Theory
XX
39.76
38.85
7.71
9.52
45.06
44.05
0.00
0.00
0.00
0.00
0.00
0.00
0.98
0.92
0.00
0.00
0.00
0.20
.24
.22
1.71
2.00
1.30
1.30
2.24
2.41
0.00
0.70
100.00
101.17
.__
Theory
LXVIII
39.15
38.07
8.54
9.99
42.99
42.24
0.00
0.00
0.00
0.26
0.00
0.00
0.00
0.35
0.76
0.56
0.00
0.07
.63
.59
2.53
2.18
0.00
0.44
4.40
4.26
0.00
0.28
100.00
100.29
Theory
LXII
39.01
38.19
8.52
9.97
42.83
42.63
0.00
0.00
0.00
0.00
0.00
0.00
1.92
1.94
0.76
0.45
0.00
0.39
.22
.17
2.52
2.60
1.27
0.68
1.95
2.00
0.00
1.18
100.00
101.20
Theory
XXXI
39.00
38.26
7.57
9.29
44.20
43.97
0.00
0.00
0.00
0.00
0.00
0.00
1.92
1.53
0.76
0.62
1.62
1.62
0.81
0.48
1.68
1.53
0.00
0.21
2.44
2.49
0.00
0.70
100.00
100.70
Theory
XIX
38.97
37.71
9.45
9.99
41.41
41.89
0.00
0.00
0.97
1.38
0.00
0.00
2.88
2.51
0.00
0.00
0.54
0.41
0.82
0.74
2.52
2.40
0.00
0.34
2.44
2.60
0.00
0.50
100.00
100.47
Theory
VIII
37.94
38.49
8.28
8.25
41.66
41.49
0.00
0.00
0.00
0.35
0.00
0.00
0.94
0.60
0.74
1.82
0.00
0.00
1.58
1.68
1.64
1.32
2.48
2.14
4.74
4.61
0.00
0.43
100.00
100.00
Theory
XLII
37.63
37.05
9.13
9.09
39.98
40.03
0.00
0.00
2.82
2.36
0.00
0.00
2.78
2.35
0.73
0.47
0.00
0.32
0.40
0.60
3.24
3.18
0.00
Trace
3.29
3.23
0.00
1.15
100.00
99.83
Theory
XXXVIII
38.18
37.39
10.18
10.29
39.22
39.65
0.00
0.00
1.91
2.29
0.00
0.00
1.88
1.47
0.74
0.49
0.00
0.00
1.59
1.71
2.47
2.42
0.00
0.25
3.83
3.63
0.00
0.32
100.00
99.91
406
THE TOURMALINE GROUP
Source
Analyst
9
6 MO
4(5 R 2 O 3
6 SiO 2 )
6 MO = 1 FeO 1 MnO 0.5 CaO 2 Li 2 O
Auburn
Riggs
9H 2
1.5 Na 2 ; 20 R 2 O 3 = 14.5 Al 2 O 3 -5.5 B 2 O 3
10
6 MO
4(5 R 2 O 3
6 Si0 2 )
6 MO = 2 FeO-0.5 CaO 2 Li 2 O 1.5 Na 2 O
9H 2
20 R 2 O 3 = 14 A1 2 O 3 6 B 2 O 3
11
7 MO
4(5 R 2 O 3
6 SiO 2 )
7 MO = 1 .5 FeO-0.5 CaO 4 MgO 1 Na 2 O
N. Issetsk
Cossa
5H 2
20 R 2 O 3 = 11.5 A1 2 O 3 -5.5 B 2 O 3 3 Cr 2 O 3
12
7 MO
4(5 R 2 3
6 SiO 2 )
7MO = 1.5FeO-1.5MnO-0.5CaO- 1.5Li 2 O
Brazil
Jannasch
6H 2
2 Na 2 O ; 20 R 2 O 3 = 14.5 A1 2 O 3 5.5 B 2 O 3
and Calb
13
7 MO
4(5 R 2 3
6 SiO 2 )
7 MO = 1.5 FeO- 1.5MnO-0.5CaO-2 Li 2 O
M
Riggs
8H 2 O
1.5 Na 2 O ; 20 R 2 O 3 =14.5 A1 2 O 3 5.5 B 2 O 3
14
7 MO
4(5R 2 3 -
6 SiO 2 )
7 MO = 3.5 FeO - 1.5 Li 2 O 2 Na 2 O
Rurnford
M
8H 2 O
20 R 2 O 3 = 14.5 A1 2 O 3 5.5 B 2 O 3
15
8 MO
4(5 R 2 O 3
6 Si0 2 )
8 MO = 3 FeO 0.5 MnO 1 MgO 2 Li 2 O
Brazil
Rammelsberg
4H 2 O
1 .5 Na 2 O ; 20 R 2 O 3 = 14 A1 2 O 3 6 B 2 O 3
16
8 MO
4(5 R 2 O 3
6 SiO 2 )
8 MO = 4 FeO-0.5 MnO 1.5 Li 2 O 2 Na 2 O
Auburn
Riggs
9H 2
20 R 2 O 3 = 14.5 A1 2 O 3 5.5 B 2 O 3
17
8 MO
4(5 R 2 O 3
6 SiO 2 )
8 MO = 2.5 FeO-1.5 MnO-2 Li 2 O 0.5 K 2 O
Schiitten-
Scharizer
10H 2
1.5 Na 2 O ; 20 R 2 O 3 = 15.5 Al 2 O 3 -4.5 B 2 O 3
hofen
18
10 MO
4(5 R 2 O 3
6 Si0 2 )
10 MO = 3 FeO-0.5 MnO-4 MgO-0.5 K 2 O
M. Bisch
Sommerland
2H 2
2 Na 2 O ; 20 R 2 O 3 = 14 A1 2 O 3 6 B 2 O 3
19
10 MO
4(5R 2 3 -
6 SiO 2 )
10 MO -7. 5 FeO- 1.5 MgO- 1 Na 2 O
Saar
Rammelsberg
3H 2
20 R 2 O 3 = 14 A1 2 O 3 6 B 2 O 3
20
10 MO
4(5 R 2 3
6 SiO 2 )
10MO = 6.5FeO-lMgO-0.5MnO- 1 Li 2 O
Goshen
w
5H 2 O
1 Na 2 O ; 20 R 2 O 3 = 13 A1 2 O 3 7 B 2 O 3
21
10 MO
4(5 R 2 3
6 Si0 2 )
10 MO = 8 FeO 1 MgO 1 Na 2 O
Auburn
Riggs
8H 2
20 R 2 O 3 = 13 A1 2 O 3 7 B 2 O 3
22
10 MO
4(5 R 2 3
6 SiO 2 )
10 MO = 7 FeO- 1.5 MgO- 1.5Na a O
Paris
8H 2
20 R 2 O 3 = 14.5 A1 2 O 3 5.5 B 2 O 3
23
10 MO
4(5 R 2 3
6 Si0 2 )
10 MO = 7.5 FeO -1.5 MgO- 1 Na 2 O
Alabaschka
Jannasch
8H 2 O
20 R 2 O 3 = 13.5 A1 2 O 3 6.5 B 2 O 3
and Calb
24
12 MO
4(5R 2 O 3 -
2H 2 O
6 Si0 2 )
12 MO = 8.5 FeO-0.5 MnO -2 MgO-0.5 Na 2 O
0.5 H 2 O ; 20 R 2 O 3 = 12 A1 2 O 3 8 B 2 O 3
M
Rammelsberg
25
12 MO
4(5 R 2 3
6 Si0 2 )
12 MO = 8.5 FeO 1.5 MgO 2 Na 2 O
Mursinka
Jannasch
6H 2
20 R 2 O 3 = 14 A1 2 O 3 6 B 2 O 3
and Calb
20
12 MO
4(5 R 2 3
6 Si0 2 )
12 MO = 4.5 FeO 5.5 MgO 0.5 CaO
Stony
Riggs
8H 2
1.5 Na 2 O ; 20 R 2 O 3 = 13.5 A1 2 O 3 6.5 B 2 O 3
27
12 MO
4(5 R 2 3
6 Si0 2 )
12 MO = 6 FeO 4 MgO 2 Na 2 O
Piedra
Jannasch
8H 2
20 R 2 O 3 = 13 A1 2 O 3 6 B 2 O 3 1 Fe 2 O 3
and Calb
B. Tourmalines of the type
R Si R Si R = 8 R 2 3 12 Si0 2
Source
Analyst
28
7 MO
2(8R 2 3 -
12 Si0 2 )
7 MO = 3 FeO 0.5 CaO 1 MgO 0.5 K 2 O
Waldheim
Sauer
6H 2 O
2 Na 2 ; 16 R 2 O 3 = 14 A1 2 O 3 2 B 2 O 3
29
13 MO
2(8 R 2 3
12 SiO 2 )
13 MO = 2 FeO 1 CaO 9 MgO 1 Na 2 O
Monroe
Rammelsberg
6H 2
16 R 2 O 3 = 11.5 A1 2 O 3 4.5 B 2 O 3
30
14 MO
2(8R 2 O 3 -
12 Si0 2 )
14 MO = 5 FeO 0.5 MnO-0.5 CaO-6.5 MgO
Elba
5H 2 O
1.5Na 2 O; 16 R 2 O 3 = 11 A1 2 O 3 5 B 2 O 3
31
14 MO
2(8R 2 O 3 -
12SiO 2
14MO = 4.5FeO- 1.5 CaO 7 MgO-1 Na 2 O
Tamatave
Jannasch
6H 2 O
16R 2 O 3 =10A1 2 O 3 -4.5B 2 O 3 - 1.5Fe 2 O 3
and Calb
THE TOURMALINE GROUP
407
Si0 2
B 2 3
A1 2 S
Fe 2 o s
FeO
Ti0 2
MnO
CaO
Mgo
Li 2 o
Na 2
K 2
H 2 o
Fl
Total
Loss on
Ignition
Theory
LXIV
38.02
38.14
10.14
10.25
39.03
39.60
0.00
0.30
1.90
1.38
0.00
0.00
1.87
1.38
0.73
0.43
0.00
Trace
1.58
1.34
2.45
2.36
0.00
0.27
4.28
4.16
0.00
0.62
100.00
100.23
4.09
Theory
LXV
38.16
37.85
11.10
10.55
37.84
37.73
0.00
0.42
3.82
3.88
0.00
0.00
0.00
0.51
0.74
0.49
0.00
0.04
1.59
1.34
2.46
2.16
0.00
0.62
4.29
4.18
0.00
0.62
100.00
100.39
Theory
XXXII
36.91
36.79
9.84
9.51
30.06
30.56
11.70Cr 2 3
10.86Cr 2 O 3
2.77
2.91
0.00
0.00
0.00
Trace
0.72
0.72
4.10
4.47
1.59
1.36
0.00
0.00
0.00
Trace
2.31
2.25
0.00
0.65
100.00
100.08
Theory
XLI
37.68
37.40
10.05
10.74
38.69
39.02
0.00
0.00
2.82
2.35
0.00
0.00
2.79
2.57
0.73
0.60
0.00
0.20
1.17
1.33
3.25
3.59
0.00
0.29
2.82
3.08
0.00
0.98
100.00
102.15
z
Theory
XXXIX
37.48
36.91
9.99
9.87
38.49
38.13
0.00
0.31
2.81
3.19
0.00
0.00
2.77
2.22
0.73
0.38
0.00
0.04
1.56
1.61
2.42
2.70
0.00
0.28
3.75
3.64
0.00
0.14
100.00
99.42
3.62
Theory
LXIX
37.21
36.53
9.93
10.22
38.23
38.10
0.00
0.00
6.51
6.43
0.00
0.00
0.00
0.32
0.00
0.34
0.00
0.00
1.19
0.95
3.21
2.86
0.00
0.38
3.72
3.52
0.00
0.16
100.00
99.81
3.31
Theory 37.86
XXXVI 38.06
11.02
10.09
37.55
37.81
0.00
0.00
5.68
5.83
0.00
0.00
0.93
1.13
0.00
0.00
1.05
0.92
1.58
1.30
2.44
2.21
0.00
0.42
1.89
2.23
0.00
0.70
100.00
100.70
Theory
LXVI
36.39
36.26
9.70
9.94
37.37
36.68
0.00
0.15
7.28
7.07
0.00
0.00
0.90
0.72
0.00
0.17
0.00
0.16
1.14
1.05
3.13
2.88
0.00
0.44
4.09
4.05
0.00
0.71
100.00
100.28
-
Theory
VII
35.99
36.38
7.85
8.12
39.50
39.77
0.00
0.00
4.50
4.17
0.00
0.00
2.66
2.83
0.00
0.00
0.00
0.00
1.50
1.54
2.33
1.93
1.17
0.93
4.50
4.29
0.00
0.00
100.00
100.00
-
Theory
XXXIV
36.87
36.86
10.74
10.56
36.56
36.72
0.00
0.00
5.53
5.66
0.00
0.00
0.91
0.66
0.00
0.34
4.10
3.92
0.00
0.00
3.17
3.57
1.20
1.11
0.92
1.16
0.00
0.61
100.00
101.17
Theory
X
35.97
36.11
10.47
11.64
35.67
35.46
0.00
0.00
13.49
13.17
0.00
0.00
0.00
0.28
0.00
0.00
1.50
1.52
0,00
0.00
0.55
0.98
0.00
0.09
1.35
1.26
0.00
0.41
100.00
100.92
Theory
LVIII
36.18
36.22
12.28
10.65
33.31
33.35
0.00
0.00
11.75
11.95
0.00
0.00
0.89
1.25
0.00
0.00
1.00
0.63
0.75
0.84
1.56
1.75
0.00
0.40
2.26
2.21
0.00
0.82
100.00
100.07
Theory
LXVII
35.04
34.99
10.20
9.63
34.76
33.96
-
14.02
14.23
-
0.06
0.15
0.97
1.01
Trace
1.51
2.01
0.34
3.50
3.62
0.00
100.00
100.00
2.17
Theory
LXIII
35.09
35.03
9.34
9.02
36.04
34.44
1.13
12.28
12.10
0.00
0.08
0.00
0.24
.46
.81
0.00
0.07
2.27
2.03
0.25
3.50
3.69
0.00
100.00
99.89
2.30
Theory
XXVIII
35.32
35.41
11.14
10.14
33.78
33.75
13.25
13.42
Trace
0.17
.47
.57
~
1.52
2.08
0.34
3.53
3.41
0.28
100.00
100.57
Theory
XXVII
35.76
36.19
13.88
12.79
30.40
30.40
15.20
15.59
0.88
0.54
~
.98
.88
0.77
1.04
0.47
1.11
1.11
0.76
100.00
100.76
Theory
XXIX
34.35
34.88
9.99
8.94
34.07
34.58
-
14.62
14.40
0.27
0.24
0.20
.43
1.32
~
2.96
2.70
0.05
2.58
2.87
0.51
100.00
100.96
Theory
XLIV
35.30
35.56
11.12
10.40
33.75
33.38
7.94
8.43
0.55
0.04
0.69
0.53
5.39
5.44
Trace
2.28
2.16
0.24
3.53
3.63
0.00
100.00
100.36
2.86
Theory
XLIII
34.24
34.73
9.96
9.64
31.53
31.69
3.81
3.18
10.28
10.14
0.30
0.16
0.36
3.81
3.47
2.95
2.85
0.15
3.42
3.44
0.47
100.00
100.58
or the general formula
m MO 2 (8 R 2 O 3 12 Si0 2 ) n H 2 0.
Si0 2
B 2 O 3
Al,0, |Fe 2 3 | FeO
Ti0 2
MnO
CaO
MgO
Li 2 o Na 2 o
K 2
H 2 o
Fl
Total
Theory
36.64
3.55
36.33
5.49
_
0.71
10.18
3.15
1.19
2.76
100.00
III
36.35
4.61
35.76
4.78
0.41 SnO 2
0.47
10.01
3.89
1.22
2.87
99.67
Theory
39.38
8.59
32.07
3.94
1.54
9.84
1.69
2.95
100.00
LIII
39.01
8.95
31.18
4.07
1.81
9.90
1.82
0.44
2.82
100.00
Theory
38.13
9.24
29.71
9.53
0.94
0.74
6.87
2.46
2.38
100.00
XVII
38.20
9.03
30.02
9.93
0.58
0.74
6.87
2.19
0.25
2.29
0.15
100.15
Theory
37.19
8.12
26.34
6.20
8.37
2.16
7.23
1.60
2.80
100.00
LXXIII
35.48
9.49
25.83
6.68
7.99
1.22
Trace
2.03
6.90
1.92
0.29
2.58
0.33
100.74
408
THE TOURMALINE GROUP
Source
Analyst
32
15 MO
2(8 R 2 3
12SiO 2 )
15 MO = 4.5 FeO 1 CaO 8 MgO 0.5 K 2 O
Haddam
Rammels-
4H 2
1 Na 2 O ; 16 B 2 O 8 = 11.5 A1 2 O 3 4.5 B 2 O 3
berg
33
15 MO
2(8 R 2 3
12SiO 2 )
15 MO = 2 FeO 0.5 CaO-11 MgO-1.5 Na 2 O
Eibenstock
it
6H 2 O
16 R 2 O 3 =11.5 A1 2 O 3 4.5 B 2 O 3
34
16 MO
2(8 R 2 3
12 Si0 2 )
16 MO = 6 FeO 0.5 CaO 8 MgO 0.5 K 2 O
Snarum
?>
4H 2 O
1 Na 2 O ; 16 R 2 O 3 = 11 A1 2 O 3 5 B 2 O 3
35
16 MO
2(8 R 2 3
12 SiO a )
16 MO = 0.5 FeO-1 CaO-14 MgO-0.5 Na 2 O
Gouverneur
H
5H 2
16 R 2 O 3 = 11.5 A1 2 3 4.5 B 2 O 3
36
17 MO
2(8 R 2 3
12 SiO 2 )
17 M0 = 0.5 FeO-2 CaO-13.5 MgO-1 Na 2 O
,,
Riggs
8H 2
16 R 2 O 3 = 10.5 A1 2 O 3 5.5 B 2 O 3
37
18 MO
2(8 R 2 O 3
12SiO 2 )
18 MO = 0.5 FeO-2.5 CaO-14 MgO-1 Na 2 O
Dekabb
M
8H 2 O
16 R 2 O 3 = 11 A1 2 O 3 5 B 2 O 3
38
19 MO
2(8 R 2 O 3
12SiO 2 )
19 MO = 4.5 FeO-2.5 CaO-11 MgO-1 Na 2 O
Pierrepont
If
8H 2 O
16 R 2 O 3 = 10 A1 2 O 3 6 B 2 O 3
C. Tourmalines of the type
R - S A i R Si R = 9 R 2 3 - 12 Si0 2
Source
Analyst
39
3 MO 2(9 R 2 3
12SiO 2 )
3 MO = 0.5 MnO-0.5 MgO-1 Na 2 O-l K 2 O
Rozna
Rammels-
5H 2
18 R 2 O 3 = 14 A1 2 O 3 4 B 2 O 3
berg
40
5 MO 2(9 R 2 O 3
12Si0 2 )
5 MO = 2.5 FeO-0.5 MnO-0.5 MgO-1.5 Na 2 O
Campol
Engel-
5H 2 O
18 R 2 O 3 = 13.5 A1 2 O 3 4.5 B 2 O 3
mann
41
8 MO 2(9 R 2 O 3
12 SiO 2 )
8 MO = 3.5 FeO- 0.5 MnO- 1.5MgO-lLi 2 O
Chester-
Rammels-
5H 2
1.5 Na 2 O ; 18 R 2 O 3 = 13.5 Al 2 O 3 -4.5 B 2 O 3
field
berg
42
10 MO 2(9 R 2 O 3
12 Si0 2 )
10 MO = 5.5 FeO 1.5 MnO-1 MgO-1.5 Na 2 O
Sarapulka
H
3H 2 O
0.5 H 2 O ; 18 R 2 O 3 = 11.5 A1 2 O 3 6.5 B 2 O 3
43
10MO-2(9R 2 3 -
12 Si0 2 )
10 MO = 5.5 FeO-1 MnO-1.5 MgO-1.5 Na 2 O
Elba
M
4H 2
0.5 K 2 O ; 18 R 2 O 3 = 13 A1 2 O 3 5 B 2 O 3
44
11MO-2(9R 2 O 3 -
12Si0 2 )
11 MO = 8 FeO 0.5 MgO 2.5 Na 2 O
Buchw.
Jannasch
8H 2 O
18 R 2 O 3 = 13.5 A1 2 O 3 4.5 B 2 O 3
and Calb
45
11MO-2(9R 2 3 -
12SiO 2 )
11 MO = 9 MgO 1.5 Na 2 O 0.5 CaO
Maryland
Gill
8H 2
18R 2 O 3 =12.5A1 2 O 3 -4.5B 2 O 3 - 1 Cr 2 O 3
46
11MO-2(9R 2 3 -
12SiO 2 )
11 MO = 4.5 FeO 0.5 CaO 4 MgO- 2 Na 2 O
Tamaya
Schwarz
9H 2
18 R 2 O 3 = 12.5 A1 2 O 3 5.5 B 2 O 3
47
12MO-2(9R 2 O 3 -
12 SiO 2 )
12 MO = 6.5 FeO-0.5 CaO-3.5 MgO-1 Na 2 O
Langenb.
Rammels-
3H 2 O
0.5 K 2 ; 18 R 2 3 = 12 A1 2 O 3 6 B 2 O 3
berg
48
12MO-2(9R 2 O 3 -
12SiO 2 )
12 MO = 6.5 FeO 0.5 CaO 4 MgO 1 Na 2 O
Krumrn
,,
3H 2 O
18R 2 3 =13A1 2 3 -5B 2 3
49
12MO-2(9R 2 O 3 -
12 SiO 2 )
12 M0 = 9.5 FeO 0.5 CaO 1 MgO 1 Na 2 O
Andreasb.
,,
4H 2
18R 2 3 =12A1 2 3 -6B 2 3
50
12 MO 2(9 R 2 O 3 -
12SiO 2 )
12 MO = 7.5 FeO-0.5 CaO-2.5 MgO-0.5 K 2 O
Bovey
4H 2
1 Na 2 O ; 18 R 2 O 3 = 11.5 Al a O 3 6.5 B 2 O 3
Tracey
51
12MO-2(9R 2 O 3 -
12SiO 2 )
12 MO = 7 FeO 0.5 CaO 2.5 MgO 1 MnO
Krumm
5H 2
1 Na 2 O ; 18 R 2 O 3 = 12.5 Al 2 O 3 -5.5 B 2 O 3
52
12 MO 2(9 R 2 O 3
12 SiO 2 )
12 M0 = 1.5 FeO-0.5 CaO-8.5 MgO-0.5 K 2 O
Texas
,,
6H 2 O
1 Na 2 O ; 18 R 2 O 3 = 13 A1 2 O 3 5 B 2 O 3
63
12MO-2(9R 2 O 3 -
12 SiO 2 )
12 MO = 8 FeO - 0.5 CaO 2 MgO 1.5 Na 2 O
Brazil
Biggs
8H 2 O
18R 2 3 =13A1 2 3 -5B 2 O 3
54
12MO-2(9R 2 O 3 -
12 SiO a )
12 MO = 7.5 FeO 1 MnO 1.5 MgO-0.5 K 2 O
Schutten-
Scharizer
9H 2
1.5 Na 2 ; 18 R 2 O 3 = 14 A1 2 O 3 4 B 2 O 3
hofen
THE TOURMALINE GROUP
409
SiO
B a o,
AlgO s
Fe a o a
FeO
TiO
MnO
CaO
MgO
Li,o
Nao
K,0
H,o
Fl
Total
Loss on
Ignition
Theory
LV
37.81
37.50
8.25
9.02
30.80
30.87
8.52
8.54
z
z
1.47
1.33
8.40
8.60
z
1.63
1.60
1.23
0.73
1.89
1.81
100.00
100.00
Theory
II
38.50
37.75
8.40
9.14
31.36
30.86
-
3.85
4.36
~
-
0.75
0.88
11.76
11.62
z
2.49
2.27
0.30
2.89
2.82
100.00
100.00
____^
Theory
XXV
37.20
37.22
9.02
9.73
28.98
30.00
11.16
11.16
~
-
0.72
0.65
8.26
7.94
-
1.60
1.13
1.21
0.53
1.85
1.64
0.55
100.00
100.55
Theory
XLVII
38.91
38.85
8.49
8.35
31.70
31.32
z
0.98
1.14
~
-
1.51
1.60
15.13
14.89
0.84
1.28
0.26
2.44
2.31
~
100.00
100.00
z
Theory
XLIX
38.00
37.39
10.14
10.73
28.26
27.79
0.10
0.95
0.64
1.19
2.96
2.78
14.25
14.09
Trace
1.64
1.72
0.16
3.80
3.83
Trace
100.00
100.42
Theory
LII
37.37
36.88
9.06
10.58
29.12
28.87
0.93
0.52
0.12
3.63
3.70
14.54
14.53
Trace
1.61
1.39
0.18
3.74
3.56
0.50
100.00
100.83
Theory
L
36.09
35.61
10.50
10.15
25.57
25.29
0.44
8.12
8.19
0.55
Trace
3.51
3.31
11.03
11.07
Trace
1.55
1.51
0.20
3.63
3.34
0.27
100.00
99.93
2.69
or the general formula
m MO 2 (9 R 2 3 - 12 Si0 2 ) n H 2 0.
SiO a
B 8 o,
Al,0,
Fe 2 0,
FeO
TiO,
MnO
CaO
MgO
Li,0 JNa,C
> K,0
H.OJ Fl
Total
Theory
IX
41.75
41.16
8.10
8.93
41.40
41.83
1.03
0.95
0.58
0.61
0.41
1.80
1.37
2.73
2.17
2.61
2.57
1.19
100.00
101.19
Theory
XV
40.57
39.26
8.86
9.40
38.80
38.33
5.06
4.51
1.00
1.12
0.56
1.02
2.61
2.43
0.38
2.54
2.41
0.61
100.00
99.46
Theory
LVII
39.01
38.46
8.51
9.73
37.29
36.80
6.83
6.38
0.96
0.78
1.63
1.88
0.81
0.72
2.52
2.47
0.47
2.44
2.31
0.55
100.00
100.55
Theory
XXX
38.24
38.30
12.06
11.62
31.15
31.53
10.52
10.30
2.83
2.68
1.06
1.06
2.47
2.37
0.33
1.67
1.81
0.80
100.00
100.80
Theory
XVIII
37.35
37.14
9.06
9.37
34.41
34.15
10.28
10.52
1.84
1.87
1.56
1.68
0.32
2.41
2.30
1.22
0.75
1.87
1.90
0.47
100.00
100.47
Theory
XXXIII
35.77
35.50
7.80
8.34
34.20
34.39
-
14.30
14.26
Trace
Trace
0.50
0.51
Trace
3.85
3.43
3.58
3.34
0.77
100.00
100.54
Theory
XLV
Theory
XXXV
37.83
36.56
36.96
36.34
8.25
8.90
9.86
10.87
33.49
32.58
32.72
32.22
4.00 Cr 2 0,
4.32Cr 2 3
0.79Fe 2 3
8.30
8.31
0.09
Trace
0.74
0.75
0.72
0.79
9.46
9.47
4.10
3.92
Trace
2.44
2.22
3.18
3.14
0.13
0.22
3.78
3.74
4.16
3.89
0.06
100.00
99.70
100.00
99.70
Theory
IV
37.09
37.24
10.79
11.02
31.53
31.63
12.06
11.64
___
~
0.72
0.62
3.61
3.65
~
1.60
1.93
1.21
0.82
1.39
1.45
100.00
100.00
Theory
V
37.05
36.43
8.98
9.82
34.11
34.12
-
12.04
11.58
-
0.72
0.44
4.12
3.84
-
1.59
1.36
0.30
1.39
2.11
100.00
100.00
Theory
I
36.28
36.06
10.56
11.11
30.84
30.34
17.23
17.40
-
0.11
0.71
0.72
1.00
0.78
~
1.56
1.36
0.58
1.82
1.54
0.85
100.00
100.85
Theory
XXI
36.77
37.94
11.60
10.72
29.96
30.22
___
13.79
13.82
-
0.40
0.71
0.50
2.55
2.62
~
1.58
1.39
1.20
0.65
1.84
1.74
0.45
100.00
100.45
Theory
XII
36.42
36.25
9.71
10.27
32.24
32.21
12.75
12.82
1.80
1.50
0.70
0.40
2.53
2.32
1.57
1.43
0.46
2.28
2.34
0.64
100.00
100.64
Theory
XLVII
37.81
38.45
9.17
8.57
34.82
34.56
2.84
2.98
0.09
0.73
0.71
8.93
9.11
1.62
2.00
1.23
0.73
2.84
2.80
100.00
100.00
Theory
XL
35.68
34.63
8.65
9.63
32.86
32.70
0.31
14.27
13.67
0.12
0.69
0.33
1.98
2.13
0.08
2.30
2.11
0.24
3.57
3.49
0.06
100.00
99.52
Theory
VI
34.95
35.10
6.78
7.09
34.65
35.10
..
13.10
13.36
0.08 SnO 2
1.72
1.48
1.46
0.98
~
2.26
1.92
1.14
0.88
3.94
4.01
__
100.00
100.00
410
THE TOURMALINE GROUP
Source
Analyst
55
13 MO
2(9 R 2 3
5H 2
12SiO 2 )
13 MO = 7 FeO-0.5 MnO-3.5 MgO-1.5 Na 2 O
0.5H 2 O; 18R 2 O 3 =12A1 2 O 3 - 6B 2 O 3
Dekalb
Rammels-
berg
50
13 MO
2(9R 2 3 -
6H 2
12 SiO 2 )
13 MO = 1.5 FeO 10 MgO 1.5 Na 2 O
18 R 2 O 3 = 12 A1 2 O 3 6 B 2 O 3
Zillertal
5
57
13 MO
2(9 R 2 3
6 H 2
12 SiO 2 )
13 MO=4 FeO 1 CaO 7 MgO 1 Na 2 O
18R 2 3 =12A1 2 3 -6B 2 3
St. Gott-
hard
>
58
13 MO
2(9 R 2 3
6H 2
12SiO 2 )
13 MO = 1.5 FeO-0.5 CaO-10 MgO-1 Na 2 O
18 R 2 O 3 = 12.5 A1 2 O 3 5.5 B 2 O 3
Orford
n
59
13 MO
2(9 R 2 O 3
8H 2 O
12 SiO 2 )
13 MO = 2 FeO -0.5 CaO-9 MgO-1.5 Na 2 O
18 R 2 O 3 = 12 A1 2 O 3 6 B 2 O 3
Monroe
Riggs
GO
14 MO
2(9 R 2 O 3
4H 2 O
12 Si0 2 )
14 MO = 0.5 FeO-1 CaO-11 MgO-1.5 Na 2 O
18R 2 3 =12A1 2 3 -6B 2 3
Dobrawa
Raminels-
berg
61
14 MO
2(9 R 2 3
6H 2
12 Si0 2 )
14MO = 2.5FeO-lCaO-9MgO-1.5Na 2 O
18R 2 3 =13A1 2 3 -5B 2 3
Godhaab
-
62
14 MO
2(9 R 2 3
7H 2
12 Si0 2 )
14 MO = 3 FeO 1 CaO 8 MgO 2 Na 2 O
18 R 2 3 = 12 A1 2 3 5 B 2 3 1 Fe 2 O 3
Ohlapian
Jannasch
63
HMO
2(9R 2 3 -
8H 2 O
12SiO 2 )
UMO = 1.5FeO- 1 CaO-10MgO-1.5Na 2 O
18 R 2 O 3 = 12.5 A1 2 O 3 5.5 B 2 O 3
Orford
Riggs
64
14 MO
2(9R 2 3 -
8H 2
12Si0 2 )
14 MO = 7 FeO-0.5 CaO-4.5 MgO-1.5Na 2 O
0.5 H 2 O ; 18 R 2 O 3 = 12.5 Al 2 O 3 -5.5 B 2 O 3
Haddam
"
65
15 MO
2(9R 2 3 -
5H 2
12SiO 2 )
15 MO = 4 FeO-0.5 CaO-9.5 MgO-1 Na 2 O
18 R 2 O 3 = 12 A1 2 O 3 6 B 2 O 3
Kragerfi
Rammels-
berg
66
15 MO
2(9 R 2 3
6H 2 O
12SiO 2 )
15 M0 = 3.5 FeO-1.5 CaO-8 MgO-2 Na 2 O
18 R 2 O 3 = 11.5 A1 2 O 3 6 B 2 O 3 -0.5 Fe 2 O 3
Snarum
Jannasch
and Calb
67
15 MO
2(9R 2 3 -
8H 2
12SiO 2 )
15 MO = 4.5 FeO-1.5 CaO-8 MgO-1 Na 2 O
18 R 2 O 3 = 12 A1 2 O 3 6 B 2 O 3
Baffins-
land
Riggs
6S
16 MO
2(9R 2 O 3 -
4H 2
12 Si0 2 )
16 MO = 7.5 FeO-0.5 CaO-6.5 MgO-1.5Na 2 O
18R 2 3 =12A1 2 8 -6B 2 3
Unity
Rammels-
berg
69
20 MO
2(9 R 2 3
7H 2
12Si0 2 )
20 MO = 0.5 FeO-4 CaO-15 MgO-0.5 Na 2 O
18 R 2 O 3 =11.5 A1 2 O 3 6.5 B 2 O 3
Hambg.
Riggs
The Fel-
The following analyses of the minerals of the
A. Si R S A i Si R Si = 5 R 2 3 22 Si0 2 ,
B. Si R Si Si R Si = 5 R 2 3 24 Si0 2 ,
C. Si R Si Si R Si = 6 R 2 3 20 Si0 2 ,
A. Felspars of the type
Si R Si Si R Si = 5 R 2 3 22 Si0 2
1
Source
1
3 MO
5 R 2 O 3
22 SiO 2
3MO = 1
5 Na 2 O-0.5 CaO-0.5 MgO 0.5 K 2 O
Oligoclase
Cape Wrath
1H 2 O
5R
2 O 3 =4.75 A1 2 O 3 0.25 Fe 2 O 3
2
4 MO
5 R 2 O 3
22 SiO 2
4MO =
= 1.5 Na 2 O 1.75 CaO 0.5 MgO
Andesine
Ale bei
2H 2 O
0.25K 2 O
Lima
3
4 MO
5 A1 2 3
22 SiO 2
4MO =
1.75 Na 2 O 1.75 CaO 0.25 MgO
w
Marmato bei
1 H 2 O
0.25 K 2 O
Popayan
THE FELSPAR GROUP
411
SiO,
B,0,
A1.0,
FejO,
FeO
Ti0 2
MnO
CaO
MgO
Li 2 o
Na 2
K0
H 2
Fl
Total
Loss on
Ignition
Theory
36.42
10.60
30.95
12.74
0.90
3.54
2.35
2.50
100.00
LI
37.07
9.70
31.86
12.55
0.51
3.49
2.04
0.30
2.48
0.31
100.31
Theory
37.97
11.05
32.28
2.85
10.55
2.45
2.85
100.00
XIV
38.51
9.52
32.65
2.80
0.36
0.16
10.46
2.13
0.37
3.04
0.36
100.36
Theory
37.14
10.87
31.57
7.43
1.44
7.21
1.60
2.80
100.00
XVI
38.00
10.32
31.41
7.23
1.31
7.27
1.43
0.28
2.75
100.00
Theory
37.84
10.09
33.51
2.84
0.74
10.51
1.63
2.84
100.00
LIX
38.33
9.86
33.15
2.88
0.77
10.89
2.81
100.21
Theory
37.38
10.80
31.78
3.74
0.73
9.35
2.40
3.74
100.00
LIV
36.41
9.65
31.27
3.80
1.61
Trace
0.98
9.47
2.68
0.21
3.79
99.87
3.59
Theory
38.09
11.08
32.38
0.95
1.48
11.64
2.46
1.92
100.00
XIII
38.09
11.15
32.90
0.66
1.25
11.79
2.37
0.47
2.05
0.64
101.37
Theory
36.81
8.93
33.89
4.60
.43
9.20
2.38
2.76
100.00
LXXII
37.70
7.82
34.26
4.42
.25
9.51
2.00
0.43
2.61
100.00
Theory
35.87
8.70
30.48
3.98
5.38
.39
7.97
3.09
3.14
100.00
XI
35.69
9.84
30.79
3.65
5.46
0.86
Trace
.54
8.12
2.53
0.27
3.12
101.95
Theory
36.92
9.85
32.69
2.77
.44
10.26
2.38
3.69
100.00
LX
36.66
10.07
32.84
2.50
0.23
Trace
.35
10.35
Trace
2.42
3.78
Trace
100.42
Theory
35.51
9.47
31.42
12.42
0.69
4.43
2.29
3.77
100.00
LVI
34.95
9.92
31.11
11.87
0.57
0.09
0.81
4.45
Trace
2.22
0.24
3.62
100.35
2.41
Theory
36.63
10.66
31.14
7.33
0.71
9.67
1.57
2.29
100.00
XXIV
37.11
9.29
31.26
7.58
0.80
9.43
1.78
0.32
2.43
100.00
Theory
36.00
10.48
29.32
2.00
6.30
2.10
8.00
3.10
2.70
100.00
XXVI
35.64
9.93
29.41
2.90
6.56
1.10
Trace
1.65
8.00
3.03
0.16
2.94
101.32
Theory
35.85
10.43
30.47
8.07
2.09
7.97
1.54
3.58
100.00
LXXI
35.34
10.45
30.49
8.22
0.40
Trace
2.32
7.76
Trace
1.76
0.15
3.60
100.49
2.88
Theory
35.23
10.29
30.02
13.25
0.69
6.38
2.28
1.76
100.00
LXX
26.29
9.04
30.44
13.23
1.02
6.32
1.94-|-K 2
1.72
100.00
Theory
35.26
11.12
28.72
0.88
5.49
14.69
0.76
3.08
0.00
100.00
XLVI
35.26
10.45
28.79
^^_
0.86
0.65
5.09
14.58
Trace
0.94
0.18
3.10
0.78
100.37
spar Group.
Felspar group conform to the following types
D. Si R Si Si R Si = 6 R 2 2 22 SiO 2 ,
E. S A i R Si Si - R Si = 6 R 2 3 24 Si0 2 .
or the general formula
m MO 5 R 9 0, 22 SiO
2 n H 2 0.
Analyst
Si0 2
A1 2 8
Fe 2 s
FeO
CaO
MgO
K 8 O
Na 2
H,o
Total
Heddle
Theory
LXVI
64.38
64.54
23.63
24.04
1.95
2.31
1.37
1.21
0.97
0.77
2.29
2.59
4.53
4.13
0.88
0.84
100.00
100.43
Raimondi
Theory
XCV
62.98
63.20
23.12
24.00
1.91
1.50
-
4.68
4.36
0.95
0.72
Trace
4.43
4.20
1.93
1.90
100.00
99.88
Deville
Theory
CIX
63.32
63.85
24.43
24.05
z
~
4.69
5.04
0.47
0.38
1.12
0.88
5.20
5.04
0.87
0.76
100.00
100.00
412
THE FELSPAR GROUP
Source
4
4 MO 5 A1 2 O 3 22 SiO 2
4 MO = 2.25 Na 2 1.25 CaO 0.5 K 2 O
Oligoclase
Mer de Glace
5
4MO-5R 2 3 -22Si0 2
4 MO = 2.25 Na 2 O 1.5 CaO 0.25 K 2 O
Rispond
1H 2
6
4MO-5Al 2 O 3 -22Si0 2
4 MO = 2.5 Na 2 O 1 CaO 0.5 K 2 O
Vesuvius
t
>
t>
>
Freiberg
8
>
M
Marienberg
9
4 MO 5 A1 2 O 3 22 SiO 2
M
Arendal
1H 2
10
4 MO 5 A1 2 O 3 22 SiO 2
4 MO = 2. 75 Na 2 O 0.75 CaO 0.25 MgO
Danviks
0.25K 2
||
Tulb
11
4 MO 5 B 2 O 3 22 SiO 2
4 MO = 2.75 Na 2 O 0.75 CaO 0.25 MgO
ff
Rottchen
0.25 K 2 O ; 5 R 2 O 3 = 4.75 A1 2 O 3 -0.25 Fe 2 O 3
12
4 MO 5 A1 2 O 3 22 SiO 2
4MO = 3Na 2 O-lCaO
Ariege
13
Culsagee,
N.C.
14
5MO-5R 2 O 3 -22SiO 2
5 MO = 1.75 Na 2 O 2.5 CaO 0.75 K 2 O
>
Neurode
5 R 2 O 3 = 4.75 A1 2 O 3 0.25 Fe 2 O 3
15
5MO-5Al 2 3 -22SiO a
5 MO = 2 Na 2 O 2 CaO 0.5 H 2 O-0.25 MgO
M
Aberdeen
0.25K 2
16
>f >
5 MO = 2 Na 2 O 2.5 CaO 0.5 K 2 O
Hierro
17
> >
5MO = 2Na 2 O-3CaO
Campo
maior
18
> )
5 MO = 2.25 Na 2 O 2.25 CaO 0.5 K 2 O
y9
Rosetown,
N.J.
19
5 MO 5 A1 2 O 3 22 SiO 2
ff
Pytterlaks
1H 2 O
20
5 MO 5 A1 2 3 22 SiO 2
Andesine
Pikruki
1H 2
21
5 MO 5 A1 2 O 3 22 SiO 2
5 MO = 2.25 Na a O 2.5 CaO 0.25 K 2 O
n
Sardinia
22
5 MO 5 A1 2 O 3 22 SiO 2
5 MO = 2.5 Na 2 O 1 CaO 0.75 FeO
Oligoclase
KjSrrestad
1H 2
0.5 H 2 O- 0.25 K 2 O
23
5 MO 5 A1 2 O 3 22 SiO 2
5 MO = 2.5 Na 2 O 2 CaO - 0.25 K 2 O
t>
Ditr6
1H 2
0.25H 2
24
5 MO 5 A1 2 O 3 22 SiO 2
5 MO = 2.5 Na 2 2 CaO 0.5 K 2 O
M
Com j os,
Colorado
25
5 MO = 2.5 Na 2 2 CaO 0.5 H 2 O
M
Anna-See
26
>
5MO = 2.5Na 2 O 2.25 CaO 0.25 K 2 O
H
M. Mulatto
27
t
t>
>
Knader
28
> >
5 MO = 2.75 Na 2 O 1.5 CaO 0.5 MgO
>
Chester,
0.25 H 2
Mass.
THE FELSPAR GROUP
413
Analyst
SiO a
Al0,
Fe 8 0,
FeO
CaO
MgO
KO
Na 2
H a o
Total
Delesse
Theory
LVII
63.27
63.25
24.44
23.92
z
3.36
3.23
0.32
2.25
2.31
6.68
6.78
100.00
99.91
Heddle
Theory
XLIX
62.15
61.85
21.61
21.70
3.77
3.37
0.20Mn 2 O 3
3.95
4.13
0.09
1.11
1.63
6.57
6.95
0.85
0.37
100.00
10U.29
G. v. Rath
Theory
XLIX
63.22
62.36
24.42
23.38
2.68
2.88
2.35
2.66
7.43
7.42
0.13
100.00
98.83
Kersten
Theory
VII
63.22
62.97
24.42
23.48
0.51
z
2.68
2.83
0.24
2.35
2.42
7.43
7.22
~
100.00
99.69
M
Theory
XXXIV
63.22
63.20
24.42
23.50
0.31
z
2.68
2.42
0.25
2.35
2.22
7.43
7.42
~
100.00
99.32
Dirvell
Theory
LXXVIII
62.68
63.53
24.22
24.05
z
2.66
2.60
2.33
1.86
7.36
8.02
0.85
0.90
100.00
100.96
Berzelius
Theory
XCII
63.28
63.70
24.45
23.95
0.50
z
2.01
2.05
0.96
0.65
1.13
1.20
8.17
8.11
z
100.00
100.16
Bothe
Theory
XVI
63.14
63.16
23.18
22.14
1.92
2.51
2.01
2.07
0.48
0.65
1.12
1.34
8.15
8.13
z
100.00
100.00
Laurent
Theory
LIII
63.70
62.60
24.62
24.60
2.70
3.00
0.20
z
8.98
8.90
z
100.00
99.40
J. L. Smith
Theory
63.72
24.61
2.70
8.97
100.00
CXXXII
64.12
24.20
0.14
2.80
9.28
100.54
Konig
Theory
II
61.00
61.54
22.40
22.36
1.85
1.75
z
6.47
6.23
~
3.26
2.82
5.02
4.91
z
100.00
99.61
Heddle
Theory
LXX
62.61
62.53
24.19
23.52
1.28
5.31
4.97
0.47
0.37
1.11
1.32
5.88
6.19
0.43
0.60
100.00
100.78
Schnorf
Theory
CLIII
61.66
60.99
23.82
23.98
0.90
z
6.54
6.46
.
2.19
2.08
5.79
5.44
z
100.00
99.85
Merian
Theory
LII
62.20
61.81
24.04
24.45
~
z
7.92
8.04
0.34
0.59
5.84
6.19
z
100.00
101.42
Kemp
Theory
CXXXIV
61.61
61.12
23.81
23.90
~
z
5.88
5.80
z
2.19
2.58
6.51
6.78
~
100.00
100.18
Struve
Theory
cm
61.09
60.90
23.60
24.32
~
5.83
5.78
2.20
1.87
6.46
6.51
0.82
0.62
100.00
100.00
n
Theory
LXXXIII
61.10
60.90
23.60
24.32
~
z
5.83
5.78
z
2.18
1.87
6.46
6.51
0.83
0.62
100.00
100.00
Dupare
Theory
LIV
61.88
62.65
23.91
24.19
~
z
6.56
6.28
z
1.11
1.24
6.54
6.48
100.00
100.84
Dirvell
Theory
XC
61.50
61.80
23.77
25.11
2.52
2.50
2.60
2.38
z
1.09
0.97
7.22
7.18
1.30
1.60
100.00
101.54
Fellner
Theory
XXXVI
61.60
61.68
23.80
23.95
-
z
5.23
5.35
1.10
1.09
7.22
6.99
1.05
1.05
100.00
100.27
G. v. Rath
Theory
CXXVIII
61.57
61.88
23.79
24.18
-
z
5.22
4.79
2.19
2.50
7.23
6.95
100.00
100.30
>
Theory
XXXVII
62.68
63.05
24.32
23.61
5.31
5.28
7.36
7.82
0.43
0.24
100.00
100.00
Petersen
Theory
XLI
61.84
62.84
23.89
23.53
-
5.91
5.50
-
1.10
1.15
7.26
7.65
z
100.00
100.67
Haughton
Theory
LXIV
61.84
62.40
23.89
23.60
-
-
5.91
5.62
1.10
1.66
7.26
7.04
___
100.00
100.40
Jackson
Theory
CXLIII
62.05
62.00
23.98
24.40
3.95
3.50
0.94
0.70
_
8.02
8.07
1.06
1.00
100.00
99.67
414
THE FELSPAR GROUP
Source
29
5 MO
5 A1 2 O 3
22 Si0 2
5 MO = 2.75 Na 2 O 1.5 CaO-0.5K 2 O-0.25H 2 O
Oligoclase
Monnoir,
Canada
30
5 MO
5 R 2 3
22 Si0 2
5 MO = 2.75 Na 2 O-1.5 CaO-0.5 H 2 O-0.25 K 2 O
"
Cragie
31
5 MO
5 A1 2 O 3
22 Si0 2
5 MO = 2.75 Na 2 O-1.5 CaO-0.5H 2 O-0.25 MgO
Chester,
1H 2
Mass.
32
5 MO
5 A1 2 3
22 Si0 2
5 MO = 2.75 Na 2 O-1.5 CaO-0.5 FeO-0.25 K 2 O
M
Kyffhauser
1H 2
33
5 MO
5 A1 2 3
22 Si0 2
5 M0 = 2.75 Na 2 1.75 CaO 0.25 MgO
M
Moland,
1 H 2
- 0.25 K 2 O
Arendal
34
5 MO
5 A1 2 3
22 Si0 2
5 MO = 2.75 Na 2 O 1.75 CaO 0.25 FeO
N
Arendal
0.25 K 2
35
5 MO
5 A1 2 3
22 Si0 2
5 M0 = 2.75 Na 2 O 2 CaO 0.25 K 2 O
n
1H 2
36
5 MO
5 A1 2 3
22 Si0 2
Rhiconieh
37
Fredriks-
varn
88
M
-
5 MO = 2.75 Na 2 O 2.25 CaO
Alausi
39
M
N
5 MO = 3 Na 2 O 0.5 CaO 1.5 K 2 O
m
Ditro
40
M
5 MO = 3 Na 2 2.75 CaO 0.25 K 2 O
Tvedestrand
41
,r~
H
Orenburg
42
M
5MO = 3Na 2 O 2 CaO
M
Perlenhardt
43
M
M
M
Itterby
44
M
5 MO = 3.25 Na 2 O 1.25 CaO 0.5 MgO
n
H
45
>f
tf
f>
5 MO = 3.25 Na 2 O 1.75 CaO
n
JestreKjorre-
stadb.Bamle
46
M
M
>?
n
Cragie
Bukler
47
6 MO
5 R 2 O 3
1H 2
22 Si0 2
6 MO = 2 Na a O-2.25 CaO-1 MgO-0.75 K 2 O
5 R 2 O 3 = 4.5 A1 2 O 3 0.5 Fe 2 O 3
Jamaica-
Mts. Can.
48
6 MO
5 A1 2 O 3
22 Si0 2
6 MO = 2.25 Na 2 O-3 CaO-0.5 MgO-0.25 K 2 O
9t
Santorine
49
6 MO
5 R 2 O 3
22 SiO 8
6 MO = 2.5 Na 2 O 1.5 CaO 1 K 2 O 0.5 MgO
Buxburn
1H 2
0.5 H 2 O ; 5 R 2 O 3 =4.75 A1 2 O 3 0.25 Fe 2 O 3
50
6 MO
5 A1 2 O 3
22 Si0 2
6 MO = 2.5 Na 2 O 2.25 CaO-1 MgO-0.25 K 2 O
ft
Gebel
2H 2
Duchan
THE FELSPAR GROUP
415
Analyst
Si0 2
A1 2 0,
Fe 2 3
FeO
CaO
MgO
K,0
Na,0
H,0
Total
Hoffmann
Theory
61.29
23.68
,
3.90
2.18
7.91
1.04
100.00
CXLIV
62.05
22.60
3.96
1.80
7.95
0.80
99.91
Heddle
Theory
61.93
22.73
3.94
1.10
8.00
0.42
100.00
LXXI
61.58
22.00
4.19
1.52
8.27
0.54
99.66
Jackson
Theory
62.05
23.98
3.95
0.94
8.02
1.06
100.00
CXLIII
62.03
24.40
3.50
0.70
8.07
1.00
99.67
Streng
Theory
61.11
23.61
1.66
3.89
1.09
7.80
0.84
100.00
XII
60.94
24.22
1.66
3.94
0.95
7.65
0.79
100.15
Dirvell
Theory
61.39
23.72
4.56
0.46
1.09
7.93
0.85
100.00
LXXXIII
61.84
24.77
4.20
0.30
0.88
8.14
0.50
100.63
Theory
62.68
24.22
2.66
2.33
7.36
0.85
100.00
LXXVII
63.53
24.05
2.60
1.86
8.02
0.90
100.96
Konig
Theory
61.28
23.68
5.19
1.09
7.91
0.85
100.00
CXIV
60.69
24.24
0.71
4.63
1.28
7.75
0.85
100.15
Haughton
Theory
61.81
23.87
5.24
1.10
7.98
100.00
LXXV
61.88
24.80
4.93
0.98
8.12
100.71
Pisani
Theory
61.81
23.87
5.24
1.10
7.98
100.00
LXXXVII
62.25
24.80
0.25
4.90
0.80
7.80
0.20
101.00
Siemiradzki
Theory
62.08
23.98
5.92
,
8.02
.
100.00
CXXIV
61.58
25.30
6.08
8.14
101.10
Fellner
Theory
59.43
22.97
1.96
6.35
8.37
1.62
100.00
XXXV
60.28
22.40
1.17
0.09
6.37
8.44
1.61
100.36
Scheerer
Theory
61.75
23.86
4.58
1.10
8.71
100.00
LXXXVI
61.30
23.77
0.36
4.78
1.29
8.50
100.00
G. v. Rath
Theory
61.75
23.86
4.58
1.10
8.71
100.00
CXVII
60.34
24.39
0.18
5.56
0.73
8.44
0.33
99.97
Theory
62.04
23.96
5.26
8.74
100.00
XV
62.18
23.52
5.33
8.97
100.00
Jannetaz
Theory
62.04
23.96
5.26
8.74
100.00
XCV
63.19
23.52
4.81
9.01
100.53
Berzelius
Theory
62.23
24.04
3.29
0.94
9.50
100.00
XCIII
61.55
23.80
3.18
0.80
0.38
9.67
99.38
G. v. Rath
Theory
61.98
23.95
4.61
9.46
100.00
LXXXIX
61.91
23.68
4.45
9.64
100.00
Haughton
Theory
61.98
23.95
4.61
9.46
100.00
LXXII
62.00
23.20
4.71
9.20
100.00
Hunt
Theory
59.26
20.16
3.59
5.66
1.80
3.16
5.57
0.80
100.00
CXLVII
58.60
21.10
2.88
5.40
1.84
3.08
5.51
0.80
99.21
Fouque
Theory
60.52
23.39
7.71
0.92
1.07
6.39
100.00
LI
59.70
23.20
0.40
7.90
1.00
0.80
6.60
99.60
Heddle
Theory
59.34
21.78
1.80
3.77
0.90
4.23
6.97
1.21
100.00
LXIX
59.53
21.05
1.81
3.63
0.88
4.73
7.23
1.88
100.74
Delease
Theory
59.71
23.07
5.70
1.81
1.06
7.01
1.64
100.00
CXLVIII
58.92
22.49
0.75
0.60MnO
5.53
1.87
0.93
6.93
1.64
99.60
416
THE FELSPAR GROUP
B.
sVR-Si-Si-R-
Felspars of the type
Si = 5 R 2 3 24 Si0 2
Source
51
4 MO 6 A1 2 O 3 24 SiO 2
4MO = 2.25Na 2 0.5 CaO 0.75 K 2 O
Oligoclase
Lessines
1H 2
0.5 MgO
62
4MO-5R 2 3 -24Si0 2
4 MO = 2.75 Na 2 - 0.75 CaO - 0.5 K 2 O
M
Old Meldrum
63
5MO-5Al 2 3 -24SiO 2
5MO = 2.25Na 2 O 2.5 CaO 0.25 K 2 O
;
Furth
64
5 MO = 2.5 Na 2 O 1 CaO 1 K 2 O 0.5 MgO
M
Hartenberg
55
,
5 MO = 2.5 Na 2 O 1.5 CaO 0.75 H 2 O
m
Visembach
0.25K 2
56
,,
5 MO = 2.5 Na 2 O 1.5 CaO 1 K 2 O
, t
Pierrepont,
N.S.
57
5 MO = 2.75 Na 2 O-0.75 CaO-1 K 2 O-0.5 MgO
?>
Ajatskaja
5 R 2 O 3 =4.5 A1 2 O 3 0.5 Fe 2 O 3
58
5MO-5R 2 O 3 24Si0 2
5 MO = 2.75 Na 2 O 1.5 CaO 0.5 H 2 O
M
Coyle,
0.25K 2
Aberdeen
59
5MO-5Al 2 O 3 -24Si0 2
5 MO = 3 Na 2 O - 0.75 CaO-1 K 2 O-0.25 MgO
n
Pico de
Teneriffe
60
M
61
5 MO 5 A1 2 O 3 24 SiO 2
1H 2
5 MO-3 Na 2 O 1 CaO 0.5 K 2 O 0.5 H 2 O
"
Badenweiler
62
5 MO 5 A1 2 O 3 . 24 SiO 2
5 MO = 3 Na 2 O 1.5 CaO 0.5 K 2 O
'
Wittichen
63
> >
M
Gaggenau
64
.> >
5 MO = 3.25 Na 2 O 1 MgO 0.75 K 2 O
Laacher See
65
5MO = 3.25Na 2 1.25 CaO 0.25 MgO
n
Coromandel
0.25 K 2
66
5MO-5Al 2 O 8 '24SiO 2
5 MO = 3.25 Na 2 O -1.5 CaO 0.25 K 2 O
n
Veltlin
67
Niedermendig
68
M
Itterby
69
,-
(Granite)
70
M
Lairg
71
5 MO 5 A1 2 O 3 24 SiO 2
5 MO = 3.5 Na 2 O 0.5 CaO 0.75 K 2 O
Pico de
0.25 MgO
Teneriffe
72
5 MO = 3.5 Na 2 O 0.75 CaO 0.5 K 2 O
n
Arendal
0.25 MgO
73
5 MO = 3.5 Na 2 O 0.75 CaO 0.75 K 2 O
"
Boden
74
5 MO = 3.5 Na 2 O 1.25 CaO 0.25 K 2 O
n
Danbury,
Conn.
THE FELSPAR GROUP
417
or the general formula
mMO 5R 9 0, 24S10.
n H 9 0.
Analyst
| SiO s
Al,0,
Fe,0,
FeO
CaO
MgO
K,O
NajO
H,0
Total
Delesse
Theory
LXI
64.66
63.70
22.91
22.64
0.53
1.28
1.44
0.90
1.20
3.17
2.81
6.27
6.15
0.81
1.22
100.00
99.69
Heddle
Theory
LXVIII
64.75
64.67
21.78
22.18
1.80
1.44
z
1.89
1.89
0.02
2.11
1.54
7.67
7.64
0.15
100.00
99.53
v. Giimbel
Theory
XXXI
63.92
64.40
22.64
23.07
z
0.27
6.21
5.61
1.04
0.96
6.19
5.85
100.00
100.16
G. v. Rath
Theory
XIV
63.30
63.50
22.42
21.81
0.66
~
2.46
2.32
0.88
0.95
4.13
3.65
6.81
6.84
100.00
99.81
Delesse
Theory
XXIII
64.69
63.88
22.91
22.27
3.77
3.45
1.06
1.21
6.96
6.66
0.61
0.70
100.00
98.68
Penfield and
Sperry
Theory
CXL
63.08
63.76
22.34
22.67
0.41
3.68
3.05
4.12
3.60
6.78
6.89
0.40
100.00
100.78
Francis
Theory
CXI
62.45
61.06
19.92
19.68
3.48
4.11
1.82
2.16
0.87
1.05
4.07
3.91
7.39
7.55
-
100.00
99.52
Heddle
Theory
LXVII
63.95
63.54
21.54
21.45
1.78
1.86
3.73
3.88
0.23
1.04
1.07
7.57
7.64
0.39
0.44
100.00
100.11
Delesse
Theory
CXLIX
63.11
62.97
22.35
22.29
1.84
2.06
0.44
0.54
4.11
3.69
8.15
8.45
100.00
100.00
>
Theory
CL
63.11
62.54
22.35
22.49
1.84
2.18
0.44
0.41
4.11
4.54
8.15
7.84
100.00
100.00
Wollemann
Theory
XXIV
63.55
63.22
22.51
22.95
2.47
2.50
~
2.07
1.93
8.21
8.12
1.19
1.36
100.00
100.35
Hebenstreit
Theory
XXV
63.52
62.90
22.50
22.23
3.71
4.45
~
2.07
2.09
8.20
8.48
100.00
100.15
Seneca
Theory
XXVIII
63.52
63.63
22.50
22.52
3.71
3.85
0.44
2.07
2.29
8.20
8.39
-
100.00
100.12
Fouque
Theory
XIX
63.66
63.50
22.55
22.10
0.30
1.77
1.80
3.11
3.40
8.91
8.90
100.00
100.00
Pisani
Theory
CXXI
63.86
64.00
22.63
23.50
3.10
2.72
0.44
0.60
1.04
0.77
8.93
9.00
0.16
100.00
100.75
G. v. Rath
Theory
XLVI
63.74
64.58
22.58
23.08
3.72
3.49
~
1.04
0.62
8.92
8.98
100.00
100.75
>
Theory
XVII
63.74
63.06
22.58
23.27
3.72
4.16
~
1.04
0.62
8.92
8.93
100.00
100.04
Lemberg
Theory
XCIX
63.74
63.38
22.58
22.98
3.72
3.62
~
1.04
0.55
8.92
9.10
0.37
100.00
100.00
G. v. Rath
Theory
CXIII
63.74
63.83
22.58
22.58
3.72
3.42
1.04
1.02
8.92
8.86
100.00
100.15
Heddle
Theory
LXXIII
63.74
62.81
22.58
22.92
0.16
3.72
4.25
0.08
1.04
0.84
8.92
8.53
0.29
100.00
99.88
Delesse
Theory
CLI
63.28
63.81
22.43
21.98
1.23
1.10
0.44
0.66
3.09
2.99
9.54
9.46
100.00
100.00
Hagen
Theory
LXXVI
63.56
63.51
22.51
23.09
1.85
2.44
0.44
0.77
2.07
2.19
9.57
9.37
100.00
101.37
Kerndt
Theory
IV
63.17
61.66
22.38
22.56
0.35
0.40 MnO
1.84
2.02
0.10
3.09
3.08
9.52
9.43
~
100.00
100.00
Smith and
Brush
Theory
CXLI
63.71
63.76
22.56
22.56
z
3.09
3.09
z
1.04
0.55
9.60
9.72
0.26
100.00
99.94
2 E
418
THE FELSPAR GROUP
Source
75
5 MO 5 AljjO, 24 SiO 2
5MO = 3.5Na 2 O 1.25 CaO 0.25K 2 O
Oligoclase
Telemarken
76
5 MO 5 A1 2 O 3 24 SiO 2
1H 2
5 MO = 3.5 Na 2 O 1.5 CaO
Srnin
77
5 MO 5 A1 2 O 3 24 SiO 2
5 MO = 4 Na 2 O 0.75 CaO 0.25 K 2 O
M
Turin
78
6 MO 5 A1 2 O 3 24 SiO 2
6 MO = 2. 75 Na 2 O 2.25 CaO 0.5 FeO
Kyffhauser
0.25MgO-0.25K 2 O
79
6 MO = 3.25 Na 2 2.75 CaO
-
Alagnon
80
6MO = 4Na 2 O-2CaO
Pargas
C. Felspars of the type
Si R Si Si R Si = 6 R 2 3 20 Si0 2
Source
81
5MO-6Alo0 3 -20SiO 2
5 MO = 1.75 Na 2 O-2.75 CaO 0.25 MgO
Andesine
St. Raphael in
1 H 2 "0
0.25 H 2 O
Esterelgebirge
bei Trejus
82
5MO-6Al 2 3 -20SiO 2
5 MO = 2 Na.O 2.75 CaO 0.25 K 2 O
M
Dubnick
4H 2
83
5MO-6Al 2 3 -20SiO 2
5MO = 2Na 2 O-3CaO
M
Adamelle-
Gebirge
84
5 MO 6 R 2 O 3 20 SiO 2
5 MO = 2.25 Na 2 O-2.5 CaO-0.25 MgO
Descaberado
6 R 2 O 3 = 5.5 A1 2 O 3 0.5 Fe 2 O 3
Chico
85
6 MO 6 A1 2 O 3 20 SiO 2
6MO=4.75CaO-1.25FeO
Labradorite
Silicite, Antrim
1H 2
86
6 MO 6 A1 2 O 3 20 SiO 2
6MO = 1.25Na 2 0-3.25CaO-0.75K 2 O
,,
Lakonien
3H 2
0.5MgO-0.25H 2 O
87
6MO-6R 2 O a -20SiO 2
6 MO = 1.25 Na 2 O 4 CaO 0.5 MgO
tt
Nicolosi
0.25 K 2 O ; 6 R 2 O 3 =5.5 A1 2 O 3 -0.5 Fe 2 O 3
88
99 99 99
6 MO = 1.25 Na 2 O 4.25 CaO 0.5 H 2 O
n
Kiew
6 R 2 O 3 =5.75 A1 2 O 3 0.25 Fe 2 O 3
89
6 MO 6 A1 2 O 3 20 SiO 2
6 MO = 1.25 Na 2 O 4.25 CaO 0.5 K 2 O
Andesine
Tunguragua
90
6MO-6R 2 O 3 -20Si0 2
6 MO = 1.25 Na 2 O 4.5 CaO 0.25 MgO
Labradorite
Lhama
6 R 2 O 3 =5.75 A1 2 3 0.25 Fe 2 O 3
91
6 MO 6 A1 2 O 3 20 SiO 2
6MO = 1.5Na 2 3.5 CaO 0.75 FeO
Andesine
Recsk b. Erlau
2H 2
0.25K 2 O
92
6MO-6Al 2 O 3 --20SiO 2
6 MO = 1.5 Na 2 O 4.5 CaO
Muretto Pass
93
6MO-6Al 2 O 3 -20SiO 2
2H 2
6 MO = 1.75 Na 2 O 3 CaO 0.75 K 2 O
0.25MgO-0.25H 2 O
Odenwald
94
6MO-6Al 2 3 -20Si0 2
6 MO = 1.75 Na 2 O 3.25 CaO 0.75 H 2 O
Oberstein
3H 2
0.25K 2
95
6MO-6R 2 O 3 -20Si0 2
6 MO = 1.75 Na 2 O 3.5 CaO 0.5 H 2 O
>
ChateauRicher,
0.25 K 2 O; 6 R 2 O 3 =5.75A1 2 O 3 -0.25 Fe 2 O 3
Canada
96
6 MO 6 A1 2 O 3 20 SiO 2
6 MO = 1.75 Na 2 O 4 CaO 0.25 K 2 O
>
Le Prese
97
99
Hohe Wald,
Odenwald
THE FELSPAR GROUP
419
Analyst
SiO,
A1 2 0,
Fe,0,
FeO
CaO
MgO
K,0
Na,0
H,o
Total
Pisani
Theory
LXXXVIII
63.71
65.30
22.56
23.00
3.09
2.42
z
1.04
0.70
9.60
9.65
0.20
100.00
101.27
C. v. Hauer
Theory
XXXIII
63.46
63.16
22.49
23.16
z
3.70
3.00
~
0.17
9.56
9.72
0.79
0.79
100.00
100.00
Rocholl
Theory
XLVII
63.62
62.52
22.53
22.40
-
1.85
2.29
~
1.04
1.19
10.96
10.78
100.00
99.18
Streng
Theory
XI
60.76
60.01
21.52
21.66
-
~
5.32
5.15
0.42
0.68
0.99
1.37
7.19
7.06
2.28
2.59
100.00
100.08
Fouque
Theory
LIX
62.46
62.40
22.12
22.80
-
~
6.68
7.00
~
0.50
8.74
8.40
100.00
101.10
Bonsdorff
Theory
CI
62.34
62.03
22.08
21.34
1.00
~
4.84
4.86
z
10.74
10.77
100.00
100.00
or the general formula
m MO 6 R 2 3 20 Si0 2 n H 2 0.
Analyst
Si0 2
Al,0 3
Fe,0,
FeO
CaO
MgO
K,0
Na 8
H a O
Total
Deville
Theory
56.96
29-04
7.31
0-47
5.15
1.07
100.00
LVII
57.01
28.05
7.53
0.39
0.12
5.47
1.43
100.00
K. v. Hauer
Theory
54.91
28.00
__
7.05
1.08
5.67
^_
100.00
XXXVII
55.61
28.64
7.00
1.55
5.59
101.63
Val. San
Theory
57.04
29.09
7.98
5.89
100.00
Valentino
XLIX
56.79
28.48
8.56
0.34
6.10
0.24
100.51
Domeyko
Theory
56.33
26.33
3.75
6.57
0.47
6.55
100.00
XCII
55.30
26.50
4.30
6.20
0.60
6.70
99.60
Thomson
Theory
54.90
28.00
4.12
12.17
0.81
100.00
LXXVI
54.80
28.40
4.00
12.40
0.60
100.20
Delesse
Theory
54.04
27.56
8.19
0.90
3.18
3.49
2.64
100.00
CXXI
53.20
27.31
1.03
8.02
1.01
3.40
3.52
2.51
100.00
S. v. Walters-
Theory
54.90
25.66
3.66
10.25
0.91
1.08
3.54
100.00
hausen
LXXI
55.83
25.31
3.63
10.49
0.74
0.83
3.52
100.35
Segeth
Theory
55.79
27.27
1.86
11.07
3.60
0.41
100.00
CXVIII
55.49
26.83
1.60
10.93
0.15
0.36
3.96
0.51
99.83
Siemiradzki
Theory
55.19
28.14
10.95
2.16
3.56
100.00
cm
54.89
28.97
10.28
1.72
3.61
99.47
Koto
Theory
55.41
27.07
1.85
11.63
0.46
3.58
100.00
CXXVIII
55.97
27.60
1.68
11.88
0.66
0.08
3.83
101.70
K. v. Hauer
Theory
54.19
27.63
2.43
8.85
1.06
4.20
1.64
100.00
XXXVI
53.99
26.78
2.22
9.09
0.30
0.82
4.21
1.90
99.31
Mattirolo
Theory
55.63
28.37
11.68
4.32
100.00
LII
55.53
28.38
11.72
4.13
0.24
100.00
Behr
Theory
54.32
27.70
7.60
0.45
3.19
4.91
1.83
100.00
XIX
54.70
27.49
0.55
7.64
0.42
2.76
4.64
1.65
99.85
Delesae
Theory
54.71
27.90
8.30
1.07
4.94
3.08
100.00
XI
53.89
27.66
0.97
8.28
1.28
4.92
3.00
100.00
Hunt
Theory
55.47
27.11
1.85
9.06
1.08
5.01
0.42
100.00
CXXII
55.80
26.90
1.53
9.01
0.27
0.86
4.77
0.45
99.59
G. v. Rath
Theory
55.36
28.23
10.33
1.08
5.00
100.00
LI
55.15
29.15
9.90
0.80
5.23
100.23
Swiatkowski
Theory
55.36
28.23
10.33
1.08
5.00
100.00
XVIII
55.24
29.02
9.91
0.19
1.31
5.13
100.80
420
THE FELSPAR GROUP
Source
98
6MO-6A1 2 3
20 SiO 2
6 M0 = 1.75 Na 2 - 4 CaO 0.25 K 2 O
Labrador! te
Labrador
99
5J
> * }>
100
J> ?>
it
j it
n
Campsie
101
>
Schriesheim
102
i
6 MO = 1.75 Na 2 O 4 CaO 0.25 H 2 O
"
Suligata
103
w
>
>
Nagyag
104
105
5J
Piatra
Poienitia
Palma
106
JJ
M
>
,,
Rotundo
107
pi
> >
H
Kisbanya
108
J>
n
6 MO = 1.75 Na 2 O 4.25 CaO
Andesine
Pomasque
109
>5 >J
5>
6 MO = 2 Na 2 O 3. 75 CaO 0. 25 K 2 O
5>
Langlangchi
110
6 MO 6 R 2 O 8
20SiO 2
6 MO = 2 Na 2 3.75 CaO 0.25 MgO
6 R 2 O 3 =5.25 A1 2 O 3 0.75 Fe 2 O 3
Labradorite
Baumholder
111
7 MO 6 A1 2 O S
20 SiO 2
7 M0 = 0.5 Na 2 3.75 CaO 1.75 K 2 O
0.75 H 2 0- 0.25 MgO
"
Labrador
112
7 MO 6 R 2 O 3
20 SiO 2
7 MO = 1.5 Na 2 0-3.75 CaO-1 MgO-0.5H 2
0.25 MnO;6 R 2 O 3 =5.75 A1 2 O 8 -0.25 Fe 2 O 3
>?
Val del Bove
113
7 MO 6 R 2 O 3
1H 2 O
20 SiO 2
7MO-1.5Na 2 0-4CaO-lMgO-0.25 MnO
0.25H 2 O ; 6R 2 O 3 =5.75Al 2 O 3 -0.25Fe 2 O 3
>
Etna
114
7MO-6R 2 O 3 -
1H 2
20 SiO 2
7 MO = 1.5 Na 2 4.75 CaO 0.25 MgO
- 0.25 K 2 0- 0.25 H 2 O
Mascali
115
7MO-6A1 2 3
1H 2 O
20 SiO 2
7 MO = 1.5 Na 2 O 4.75 CaO 0.5 MgO
0.25 K 2 O
Montarville
116
7MO-6A1 2 3
2H 2 O
20 SiO 2
7MO = 1.75Na 2 3 CaO 0.75 H 2 O
0.75 FeO 0.5 MgO - 0.25 K 2 O
Andesine
Ilfeld
117
7 MO 6 A1 2 O 3
20 SiO 2
7MO = 1.75Na 2 4.5 CaO 0.5 FeO
0.25K 2 O
Labradorite
Labrador
118
'
H
7 MO = 2 Na 2 O 4.25 CaO 0.5 H 2 O
0.25K 2
Monte Amiata
119
> j>
7MO = 2Na 2 O-5CaO
Geschiebe bei
Berlin
120
7MO-6A1 2 3
1H 2 O
20 Si0 2
7 MO = 2.25 Na 2 O 3.75 CaO 0.5 H 2 O
0.5K 2
Andesine
Illowa
121
7MO-6A1 2 3
20 Si0 2
7 MO = 2.25 Na 2 O 3.75 CaO 0.75 H 2 O
0.25K 2 O
>
Rawdon
122
8 MO 6 R 2 O 3
20 SiO 2
8 MO = 2.75 Na 2 O 5.25 CaO
>
Los
Pescadores
THE FELSPAR GROUP
421
Analyst
| SiO,
A1.0,
Fe,0 s
FeO
CaO
MgO
K,0 | Na a O
H a O
Total
Tschermak
Theory
CLII
55.35
56.00
28.23
27.50
0.70
z
10.33
10.10
0.10
1.08
0.40
5.01
5.00
100.00
99.80
Klement
Theory
CLIII
55.35
56.10
28.23
27.33
1.38
10.33
10.33
~
1.08
0.36
5.01
5.17
100.00
100.75
Lehunt
Theory
LXXXIX
55.35
54.67
28.23
27.89
0.31
0.18 MnO
10.33
10.60
~
1.08
0.49
5.01
5.05
100.00
99.19
Theory
XXIX
55.35
55.24
28.23
29.02
~
10.33
9.91
0.19
1.08
1.31
5.01
5.13
100.00
100.80
Belter
Theory
XLI
55.35
55.22
28.23
28.93
10.33
9.95
~
1.08
0.28
5.01
5.01
100.00
99.39
Theory
XLIII
55.35
54.76
28.23
29.09
10.33
10.10
1.08
0.62
5.01
5.00
-
100.00
99.57
Theory
XLII
55.35
55.95
28.23
28.41
___
10.33
9.85
z
1.08
0.43
5.01
5.05
100.00
99.67
G. v. Rath
Theory
CLXXI
55.35
55.64
28.23
28.89
__
10.33
10.92
z
1.08
0.71
5.01
5.09
-
100.00
101.25
Delter
Theory
XLIV
55.35
55.93
28.23
28.15
z
10.33
9.84
z
1.08
0.69
5.01
5.27
100.00
99.88
Delesse
Theory
XLVIII
55.35
56.05
28.23
28.11
10.33
10.10
1.08
0.99
5.01
4.65
100.00
99.90
G. v. Rath
Theory
CV
55.60
55.86
28.35
28.10
11.03
10.95
5.02
5.09
100.00
100.00
Theory
XCVII
55.31
55.64
28.21
28.19
1.02
9.68
9.79
0.19
1.08
2.63
5.72
5.48
100.00
100.44
E. E. Schmid
Theory
XXI
54.56
53.41
24.35
24.88
5.46
4.89
9.55
9.42
0.44
0.44
5.64
5.62
100.00
98.66
S. v. Walters-
hausen
Theory
CLI
53.55
53.75
27.31
27.06
0.99
9.37
9.58
0.45
0.47
7.34
7.53
1.38
1.25
0.60
0.62
100.00
101.25
Abich
Theory
LXVII
54.63
53.48
26.71
26.46
1.82
1.60
0.81 MnO
0.89 MnO
9.56
9.47
1.82
1.74
0.22
4.23
4.10
0.42
0.42
100.00
98.40
Ricciardi
Theory
LXXII
53.51
53.33
26.15
26.13
1.78
2.87
0-79 MnO
0.59 MnO
9.99
10.34
1.78
1.64
1.05
0.51
4.15
3.97
0.80
0.84
100.00
100.22
S. v. Walters-
hausen
Theory
LXX
53.19
53.56
24.87
25.82
3.55
3.41
11.79
11.68
0.44
0.52
1.04
0.58
4.12
4.00
1.00
0.95
100.00
100.42
Hunt
Theory
CXLV
53.75
53.10
27.42
26.80
1.35
11.92
11.48
0.89
0.72
1.05
0.71
4.16
4.24
0.81
0.60
100.00
99.00
Streng
Theory
III
53.68
53.11
27.38
27.27
z
2.42
2.53
7.51
7.47
0.89
0.91
1.05
1.08
4.85
5.09
2.22
2.38
100.00
99.84
Jannasch
Theory
CLV
53.76
54.09
27.42
27.82
-
1.61
1.50
11.29
11.20
0.05
1.06
0.43
4.86
4.76
0.19
100.00
100.04
Williams
Theory
LVIII
54.38
55.04
27.74
28.09
~
10.79
10.65
z
1.06
1.26
5.62
5.61
0.41
0.50
100.00
101.15
Dulk
Theory
VII
54.15
54.66
27.62
27.87
12.64
12.01
5.59
5.46
z
100.00
100.00
K. v. Hauer
Theory
XL
53.69
54.53
27.37
27.37
9.39
9.62
2.10
1.81
6.24
5.98
1.21
1.21
100.00
100.52
Hunt
Theory
CXXVI
54.58
54.45
27.84
28.05
0.45
z
9.55
9.68
z
1.07
1.06
6.35
6.25
0.61
0.55
100.00
100.49
Domeyko
Theory
XCI
52.38
50.50
25.60
25.40
1.75
2.10
z
12.83
12.25
0.35
___
7.44
7.30
0.04
100.00
97.94
422
THE FELSPAR GROUP
D. Felspars of the type
Si R Si Si R Si = 6 R 2 3 22 Si0 2
Source
123
4 MO
6R 2 3
22 SiO 2
4 MO = 2.5 Na 2 O 0.5 CaO 0.5 MgO
Andesine
Mairus (Ar-
3H 2
0.5K 2 O ; 6R 2 O 3 =5.75Al 2 O 3 -0.25Fe 2 O 3
dennes)
124
5 MO
6A1 2 3
22 SiO 2
5 MO = 2. 75 Na 2 O -2.25 CaO
Jt
Tilasinvuori
2H 2
125
6 MO
6 A1 2 O 3
22 Si0 2
6 MO = 1.75 Na 2 3.25 CaO 0.75 H 2 O
0.25 MgO
M
St. Raphael
in Esterelgeb.
126
99
j?
99
6 MO = 2 Na 2 O 3.25 CaO 0.5 H 2 O
>f
Chateau
0.25K 2
Richer, Can.
127
99
99
6 MO = 2 Na 2 O 3.25 CaO 0.5 H 2 O
?J
Lachute
0.25 K 2 O
128
6 MO
6A1 2 O 3
22 SiO 2
6 MO = 2 Na 2 O 3.5 CaO 0.5 K 2 O
J?
St. Raphael
1H 2
in Esterelgeb.
129
6 MO
6A1 2 O 3
22 SiO 2
6 MO = 2 Na 2 3.75 CaO 0.25 K 2 O
-
St. Joachim
130
6MO = 2Na 2 O-4CaO
Labradorite
Ojamo
131
M
79
>
6 MO = 2.25 Na 2 O 3.5 CaO 0.25 K 2 O
Andesine
St. Raphael
in Esterelgeb.
132
M
M
Labradorite
Labrador
133
--
Krakatan
134
6 MO
6A1 2 3
22 SiO 2
Andesine
Chateau
1H 2
Richer, Can.
135
6 MO
6 A1 2 O
22 SiO 2
s>
Sanford, Me.
2H 2 O
136
6 MO
6A1 2 3
22 SiO 2
6 MO = 2.25 Na 2 O 3.75 CaO
Tunguragua
137
6 MO = 2.5 Na 2 O 3.25 CaO 0.25 MgO
M
Nieder-
mendig
138
ft
M
tf
6 MO = 2.5 Na 2 O 3.5 CaO
?>
Guaqua
Pichincha
139
J>
Trifail
140
M
>
,,
Labradorite
Ojamo
141
7 MO
6A1 2 3
22 SiO 2
7 MO = 1.75 Na 2 O 4 CaO 0.75 H 2 O
Andesine
Gratlue
2H 2
0.5 K 2 O
142
7 MO
6A1 2 3
22 Si0 2
7MO = 1.75 Na 2 O 4.25 CaO 0.75 H 2 O
Labradorite
Monte
1H 2
0.25 K 2 O
Amiata
143
7 MO
6A1 2 3
22 Si0 2
7 MO = 1.75 Na 2 O 5 CaO 0.25 MgO
Verespatek
144
7 MO = 2 Na 2 O 3 CaO-1 FeO-0.75 K 2 O
Andesine
Luccivna,
0.25 MgO
N. Tatra
145
7 MO
6A1 2 3
22 SiO 2
7 MO = 2 Na 2 O-3 CaO-1 FeO-0.75 K 2 O
}r
,,
5H 2 O
0.25 MgO
146
9 MO
6 A1 2 3
22 SiO 2
9 MO = 2 Na 2 O -6.75 CaO -0.25 MgO
}>
St. Raphael
3H 2 O
in Esterelgeb
THE FELSPAR GROUP
423
or the general formula
m MO 6 R 2 3 22 Si0 2 n H 2 0.
Analyst
Si0 2
A1 2 0,
Fe 2 3
FeO
CaO
MgO
K 2
Na 2
H 2
Total
Klement
Theory
58.65
26.06
1.78
1.24
0.89
2.09
6.89
2.40
100.00
LXVIII
59.78
26.69
2.05
1.35
0.58
1.69
7.29
225
101.68
Wilk
Theory
58.37
27.06
6.16
6.82
1.59
100.00
LXXVIII
58.39
26.68
5.63
7.69
1.61
10000
Deville
Theory
58.78
27.25
8.10
0.44
4.83
0.60
100.00
LVI
59.07
26.67
7.96
0.58
Trace
4.95
0.77
100.00
Hunt
Theory
58.13
26.95
8.02
1.04
5.46
0.40
100.00
CXXI
58.50
25.80
1.00
8.06
0.20
1.16
5.45
0.40
100.57
>?
Theory
58.13
26.95
8.02
1.04
5.46
0.40
100.00
cxxv
58.15
26.09
0.50
7.78
0.16
1.21
5.55
0.45
99.89
Rammelsberg
Theory
56.98
26.41
8.46
2.03
5.35
0.77
100.00
LV
58.32
26.52
8.18
0.11
2.36
5.27
0.60
101.36
Hunt
Theory
57.66
26.72
9.17
1.03
5.42
100.00
CXXIV
57.55
27.10
0.20
8.73
0.79
5.38
99.75
Bonsdorff and
Theory
57.90
26.85
9.82
5.43
100.00
Laurell
CXIV
57.69
26.00
0.67
9.87
5.50
99.73
Rammelsberg
Theory
57.62
26.71
8.55
1.03
6.09
100.00
LIX
58.03
26.64
8.07
0.97
6.16
0.30
99.87
Lemberg
Theory
57.62
26.71
8.55
1.03
6.09
100.00
CLVII
57.36
27.01
8.55
0.65
6.03
100.00
n
Theory
57.62
26.71
8.55
1.03
6.09
100.00
CXXV
58.29
27.19
8.27
1.22
5.82
100.79
Hunt
Theory
57.17
26.51
8.49
1.02
6.04
0.77
100.00
CXXIII
57.20
26.40
0.40
8.34
0.84
5.83
0.65
99.60
Payne
Theory
56.72
26.30
8.42
1.01
6.00
1.55
100.00
CXVI
56.65
25.56
0.22
8.25
1.34
6.18
1.58
99.78
G. v. Rath
Theory
57.86
26.82
9.20
6.12
100.00
CII
57.80
26.75
9.05
6.40
100.00
Laspeyres
Theory
57.92
26.86
7.98
0.44
6.80
100.00
X
57.29
26.78
8.01
0.28
6.84
Trace
99.20
G. v. Rath
Theory
57.82
26.81
8.58
__
6.79
100.00
C "
58.15
26.10
9.05
6.70
100.00
Maly
Theory
57.82
26.81
8.58
6.79
100.00
XLVII
57.53
26.62
8.48
0.23
0.39
6.90
100.15
Williams
Theory
57.82
26.82
8.58
6.78
100.00
cxv
57.75
26.15
0.60
8.48
6.25
99.23
Heddle
Theory
55.91
25.92
9.49
1.99
4.60
2.09
100.00
LXXII
56.30
25.71
0.97
9.35
1.49
4.72
1.82
100.36
Williams
Theory
56.56
26.23
10.20
1.01
4.65
1.35
100.00
LVI
55.68
26.66
10.30
1.43
4.70
1.23
100.00
Sipocz
Theory
56.64
26.26
12.02
0.42
4.66
100.00
XXXVII
55.21
25.56
1.00
11.76
0.53
4.37
101.43
Hofer
Theory
55.54
25.75
3.03
7.07
0.42
2.97
5.22
100.00
XXIX
56.04
25.55
3.12
7.19
0.59
2.59
4.92
100.00
j>
Theory
53.51
24.81
2.92
6.81
0.41
2.86
5.03
3.65
100.00
XXVIII
53.26
24.28
2.96
6.83
0.56
2.47
4.68
3.98
99.02
Deville
Theory
52.84
24.51
15.13
0.40
4.96
2.16
100.00
LVIII
52.42
24.78
15.02
0.51
0.14
5.10
2.03
100.00
424
THE FELSPAR GROUP
Si R Si Si
E. Felspars of the type
R S A i = 6 R 2 O 3 24 Si0 2
Source
147
4 MO 6 R 2 O 3
24 Si0 2
4 MO = 2 Na 2 O 0. 75 CaO 0. 75 K 2 O
Oligoclase
Helsingfors
6H 2 O
0.5 MgO ; 6 R 2 O 3 =5.5 A1 2 O 3 -0.5 Fe 2 O 3
148
4 MO 6 A1 2 O 9
24 SiO 2
4 MO = 2 Na 2 O 1.75 CaO 0.25 K 2 O
if
Tokowaja
149
4 MO = 2.25 Na 2 O 1.5 CaO 0.25 K 2 O
M
Bakersville, N.C.
150
5 MO 6 A1 2 3
24Si0 2
5 MO = 2 Na 2 O 2 CaO 1 K 2 O
Andeaine
Horberig
151
5 MO 6 R 2 O 3
24SiO 2
5MO = 5Na 2 2.25 CaO - 0.75K 2 O
Milltown
5H 2
6 R 2 O 3 = 5.5 A1 2 O 3 0.5 Fe 2 O 3
152
5 MO 6 A1 2 O 3
24 Si0 2
5 M0 = 2.25 Na 2 O 2 CaO 0.75 K 2 O
Oligoclase
Durrmorsbach
2H 2 O
153
5 MO 6 R 2 O 3
24 SiO 2
5 MO = 2.5 Na 2 O 2 CaO 0.5 K 2 O
?
Ardara
6 R 2 O 3 =5.75 A1 2 O 3 0.25 Fe 2 O 3
154
5 MO 6 A1,O 3
24 SiO 2
5 MO = 2.5 Na 2 O 2.5 CaO
Andesine
Milltown
1 H 2 O
Csicso-Berg
155
5 MO 6 A1 2 O
24 SiO 2
5 MO = 2.75 Na 2 O 1.5 CaO 0.75 K 2 O
Oligoclase
Allemont
2 H 2 O '
156
5 MO 6 A1 2 O 3
24SiO 2
5 MO = 2.75 Na 2 O 1.5 CaO 0.5 MgO
>
Bourg d'Ofsans
2 H 2 O
0.25K 2 O
157
5 MO 6 A1 2 3
24 Si0 2
5MO = 3Na 2 O-2CaO
>
Carter-MineN.C.
158
6 MO 6 A1 2 3
24 SiO 2
6 MO = 1.5 Na 2 4 CaO 0.25 K 2 O
Andesine
Kyffhauser
1H 2
0.25 FeO
159
6 MO 6 A1 2 3
24 SiO 2
6 MO = 2 Na 2 O 3.25 CaO - 0.5 H 2 O
M
Chateau Richer,
0.25 K 2
Canada
160
6 MO = 2.25 Na 2 O 3.25 CaO-0.25 MgO
>
Frauenberg bei
0.25K 2
Schluchtern
161
6 MO 6 A1 2 O 3
24 SiO 2
6 MO = 2. 5 Na n O 2.25 CaO 0.75 MgO
n
La Bresse
1H 2
0.5K 2
162
6MO-6A1 2 3
24 SiO 2
6 MO = 2.5 Na 2 O 2.5 CaO 0.5 K 2 O
19
Cullakenee,
1H 2
0.5 H 2 O
Clay Co., N.C.
163
6 MO 6 A1 2 O 3
24SiO 2
6 MO = 2.5 Na 2 O 2.5 CaO 0.75 H O
n
Faymont
1H 2
0.25 K 2
164
6 MO 6 A1 2 O 3
24 Si0 2
6 MO = 2.5 Na 2 O 2.5 CaO 0.75 H 2 O
Sebesvar
lH a O
0.25K 2 O
165
6 MO 6 R 2 O 3
24SiO 2
6 MO = 2.5 Na 2 O 2.5 CaO 0.75 MgO
Marmato
0.25K 2 0;6R 2 3 =5.75Al 2 3 -0.25Fe 2 3
bei Popayan
166
6 MO 6 A1 2 O 3
24 Si0 2
6 MO = 2.5 Na 2 O 2.75 CaO 0.5 H 2 O
s>
Coromandel
0.25 K 2 O
167
>j
,,
6 MO = 2.5 Na 2 O 3 CaO 0.25 MgO
t _
Budenmais
0.25 H 2 O
168
>
6 MO = 2.5 Na 2 O 3.5 CaO
>
Pululagua
169
6 MO 6 A1 2 O 3
24Si0 2
6 MO = 2. 75 Na 2 O 1.5 CaO 1 K.O
Oligoclase
Unionville, Pa.
2 H 2 O '
0.5 H 2 0- 0.25 MgO
170
6 MO 6 A1 2 O 3
24 Si0 2
6 MO = 2. 75 Na 2 O 2 CaO 0.5 K 2 O
Andesine
Servance
1H 2 O
0.5 H 2 0- 0.25 MgO
THE FELSPAR GROUP
425
or the general formula
m MO 6 R 2 O 3 24 Si0 2 n H 2 0.
Analyst
SiO a
AIsO,
Fe 2 3
FeO
CaO
MgO
K a O
Na,0
H a o
Total
Lemberg
Theory
58.88
22.94
3.27
1.72
0.82
2.88
5.07
4.42
100.00
CVI
58.30
23.15
4.09
1.65
0.59
2.52
5.26
4.44
100.00
Jewreinow
Theory
62.68
26.64
4.26
1.02
5.40
100.00
cxv
60.63
26.35
0.40
4.15
0.25
1.17
5.60
98.55
Clarke
Theory
62.64
26.61
3.65
1.02
6.07
100.00
CXXIX
62.92
25.32
4.03
0.96
6.18
0.25
99.66
Knop
Theory
60.45
25.69
4.71
3.94
5.21
100.00
XVII
60.01
25.49
4.71
4.06
5.77
100.04
Heddle
Theory
57.81
22.51
3.21
5.06
2.83
4.97
3.61
100.00
LXIX
58.38
22.50
2.12
O.lSMnO
5.34
3.20
5.21
3.41
100.31
Haushofer
Theory
59.75
25.40
4.65
2.92
5.79
1.49
100.00
XXIX
59.30
25.75
4.79
2.78
5.63
1.29
99.54
Haughton
Theory
60.49
24.64
1.68
4.71
1.97
6.51
100.00
LXIII
59.28
22.96
1.94
0.32 MnO
4.65
0.21
2.38
6.48
98.22
Koch
Theorv
60.89
25.88
5.92
6.55
0.76
100.00
XL VI
61.62
25.47
5.72
6.31
0.88
100.00
Lory
Theory
59.68
25.36
3.48
2.92
7.07
1.49
100.00
LIV
59.40
24.20
0.60
3.70
3.80
7.00
1.50
99.80
5>
Theory
60.35
25.65
3.52
0.84
0.98
7.15
1.51
100.00
LV
59.90
25.10
3.70
0.70
1.20
7.40
1.70
99.70
Keller
Theory
61.29
26.04
4.76
7.91
100.00
CXXXI
62.32
25.19
5.01
0.25
8.02
10079
Streng
Theory
59.30
25.20
0.74
9.23
0.96
3.83
0.74
100.00
V *
59.16
25.97
1.04
9.23
0.03
0.47
3.91
0.68
100.49
Hunt
Theory
60.24
25.60
7.61
0.98
5.19
0.38
100.00
CXVII
59.55
25.62
0.75
7.73
Trace
0.96
5.09
0.45
100.15
Wedel
Theory
59.82
25.42
7.65
0.43
0.98
5.79
100.00
VII
59.19
25.77
0.34 (Fe 2 O a +FeO)
7.27
0.27
0.80
5.88
0.37 Ti0 2
99.89
Delesse
Theory
59.31
25.21
5.19
1.24
1.93
6.38
0.74
100.00
XVI
58.55
25.26
0.30
5.03
1.30
1.50
6.44
0.91
99.29
Chatard
Theory
59.48
25.28
5.78
1.94
6.40
1.12
100.00
CXV
58.41
25.93
0.38
5.82
0.18
2.10
6.42
0.93
100.20
Delesse
Theory
59.96
25.48
5.83
0.97
6.45
1.31
100.00
XV
59.38
25.57
6.50
7.03
1.25
100.00
K. v. Haue
Theory
59.96
25.48
5.83
0.97
6.45
1.31
100.00
XLII
59.50
25.48
5.82
1.43
6.43
1.35
100.07
Abich
Theory
59.63
24.28
1.66
5.80
1.24
0.97
6.42
100.00
CVI
59.60
24.28
1.58
5.77
1.08
1.08
6.53
99.92
Dirvell
Theory
60.16
25.57
6.43
0.98
6.48
0.38
100.00
LXXXIV
61.32
25.30
6.50
1.19
6.30
0.50
101.11
Foullon
Theorv
59.79
25.41
6.99
0.41
0.97
6.43
100.00
XXVI
59.22
25.08
0.96
7.08
0.28
0.54
6.79
100.78
G. v. Rath
Theory
59.93
25.47
8.15
6.45
100.00
XCIX
59.39
26.08
820
0.22
6.74
100.63
Chatard
Theorv
58.65
24.92
3.42
0.41
3.83
6.94
1.83
100.00
CXXXVII
59.35
24.16
0.61
3.08
0.34
3.78
7.22
1.96
100.50
Delesse
Theory
59.54
25.31
4.63
0.41
1.94
7.05
1.12
100.00
XIII
58.92
25.05
4.64
0.41
2.06
7.20
1.27
99.50
THE FELSPAR GROUP
Source
171
6 MO 6A1 2 3
24 Si0 2
6MO = 2.75Na,0-2.25CaO-0.75K 2 O
0.25MgO
Oligoclase
Beloceil
172
n
6 MO = 2.75 Na 2 3 CaO 0.25 K 2 O
Andesine
Heubach
173
>
H
J5 >J
(Chateau Richer,
Canada) Toluca
174
>
>
6MO = 3Na 2 1.75 CaO 0.75 H 2 O
0.25MgO-0.25K 2 O
Oligoclase
Norway
175
6MO-6A1 2 3
1H 2
24 SiO 2
6 MO = 3 Na 2 O 1.75 CaO 0.75 K 2 O
0.25MgO-0.25H 2 O
Andesine
Coravillers
176
6 MO 6 A1 2 O 3
1H 2
24 SiO 2
6 MO = 3 Na 2 O-2 CaO-0.5 K 2 O-0.5H 2 O
Oligoclase
Altai
177
6 MO 6R 2 O,
-3H 2 0*
24 SiO 2
6 MO = 3 Na 2 O 2.5 CaO 0.25 MgO
0.25Na 2 0;6R 2 3 =5.75Al 2 3 -0.25Fe 2 3
Andesine
Frankenstein
178
6 MO 6 A1 2 O 3
24 SiO 2
6 MO = 3 Na 2 O 2.75 CaO - 0.25 K 2 O
"
Marmato
bei Popayan
179
>
j>
6MO = 3Na 2 O-3CaO
Mojanda
180
>
H
6MO = 3.75Na 2 O- 2.25 CaO
H
Bodenmais
181
6 MO 6 A1 2 O 3
3H 2
24Si0 2
6MO = 4Na 2 O-2CaO
J>
182
7 MO 6 A1 2 O 8
3H 2
24 SiO 2
7 MO = 2.5 Na,O 3.25 CaO 0.75 H 2 O
"0.5K 2 O
J>
Szaszka
183
7MO-6R 2 3
1H 2
24 SiO a
7 MO = 2.5 Na 2 O 3.5 CaO 0.5 K 2 O
0.5H 2 O;6R 2 O 3 =5.75Al 2 O 3 -0.25Fe 2 O 3
Chateau Richer,
Canada
184
7MO-6A1 2 3
-2H 2
24 SiO 2
7 MO = 2.75 Na 2 O 3.5 CaO 0.75 K 2 O
"
Delnabo
Glen Gairu
185
7 MO 6 A1 2 O,
2H 2
24 SiO 2
7 MO = 3 Na 2 O 3.25 CaO 0.5 K 2 O
0.25H 2
H
Nagy Sebes
186
7 MO 6 A1 2 O 3
24 SiO 2
7 MO = 3 Na 2 O 3.25 CaO 0.5 K 2 O
0.25MgO
*
Marmato
bei Popayan
187
7 MO = 3.5 Na 2 O 3 CaO 0.5 MgO
Oligoclase
Baumgarten
THE FELSPAR GROUP
427
Analyst
Si0 2
A1 2 3
Fe 2 3
FeO | CaO
MgO
K 2
Na t O
H t O
Total
Hoffmann
Theory
CXLV
59.28
58.30
25.19
24.72
Z
5.19
5.42
0.42
0.91
7.02
2.74
7.02
6.72
0.50
100.00
99.32
Petersen
Theory
XX
59.66
58.77
25.36
25.30
0.31 (1
^e 2 O s +FeO)
6.95
6.90
0.18
0.97
0.60
7.06
6.67
0.28 TiO 2
100.00
99.01
G. v. Rath
Theory
CXIII
59.66
59.79
25.36
25.43
6.95
7.41
0.97
0.64
7.06
7.24
100.00
100.51
Dirvell
Theory
LXXV
60.42
61.14
25.68
25.10
4.11
4.39
0.42
0.50
0.99
1.17
7.81
7.66
0.57
0.80
100.00
100.76
Delesse
Theory
XIV
59.04
58.91
25.09
24.59
0.99
4.02
4.01
0.41
0.39
2.89
2.54
7.63
7.59
0.92
0.98
100.00
100.00
Christschoff
Theory
CXVIII
59.16
58.89
25.15
25.38
z
4.60
4.69
1.93
1.35
8.05
7.65
1.11
1.17
100.00
99.25
Schmidt
Theory
I
58.10
58.93
23.70
23.50
1.61
1.27
0.75NiO
0.39 NiO
5.66
5.67
0.40
0.56
0.50
7.52
7.42
2.18
2.21
100.00
100.00
Rammels-
berg
Theory
CVII
59.62
60.26
25.23
25.01
6.38
6.87
0.14
0.97
0.84
7.70
7.74
100.00
100.86
G. v. Rath
Theory
XCVIII
59.85
60.48
25.44
25.35
6.98
7.25
0.08
7.73
7.28
100.00
100.44
A. Ohl
Theory
XXIV
59.74
60.35
25.39
26.13
5.23
5.14
9.64
9.32
100.00
100.94
H. Schulze
Theory
XXIII
5926
58.36
25.17
25.72
4.62
4.76
z
10.21
10.18
0.74
0.51
100.00
99.63
Sommaruga
Theory
XXXIX
57.52
56.51
24.46
24.94
7.26
7.08
z
1.88
1.28
6.19
6.37
2.69
2.55
100.00
98.73
Franke
Theory
cxx
57.80
58.38
23.53
23.86
1.61
1.18
7.87
7.83
1.89
1.68
6.22
6.05
1.08
1.03
100.00
100.11
Heddle
Theorv
LXXI
57.03
56.96
24.23
23.81
0.94
7.77
7.98
0.09
2.79
2.56
6.75
6.85
1.43
1.62
100.00
100.81
K. v. Hauer
Theory
XLI
57.42
57.20
24.41
25.12
~
z
7.26
6.96
__
1.87
1.87
7.42
7.28
1.62
1.68
100.00
100.11
Jacobson
Theory
CVIII
58.13
60.14
24.71
25.39
0.87
z
7.35
7.93
0.40
0.53
1.90
1.66
7.51
7.99
100.00
104.51
Varrentrapp
Theory
III
58.61
58.41
24.92
25.23
6.83
6.54
0.81
0.41
8.83
9.39
100.00
99.98
428
ALLOPHANES AND CLAYS
A. Formulae from a Series of Analyses of Allophanes.
I
0.5 CaO
6 A1 2 3
6 Si0 2 32 H 2
II.
0.5 CaO
6 A1 2 O 3
6 Si0 2
38 H 2 O
Calcd.
Found
1.77
1.92
38.77
37.73
22.96
23.53
36.50
36.86
Calcd.
Found
1.66
1.96
36.29
35.20
21.48
21.39
40.57
40.86
III.
0.75 CaO
6 A1 2 3
6 SiO 2 32 H 2 O
IV.
.25 CaO
6 A1 2 3
5 Si0 2
32H,0
Calcd.
Found
2.63
2.83
38.44
38.76
22.75
22.65
36.17
35.14
Calcd.
Found
0.93
0.70
40.69
41.00
20.07
19.80
-^^-2 ^
38.30
37.70
V. 0.75 CaO 6 Al
2 3
6Si0 2
42H 2
Calcd.
2.37 34.
53
20.45
42.65
Found
2.23 31
.34
20.50
42.91
B. Formulae from Clay Analyses in C. Bischof s Book.
(a) Si E Si.
K,0
MgO
CaO | Fe 2 3
Al,o,
Si0 2
H 2 o
Na 2 o| Total
K 2 o
K a 3
SiOj
H 2 o
5.37
5.65
4.90
4.69
Page | source
2.87
0.27
3.15
1.45
0.28
0.54
0.52
0.54
0.23
0.13
0.10
0.51
0.44
3.06
1.12
0.83
26.73
24.52
26.27
26.93
61.46
62.73
61.35
62.66
8.26
8.88
7.53
7.38
100.27
100.13
100.04
100.30
0.48
0.21
0.56
0.43
3.10
2.98
3.10
3.09
12.00
12.00
12.00
12.00
78
66
68
68
Mahren, Briesen
Goppersdorf, Silesian Prussia
Tschirne, Silesian Prussia
(b) Si - R - Si.
K,o|MgO
CaO
Fe 2 a
A1 2 3 | Si0 2
H 2
Na 8 O
Total
E 2 o
E 2 3
Si0 2
H 2
Page
Source
2.11
2.11
1.24
2.99
1.26
0.88
1.26
0.75
0.73
0.54
0.60
Trace
0.47
0.55
0.37
0.28
0.33
0.24
0.34
0.15
Trace
0.13
0.15
0.40
0.61
0.26
0.34
0.36
0.13
0.28
0.46
0.07
0.12
3.42
1.86
2.03
1.35
1.71
1.04
0.97
1.17
0.89
1.16
0.76
26.94
28.55
27.98
28.31
28.31
29.26
28.88
29.15
29.57
28.68
29.99
58.02
58.35
56.59
59.01
59.78
57.97
58.63
58.26
57.71
59.58
58.04
9.39
8.59
9.92
7.93
8.27
9.98
10.50
10.00
10.68
9.87
10.59
1.08 C.
0.052
0.09 S.
0.08 S.
100.03
100.33
100.15
100.22
100.02
99.91
100.01
100.05
100.19
99.90
100.31
0.26
0.42
0.39
0.46
0.26
0.25
0.22
0.22
0.21
0.07
0.12
2.95
2.99
3.03
2.91
2.89
3.03
2.90
3.02
3.06
2.91
3.08
10.00
10.00
10.00
10.00
10.00
10.00
10.00
10.00
10.00
10.00
10.00
5.39
4.91
5.83
4.48
4.61
5.74
5.97
5.77
6.17
5.52
6.08
71
87
86
53
83
86
71
71
75
71
71
Lothain b. MeiCen, Saxony.
Serge jewka, Russia.
Borowitschi, Russia.
Neitzert i. Bendorf, Prussia.
Sonkolyo, Hungary.
Borowitschi, Russia.
L6thain b. MeiBen, Saxony.
Michelob, Bohemia.
LOthain b. Meifien, Saxony.
(c) R
Si
K.O
MgO
CaO
Fe 2 3
A1 2 3
Si0 2
H 2
Na 2 O
Total
E 2
R 2 3 | SiO z
H 2
Page 1 Source
1.02)
1.77|18.93)72.05)6.13J 0.10 S.|lOO.OO|o.l4|2.98|l8.00J5.12| 59 1 GroBalmerode, Prussia.
(d)
M
K,O
Mgo|cao|Fe 2 O a
A1 2 3 | Si0 8
H 2 o
Na 2 | Total
R 2
K 2 8
SiO 2
H a o
Page
Source
0.55
2.19
0.33
0.16
0.18
0.24
0.63
1.67
23.65
23.08
65.69
65.35
9.11
7.46
0.09 S.
100.23
100.15
0.23
0.43
3.22
3.25
15.00
15.00
6.93
5.70
71
67
LSthain b. MeiSen, Saxony.
Ober-Horka, Prussia.
0.85
0.80
0.08
0.09
0.0V
0.43
1.40
0.71
23.02
23.61
67.48
66.58
7.34
7.90
~*~'
100.24
100.12
0.16
0.25
3.12
3.18
15.00
15.00
5.44
5.93J
50
77
Dillenburg, Prussia.
Blansko, Mahren.
CLAYS
(e) Si R - R Si.
429
K 2
MgO
CaO |Fe 2
A1 2 0, | SiO,
H,0 |Na 2
Total
RaO |R 2 O 8
Si0 2
H 2 O
Page
Source
0.57
1.32
3.00
2.00
0.51
38.46
0.07
0.11
0.18
0.21
0.02
0.06
0.04
0.12
0.32
0.29
2.74
0.95
1.65
0.41
24.51
37.09
37.95
38.17
37.73
28.12
47.22
46.97
44.90
46.21
6.38
10.79
10.02
12.85
14.22
1.87
0.39
100.22
100.19
99.04
99.93
100.02
24.62
0.26
0.54
0.63
0.35
6.19
5.81
5.79
6.16
5.81
12.00
12.00
12.00
12.00
12.00
9.08
6.09
8.53
11.45
12.31
57
74
52
74
57
Westerland, Prussia.
Eger, Austria.
Ebernhalm, Prussia.
Eger, Austria.
Westerland, Prussia.
(f) Si R R Si.
K 2
MgO
CaO
Fe 2 0,
A1 2 0,
SiO,
H 2 o
Na,0
Total
E a o |R,O,| sio,
H 2
Page
Source
4.28 0.950.62
1.2432.72
48.92
11.49
100.23
1.18
4.83
12.00
9.39
78
Briesen, Mahren.
1.64
15.790.13
0.33 29.64
42.53
7.52
2.61
100.91
7.72
4.92
12.00
7.07
57
Westerland, Prussia.
2.73
0.490.32
2.9433.63
49.43
10.59
100.13
0.83
5.09
12.00
8.54
44
G runstadt, Bavaria .
3.211 0.410.48
1.79 ! 33.09
50.72
10.49
100.19
0.75
4.77
12.00
8.27
44
2.30
0.790.56
2.2224.76
49.60
9.96
100.19
0.78
4.91
12.00
8.03
44
99 99
2.65
0.690.34
1.7333.57
50.39
10.85
100.22
0.73
4.86
12.00
8.61
44
3.86
3.14
0.630.43 1.27
0.67 0.40! 2.24
35.39
33.91
49.76
48.92
8.83
10.92
100.17
100.10
0.93
0.84
5.12
5.09
12.00
12.00
7.09
8.84
54
44
H6hr b.Grenzhausen.Prus.
Grunstadt, Bavaria.
3.38
0.550.331 2.07
34.61
48.85
10.18
99.97
0.82
5.19
12.00
8.33
44
99 99
2.73
0.450.34
2.00
33.76
50.12
10.63
100.03
0.67
4.94
12.00
8.48
44
99 99
1.51
0.730.76
1.66
34.95
49.48
11.04
0.26 S.
100.39
0.69
5.13
12.00
8.92
58
Grofialmerode, Prussia.
1.81
0.440.48
1.90
34.09
49.49
11.63
0.036S.
99.87
0.56
5.03
12.00
9.40
46
Gem.Mechenhart,Bavaria.
1.5914.560.02
0.08
30.33
41.14
10.02
2.10
99.84
7.20
5.17
12.00
9.63
57
Westerland,Prussia.
2.66
0.21 0.40
2.00
33.71
49.86
11.13
99.97
0.58
4.95
12.00
8.92
44
GrunstadtjBavaria.
3.79
0.15:0.23
1.1633.71
47.76
13.26
100.06
0.72
5.09
12.00
11.10
80
Briesen, Mahren .
1.33
0.76 0.51! 1.84 35.60
49.66
10.04
99.74
0.67
5.23
12.00
8.09
44
Grunstadt, Bavaria,
2.78 0.180.33
1.06
34.41
50.03
11.46
100.25
0.57
4.95
12.00
9.16
76
Wildstein, Bohemia.
1.30 0.280.05
1.8933.64
48.23
14.63
0.15 S.
100.78
0.32
5.10
12.00
12.13
83
Gflttweig, South Austria.
1.41 0.230.34
1.0034.89
51.17
10.85
99.89
0.38
5.02
12.00
8.48
77
Blansko, Mahren.
1.04 0.290.21
0.60,35.71
50.00
11.98
99.94
0.31
5.08
12.00
9.56
77
> >
(g) Si R Si R Si.
K 2
MgO
CaO |Fe 2 0,
A1 2 S
SiO,
H,0
Na,0
Total
B,o
R,0
SiO,
H,0
Page
Source
2.41
0.38
0.68'0.42| 1.00J30.11
0.250.15|0.70|31.71
56.04
55.47
9.441
11.40|
100.10
100.06
0.96
0.25
5.81
6.13
18.00
18.00
10.10
12.33
68
72
Tschirne, Prussia.
LOthain b. MeiBen, Saxony.
(h) Si R Si R Si.
K,O | MgOJ CaO Fe,0,| A1,O S
SiO, | H 2 O
Na,o
Total |R,O|R,O,
SiO,
H,O
Page
Source
1.67:0.57,0.43
3.01 0.39 0.42
&600.311.31
2.920.28i0.31
1.370.450.49
1.37'0.450.49
0.6l|0.230.13
1.78
2.00
1.20
1.23
1.50
1.50
0.65
31.58
32.54
30.65
33.56
33.11
34.08
33.61
53.1410.69
50.9110.42
50.4015.65
51.961 9.62
54.66; 8.73
53.09 8.71
52.11112.80
0.04
0.10
0.11 S
99.98J0.71
99.790.87
100.120.71
99.84|1.41
99.69,0.61
100.00 ! 0.62
100.14J0.24
5.79
6.25
5.87
6.22
5.93
6.20
6.14
16.00
16.00
16.00
16.00
16.00
16.00
16.00
10.73
10.94
16.56
9.87
8.61
8.75
13.10
46
54
87
76
46
61
71
Gem.Mechenhart,Bavaria.
H6hr b.Grenzhausen,Prus.
Novgorod, Russia.
Wildstein, Bohemia.
Klingenberg a.M. Bavaria.
Ahrtal, Prussia.
Lothain b.MeiBen,Saxony.
(i) Si R - Si R Si.
!K 2
MgO CaO |Fe,0,| A1 2 0,
SiO,
H,o| Na,0
Total |R,O,
B,0,
SiO,
H 2
Page
Source
1.40
1.99
0.34J0.10| 0.72|27.40|60.158.00
030i0.2l| 0.79128.30 60.2118.59
0.21 FeO
98.320.45
100.39|0.57
4.9lH8.00|7.97 84
5.06|l8.00|8.59| 49
Namur, Belgium.
Odenwald,Hessen-Dannstadt.
430
CLAYS
C. Formulae from Clay Analyses in C. Bischofs Book.
I 0.5 CaO 2.75A1 2 O 3 0.25Fe 2 O 3 15SiO 2 5.5 H 2 O
Calcd. 2.06 20.72 2.95 66.95 7.32 /Source : Tiegelerdberg (Bavaria).
Found. 2.25 20.97 2.25 66.70 7.53 \Analyst : H. Kaul, 1. c. p. 47.
II. 0.25 K 2 O 19.75 H 2 O 0.25Fe 2 O 3 9.75A1 2 O 3 24 SiO 2 ( Source : Winkelhaid (Bavaria).
Calcd. 0.82 12.42 1.40 34.73 50.62 \ Analyst : H. Kaul, 1. c. p. 47.
Found. 0.95 12.11 1.38 35.72 49.80 0.15 CaO 0.18 Na 2 O 0.09 S
III. 0.25 MgO 0.25 K 2 0.25Fe 2 O 3 5.75 A1 2 O 3 16SiO 2 1 5. 5 H 2 O/ Source: Wolf shohe (Bavaria)
Calcd. 0.52 1.23 2.09 ' 30.77 50.73 14.64 \Analyst : H. Kaul, 1. c. p. 47.
Found. 0.59 1.09 1.56 31.26 49.61 14.43 0.26 CaO 0.29 Na 2 O
IV. O.SCaO 15.5H 2 O 0.25Fe 2 O 3 5.75A1 2 O 3 16SiO 2 /Source : Passau (South Bavaria).
Calcd. 1.47 14.68 2.10 ' 30.86 50.88 \Kerl, Handb. d. ges. Tonw. 1879, 505, I.e. 48.
Found. 1.63 14.23 1.05 31.11 51.02 0.80 H 2 O
VI.
Calcd.
Found.
0.25 Fe 2 O 3 5.75 A1 2 O 3 16 SiO 2 /Source : Stabbarp (Sweden).
2.51 ' 36.81 * 60.68 \Analyst : Cronquist, Stockholm (I. c. p. 41).
1.70 36.10 60.80 0-5 CaO 0.5 K 2 O 0.2 MgO
VIII.
Calcd.
Found.
0.5 K 2
2.80
3.17
8.5 H 2 O 5 A1 2 O 3 16 SiO 2 /Source : Finsing b. Deggendorf.
9.12 30.41 57.66 \Analyst : C. Bischof, 1. c. p. 43.
8.67 29.47 57.45 0.75Fe 2 O 3 0.76 (MgO + CaO)
IX.
Calcd.
Found.
0.25 Fe 2 O
2.28
1.79
3 5.75 A1 2 O 3 15 SiO 2 0.5 K 2 O 9.5 H 2 O /Source : Grunstadt (Rheinpfalz).
33.50 51.77 2.68 9.77 \ Analyst : C. Bischof .
33.09 50.70 3.21 10.49 0.41 MgO 0.18 CaO
X.
Calcd.
Found.
6A1 2 3
45.78
45.07
12 SiO 2 /Source : Altwasser, Grube Morgen- und Abendstern.
54.22 \Analyst : C. Bischof (L c. p. 36).
54.03 0.15 MgO 0.25Fe 2 O 3 0.54 K 2 O
XI. 0.25K 2 O 0.25CaO 0.25Fe 2 O 3 5.75A1 2 O 3 16 SiO 2
Calcd. 1.44 0.86 2.45 35.96 59.29/Source : Passau (Bavaria).
Found. 0.90 1.20 1.90 36.40 59.60\Analyst : Cronquist, Stockholm, Z.c. p. 48.
XII. 0.25 K 2 O 9.75 H 2 O 0.5Fe 2 O 3 5.5A1 2 O 3 16SiO 2 /Source : Schwarzwald (Oberpfalz).
Calcd. 1.30 9.71 4.42 31.05 53.51 \Analyst : C. Bischof (I. c. p. 48).
Found. 1.33 10.50 3.41 30.69 53.10 0.32 MgO 0.26 CaO
XIII. 12 H 2 O
Calcd. 11.19
Found. 11.14
5.75 A1 2 O 3
30.39
30.47
0.25Fe 2 O 3
2.07
1.51
XIV. 0.5Fe 2 3
Calcd. 4.38
Found. 3.54
5.5 A1 2 3
30.76
31.61
16 SiO 2 :
53.01
52.32
XV. 0.5 Fe 2 O 3
Calcd. 5.54
Found. 4.22
4.5 A1,O 3
31.79
32.00
12 Si0 2
50.20
51.05
18 SiO 2 /Source : Klingenberg a. M.
56.34 \Analyst : unknown (L c. p. 46).
56.44 0.30 MgO 0.79 CaO 0.30 K 2 O
1 2 H 2 O/ Source : Klingenberg a. M.
11.81 \Analyst : Vohl, 1875.
11.81 0.48 CaO
10 H 2 O/ Source : Klingenberg a. M.
12.47 \
12.14 0.46 CaO
XVI. 0.25 MgO 0.25 CaO 0.25 K 2 O 9.25 H 2 O 0.25Fe 2 O 3 5.75A1 2 O 3 16SiO 2
Calcd. 0.55 0.77 1.30 9.21 2.21 32.45 53.50
Found. 0.50 0.50 1.37 9.12 1.50 33.11 54.06
Source : Klingenberg. Analyst : C. Bischof, 1887.
ULTRAMARINES
431
D. Behaviour of Clays, dried at 100 C., towards Sulphuric Acid, according
to C. Bischof.
Number
HjO
K a o
MgO
FeO
%
CaO
A1 2 0,
Fe 2 3
SiO a
Total
Mo
H 2
leculai
K,0
Eatio
E,0s
s
Si0 8
Separated
SiO in
% | Mol.
Al,0,:
SiOi in
Solution
1
2
3
4
5
6
7
9.40
8.41
7.44
10.03
7.27
8.14
15.13
1.15
2.09
2.31
3.22
1.21
1.42
1.61
0.20
0.28
0.25
0.45
0.64
0.34
0.85
0.44
0.40
0.21
0.04
0.56
0.06
0.28
0.08
0.10
0.42
29.96
30.34
25.73
27.99
22.30
27.87
36.32
0.45
0.67
0.60
0.44
0.50
0.73
1.00
58.80
57.65
63.61
56.98
67.60
61.19
44.67
100
100
100
100
100
100
100
9.11
7.83
4.70
10.04
5.41
8.03
11.60
0.31
0.65
0.36
1.01
0.46
0.49
0.75
5.17
5.05
2.91
5.00
2.97
4.93
5.94
17
16
12
17
15
18
12
25.66
21.35
36.68
21.28
41.87
26.91
4.67
7.42
5.8
6.91
6.34
9.29
7.91
1.26
5: 10
5: 10
6: 10
5: 11
6: 10
5: 10
6: 11
Ultramarines.
Formulae from a series of Ultramarine Analyses.
1.
Theory.
Found.
Si
16.60
16.45
Si w
A1 12
16.01
14.36
A1 12
Na 12
13.64
14.45
Na 13 . 5
S 4
6.32
6.00
K -5
60
47.43
48.74
S 4
5?
Total
100.00
100.00
Rickmann, Dingl. Journ.
232,
164.
2.
Theory.
16.55
15.96
15.30
0.96
6.31
44.92
100.00
Found.
16.87
15.39
15.66
0.72
5.69
45.67
100.00
Philipp, Ann. d. Chem.
184,
99
16.81
15.27
15.21
1.08
6.42
45.21
100.00
132.
Si 12
A1 M
Agie
Na 2
S 4
59
(H 2 0) 4
3.
Theory.
9.39
9.06
48.28
1.29
3.58
26.39
2.01
100.00
Found.
9.78
9.40
48.82
1.07
3.96
26.07
1.90
100.00
J. Szilasi, Ann. d. Chem.
251,
M
8.63
9.42
48.79
1.03
4.03
26.29
1.81
100.00
97-114.
Si 12
A1 12
Pb 8
Na 2
S 4
59
(H 2 0) 8
4.
Theory.
9.41
9.08
46.16
1.29
3.59
26.44
4.03
100.00
Found.
9.58
8.21
46.02
0.93
4.06
27.27
3.93
100.00
J. Szilasi, Ann. d. Chem.
251,
9.51
8.16
46.23
1.06
3.94
27.11
3.99
100.00
97-114.
Si
A1 12
Zn 8
Na 2
S 4
59
(H 2 0) 16
5.
Theory.
12.99
12.53
20.11
1.77
4.95
36.51
11.14
100.00
Found.
14.14
11.80
19.78
5.86
37.52
10.90
100.00
J. Szilasi, Ann. d. Chem.
251*
,,
14.17
11.86
19.98
0.72
5.66
36.51
11.10
100.00
97-114.
Si 12 AI 12 Agi, N &1 S 5 O 56 K
6. Theory. 10.69 10.31 44.67 0.73 5.09 28.51
Found. 10.76 9.90 43.69 0.81 4.89 29.60 0.35
10.54 44.08 0.73 0.50
Si 12
7. Theory. 9.96
Found. 10.09
10.09
',', 10.24
8. Theory.
Found.
16.86
16.80
16.84
A1 12
9.60
9.00
9.11
9.21
9.23
A1 M
16.27
16.32
16.30
Ag 15
47.99
48.08
47.89
47.96
48.66
Na 12
13.85
13.94
13.98
,
0.68
1.15
1.17
0.89
4.81
4.73
4.68
4.82
5 ,
27.04
27.00
26.92
9.64 43.33
9.70 43.24
9.80 43.08
100.00
100.00 J. Philipp Ber. d. D. chem.
100.00 Ges. 10, 1227.
100.00)
100.00 IK. Heumann, Ann. d. Chem.
100.00 | 199, 271.
K. Heumann, Ann. d. Chem.
203, 174.
100.00
100.00 G. Guckelberger, Dingl. Journ.
100.00 247, 343, 1883.
432
ULTRAMARINES
Si 12
A1 12
Na 16
S 4
S2
(H 2 0) 2
Total
9.
Theory.
16.60
16.01
18.18
6.32
41.11
1.78
100.00 \
Found.
16.70
15.97
18.48
7.14
39.52
2.19
100.00
Jr
16.76
15.82
18.23
7.20
39.78
2.21
100.00
tp
16.73
15.94
18.55
7.22
17.14
17.21
15.87
18.24
18.12
6.92
7.02
40.55
1.18
1.23
100~00 J * Szilasi Ann ' d< Chem - 2 5 X > 97-114.
, t
16.75
16.15
18.08
6.75
41.05
1.22
ioo!oo
n
16.73
18.12
6.95
1.16
fi
16.39
15.08
18.24
6.60
42.16
1.53
100.00
"
16.45
15.44
18.40
6.80
41.40
1.51
100. 00 '
Si 12
Alt,
Na 14
K
8,
50
10
Theory.
17.30
16.68
16.59
8.24
41.19
100.00
Found.
17.32
15.94
16.64
0.75
7.91
41.44
100.001
17.51
15.84
^
j
7.91
40.66
hPhilipp, Ann. d. Chem. J<*4,132, 1876.
100.00J
17.
08
t
18.00
16.11
17.05
8.04
40.80
100.00
t
18.24
16.33
8.36
40.68
,
18.06
15.78
17.30
8.18
40.68
100.00 1 Hoffmann's Analyses, according to
t
18.11
16.01
17.16
8.05
40.67
100.00 [K. Heumann, Ann. d. Chem. 203, 174,
18.33
16.25
17.14
8.42
39.86
100.00 1880.
18.20
16.10
17.30
8.40
40.00
100.00,
,
17.69
16.13
17.07
8.02
41.09
100.00) According to K. Heumann, Ann. d.
.
17.88
16.47
16.61
7.67
41.37
100.00 / Chem. 203, 174, 1880.
17.77
16.10
17.06
8.02
41.05
100.00 K. Heumann, Ann. d. Chem. 199, 263.
Si 12
A1 12
Na 12
s.
o
11
Theory.
18.34
17.69
15.07
6.98
41.92
100.00
Found.
18.47
16.88
15.43
6.17
43.05
100.00 Rickmann, Dingl. Journl. 232, 164.
Si 12
Al ]2
Na u
s 4
o
J2
Theory.
17.89
17.25
17.14
6.8*3
40."9
100.00
Found.
18.00
17.32
16.20
6.62
41.86
100.00,
w
18.28
17.15
16.40
6.78
41.39
100.00
tt
18.30
17.38
16.10
6.59
41.63
100.00 G. Guckelberger, Dingl. Journ. 247,
t
17.98
17.30
16.52
6.88
41.32
100.00 f 343,1883.
f
18.08
17.35
16.46
6.69
41.42
100.00
5j
17.89
17.43
16.38
6.89
41.41
100.00J
M
18.41
17.00
16.40
6.81
41.38
100.00
18.21
17.63
1680
7.01
40.35
100.00
18.08
17.32
17.01
6.89
40.70
100.00
ff
18.00
17.68
16.92
7.05
40.35
100.00 VG. Guckelberger Dingl. Journ. 247,
11
18.90
17.82
16.21
6.40
40.67
100.00 386, 1883.
i
18.34
17.60
16.78
6.79
40.49
100.00
f
18.61
17.12
16.38
6.75
41.14
100.00 )
i
17.86
18.09
17.56
17.28
16.60
17.00
6.79
6.90
41.19
40.73
100.00
100.00 VG. Guckelberger, Dingl. Journ. 247,
i
17.29
16.91
16.48
6.60
41.72
100.00) 383, 1883.
Si 12
A1 12
Na ie
s 4
o 4g
13
Theory.
17.46
16.84
19.13
6.65
39.92
100.00
Found.
17.35
16.95
18.98
6.70
4002
100.00)
17.52
16.84
18.88
6.60
40.16
100.00 1 G. Guckelberger, Dingl. Journ. 247,
17.65
16.50
18.98
6.72
40.15
100.00) 343, 1883.
?>
17.67
16.40
19.05
6.80
40.08
100.00)
w
17.83
16.41
18.97
6.62
40.17
100.00 }-G. Guckelberger, Dingl Journ. 247,
,}
18.01
16.24
19.20
6.78
39.77
100.00) 383, 1883.
18.02
17.00
18.92
6.82
39.24
100.00 G. Guckelberger Dingl. Journ. 247,
386, 1883.
ULTRAMARINES
433
14.
Theory.
Si lf
14.84
A1 M
14.31
Na 12
12.19
Ag 4
19.08
5.65
48
33.93
Total
100.00
Found.
15.00
14.22
12.50
19.00
5.29
33.99
100.00
G. Guckelberger, Dingl. Journ. 247,
343, 1883.
Sii,
Al u
Na 6
Agio
S 4
48
15.
Theory.
12.12
11.68
4.98
38.93
4.61
27.68
100.00
Found.
12.02
11.82
4.58
39.20
4.40
27.98
100.00
G. Guckelberger, Dingl. Journ. 247 \
347, 1883.
Sii2
All.
Na 13 . 6
K
S 4
46
16.
Theory.
18.12
17.48
16.75
1.05
6.90
39.70
100.00
Found.
18.29
16.50
17.85
1.33
6.20
39.93
100.00
H. Ritter, Inaug.-Diss. Gottingen,
1860.
e,'
A 1
"NTn
*^M2
XA.li o
IMttjg
4
48
17.
Theory.
17.05
16.45
21.02
6.50
38.98
100.00
- ->
Found.
17.00
16.60
21.50
6.50
38.40
100.00
Rickmann, Ann. d. Chem. 79^,1-22.
16.74
16.59
15.95
16.14
20.59
20.92
6.22
5.72
40.50
40.63
100.00
100.00
i Rickmann, Dingl. Journ. 232, 164.
16.53
16.27
21.02
5.51
40.67
100.00
Rickmann, Dingl. Journ. 232, 170.
Sii 2
A1 12
Na 16
S 4
46
18.
Theory.
17.75
17.12
19.45
6.77
38.91
100.00
Found.
18.20
16.60
19.00
6.10
40.10
100.00
R. Hoffmann, Ann. d. Chem. 194,
1-22, 1878.
Si J6
A1 12
Na 14
So
O 6 .
19.
Theory.
18.62
13.47
13.38
11.97
42.56
100.00
Found.
18.80
13.00
13.70
11.80
42.70
100.00
C. Griinzweig per R. Hoffmann, Ann.
d. Chem. 194, 18.
Siie
A1 12
Na ie
K
S 9
65
20.
Theory.
18.15
13.13
14.91
11.67
42.14
100.00
Found.
17.29
12.55
14.66
11.38
44.12
100.00
Philipp, Ann. d. Chem. 7^,132,1876.
17.57
12.54
14.51
0.80
11.38
43.20
100.00
Si 12
A1 6
Na 9
Se
88
21.
Theory.
23.40
11.28
9.61
13.37
42.34
100.00
Found.
23.12
11.71
8.97
13.22
42.98
100.00
G. Scheffer, Ber. d. D. Chem. Ges.
1451, 1873.
Siio
A1 6
Na
g
34
22.
Theory.
20.77
12.02
10.24
14.24
42.73
100.00
Found.
21.63
12.33
9.93
13.96
42.15
100.00
G. Scheffer, Ber. d. D. Chem. Ges.
1451, 1873.
Siie
A1 12
Na 20
Sic
62
23.
Theory.
17.61
12.74
18.08
12.58
38.99
100.00
Found.
17.70
13.80
17.70
12.20
38.60
100.00
R. Hoffmann, Ann. d. Chem. 194,
14. 1878.
24. Theory.
Siis
20.34
A1 M
13.08
Na 14
12.99
15 Q
38.09
100.00
Found.
20.20
13.50
12.90
15.50
37.09
100.00
R. Hoffmann, Ann. d. Chem. 194,
17, 1878.
Si w
A1 12
Na 18
Sl2
8 i
25.
Theory.
19.37
12.45
15.91
1476
37.51
100.00
Found.
19.20
12.60
16.50
14.20
37.50
100.00
19.00
12.70
16.80
14.00
37.50
100.00
19.00
19.30
19.30
13.00
12.50
12.80
16.50
16.80
16.10
13.80
13.90
14.00
37.70
37.50
37.80
100.00
100.00
100.00
G. Guckelberger, Dingl. Journ. 247 ,
343, 1883.
19.00
13.00
15.90
14.00
38.10
100.00
26.
Theory.
18*92
All.
12.17
Na 20
17.27
1 S 4'.42
62
37.22
100.00
Found.
19.00
12.70
17.40
13.60
37.30
100.00
R. Hoffmann, Dingl. Journ. 247,
1883 ; Ann. d. Chem. 194, 14.
Siie
A1 12
Na 12
S 12
59
27.
Theory.
19.00
13.74
13.66
16.28
37.32
100.00
Found.
18.80
13.80
14.10
16.30
37.00
100.00
R. Hoffmann, Ann. d. Chem. 794, 17,
2 F
434
PORTLAND CEMENTS
Si
A1 6
Na 8
S 6
36
Total
28. Theory.
23. 1 17
11.18
12.69
13.24
39.72
100.00
Found.
23.04
23.63
10.77
11.09
11.90
12.00
14.02
13.46
40.27
39.82
100.00 |
100.00
G. Scheffer, Ber. d. D. chem. Ges. 1451, 1873
Si
A1 12
Na 16
S 6
60
29.
Theory.
Found.
2L47
21.53
13.79
13.42
15.68
15.38
8.18
9.25
40.88
40.42
100.00
100.00
E. Btichner, Ber. d. D. chem. Ges. 7, 989, 1874
Si
A1 12
Na 18
S 5
62
30.
Theory.
21. ^5
13.55
17.29
6.68
41.43
100.00
Found.
20.75
13.53
17.01
6.78
41.93
100.00 \
21.00
13.08
16.98
6.79
42.15
100.00
|
"
20.89
20.51
13.28
13.50
17.28
18.00
6.80
6.90
41.75
41.09
100.00 !
100.00 |
>G. Guckelberger, Dingl. Journ. 247, 343, 1883,
21.00
13.12
17.80
7.02
41.06
100.00
|
99
20.69
13.30
17.20
6.90
41.91
100.00 ;
Portland Cements
Formulae of a Series from Analyses of Portland Cements
SiO,
Al 4 0a
Fe,0 3
CaO
MgO K,0
Na,0
CO,
SO a
H 2 Total
1. Theory.
Found.
25.34
25.29
5.37
5.41
8.39
8.64
50.891.39
50.401.24
0.82
0.50
0.544.61
0.734.61
1.39
1.10
1.26
1.30
100.00
99.92
Feichtinger, Dingl. Journ., 40-6]
108-118, 185 ( .
2. Theory.
24.09
6.83
5.35
63.73
100.00
Found.
24.30
6.90
4.8064.10
'
100.10
) A. W. Hoffmann, Amtl. Ber. c
3. Theory.
23.65
6.70
5.2664.39
100.00
f Wien. Ausst. 3, I, 583, 1871
Found.
23.30
6.50
4.7065.40
99.90
)
4. Theory.
22.78
6.45
5.06
63.78
0.67
1.26
100.00
Found.
22.48
6.52
4.46
62.931.48
1.39
99.26
K. Pietrusky, J. B. T. 48, 1, 474
99
21.94
6.02
4.38
64.63
1.25
1.12
99.34
Chem. Ind. 190;
23.44
6.35
3.99
63.21
1.16
1.22
99.36
5. Theory.
22.50
6.38
5.00
63.00
1.88
1.24
100.00
Found.
22.00
6.50
3.2062.10
2.10
1.10
97.00
J. B. T. 43, 765.
22.42
6.28
3.6262.82
2.09
1.29
98.52
99
22.10
6.25
3.7062.50
1.75
1.20
97.50
22.07
6.59
3.41
62.00
1.04
1.53
96.64
6. Theory.
22.59
6.36, 4.98
63.26
1.56
1.25
100.00
Found.
22.48
6.52
4.4662.93
1.48
1.30
99.17
Tonind.-Ztg., 1826, 1901.
>
23.44
6.35
3.99
63.21
1.15
1.22
99.36
7. Theory
22.30
7.06
3.69
62.02
2.46
2.46
100.00
Found.
21.86
7.17
3.73
61.14
2.34
1.94
98.18
Tonind.-Ztg., 1826, 1901.
8. Theory
22.22
7.03
3.67
65.23
0.61
1.23
100.00
Found.
22.10
6.40
3.04
65.44
0.81
1.61
99.40
Tonind.-Ztg., 2015, 1901.
9. Theory
21.83
6.13
4.82
64.50
1.51
1.21
100.00
Found.
21.94
6.02
4.38
64.62
1.25
1.12
99.33
10. Theory
21.55
7.58
2.38
64.93
1.19
2.37
100.00
Found.
21.26
7.64
2.86
63.7411.10
2.18
0.60
99.38
Tonind.-Ztg., 2015, 1901.
11. Theory.
23.71
12.10
64.19
___
__
100.00
Found.
23.80
11.40
64.80
100.00
A. W. Hoffmann, Amtl. Ber. <
12. Theory.
21.17
8.04
4.20
61.82 3.50 ,
1.27
100.00
Wien. Ausst. 3, I, 583, 187
Found.
20.72
7.57
4.48
60.523.02 1.02
0.52
0.37
1.22
99.44
Fischer, H. d. ch. T. 828.
13. Theory.
20.64
7.89
4.13
62.59 2.06 1.62
1.07
100.00
Found.
20.33 8.67
3.80,62.33 2.48 1.20
0.85
99.66
J. B. T. 43, 732.
,,
20.33
7.19
3.6563.65|2.62
1.04
0.80
99.28
14. Theory.
24.16
10.7365.12!
___
__
100.00
Found.
23.80
11.40
64.80
._._
.
100.00
A. W. Hoffmann, Amtl. Ber. <
Wien. Ausst. J, I, 583, 187,
PORTLAND CEMENTS
435
SiO,
Al,0,
Fe a O,
CaO
MgO
K,O
Na,0
CO,
SO,
H a o
Total
15. Theory.
23.65
5.02
2.63
65.87
1.09
_^ . j-
.74
100.00
Found.
23.40
5.18
2.79
65.80
1.13
0.48
.42
100.20
Loebell, J. B. T. 48, 1,
32.68
5.03
2.82
65.47
1.08
0.53
.36
99.97
466.
16. Theory.
32.52
7.37
5.79
44.56
1.45
0.85
0.57
4.78
.46
0.66
100.00
Found.
32.60
7.17
6.23
44.96
1.52
0.45
0.64
4.52
.20
0.72
100.00
Fehling, H. d. Chem. 482,
17. Theory.
34.15
7.73
6.06
46.76
0.76
1.66
.51
1.37
100.00
1875.
Found.
34.07
7.49
5.58
46.07
0.90
1.38
.96
1.47
98.92
Fehling, H. d. Chem. 482,
18. Theory.
32.63
7.34
5.76
45.37
1.44
0.85
0.56
3.96
.44
0.65
100.00
1875.
Found.
32.60
7.17
6.23
44.96
1.52
0.45
0.64
4.52
.20
0.72
100.01
Feichtinger, Dingl. Jour.
19. Theory.
34.08
7.67
6.02
46.33
0.75
0.88
0.58
0.82
.50
1.35
100.00
40-61, 108-118, 1859.
Found.
34.07
7.49
5.58
46.07
0.90
0.27
0.56
1.38
.96
1.47
99.75
Feichtinger, Dingl. Jour.
20. Theory.
29.33
4.95
7.72
48.01
1.94
0.05
0.50
5.69
0.65
1.16
100.00
40-61, 108-118, 1859.
Found.
28.56
4.75
8.14
47.53
2.04
0.48
0.68
5.58
0.40
1.20
99.36
Feichtinger, Dingl. Jour.
21. Theory.
28.89
4.92
7.71
48.47
1.93
0.76
0.50
5.66
1.16
100.00
40-61, 108-118, 1859.
Found.
28.56
4.75
8.14
47.53
2.04
0.48
0.60
5.58
1.20
98.88
Fehling, H. d. Chem. 482,
22. Theory.
25.39
7.19
2.26
56.87
2.82
1.33
0.87
1.00 MnO
2.27
100.00
1875.
Found.
24.26
6.97
2.88
56.90
2.15
0.90
0.54
1.60 MnO
1.28
97.48
J. B. T. 44, 749.
24. Theory.
23.35
6.57
2.06
64.93
1.03
2.06
100.00
Found.
22.96
6.78
2.54
63.95
0.98
1.96
99.17
Tonind.-Ztg. 2015, 1901.
25. Theory.
23.19
5.87
3.06
63.03
1.02
0.60
1.19
2.04
100.00
Found.
23.40
6.07
2.51
63.870.97
0.80
1.22
1.45
100.29
v. Teichek, Chem. Ind.
26. Theory.
23.21
5.92
3.09
65.72
1.03
1.30
100.00
24, 445, 1901.
Found.
22.71
6.42
2.81
63.14
1.04
1.64 CaSO 4
O.SOCaCO.,
93.56
Tonind.-Ztg. 409, 1879.
27. Theory.
22.94
5.81
3.03
65.18
1.02
2.02
100.00
Found.
22.33
5.53
3.28
64.40
1.20
2.41
99.15
Tonind.-Ztg. 2015, 1901.
28. Theory.
10.39
7.37
2.31
71.96
3.47
.
1.91
2.59
100.00
Found.
10.38
6.66
1.99
72.10
3.27
0.85
1.64
0.43
2.56
99.88
Fischer, H. d. ch. T. 828.
29. Theory.
25.29
8.35
9.36
52.43
0.72
2.06
0.94
0.85
100.00
Found.
25.21
8.26
8.35
52.46
0.78
2.25
1.30
0.68
99.29
Fehling, H. d. Ch. 482,
30. Theory.
25.13
8.25
9.24
52.42
0.46
0.71
2.03
0.92
0.83
100.00
1875.
Found.
25.21
8.26
8.35
52.46
0.50
0.30
0.78
2.25
1.30
0.68
100.09
Feichtinger, Dingl. Jour.
31. Theory.
17.25
8.18
2.57
63.71
3.85
_ > _._ | _^
2.12
2.32
100.00
40-61, 108-118, 1859.
Found.
16.75
7.97
2.71
61.92
4.03
1.25
2.42
0.42
2.24
94.64
Fischer, H. d. ch. T. 828.
32. Theory.
17.71
8.37
2.62
66.12
3.28
^~~~~~~-^
0.72
1.18
100.00
Found.
17.04
8.09
3.25
65.05
3.04
0.92
0.83
0.30
1.06
99.58
Fischer, H. d. ch. T. 828.
33. Theory.
15.00
7.03
2.20
66.44
4.41
; x
2.42
2.50
100.00
Found.
14.76
7.52
2.15
65.42
3.89
0.86
2.19
0.52
2.32
99.63
Fischer, H. d ch. T. 828.
34. Theory.
21.78
13.89
45.06
3.18
2.00
1.83
12.26
100.00
Found. |21.02
13.02
43.57
3.09
1.76
2.29
11.87
96.62
J. B. T. 44, 745.
35. Theory.
20.59
13.04
42.64
2.77
1.01
0.66
1.40
2.55
13.82
98.48
Found.
20.22
14.52
41.87
3.02
077
0.71
1.86
3.02
13.77
99.76
Zulkowski.
36. Theory.
24.59
15.68
0.91 MnO
48.77
3.08
2.41
1.59
0.92 FeO
2.05
100.00
t 2jU.lo\vski
Found.
24.64
15.27
0.82MnO
49.70
3.29
1.67
1.37
1.12 FeO
1.72
99.60
1 J. B. T. 44, 745.
37. Theory.
21.04ll3.32
0.78 FeO
43.57
2.83
1.02
1.35
0.96
2.61
11.75
100.00
0.77 MnO.
Found'.
21.02 13.02
0.85 FeO
43.57
3.090.31
0.84
1.76
2.29
11.87
99.28
0.66 MnO Zulkowski.
436
PORTLAND CEMENTS
SiO,
AI.O,
Fe 2 0,
CaO |MgO
K a O |Na,0
CO,
so,
H 2
Total
38. Theory.
Found.
24.73
24.64
15.65
15.27
0.92 FeO
1.12 FeO
49.77|3.32
49.703.29
1.80
1.67
1.59
1.37
0.281.03
0.5411.72
0.9 iMnO 100.00
0.82MnO 100.14
Zulkowski
39. Theory.
Found.
pf
23.71
22.23
23.72
7.78
7.75
7.36
5.23
5.30
5.50
54.370.87
54.100.75
54.400.86
1.02
1.10
0.86
2.03
1.66
1.78
3.14
2.15
2.80
0.87
1.00
1.12
0.98
1.00
0.96
100.00
97.04
99.36
Feichtinger, Dingl. Journ
40-61, 108-118, 1859
40. Theory.
Found.
23.64
22.47
8.93
7.81
3.51
3.42
61.29
61.13
0.87
1.06
z
1.76
2.03
_
100.00
97.92
J. B. T. 35, 852.'
23.57
8.89
3.51
60.10
0.95
0.90
97.92
22.96
9.14
3.23
61.19
1.03
1.45
99.00
M
23.36
8.12
3.21
60.57
1.19
1.81
98.26
41. Theory.
Found.
28.72
28.54
29.08
3.05
3.43
3.40
1.59
1.13
1.24
65.85
66.62
66.07
0.79
0.30
0.20
E
E
E
100.00
100.02
99.99
Tonind.-Ztg. 981, 1902.
42. Theory.
27.39
2.92
1.52
68.17
100.00
Found.
27.06
3.19
1.29
68.06
0.35
99.95
43. Theory.
26.49
3.75
69.03
0.73
100.00
Found.
26.30
3.50
0.77
68.84
0.54
99.95
44. Theory.
Found.
23.96
23.75
3.38
3.11
0.85
72.66
72.01
.^ _
100.00
100.02
0.30
REFERENCES TO ANALYSES
Topazes.
1, Berzelius, Abhandl. </, 247 ; Schweigg. Journ. 16, 423. 2, Berzelius, I. c. 3,
Berzelius, I. c. 4, Rammelsberg, Berl. Akad. 1865, 264. 5, Hildebrand, Geol. Survey
Bull. No. 20. 6, Klemm, Beitr. z. Kenntnis. des Topas, Inaug.-Diss., Jena 1873, 12.
7, Klemm, 1. c. 8, Klemm, I. c. 9, 10-13, Klemm, I. c. 14, Sommerland quoted by v.
Groddeck, Zeitschr. d. Geol. Ges. 1884, 36, 642. 15, Ranmelsberg, I.e. 16-18,
Rammelsberg, I. c.
Epidotes.
1, Nanke per Bauer, N. Jahrb. 1880, 2, 81. 2, Stockar-Escher, Pogg. Ann. 95,
501. 3-6, Stockar-Escher, I. c. 7, Wilk, Groths Zeitschr. 12, 517. 8, 9, Stockar-
Escher, I. c. 10, F. Heddle, Min. Soc., London 1879, 3, 18. 11, Scheerer, Pogg. Ann.
95, 501. 12, Richter, Pogg. Ann. 95, 501. 13, Hermann, Erdm. Journ. Chem. 43, 88.
14, A. G. Dana, Groths Zeitschr. Jo, 490. 15, Mauthner, Tscherm. Mitt. 1872, 259.
16, Laspeyres, Groths Zeitschr. 3, 564. 17, Renard, Groths Zeitschr. 6, 177. 18,
Hermann, Erdm. Journ. 43, 81. 19, v. Drasche per Klein, N. Jahrb. 1872, 120. 20,
Ludwig, Groths Zeitschr. 6, 180. 21, Ludwig, Tscherm. Mitt. 1872, 194. 22, Las-
peyres, Groths Zeitschr. 3, 564. 23, Wulf, Tscherm. Mitt. N. F. 8, 235. 24, Rammels-
berg, Zeitschr. d. Geol. Ges. 24, 650. 25, Scheerer, Pogg. Ann. 95, 501. 26, Scheerer,
/. c. 27, Stockar-Escher, Pogg. Ann. 95, 501. 28, Rammelsberg, Pogg. Ann. 76, 93.
29, Scheerer, Pogg. Ann. 95, 501.
Mesolites.
1, Thomson, Edinb. N. Phil. Journ. 1834, 17, 186 ; Outl. Min. 1836, 326, 328. 2,
Luedecke, N. Jahrb. 1881, 2, 33. 3, Marsh quoted by Dana, Min. 1868, 431. 4, Thomson
Edin. N. Phil. Journ. 1834, 17, 186. 5, Thomson, Ed. N. Phil. Journ. 1834, 17, 186.
6, E. E. Schmid, Pogg. Ann. 1871, 142, 121. 7, Breidenstein quoted by Rammelsberg,
Mineralch., 5. Suppl., 1853, 168. 8, Riegel, Journ. f. prakt. Chem. 1847, 40, 319.
9, Fuchs & Gehlen, Schweigg. Journ. 1816, 18, 1. 10, Heddle, Phil. Mag. 1857, 13,
148. 11, Heddle, ibid. 12-14, Heddle, Phil. Mag. 1857, 13, 50, 148. 15, Berzelius,
Jahresber. 1823, j, 147. 16, Heddle, Phil. Mag. 1857, 13, 50. 17, Fuchs & Gehlen,
Schweigg. Journ. 1816, 18, 1. 18, Durscher, Ann. mines 1841, 19, 578. 19, E. E.
Schmid, Pogg. Ann. 1871, 142, 121. 20, Sart. v. Waltershausen, Vulk. Gest. 1853,
267. 21, Fuchs & Gehlen, Schweigg. Journ. 1816, 18. 1. 22, Fuchs & Gehlen, ibid.
23, E. E. Schmid, Pogg. Ann. 1871, 142, 121. 24, Lemberg, Zeitschr. d. Geol. Ges.
1876, 28, 552. 25, How, Am. Journ. Sc. 1858, 26, 32. 26, How, ibid. 27, Marsh
quoted by Dana, Min. 1868, 431. 28, Darapsky, N. Jahrb. 1888, i, 66. 29, Sadtler,
Am. Chem. Journ. 1883, 4, 357.
The Glintonite Group.
1, Kobell, Journ. f. prakt. Chem. 1853, 58, 39. 2, Hunt, Am. Journ. Sc. 1861, 31,
442. 3, Damour, Bull. soc. min., Paris 1884, 7, 84. 4, Hermann, Journ. f. prakt.
Chem. 1851, 53, 13. 5, Suida per Tschermak, Groths Zeitschr. 3, 5, 11. 6, Heddle,
Groths Zeitschr. 5, 618. 7, Delesse, Compt. rend. 1846, 22, 595 ; Ann. mines 1846,
jo, 232. 8, Erdmann, Journ. f. prakt. Chem. 1834, 4, 127 ; 6, 89. 9, L. Smith, Ann.
mines 1850, 18, 300. 10, Renard, Bull. soc. min., Paris 1884, 7, 42. 11, Damour, Bull,
soc. min., Paris 1884, 7, 84. 12, SipQcz, Groths Zeitschr. 3, 508. 13, L. Smith, Ann.
minea 1850, 18, 300. 14, L. Smith, ibid. 15, F. Heddle, Groths Zeitschr. 5, 618.
16, Kobell, Journ. f. prakt. Chem. 1853, 58, 40. 17, Renard, Groths Zeitschr. 8, 420.
18, Jackson, Rep. geol. R. 1840, I, 88. 19, Damour, Bull. soc. min., Paris 1879, 2,
437
438 REFERENCES TO ANALYSES
167. 20, Damour, Ann. mines 1842, 2, 357. 21, Damour, ibid. 22, Sipocz, Groths
Zeitschr. 3, 502. 23, Hermann, Journ. f. prakt. Chem. 1851, 53, 13. 24, Whitney,
Proc. nat. hist, soc., Bost. 1849, 100. 25, Wagner per Knop, N. Jahrb. 1872, 788.
26, O. Schiefferdecker per Knop, N. Jahrb. 1872, 788. 27, v. Foullon, Jahrb. geol.
Reichsanst., Wien 1833, 33, 326. 28, SchrSder, Erlaut. Sect. Zwota 1884, 3. 29,
Bonsdorff quoted by G. Rose, Reise 1837, j, 253.
Micas.
1, Pisani, Compt. rend. 1876, 83, 166. 2, Genth, Groths Zeitschr. 2, 10. 3, Rumpf,
Tscherm. Mitt. 1874, 177. 4, Crawe, Am. Journ. Sc. 1850, 10, 383. 5, Thomson,
Outl. Min. 1836, i, 373. 6, Bromeis, Pogg. Ann. 1842, 55, 112. 7, Igelstrom, N.
Jahrb. 1872, 296. 8, Chatard, Amer. Journ. Sc. 1888, 36, 263. 9, Cohen, Groths
Zeitschr. 7, 405. 10. v. Ammon quoted by v. Giimbel, Geogn. Beschr. d. Fichtelgebirges
1879, 182. 11, Chatard quoted by Genth, Amer. Phil. Soc., 19 Sept. 1873, 26. 12,
Hilger, N. Jahrb. 1879, 129. 13, Knop, N. Jahrb. 1859, 560. 14, Baltzer, N. Jahrb.
1872, 654. 15, Konig quoted by Genth, Amer. Phil. Soc., 19 Sept. 1873, 32. 16,
Konig, Proc. Nat. Sc., Philadelphia 1877, 269. 17, Chatard, Amer. Phil. Soc., 19
Sept. 1873, 44. 18, Schwager, N. Jahrb. 1878, 385. 19, Knop, N. Jahrb. 1861, 150.
20, Thoreld, Act. Soc. Fenn 3, 815 ; A. Nordenskiold, Beskrifn. Finl. Min. 1855, 146.
21, Muller quoted by Breithaupt, Min. Stud. 1866, 33. 22, Kobell, Kaetn. Arch. Nat.
12, 29. 23, Zellner, Tscherm. Mitt. 1873, 129. 24, Crossley quoted by Jackson, Sillim.
Amer. Journ. 1850, 9, 422. 25, Genth, Amer. Phil. Soc., 19 Sept. 1873, 29. 26,
Sharpless, Amer. Journ. Sc. 1869, 47, 319. 27, Smith, Amer. Journ. Sc. 1851, n, 59.
28, Smith & Brush, Amer. Journ. Sc. 1853, 15, 209. 29-31, Smith & Brush, ibid.
32, Massalin, Trommsd. N. J. 4, 2, 324. 33, Rammelsberg, Zeitschr. d. Geol. Ges.
1862, 14, 761. 34, Lemberg, Zeitschr. d. Geol. Ges. 1888, 40, 656. 35, Genth, Amer.
Phil. Soc., 19 Sept. 1873, 26. 36, Konig quoted by Genth, ibid. 37, Sauer, Zeitschr.
d. Geol. Ges. 1885, 37. 460. 38, Cossa, Accad. Torino, Dec. 1874, Ric. chim. e microscop.
1881, 75. 39, Cossa, ibid. 40, Konig, Amer. Phil. Soc., 19 Sept. 1873, 26. 41, Delesse,
Ann. chim. phys. 1845, 15, 248. 42, Blau, Tscherm. Mitt. 1873, 32. 43, Sipocz,
Tscherm. Mitt. 1873, 31. 44, Igelstrom, Berg- u. Hiittenm. Ztg. 25, 308. 45, Chatard
quoted by Gill, Johns Hopkins Univ. Circ., No. 75. 46, Dewey, Groths Zeitschr. 5, 210.
47, Mallet, Rammelsbergs Mineralchemie, 5. Suppl., 1853, 148. 48, Kjerulf, Erdm.
Journ. f. prakt. Chem. 1855, 65, 191. 49, Riepe quoted by G. v. Rath, Sitzb. Niederrhein.
Ges., Bonn 1879, 383. 50, Lehnut, Thomsons Min. 1836, i, 330. 51, Blythe, ibid.
52, Scheerer, Zeitschr. d. Geol. Ges. 1862, 14, 63. 53, Killing quoted by Sandberger,
Erzgange, Wiesbaden 1882, 1. Heft ; Groths Zeitschr. 7, 411. 54, Laspeyres, Tscherm.
Mitt. 1873, 147. 55, Cossa, Accad. Torino, Dec. 1874 ; Ric. chim. e microscop. 1881,
75. 56, Varrentrapp, Pogg. Ann. 1844, 61, 381. 57, Brush, Amer. Journ. Sc. 1861,
31, 369. 58, Chatard, Amer. Phil. Soc., 19. Sept. 1873, 32. 59, Killing quoted by
Rammelsberg, Monatsber. Akad., Berlin 1879, 845. 60, Pisani, Compt. rend. 1862,
54, 686. 61, Cooke, Proc. Amer. Acad. Arts 1874, 35. 62, Chatard, Amer. Phil. Soc.,
19 Sept. 1873, 44. 63, Konig, Amer. Phil. Soc., 19 Sept. 1873, 32. 64, C. v. Hauer,
Kenngott, Min. Forsch. 1856, 80. 65, Ficinus, Schweigg. Journ. 1819, 26, 280. 66,
Galbrath, Journ. Geol. Soc. Dublin 6, 165. 67, Galbrath, ibid. 68, Kobell, Journ. f.
prakt. Chem. 2, 295. 69, Muller quoted by Breithaupt, Min. Stud. 1866, 36. 70,
Bromeis quoted by Bischof, Lehrb. Geol. 2, 1418. 71, Konig, Proc. Nat. Sc., Philad.
1877, 269. 72, C. v. Hauer, Sitzber. Akad., Wien 1853, n, 609. 73, Bromeis, Pogg.
Ann. 1842, 55, 112. 74, Jewreinow, Pogg. Ann. 1847, 70, 854. 75, Konig quoted by
Genth, Amer. Phil. Soc., 19 Sept. 1873, 37. 76, K6nig, ibid. 77, Renard, Bull. Acad.
Belg. 1881, 2, Nr. 9. 78, Roepper quoted by Sharpless, Amer. Journ. Sc. 1869, 47, 319.
79, Boricky quoted by v. Zepharovich, Sitzber. Akad. Wien 54, 287. 80, Haughton,
Phil. Mag. 1855, 9, 272. 81, Heddle, Groths Zeitschr. 5, 627. 82, Heddle, Groths
Zeitschr. 5, 617, 618, 627. 83, Delesse, Ann. mines 1849, 16, 202. 84, Schafhautl,
Ann. chem. Pharm. 1843, 46, 325. 85, Rammelsberg, Zeitschr. d. Geol. Ges. 1862, 14,
763. 86, Rammelsberg, Glimmer, Berlin 1889, 67.
Scapolites.
1, Crossley, Phil. Mag. 1850, 37, 179. 2, Rammelsberg, Ak. Berl. 1885, 605. 3,
Wolff, Inaug.-Diss., Berl. 1843 ; N. Jahrb. 1846, 334. 4, Damour, Institut 1862, 21.
5, G. v. Rath, Pogg. Ann. 1853, 90, 88. 6, Hunt, Amer. Journ. Sc. 1849, 8, 103. 7,
Hermann, Journ. f. prakt. Chem. 1851, 54, 410. 8, Crossley, Phil. Mag. 1850, 37, 179.
REFERENCES TO ANALYSES 439
9, G. v. Rath, Pogg. Ann. 1853, go, 88. 10, Lacroix, Bull. soc. min. Paris, 12, 174. 11,
Rath, Zeitschr. d. Geol. Ges. 1863, 15, 246. 12, H. Schulze per Goldschmidt, N.
Jahrb. 1881, Beil.-Bd. j, 225. 13, Lemberg, Zeitschr. d. Geol. Ges. 1887, 39, 572.
14, G. v. Rath, Zeitschr. d. Geol. Ges. 1866, 18, 636. 15, Pisani quoted by Des Cloizeaux,
Min. 1862, 225, 234. 16, Lagus & Olkkonen per Wilk, Groths Zeitschr. 7, 110. 17,
Berkley quoted by Dunnington, Amer. Chem. Journ. 1892, 620. 18, Wolff, Diss.,
Berl., 1843. 19, Selkmann quoted by Rammelsberg, Mineralch. 1875, 471. 20, Lagus
& Olkkonen quoted by Wilk, Groths Zeitschr. 7, 110. 21, G. v. Rath, Pogg. Ann. 1871,
144, 384. 22, Hermann, Journ. f. prakt. Chem. 1845, 34, 178. 23, G. v. Rath, Pogg.
Ann. 1853, go, 87. 24, Berlin quoted by Wiebye, Pogg. Ann. 1850, 79, 302. 25, Sip5cz,
Tscherm. Mitt. N. F. 4, 266. 26, F. Heddle, Min. Soc. London 1882, 5, 19. 27, N.
Nordenskj&ld, Schweigg. Journ. 1821, 31, 417. 28, G. v. Rath, Pogg. Ann. 1853, go,
93, 297. 29, Jannetaz, Bull. soc. Paris 1889, 12, 445. 30, Vogt, Zeitschr. d. Geol.
1895, 456. 31, Wilk, Min.-Samml., Helsingf. 1887, 39 ; Groths Zeitschr. n, 312.
32, N. Nordenskjold, Schweigg, Journ. 1821, 31, 417. 33, Hartwall & Herdberg,
Berzel. Jahresb. 4, 155. 34, Hunt, Amer. Journ. 1855, 19, 428; Rep. Geol. Can.
1853, 1863, 483. 35, Hermann, Journ. f. prakt. Chem. 1851, 54, 177. 36, Hartwall &
Herdberg, Berzel. Jahresb. 4, 155. 37, Hunt, Amer. Journ. Sc. 1855, 19, 428 ; Rep.
Geol. Can. 1853, 1863, 483. 38, Th. Wolf, Zeitschr. d. Geol. Ges. 1868, 20, 30. 39,
G. v. Rath, Pogg. Ann. 1853, 90, 93, 297. 40, Rammelsberg, Ak. Berl. 1885, 605.
41, Hermann, Journ. f. prakt. Chem. 1851, 54, 410. 42, Beeke, Tscherm. Mitt. 1877,
267. 43, Bergemann, Pogg. Ann. 1827, g, 267. 44, Giwartowsky, Bull. soc. nat.
Moscow 21, 548 ; Erdm. Journ. f. prakt. Chem. 1849, 47, 380. 45, Fuchs, Leonh.
Min. Taschb. 1823, 17, 104. 46, Wolff, Inaug.-Diss., Berl. 1843. 47, Wolff, ibid.
48, Berg, Ofv. Ak. Stockh. 1844, 94. 49, Thomson, Min. I, 273. 50, Leeds, Amer.
Journ. Sc. 1873, 6, 26. 51, Hunt, Amer. Journ. Sc. 1855, 19, 368. 52, Wurtz, Amer.
Journ. Sc. 1853, 10, 325. 53, G. v. Rath, Pogg. Ann. 1853, go, 96 ; 92, 300, 303, 290.
54, G. v. Rath, Pogg. Ann. 1853, go, 93, 297. 55, Hermann, Journ. f. prakt. Chem
54, 410. 56, Fuchs, Naturg. Min. Kempt. 1824, 225. 57, Lemberg, Zeitschr. d. geol.
Ges. 1887, 39, 571. 58, G. v. Rath, Pogg. Ann. 1853, go, 93, 297. 59, G. v. Rath,
Pogg. Ann. 1853, go, 99. 60, Kiepenheuer per G. v. Rath, Niederrh. Ges., Bonn
1879, 381. 61 Salomon Tscherm. Mitt. N. F. 15, 159. 62 Wittstein quoted by
Giimbel, Geogn. Beschr. Bay. 1868 2, 358. 63, Genth, Amer. Journ. Sc. 1890, 40,
116. 64, Rammelsberg, Ak. Berl. 1885, 599. 65, Rammelsberg, Mineralch, 1886,
214. 66, Rammelsberg, Ak. Berl. 1885, 599 ; Zeitschr. d. Geol. Ges. 1884, 36, 229.
67, Grandeau, Ann. chim. phys. 1863, 67, 174. 68, Gmelin, Schweigg. Journ. 1819,
25, 36; 1822, 35, 348. 69, Muir quoted by Thomson, Min. 1836, 383. 70, Gmelin,
Schweigg. Journ. 1819, 25, 36 ; 1822, 35, 348.
Orthochlorites.
1, F. Heddle, Transact. Roy. Soc. Edinb. 29 ; Groths Zeitschr. 5, 631. 2, Heddle.
Groths Zeitschr. 5, 634. 3, Kobell, Gel, Anz., Miinchen 1854, Ap. 10. 4, Bruhl, Pogg.
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Journ. Sc. 1870, 49, 272 ; Shepard, ibid. 50, 96. 7, Heddle, Transact. Roy. Soc.
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Schlaepfer, N. Jahrb. 1891, I, 8. 10, Hermann, Journ. f. prakt. Chem. 1851, 53, 22.
11, Hunt, Rep. Geol. Can. 1863, 491. 12, Smith & Brush, Amer. Journ. Sc. 1853,
16, 47. 13, Smith & Brush, ibid. 14, Rumpf, Tscherm. Mitt. 1873, 33. 15, Ludwig,
Tscherm. Mitt. N. F. 12, Heft, 1. 16, Telek quoted by Wartha, Groths Zeitschr. 13,
72. 17, Schlaepfer, N. Jahrb. 1891, i, 8. 18, v. Fellenberg, N. Jahrb. 1868, 746.
19, v. Hamm, Tscherm. Mitt. 1872, 260. 20, Marignac, Bibl. univ. Gen. 1844, 131.
21, Marignac, ibid. 22, ibid. 23, Wartha, Journ. f. prakt. Chem. 1866, 99, 84. 24,
Hamberg, Geol. For., Forh. 1890, 12, 580. 25, Liebe, N. Jahrb. 1870, 6, 10. 26,
F. Heddle, Transact. Roy. Soc. Edinb. 29 ; Groths Zeitschr. 5, 631. 27, Hunt, Rep.
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min. Forsch. 1858, 63. 34, Marignac, Ann. de chim. et phys. 1845, 14, 60. 35, F.
Heddle, Trans. Roy. Soc. Edinb. 29 ; Groths Zeitschr. 5, 631. 36, Marignac, Ann.
de chim. et phys. 1845, 14, 60. 37, Hunt, Rep. Geol. Can. 1863, 491. 38, Liebe, N.
Jahrb. 1870, 5. 39, Schweizer, Pogg. Ann. 1840, 50, 526. 40, Schweizer. ibid. 41,
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440 REFERENCES TO ANALYSES
29, 89 ; Groths Zeitschr. 5, 633. 43, Delesse, Ann. mines 1851, 20, 155. 44, Loretz,
Jahrb. d. preufi. d. geol. Landesanstalt fiir 1884, Berl. 1885, 133. 45, Loretz, Geogn.
Beschr. d. Fichtelgebirges 1879, 210, 233. 46, Pufahl quoted by WeiB, Zeitschr. d.
Geol. Ges. 1879, 31, 801. 47, Boricky, Sitzber. Akqad., Wien 1869, 59, 599. 48,
Leeds, Amer. Journ. Sc. 1873, 6, 25. 49, Marignac, Bibl. univ. Geneve 1844, 136.
50, Marignac, Ann. de chim. et phys. 1844, 10, 430. 51, L. Smith, Amer. Journ. Sc.
1851, n, 65. 52, Marignac, Ann. de chim. et phys. 1845, 14, 56. 53, Szilasi quoted by
Wartha, Groths Zeitschr. 13, 72. 54, Jannasch, N. Jahrb. 1885, i, 94. 55, Jannasch,
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Mitt. N. F. 12, Heft 1. 60, Clarke, Amer. Journ. Sc. 1884, 28, 20. 61, Varrentrapp,
Pogg. Ann. 1839, 48, 189. 62, Tschermak, Akad. Wien 1866, 53, 521. 63, Heddle,
Transact. Roy. Soc. Edinb. 29 ; Groths Zeitschr. 5, 631. 64, Gosch per Cooke, Mem.
Amer. Acad. Sc., Boston 1874, 35 ; 1875, 453. 65, Schrauf, Groths Zeitschr. 6, 345,
383. 66, Wilk, Ofvers Finska Vetensk-Soc. Forhandl. 1868-9, u, 28 ; N. Jahrb.
1869, 357 ; Groths Zeitschr. 2, 495. 67, Schrauf, Groths Zeitschr. 6, 345, 383. 68,
Rammelsberg, Pogg. Ann. 1856, 97, 300. 69, v. Drasche, Tscherm. Mitt. 1873, 126.
70, Heddle, Groths Zeitschr. 5, 634. 71, Genth, Proc. Acad. Sc. Philad. 1852, 121.
72, Dieffenbach, N. Jahrb. 1855, 534. 73, K. v. Hauer, Sitzber, Akad. Wien, 1855,
16, 170. 74, F. Heddle, Transact. Roy. Soc. Edinb. 29 ; Groths Zeitschr. 5, 631.
75, Melville quoted by Lindgren. Proc. Calif. Akad. Sc., 20. Dec. 1887. 76, Kobell,
Journ. f. prakt. Chem. 1839, 16, 470. 77, Pearse, Amer. Journ. Sc. 1864, 37, 222.
78, Pearse, ibid. 79, Breidenbaugh, Amer. Journ. Sc. 1873, 6, 208. 80, Rammels-
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Mitt. N. F. 12, Heft 1. 85, Heddle, Groths Zeitschr. 5, 634 ; Hawes, Amer. Journ.
Sc. 1875, 9, 451. 86, Hawes, ibid. 87, Liebe, N. Jahrb. 1870, 8. 88, Liebe, N. Jahrb.
1870, 6, 10. 89, Liebe, ibid. 90, Liebe, N. Jahrb. 1870, 10. 91, Piccard, Kenngotts
tubers, min. Forsch. 1863, 203. 92, F. Heddle, Transact. Roy. Soc. Edinb. 29 ; Groths
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95, Rosam per Serba, Bohm. Ges. Wiss., 15 Jan. 1886. 96, Konig quoted by Genth,
Amer. Phil. Soc., 19 Sept. 1873, 13, 413. 97, Konig quoted by Genth, ibid. 98, Woits-
chach, Inaug.-Diss., Breslau 1881, 38. 99, Genth, Amer. Phil. Soc. 13, 417. 100,
Genth, ibid. 101, P. Keyser quoted by Genth, Amer. Journ. Sc. 1853, 16, 167. 102,
P. Keyser, Amer. Journ. Sc. 1854, 18, 411. 103, L. Smith, Amer. Journ. Sc. 1854,
18, 376. 104, L. Smith, ibid. 105, Ludwig quoted by Tschermak, Tscherm. Mitt.
N. F. 12, Heft 1. 106, L. Smith, Amer. Journ. Sc. 1854, 18, 376. 107, Gintl quoted by
v. Zepharovich, Groths Zeitschr. i, 372. 108, Steinmann, Schweigg. Journ. 1821,
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Febr. 1891, 100, 38 ; Tscherm. Mitt. N. F. 12, Heft 1. 112, v. Gumbel, Geogn. Beschr.
Bay. 1868, 2, 388. 113, Janowsky, Journ. f. prakt. Chem. 1875, JJ, 378. 114, Clarke
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Amer. Journ. Sc. 1859, 28, 250. 116, F. Heddle, Transact. Roy. Soc. Edinb. 29;
Groths Zeitschr. 5, 631. 117, F. Heddle, ibid. 118, Obermayer per Tschermak,
Tscherm. Mitt. N. F. 12, Heft 1. 119, Pisani, Amer. Journ. Sc. 1866, 41, 394. 120,
Chatard per Genth, Amer. Phil. Soc. 1873, 13, 414. 121, Websky, Zeitschr. d.
Geol. Ges. 1873, 25, 391. 122, Loretz, Geogn. Beschr. d. Fichtelgebirges 1879, 210,
233. 123, Delesse, Ann. min. 1847, 12, 221. 124, Traube, Min. Schles. 1888, 249.
125, v. Gumbel, Geogn. Beschr. Bay. 1868, 2, 395. 126, Delesse, Ann. min. 1849, 16,
520. 127, Loretz, Geogn. Beschr. d. Fichtelgebirges 1879, 210, 233. 128, Loretz,
ibid. 129, K. v. Hauer, Jahrb. Geol. Reichsanst. 16, 505. 130, Sandberger, N. Jahrb.
1850, 341. 131, Rammelsberg quoted by Websky, Zeitschr. d. Geol. Ges. 1879, 31,
212. 132, C. Schmidt, Groths Zeitschr. n, 600. 133, Erlenmeyer, Kopp & Wills
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Phil. Soc., 19 Sept. 1873, 13, 413. 136, Chatard quoted by Genth, ibid. 137, Zeynek
quoted by Tschermak, Tscherm. Mitt. N. F. 12, Heft 1. 138, K. v. Hauer, Jahrb.
Geol. Reichsanst. 5, 337. 139, Suylsteke quoted by Tschermak, Tscherm. Mitt. N. F.
12, Heft 1. 140, Klement, Tscherm. Mitt. N. F. i, 365. 141, Damour, Ann. de
chim. et phys. 1860, 58, 99. 142, Klement, Tscherm. Mitt. N. F. 12, Heft 1. 143,
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5, 631. 147, Jacobs quoted by Dathe, Zeitschr. d. Geol. Ges. 1887, 39, 505. 148*
Rammelsberg, Mineralchem. 1860, 538. 149, F. Heddle, Transact. Roy. Soc. Edinb.
REFERENCES TO ANALYSES 441
29 ; Groths Zeitschr. 5, 631. 150, Kobell, Journ. f. prakt. Chem. 16, 470. 151,
Kobell, ibid. 152, Fellenberg, N. Jahrb. 1868, 746. 153, F. Heddle, Transact. Roy.
Soc. Edinb. 29; Groths Zeitschr. 5, 631. 154, Egger, Tscherm. Mitt. 1874, 244. 155,
Bock, Inaug.-Diss., Breslau 1868, 4. 156 Igelstrom, Journ. f. prakt. Chem. 1861, 84,
480. 157, F. Heddle, Transact. Hoy. Soc. Edinb. 29 ; Groths Zeitschr. 5, 631. 158,
Heddle, ibid. 159, Santerson quoted by Eichstadt, Geol. For. Forh. 7, 333 ; Groths
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1857, Jj, 284. 162, Craw, Amer. Journ. Sc. 1852, 13, 222. 163, Craw, ibid. 164,
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168, F. Heddle, Transact. Roy. Soc. Edinb. 29 ; Groths Zeitschr. 5, 631. 169, Ort-
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401. 173, Hermann, Journ. f. prakt. Chem. 1851, 53, 22. 174, Herzog N. v. Leuchten-
berg, Russ. min. Ges. 1866, i, 33 ; Bull. acad. St. Petersb. g, 188. 175, Herzog N. v.
Leuchtenberg, ibid. 176, Lagorio, Tscherm. Mitt. N. F. 8, 497. 177, Brun, Groths
Zeitschr. 7, 390. 178, Hermann, Journ. f. prakt. Chem. 1847, 40, 15. 179, Pearse,
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186, Heddle, ibid. 187, Gintl per v. Zepparovich, Tscherm. Mitt. 1874, 7. 188,
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196, N. v. Zinin, ibid. 197, Hermann, Journ. f. prakt. Chem. 1851, 53, 21. 198,
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f. prakt. Chem. 1839, 16, 470. 208, Varrentrapp, Pogg. Ann. 1839, 48, 189. 207,
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Rammelsberg, Mineralchem. 1860, 851. 213, L. Smith, Amer. Journ. Sc. 1866, 42,
91. 214, Flight quoted by Maskelyne, Journ. Chem. Soc. 1871, 9, 9.
Tourmalines.
The numbers following the analysts' names are the numbers of their tests as
described in the following papers :
Rammelsberg, Pogg. Ann. 1870, 139, 379, 547 ; Mineralchem. 1875, 541. Riggs,
Amer. Journ. Sc. 1888, 35, 40. Jannasch & Calb, Ber. d. D. chem. Ges. 1889, 22,
219. 1, Rammelsberg 14. 2, Riggs 18. 3, Rammelsberg 31. 4, Rammelsberg 20.
5, Rammelsberg 13. 6, Scharizer, Groths Zeitschr. 15, 344. 7, Jannasch 7. 8,
Riggs 2. 9, Riggs 14. 10, Riggs 15. 11, Cossa, Groths Zeitschr. 7, 14. 12, Jannasch
6. 13, Riggs 3. 14, Riggs 19. 15, Rammelsberg 21. 16, Riggs 16. 17, Scharizer,
Groths Zeitschr. 75, 344. 18, Sommerland quoted by v. Groddeck, Zeitschr. d. GeoL
Ges. 1884, 36, 642. 19, Rammelsberg 6. 20, Rammelsberg 28. 21, Riggs 17. 22,
Riggs 13. 23, Jannasch 3. 24, Rammelsberg 18. 25, Jannasch 4. 26, Riggs 5.
27, Rammelsberg 22. 28, Sauer, Zeitschr. d. Geol. Ges. 38, 704. 29, Rammelsberg 25.
30, Rammelsberg 11. 31, Jannasch 9. 32, Rammelsberg 26. 33, Rammelsberg 2.
34, Rammelsberg 17. 35, Rammelsberg 23. 36, Riggs 7. 37, Riggs 9. 38, Riggs 8.
39, Rammelsberg 5. 40, Engelmann, Inaug.-Diss., Bern 1877. 41, Rammelsberg 27.
42, Rammelsberg 19. 43, Rammelsberg 12. 44, Jannasch 5. 45, Gill, Johns Hopkins
Univ. Circ. No. 75. 46, Schwartz quoted by v. Groddeck, Zeitschr. d. Geol. Ges. 1887,
39, 238. 47, Rammelsberg 3. 48, Rammelsberg 4. 49, Rammelsberg 1. 50, Ram-
melsberg 15. 51, Rammelsberg 7. 52, Rammelsberg 22. 53, Riggs 4. 54, Scharizer,
Groths Zeitschr. 75, 344. 55, Rammelsberg 24. 56, Rammelsberg 9. 57, Rammels-
442 REFERENCES TO ANALYSES
berg 10. 58, Rammelsberg 29. 59, Riggs 10. 60, Rammelsberg 8. 61, Rammelsberg
33. 62, Jannasch 1. 63, Riggs 12. 64, Riggs 11. 65, Rammelsberg 16. 66, Jan-
nasch 2. 67, Riggs 20. 68, Rammelsberg 32. 69, Riggs 6.
Felspars.
1, F. Heddle, Trans. Roy. Soc. Edinb. 1877, 28, 197 ; Min. Soc. Lond. 1881, 4,
197. 2, Raimondi, Min. Perou 1878, 309. 3, Deville, Ann. de chim. et phys. 1854,
40, 283. 4, Delesse, Ann. de chim. et phys. 1848, 24. 5, F. Heddle, Trans. Roy. Soc.
Edinb. 1877, 28, 197 ; Min. Soc. Lond. 1881, 4, 197 ; Groths Zeitschr. 2, 651 ; 7, 190.
6, G. v. Rath, Niederrh. Ges., Bonn 1869, 108 ; Pogg. Ann. 1869, 138, 464 ; 1871,
Erg.-Bd. 5, 431. 7, Kersten, Journ. f. prakt. Chem. 1846, 37, 174. 8, Kersten, N.
Jahrb. 1845, 653. 9, Des Cloizeaux, Bull. soc. min. Paris 1884, 7, 255. 10, Erdmann.
Min. 1853, 326. 11, Bothe quoted by G. v. Rath, Trach. Siebengeb., Bonn 1861, 14.
12, Laurent, Ann. de chim. et phys. 59, 108. 13, J. L. Smith per Genth, Min.
N. C. 1891, 55. 14, K6nig, Zeitschr. d. Geol. Ges. 1868, 20, 374. 15, F. Heddle, Trans.
Roy. Soc. Edinb. 1877, 28, 197 ; Min. Soc. London 1881, 4, 197 ; Groths Zeitschr. 2,
651 ; 7, 190. 16, Schnorf quoted by v. Fritsch, Kenngott, Ubers. min. Forsch. 1862-5,
191. 17, Merian, N. Jahrb. 1885, Beil.-Bd. 3, 296. 18, Kemp, Ann. Journ. So. 1888,
36, 247. 19, Struve, Kenngott, tJbers. min. Forsch. 1862-5, 190. 20, Struve, Ram-
melsberg, Mineralchem. 1875, 569. 21, Duparc per Fouque, Bull. soc. Paris
1894, 17, 360. 22, BrSgger & Reusch, Zeitschr. d. Geol. Ges. 1875, 27, 676. 23,
Fellner, Verh. d. Geol. Reichsanst. 1867, 770, 286. 24, G. v. Rath, Zeitschr. d.
Geol. Ges. 1895, 27, 328; Pogg. Ann. 1875, 155, 65; N. Jahrb. 1875, 397. 25,
G. v. Rath, Nat.-hist. Ver. Bonn 1875, Korr.-Bl. 95. 26, Petersen, Groths
Zeitschr. 9, 394. 27, Haughton, Qu. Journ. geol. Soc. 1862, 18, 403 ; Rep. Brit.
Assoc. 1863, 55. 28, Jackson, Amer. Journ. Sc. 1866, 42, 107. 29, Hunt, Amer.
Journ. Sc. 1864, 38, 97, 180. 30, F. Heddle, Trans. Roy. Soc. Edinb. 1877,
28, 197 ; Min. Soc. Lond. 1881, 4, 197 ; Groths Zeitschr. '2, 651 ; 7, 190. 31,
Jackson, Amer. Journ. Sc. 1866, 42, 107. 32, Streng, N. Jahrb. 1867, 537. 33,
Des Cloizeaux, Bull. soc. min. Paris 1884, 7, 255. 34, Resales, Pogg. Ann. 1842,
55, 109. 35, Konig, Zeitschr. d. Geol. Ges. 1868, 20, 372. 36, Haughton, Phil.
Mag. 1870, 40, 59. 37, Pisani, Bull. soc. Paris 1885, 8, 6. 38, Siemiradzki, N. Jahrb.
1886, Beil.-Bd. 4, 209. 39, Fellner, Verh. d. Geol. Reichsanst. 1867, 770, 286. 40,
Scheerer, Pogg. Ann. 1845, 64, 153. 41, G. v. Rath, Pogg. Ann. 1872, 147, 277. 42,
G. v. Rath, Niederrh. Ges., Bonn 1875, 60 ; Zeitschr. d. Geol. Ges. 1875, 27, 331 ;
N. Jahrb. 1875, 397, Pogg. Ann. 755, 65. 43, Des Cloizeaux, Bull. soc. min. Paris
1884, 7, 277. 44, Berzelius, Arsber. 1824, 4, 147 ; 1839, ig, 302. 45, G. v. Rath,
Berl. Akad. 1876, 164 ; N. Jahrb. 1876, 706. 46, Haughton, Phil. Mag. 1870, 40, 59.
47, Hunt, Amer. Journ. Sc. 1864, 38, 97, 180. 48, Fouque, N. Jahrb. 1876, 66. 49,
F. Heddle, Trans. Roy. Soc. Edinb. 1877, 28, 197 ; Min. Soc. Lond. 1881, 4, 197 ; Groths
Zeitschr. 2, 651 ; 7, 190. 50, Delesse, Ann. de chim. et phys. 1850, 30, 81 ; Bull,
soc. geol. 7, 528. 51, Delesse, N. Jahrb. 1851, 169. 52, F. Heddle, Trans. Roy. Soc.
Edinb. 1877, 28, 197 ; Min. Soc. Lond. 1881, 4, 197 ; Groths Zeitschr. 2, 651 ; 7, 190.
53, v. Giimbel, Beschr. Bay. 1868, 2, 344. 54, G. v. Rath, Pogg. Ann. 1871, 144, 256.
55, Delesse, Ann. mines 1849, 16, 362 ; 1851, ig, 149. 56, Penfield & Sperry, Amer.
Journ. Sc. 1887, 34, 390. 57, G. Rose, Reise 1837, J, 144 ; 1842, 2, 511 ; Pogg. Ann.
1841, 52, 470. 58, F. Heddle, Trans. Roy. Soc. Edinb. 1877, 28, 197. 59, Compt.
rend. 1844, 19, 46. 60, Delesse, ibid. 61, Wollemann, Groths Zeitschr. 14, 625. 62,
Hebenstreit, Groths Zeitschr. 2, 103. 63, Seneca, Beschr. Bad. 1861, 62. 64, Fouque,
Compt. rend. 19, 46. 65, Pisani, Bull. soc. Paris 1894, 17, 369. 66, G. v. Rath, Pogg.
Ann. 1871, 144, 20. 67, G. v. Rath, Pogg. Ann. 1871, 144, 235 ; Niederrhein. Ges.,
Bonn 1871, 16, 78. 68, Lemberg, Zeitschr. d. Geol. Ges. 1887, 39, 569. 69, G. v.
Rath, Pogg. Ann. 1872. 147, 275. 70, F. Heddle, Trans. Roy. Soc. Edinb. 1877, 28,
197 ; Min. Soc. Lond. 1881, 4, 197 ; Groths Zeitschr. 2 f 651 : 7, 190. 71, Delesse,
Compt. rend. 1844, ig, 46 : Zeitschr. d. Geol. Ges. 1853, 5, 687. 72, Hagen, Pogg.
Ann. 1838, 44, 329. 73, Kerndt, Journ. f. prakt. Chem. 1848, 43, 214. 74, Smith &
Brush, Amer. Journ. 1853, 15, 211 ; 16, 44. 75, Pisani, Bull. soc. Paris 1885, <, 6.
76, Kersten, N. Jahrb. 1845, 653. 77, Rocholl quoted by Rammelsberg, Mineralchem.
1875, 575. 78, Streng, N. Jahrb. 1867, 537. 79, Fouque, Bull. soc. min. Paris, 1894
J7, 363. 80, Bonsdorff, Moberg per Rammelsberg, Mineralchem. 1875, 574.
81, Deville, Bull. soc. geol. 1848-9, 6, 410. 82, K. v. Hauer, Verh. d. Geol. Reichsanst.
1867, 58, 14, 144; 1869, 12, 51; 1867, 146, 12, 13, 118, 60, 354, 119. 83, Delesse,
Ann. min. 1847, 12, 258. 84, Domeyko, Min. 1879, 562-5. 85, Thomson, Phil. Mag.
REFERENCES TO ANALYSES 443
1843, 22, 190. 86, Delesse, Ann. min. 1847, 12, 256. 87, Sartorius v. Waltershausen,
Vulk. Gest. 1853, 34. 88, Segeth, Bull. sc. Petersburg 1040, 7, 25 ; Journ. f. prakt.
Chem. 1840, 20, 253. 89, Siemiradzki, N. Jahrb. 1886, Beil.-Bd. 4, 223. 90, B. Koto,
Groths Zeitschr. 13, 179. 91, K. v. Hauer, Verb. d. Geol. Reichsanst. 1867, 58, 14. 144 ;
1869, 12, 51 ; 1867, 146, 12, 13, 118, 60, 354, 119. 92, Mattirolo quoted by Cossa,
Groths Zeitschr. 7, 629. 93, Behr quoted by Benecke-Cohen, Umgeg. Heidelberg 1881,
139. 94, Delesse, Ann. min. 1849, 16, 513. 95, Hunt, Erdm. Journ. 1855, 66, 149 ;
Geol. Surv. Can. 1857, 357 : 1863, 478. 96, G. v. Rath, Pogg, Ann. 1871,
144, 247. 97, Swiatkowsky quoted by Benecke-Cohen, Umgeg. Heidelberg 1881,
139. 98, Tschermak, Akad. Wien 1864, 50, 586. 99, Klement, Tscherm. Mitt.
N. F. i, 366. 100, Lehunt, Ed. N. Phil. Journ. 1832, 86. 101, Zittel, N. Jahrb.
1866, 641. 102, Doelter, Tscherm. Mitt. 1874, 15; 1873, 62. 103. Delter, ibid.
104, Doelter, ibid. 105, G. v. Rath, N. Jahrb. 1875, 397, jPogg. Ann. 155, 65 ;
Zeitschr. d. Geol. Ges. 27, 332. 106, Doelter, Tscherm. Mitt. 1873, 62 ; 1874,
15. 107, Doelter, ibid. 108, G. v. Rath, Niederrh. Ges., Bonn 1873, 231 ; Monatsber.
d. Berl. Akad. 1874, 26 ; Pogg. Ann. 1874, 152, 39 ; 1875, 155, 64 ; Zeitschr. d. Geol.
Ges. 1875, 27, 302-24. 109, G. v. Rath, Pogg. Ann. 1873, Erg.-Bd. 6, 380. 110,
E. E. Schmid, Pogg. Ann. 1863, ng, 188. Ill, Sartorius v. Waltershausen, Vulk.
Ges. 953, 24. 112, Abich, Pogg. Ann. 1840, 50, 347. 113, Ricciardi, Gazz. chim.
ital. 1881, 138. 114, Sartorius v. Waltershausen, Vulk. Ges. 1853, 34. 115, Hunt,
Amer. Journ. Sc. 1864, 38, 177. 116, Streng, Zeitschr. d. Geol. Ges. 1858, 10, 135,
Berg- u. Hiittenm. Ztg. 1861, 20, 265. 117, Jannasch, N. Jahrb. 1884, 2, 42. 118,
Williams, N. Jahrb. 1887, Beil.-Bd. 5, 417. 119, Dulk per Rammelsberg. Mineral-
chem. 1875, 564, Nr. 9. 120, K. v. Hauer, Verh. d. Geol. Reichsanst. 1867, 58, 14,
144; 1869, 12, 51; 1867, 146, 12, 13, 118, 60, 354, 119. 121, Hunt, Erdm. Journ.
1855, 66, 149 ; Geol. Surv. Can. 1857, 357 ; 1863, 478. 122, Domeyko, Min. 1879,
562-5. 123, Klement, Groths Zeitschr. 18, 529. 124, Wilk, Groths Zeitschr. 7, 77.
125, Deville. Bull. soc. geol. 1848, 1849, 6, 410. 126, Hunt, Erdm. Journ. 1855, 66,
149 ; Geol. Surv. Can. 1857, 357 ; 1863, 478. 127, Hunt, ibid. 128, Rammelsberg,
Mineralchem., 5 Suppl., 1853, 48. 129, Hunt, Erdm. Journ. 1855, 66, 149 ; Geol.
Surv. Can. 1857, 357 ; 1863, 478. 130, Bonsdorff & Laurell, Vet. Akad. 1876, 169.
131. G. v. Rath, Pogg. Ann. 1871, 144, 245. 132, Lemberg, Zeitschr. d. Geol. Ges.
1888, 40, 645. 133, Wilk, Groths Zeitschr. n, 315. 134, Hunt, Erdm. Journ. 1855,
66, 149 ; Geol. Surv. Can. 1857, 357 ; 1863, 478. 135, Payne quoted by Dana, Min.
1892, 337, 336. 136, G. v. Rath, Niederrh. Ges., Bonn 1873, 231 ; Monatsb. d. Berl.
Akad. 1874, 26 : Pogg. Ann. 1874, 152, 39 ; 1875, J55, 64 ; Zeitschr. d. Geol. Ges.
1875, 27, 302-24. 137, Laspeyres, Zeitschr. d. Geol. Ges. 1866, 18, 193. 138, G. v.
Rath, Niederrh. Ges., Bonn 1873, 231 ; Monatsb. d. Berl. Akad. 1874, 26 ; Pogg. Ann.
1874, 152, 39 ; 1875, 155, 64 ; Zeitschr. d. Geol. Ges. 1875, 27, 302-24. 139, Maly,
Sitzb. Ak. Wien 1885, gi, 65. 140, Laurell, Vet. Akad. Handl. Stockh. 1853, 14.
141, Heddle, Trans. Roy. Soc. Edinb. 1877, 28, 197 ; Groths Zeitschr. 2, 654. 142,
Williams, N. Jahrb. 1887, Beil.-Bd. 5, 417. 143, Tschermak, Min. Mitt. 1874, 269 ;
1875, 41. 144, Hofer, N. Jahrb. 1871, 128. 145, Hofer, ibid. 146, Deville, Bull.
soc. geol. 1848-9, 6, 410. 147, Lemberg, Zeitschr. d. Geol. Ges. 1870, 22, 337, 342,
361. 148, Jewreinow, Berg- u. Hiittenm. Ztg. 1853, 7, 196. 149, Clarke quoted by
Kum, Amer. Journ. Sc. 1888, 36, 222. 150, Knop, Kaiserst. 1892, 101. 151, Heddle,
Trans. Roy. Soc. Edinb. 1877, 28, 197 ; Groths Zeitschr, 2, 654. 152, Haushofer,
Groths Zeitschr. 3, 602. 153, Haughton, Qu. Journ. geol. soc. 1862, 18, 403 ; Rep.
Brit. Assoc. 1863, 55. 154, Koch, Tscherm. Mitt. 1877, 330. 155, Lory, Bull. soc.
geol. 1849-50, 7, 542. 156, Lory, ibid. 157, Keller quoted by Genth, Amer. Phil.
Soc., 2 Oct. 1885. 158, Streng, N. Jahrb. 1867, 537. 159, Hunt, Erdm. Journ. 1855,
66, 149 ; Geol. Surv. Can. 1857, 357 ; 1863, 478. 160, Wedel, Jahrb. d. Geol. Landesans
1890. 161, Delesse, Ann. min. 1853, 3, 374. 162, Chatard per Genth, Amer. Phil.
Soc. 1873, 13, 397 ; Min. N. C. 1891, 55. 163, Delesse, Ann. Min. 1848, 13, 675 ;
1853, 3, 374. 164, K. v. Hauer, Verh. d. Geol. Reichsanst. 1867, 58, 14, 144 ; 1869,
12, 51 ; 1867, 146, 12, 13, 118, 60, 354, 119. 165, Abich, Pogg. Ann. 1840, 51, 523.
166, Dirvell, Bull. soc. min. Paris 1884, 7, 329. 167, Foullon quoted by Schuster, Jahrb.
d. Geol. Reichsanst., Wien 1887, 37, 219. 168, G. v. Rath, Niederrh. Ges., Bonn 1873,
231 ; Monatsber. d. Berl. Akad. 1874, 26 ; Pogg. Ann. 1874, 152, 39 ; 1875, 755, 64 ;
Zeitschr. d. Geol. Ges. 1875, 27. 302-24. 169, Chatard quoted by Genth, Amer. Phil.
Soc., 19 Sept. 1873, 13, 397. 170, Delesse, Ann. min. 1848, 13, 675. 171, Hunt, Amer.
Journ. Sc. 1864, 38, 180, 197. 172, Petersen, N. Jahrb. 1874, 270. 173, G. v. Rath,
Zeitschr. d. Geol. Ges. 1875, 27, 325 ; Pogg. Ann. 155, 65 ; N. Jahrb. 1875, 397. 174,
Des Cloizeaux, Bull. soc. min. Paris 1884, 7, 255. 175, Delesse, Ann. min. 1848, 13,
444 REFERENCES TO ANALYSES
675. 176, Chrustschoff, Compt. rend. 1891, 112, 1070. 177, Glocker, Fogg. Ann.
1844, 61, 385 ; Journ. f. prakt. Chem. 1845, 34, 494 ; Synops Min. 1847, 143. 178,
Rammelsberg, Mineralchem., 5 Suppl., 1853, 48. 179, G. v. Rath, Niederrh. Ges.,
Bonn 1873, 231 ; Monatsber. d. Berl. Akad. 1874, 26 ; Pogg. Ann. 1874, 152, 39 ;
1875, J55, 64 ; Zeitschr. d. Geol. Ges. 1875, 27, 302-24. 180, Goldschmidt, N. Jahrb.
1881, Beil.-Bd. i, 207. 181, Goldschmidt, ibid. 182, K. v. Hauer, Verh. d. Geol.
Reichsanst. 1867, 58, 14, 144 ; 1869, 12, 51 ; 1867, 146, 12, 13, 118, 60, 354, 119. 183,
Franke per Rammelsberg, Mineralchem. 1860, 609. 184, Heddle, Trans. Roy.
Soc. Edinb. 1877, 28, 197 ; Groths Zeitschr. 2, 654. 185, K. v. Hauer, Verh. d. Geol.
Reichsanst. 1867, 58, 14, 144; 1869, 12, 51; 1867, 146, 12, 13, 118, 60, 354, 119.
186, Jacobson quoted by Rammelsberg, Mineralchem. 1860, 606. 187, Varrentrapp
quoted by G. Rose, Pogg. Ann. 52, 465.
NAME INDEX
Abegg & Bodlander, 266, 267
Abich, 421, 425
Albrecht, 230, 233
Alexander, 234
Allen & Shepherd, 158, 162, 170, 175, 305,
320
Ammon, v., 367
Apfelstadt, 206, 207, 233
Armstrong, 259, 266, 267, 311
Arrhenius, 229, 266, 326
Arzruni, 282, 292
Asch, D., 16, 235, 241
Asch, W., 16, 97, 235, 322
Asch, W., & Asch, D., 216, 235
Ascher, 199
Aston ; see Ramsay & Aston
Atterberg, 134
Azakawa, 223
B
Baeyer, Ad. v., 281, 311
Baeyer & Villiger, 278
Baldus, 230, 235
Baltzer, 367
Becke, 281, 284, 285, 307
Becquerel, H., 274
Behr, 419
Behring, 223, 224
Bel, Le, 281, 314
Bemmelen, J. M. van, 70
Benrath, 236
Berg, 380
Bergemann, 3, 380
Berlin, 376
Berthelot, 269
Berthier, 236
Berthollet, 293, 302-304
Berzelius, 3, 6, 10, 48, 270, 353, 358, 413,
415
Biel, 232
Biot, 312
Birch-Hirschfetd, 234
Bischof, C., 107, 113, 124, 126, 127, 128,
129, 131, 428, 430, 431
Black, 221, 225
Blank, 234
Blau, 369
Blomstrand, 17, 19, 21, 98, 257, 321
Blythe, 371
Bock, 399
Bodlander ; see Abegg & Bodlander
Bodecker, 4, 6
Boke, 234
Bois Reymond, 326
Bombicci, 6, 11
Bomstein, 223
Bonsdorff, 4, 6, 362, 419
Bonsdorff & Laurell, 423
Boricky, 373, 389
Bothe, 413
Bousfield, 259
Brandhorst & Kraut, 102
Braun, J. v., 277
Brauns, 6, 285, 312, 314, 315, 316
Bravais, 285, 289, 316
Bredig, 270
Breidenbaugh, 393
Breidenstein, 356
Breunlin, 136
Brewster, 312
Brogger, 9
Bromeis, 365, 373
Brongniart & Malaguti, 108
Brown, 292
Bruck, 230, 233
Briiel, 385
Bruhl, 312
Brun, 401
Brunner, 136
Brush, 371
Brush ; see Smith & Brush
Biichner, 136, 434
Bullouin, M., 283
Burton, 403
Buttlerow, 271
Calb ; see Jannasch & Calb
Caldwell, R. J., 266, 267
Candelot, E., 196
Carrara & Vespignani, 228
Chatard, 367, 371, 387, 397, 399, 425
Chatelier, H. Le, 110, 157, 158, 163, 164,
196, 197
Chatoney & Rivot, 156, 163, 164
Chrustschoff, 427
Clarke, 4, 6, 9, 23, 26, 27. 28, 65-70, 296
Clarke & Schneider, 387, 395, 401, 403
Claus, 309, 310
Cobb, J. W., 162
Cleef, van, 262
Coehn, 278
Cohen, 367
Collie & Tickle, 278
Cooke, W. F., 266, 267, 371
Cossa, 369, 371, 406
Crawe, 365
Croly, de, 223
445
446
NAME INDEX
Cronquist, 430
Crossley, 367, 374
Curie, 274
D
Dalkuhara, 7
Dalton, J., 304
Dammer, 96
Damour, 4, 65, 66, 70, 72, 77, 358, 361,
362, 374, 399
Dana, A. G., 354
Darapsky, 358
Davis & Fowler, 229
Debray, 101
Decaisne, 234
Delesse, 361, 369, 373, 397, 403, 413, 415,
417, 419, 421, 425, 427
Delter, 421
Desch, C. H., 113, 159, 162, 178, 253, 319
Detzner, 230
Deval, 198
Deville, 411, 419, 423
Dewey, 371
Diamant, 311
Dieffenbach, 391
Dirvell, 413, 415, 425, 427
Dobereiner, 3
Dollken, 226
Doelter, 11, 47, 70, 284
Domeyko, 419, 421
Donnan, 229
Donnell, M., 387
Drasche, v., 355
Dreschfeld, 202
Dulk, 421
Dumas, 236
Du-Bois-Reymond, 326
Dupare, 413
Durscher, 358
E
Ebell ; see Knapp & Ebell
Egger, 399
Ehrlich, P., 222, 223, 224, 225, 323
Eisner, 136, 151
Engelmann, 408
Erdmann, 361, 401
Erdmenger, 157, 163, 164
Erlenmeyer, 257, 324, 397
Escher, 230
Euler, 266, 267
Eykmann, 259
Federow, v., 312
Fehling, 435
Feichtinger, 154, 178, 183-188, 190, 434,
435, 436
Feiler, 230, 232
Fellenberg, v., 387, 393, 399
Fellner, 413, 415
Feret, 158
Fermi & Pernossi, 223
Ficinus, 373
Field, 393
Filippi. de F., 316
Finkener, 100, 102
Firtsch, 405
Fischer, E., 224, 271, 281
Fischer, E., & Passmore, F., 271
Fischer, F., 237, 254, 434, 435
Fletcher, T., 199, 200
Flett, 134
Flight, 405
Fock, 281, 283, 284, 285, 299
Forster, 241
Forchhammer, 108
Fouque, 415, 417, 419
Fowler ; see Davis & Fowler
Francis, 417
Franke, 427
Frankenheim, 285, 289, 316
Freinkel ; see Kehrmann & Freinkel
Fremery, 17
Fremy, 4, 155, 193
Fremy ; see Pelouze & Fremy
Freund, 231
Friedel, G., 45, 72, 257
Friedheim, 17-22, 81-87, 93, 94, 225, 321
Fuchs, 154-157, 176, 193, 380
Fuchs & Gehlen, 357, 359
Fullon, v., 362, 425
G
Galbraith, 373
Gans, 210, 211
Garret, 393
Gehlen ; see Fuchs & Gehlen
Genth, 369, 385, 391, 395, 399
Gerhardt, 48, 230
Geuther, 293
Gibbs, W., 15, 96, 100-102, 221
Gill, 408
Gintl, 395, 403
Gittelson, 265
Giwartowsky, 380
Glan, P., 228
Gluhmann, 269
Gmelin, 136, 146, 150, 322
Gmelin-Kraut, 256
Goldschmidt, V., 6, 11, 282
Golowkinski, 4
Gomberg, 276, 278
Gooch, 385, 391
Gorgeu, 24
Grabe, 246
Grandeau, 382
Grauer, 196
Graw, 401
Greve, 234
Groger, M., 242, 243
Groth, P., 6, 9, 27-29, 282, 283, 292, 294,
309, 313, 314
Griinzweig, G., 433
Guckelberger, 137, 138, 151, 322, 431-434
Giimbel, v., 395, 397, 417
Gunzert, 230
NAME INDEX
447
H
Hagen, 417
Haidinger, 316
Hamberg, 387
Hamm, v., 387
Hammerschlag, 403
Hantzsch, 266, 267, 276, 278
Hantzsch ; see Werner and Hantzsch
Hallopeau, 270
Hardmann, 401
Hardt, 156, 157
Hartwall, 378, 385
Hartwall & Herdberg, 378
Hata, 224
Hauer, K. v., 371, 373, 393, 397, 399, 419
421, 425, 427
Haughton, 373, 413, 415, 425
Haushofer, 5, 28, 425
Hautefeuille, 24, 292
Hauy, 293, 317
Hawes, 393
Hebenstreit, 417
Heddle, 354, 356, 358, 360, 373, 378 385
387, 389, 391, 393, 397, 399, 401, 403 ?
411, 413, 415, 417, 423, 425, 427
Heinsheimer, 230, 234
Heldt, 156, 163
Henry, C., 71
Hentze, 230, 233
Herdberg ; see Hartwall and Herdberg
Hermann, 311, 354, 360, 362, 374 376
378, 380, 385, 401, 403
Hersch, 66
Herz, M., 283
Herzog, N. v. Leuchtenberg, 401, 403
Heumann, 137, 147-150, 322, 431, 432
Heydweiller; see Kohlrausch & Heyd-
weiller
Higgin, A. J., 266, 267
Hilger, 367
Hillebrand, 353
Hintze, 48, 61
Hirschfeld, 234
Hofer, 423
Hoff, van't, 266, 278, 281, 284, 307 315
326
Hoffmann, 146, 322, 415, 427
Hoffmann, A. W., 434
Hoffmann, O., 208
Hoffmann, R., 137, 138, 147, 152, 322 433
Hoppe-Seyler, 271
Horstmann, 230, 312
Hovestadt, 254
How, 358
Howe ; see Penfield & Howe
Hundeshagen, 102, 212
Hunt, 283, 358, 374, 378, 380, 385, 387
389, 415, 419, 421, 423, 425
Hunt, St., 4
Hunter, J., 303
Igelstrom, 365, 371, 399, 401
Jackson, 360, 413, 415
Jacobs, 399
Jacobson, 427
Jannasch, 54, 296, 391, 410, 421
Jannasch & Calb, 404, 406, 408, 410
Jannasch & Locke, 54
Jannetaz, 378, 415
Janowsky, 395, 403
Jantsch, 131
Jantzen, 170
Jewrechow, 373, 425
Jex, 157, 163, 164
Jochum, 113
Jorgensen, 257
Johnson, A., 70
Jones, 266, 267
Jordis & Kanter, 158, 163
Jung, 205, 206, 208
K
Kanter ; see Jordis & Kanter
Karewski, 234
Kaul, H., 430
Kehrmann, 17, 20, 99, 102, 278, 321
Kehrmann & Freinkel, 20, 101
Kekule, 272, 310, 311
Keller, 425
Kemp, 413
Kerndt, 417
Kersten, 413
Keyser, 234, 395
Kiepenheuer, 382
Killing, 371
| Kitasato, 223
i Klaproth, 3
Klein, 96, 97
Klein, C., 317
Klement, 395, 399, 421, 423
Klemm, 353
Klocke, 312
Knapp, 174, 175
Knapp & Ebell, 150
Knoblauch, 228, 276
Knop, 14, 367, 425
Knorr, A., 223
Kobell, 358, 361, 367, 373, 385, 393, 395
399, 403
Koch, 425
Koch, E., 143
Koch, Robert, 223
Koch & Uhlenhut, 224
Konig, 367, 369, 371, 373, 395, 413, 415
Kohlrausch, 241, 269
Kohlrausch & Heydweiller, 260
Kohlschiitter, V., 257, 266
Kolbe, 270
Komonen, 403
Kosmann, 157, 163, 164
Kostanecki ; see Liebermann, C., & St.
Kostanecki
Koto, 419
Kraut ; see Brandhorst & Kraut
448
NAME INDEX
Kressler, 136
Kruss, G., & S. Oeconomides, 143
Kulka, 202-206, 232
Kuntze, O., 261
Lacroix, 374
Ladenburg, 310, 311
Lagorio, 401
Lagus & Olckonon, 376
Landrin, 164
Lardin, 234
Lartschneider, 231, 233
Lasaulx, v., 292
Laspeyres, 354, 355, 371, 423
Laurell ; see Bonsdorff & Laurell
Laurent, 4, 413
Lawrow, 4
Le Bel, 281, 314
Le Blanc & Noyes, 270
Le Chatelier, 157, 158, 163, 196, 197
Leduc, 163
Leeds, 380, 389
Lehmann, O., 294, 317
Lehunt, 371, 421
Lemberg, 11, 25, 29, 39-44, 47, 56, 57, 59,
340-352, 358, 369, 376, 380, 417, 423,
425
Levy, M. ; see Fouqe & M. Levy
Ley, H., 229, 260
Liebe, 387, 389, 393
Liebermann, C., 246
Liebermann, C., & St. Kostanecki, 225
Liebig, 270
List, 391
Locke ; see Jannasch & Locke
Loebell, 435
Low, 223
Loew, O., 271
Loretz, 389, 397
Lory, 425
Lossen & Zander, 312
Lowry, 259, 266, 267
Ludwig, 129, 163, 164, 355, 387, 395
Luedecke, 356
Lunge, 160, 171
M
Mach, 100
Malaguti ; see Brongniart & Malaguti
Mallard, 11, 70, 292, 312, 314
Mallet, 371
Maly, 423
Manchot, 273, 320
Manchot & Reiser, 111, 272
Marignac, 94, 95, 96, 97, 241, 269, 387,
389, 391, 401
Marsh, 356, 358
Marx, 230
Massalin, 369
Masur, A., 232
Mattirolo, 419
Maumene, 254
Mauthner, 354
Mellor & Holdcroft, 6, 29, 107, 110, 111,
112, 113, 119, 120, 121, 122, 123, 128
Melville, 393
Mene, C., 106
Merian, 413
Merz, 387
Metschnikoff, 223
Meyer, A., 163, 164
Meyer, E. v., 282
Meyer-Mahlstadt, 157
Meyer, R., 311
Meyer, V., 272
Michaelis, 17, 132, 156, 160, 163, 164, 175,
178, 186, 196
Miller, 200, 221, 232
Minor ; see Penfield & Minor
Mitscherlich, 4, 293, 294, 316, 323
Morgenstern, 199, 202-206, 218
Moroziewicz, 23
Morveau, Guy ton, 136
Miiller. 368, 373
Muir, 382
Muthmann, 307, 308
Mylius & Foster, 237
N
Nanke, 354
Nef, 276
Neminar, 401
Nernst, 228, 229, 266, 276
Newberry Bros., 157, 163, 164
Nietzki, R., 142, 143, 146
Nordenskiold, 376, 378
Noyes ; see Le Blanc & Noyes
Obermayer, 397
Odling, 4, 6
Oeconomides, S., 143
Ohl, A., 427
Olckonon ; see Lagus & Olckonon
Oppenheim, 256
Oppler, 235
Ortmann, 401
Ostwald, Wilhelm, 16, 24, 178, 187, 188,
227, 228
Ottolenguis, 232
P., J.J., 319
Pagenstecher, 234
Parmentier, 96, 97, 241, 321
Partsch, 230
Paschkis, H., 221
Passmore, F. ; see Fischer, E., & F.
Passmore
Pasteur, 224, 313
Paternos, 259
Pawel, 232, 233
Payne, 423
Pearse. 393, 401
Pechard, 98, 101, 102, 321
Peckert, 230
Pelouze, 242, 243
NAME INDEX
449
Penfield & Howe, 306
Penfield & Minor, 54
Penfield & Sperry, 405, 417
Pernossi ; see Fermi & Pernossi
Perkin, W. H., and Kipping, E. S., 309
Petersen, 413
Petrusky, K., 434
Pettenkoffer, 154
Petterson, O., 317
Pfaff, 234
Philipp, 137, 146, 147, 322, 431, 432, 433
Piccard, 393
Pisani, 365, 371, 376, 389, 397, 415, 417, 419
Port, 230
Proust, 302-304
Priickner, 136
Pufahl, 19, 100, 389
Pukall, W., 7, 111, 117-120
R
Raimondi, 413
Rammelsberg, C., 4, 6, 14, 27, 28, 55, 99,
101, 295, 300, 305, 306, 353, 355, 369,
375, 380, 382, 391, 393, 397, 399, 405,
406, 408, 410, 423, 427
Ramsay, William, 281
Ramsay <fe Aston, 259
Raoult, 266
Rath, G. v., 374, 376, 378, 380, 382, 413,
415, 417, 419, 421, 423, 425, 427
Rawitzer, 201, 202, 206, 208
Re, H., 274
Rebbufat, 163, 164, 196
Recoura, 262-264, 323
Reissner, 230, 232
Remsen, 257
Renard, 354, 361, 373
Rennie, E. H., 266, 267
Retgers, 298, 300, 302
Reusch, 312, 313, 316
Reymond, De Bois, 326
Ricciardi, 421
Richardson, 158, 163
Richter, 113, 126, 127, 131, 155, 175
Riehter, Rob., 202, 232, 354
Rickmann, 431, 432, 433
Riegel. 356
Rieke, R., 110, 111, 113, 134, 371
Riesen, van, 401
Riggs, 404, 406, 408, 419
Rinne, 70
Ritter, 137, 151, 433
Rivot & Chatoney, 156, 163, 164
Rocholl, 419
Roelig, 265
Roepper, 373
Rohland, 136, 157, 165
Rosam, 395
Rose, 4, 316, 317
Rose & Hampe, 250
Rosenheim, 271
Rostaing, 208
Rumpf, 365, 387
Rutheford & Soddy, 274
2 G
Sachs, 230, 233
Sachse, 311
Sackur, 278
Sadtler, 358
Safarik, 5, 324
Salomon, 382
Sandberger, 397, 405
Sanderson, 199
Santerson, 399
Sauer, 169, 369, 407
Sawtschenkow, 6
Schachtel, 233, 235
Schafer, 278
Schafhaiitl, 375
Scharizer, 404, 406, 408
Scharpless, 369
Scheerer, 6, 354, 355, 371, 415
Scheff, 271
Scheffer, G., 433, 434
Scheuer, 230
Schiefferdecker, 362
Schiff, 4, 312
Schiffner, 196
Schlaepfer, 385, 387, 401
Schluttig, W., 77
Schmid, E. E., 358, 397, 421
Schmidt, 234, 311, 427
Schmidt & Unger, 158, 159, 169
Schneider ; see Clarke & Schneider
Schnerr, K. H., 55, 355
Schnorf, 413
Schonaich-Carolath, 157
Schott, 157, 158, 160, 190, 192, 193, 198,
238, 240, 243
Schrauf, A., 281, 391
Schreiber, 202, 203, 204. 206, 219, 225,
230-233, 235
Schroder, 362
Schiitz, M., 142
Schulek, 234
Schuljatschenko, 155, 156, 195
Schulte, 230
Schultze, H., 300, 302
Schuster, 292, 295
Schwager, 367
Schwarz, 236, 408
Schweizer, 389
Searle, A. B., 104, 109, 112, 128, 133, 134.
161
Seger, 108, 124, 127-130, 132, 133, 135,
135, 240, 251, 252
Segeth, 419
Selkmann, 376
Selowsky, 230
Seneca, 417
Shepherd ; see Allen & Shepherd
Seidler, 211
Siem, 226
Siemiradzki, 415, 419
Silber, P., 25, 53, 62, 139, 321
Silbermann, 230, 232
Simmonds, 111
Simonis, 130
450
NAME INDEX
Singer, 11
Sipocz, A., 361, 362, 371, 378, 391, 423
Smith, L., 361, 369, 405, 413
Smith & Brush, 369, 385, 387, 417
Smithson, 3, 10
Sobolew, 16
Soddy, 274, 279
Soddy ; see Rutheford & Soddy
Soenderop, 256
Sohncke, 285, 289, 316
Sommaruga, E. v., 134, 427
Sommerfeldt, 70, 72
Sommerland, 353, 406
Spencer & Newberry, 163
Sperry ; see Penfield & Sperry
Sprenger, 17, 101, 102
Stadeler, 4, 55
Stark, J., 274
Stas, 237
Stein, 136, 230
Steinmann, 395
Stockar-Escher, 354, 355
Stolzel, C., 150, 151
Stohmann, 310
Stremme, 319, 323
Streng, 4, 415, 419, 425
Strumpel, 202
Struve, 95, 403, 413
Suida, 360
Sutherland, 259
Swiatkowski, 419
Szilasi, 137, 148, 149, 322, 391, 431, 432
Tachenius, 3
Tammann, G., 259, 268, 300, 301
Teichek, v., 181, 435
Telek, 387
Thomson, 259, 311
Thomson, 356, 365, 380, 419
Thoreld, 367
Thugutt, St. J., 11, 25, 27, 28, 44, 45, 47,
52, 53, 58-62, 64, 152, 198, 321
Tickle ; see Collie & Tickle
Tornebohm, 158
Topsoe, 300, 302
Tournier d'Albe, 266, 267
Traube, 397
Tschermak, 5, 6, 27, 295, 300, 391, 421
Tutton, A. E., 283, 312
U
Uhlenhut ; see Koche & Uhlenhut
Unger, 136
Unger ; see Schmidt & Unger
V
Vaillant, 266, 267
Valentino, 419
Varrentrapp, 136, 371, 391, 403. 427
Vaubel, 311
Vernadsky, 5, 6, 23, 27, 28, 30, 47, 106,
165, 324, 325
Vespignani ; see Carrara & Vespignani
Vicat, 154
Villiger : see Baeyer & Villiger
Vogel, H. W., 143, 228
Vogt, 284, 378
Vohl, 430
Vossius, 234
Vucnik, 284
Vuylsteke, 399
W
Wacher, 234
Wagner, G., 362
Walden, 278
Walker, 278
Walkers, 259
Waltershausen, v., 419, 421
Wartha, 5, 6, 28, 387, 391
Watson, J. A., 266, 267
Weber, 240
Websky, 397
Wedel, 425
Wedl, 234
Wege, 218, 233, 235
Werner, A., 257, 258, 266, 278, 326
Werner & Hantzsch, 282
Weryecke, van, 403
Whitney, 262, 263, 265, 323, 362
Wild, 230
Wilk, 354, 378, 391, 423
Williams, 421, 423
Winkler, 154, 155, 160, 163, 176, 234
Wislicenus, J., 281
Witt, O. N., 142, 246
Wittstein, 382
Wohler, 250
Woltzien, 4
Woitschach, 395
Wolff, 374, 376, 380
Wolff, C., 230
Wollemann, 417
Wulf, 355
Wulff, 314
Wurtz, 4, 380, 401
Wymper, 268
Wyrouboff, 300, 302
Zander ; see Lossen & Zander
Zellner, 367
Zeltner, 146
Zenker, 21
Zeynek, R. v., 395, 397
Ziem, 234
Ziemjatschewsky, 24
Zinn, N. v., 403
Zsigmondy, 157
Zulkowski 24, 28, 160, 163, 164, 176, 177,
181, 182, 193, 236, 237, 241, 243, 248,
249-251, 435, 436
SUBJECT INDEX
A-aluminosilicates, 165, 197
A-cements, 214, 235
A-cements, toxic action of, 219
A-sodalites, 153
a-complexes, 76, 78
a-hydrogen, 197
a-hydroxyl, 65, 165, 210
a- or 2-hydro-aluminosilicates, 142
a-vanadomolybdic anhydrides, 79
Acid anhydrides, 141
Acid, ferrosulphuric, 264
Acid nature of silica, 4
Acid-reacting salts, 228
Acid- water, 65
Acidity of clays, 106
Acido-philism, 210
Acids, action of, on hydraulic lime, 194
Acids, action of, on cement, 189
Acids, chromo-sulphuric, 263
Acids, complex, 15
Acids, constitution of, 268
Acids, water of crystallisation in, 265
Actinolite, 300
Aggregation, states of, 294
Alabaster glass, 237
Albite, 9, 46, 64, 295
Alite, 158
Alkalies, action of, on cements, 189, 194
Alkaline carbonates, action of, on ce-
ments, 193
Allophane group, 104, 108, 109
Alum potash, 315
Alums, water in, 262
Alumina, acid nature of, 23
Aluminium atoms, variable behaviour of,
25
Aluminium in silicates, role of, 5
Aluminophosphates, 226
Aluminophosphoric acids, 222
Aluminophosphoric acids and nerve-fibres,
225
Aluminosilicates, 6, 7, 56, 75, 90, 139, 169,
175, 261, 319
Aluminosilicates, attraction of, for acids
and bases, 210
Aluminosilicic acids, 6, 62, 103, 165
Ammonias, metallic, 17, 256
Ammonium compounds, 299, 306, 317
Ammonium salts, 299
Amphibole, 300
Amphichromatophilism, 212
Analcime, 9, 11, 14, 25, 45, 46, 47, 72, 176
Analysis, rational, 322
Andalusite, 9
Andesite, 24, 62
Anhydrobasic salt, 166
Anorthite, 5, 47, 295
Apatite, 291
Aragonite, 291, 293
Archid hypothesis, 273
Ardennite, 29, 75
Arsenates, 291, 294, 307
Arsenic acid, 294
Arseno-compounds, 93
Arsenomolybdates, 18, 93
Ascharite, 291
Atomic complexes, 165
Atoms, constitution of, 274
Atoms, transmutation of, 281
Atoms, valencies of, 275
Avasite, 78
Aventurine glass, 249
Axes, chemical, 286
B
Base-prognoses, 73
Base-water, 65
Basic group, effect of, 95, 108
Basic salts, 167
Basis-isomerism, 63
Baso-philism, 210
Belite, 158
Benzene, structural formula of, 309
/3-complexes, 76, 95
/3-hydroxyls, 65
/3-vanadomolybdates, 79
Binding materials, 153
Bischof & Richter's law, 127
Blue Staffordshire bricks, 135
Boronatrocalcite, 291
Boron compounds, 76, 77
Boulder clay, 108
Burned clay, colour of, 135
Burning clays, 111
Cadmium compounds, 299
Calcite, 293
Calcium aluminosilicates, 169, 200
Calcium carbonate, 291
Calcium compounds, 317
Calcium hydrate, 183
Calcium sulpho-aluminates, 196
Calcspar, 291
Carbon and silicon compared, 1
Carbon compounds, 270
Carbonates, action of, on cements, 193
Carbonic acid, 293
451
452
SUBJECT INDEX
Carbonic acid, action of, on hardened
mortar, 193
Carbonic acid in mortar, 190
Celite, 158
Cement, action of salts on, 160
Cement, action of sulphates on, 196
Cement, action of water on, 197
Cement, effective substances in, 157
Cement, Fletcher's, 199
Cement formulae, 179
Cement prognoses, 193
Cement, swelling of, 196
Cements, 153, 322
Cements, action of acids and alkalies on,
189, 194
Cements and sea water, 195
Cements, cracking of, 175, 198
Cements, dental, 199
Cements, expansion of, 175
Cements, hardening constituents of, 164
Cements, hardening of, 177
Cements, heat development in, 187
Cements, hydration of, 181
Cements, isomeric, 195
Cements, regenerated, 186
Cements, silicate, 199
Centralisers, 245
Centralisers, zinc phosphate, 199
Chabasite, 47
Chemical axes of crystals, 286
Chemical constitution of Portland ce-
ments, 165
China clay (see Kaolin), 110
Chlorite, 47
Chlorite ring, 325
Chlorosodalite, 59, 64
Chondrodite, 306
Chromates, 300, 302
Chrome alum, 263
Chromophores, 245
Chromo-sulphuric acids, 263
Chromotropy, 278
Clay, colloids in, 134
Clay, colour of, 135
Clay, iron oxide in. 135
Clay, plasticity of, 133
Clay, red-burning, 135
Clay substance, 106
Clay, water of constitution in, 134
Clayite, 128
Clays, 6, 7, 168, 176, 322
Clays, constitution of, 102
Clinker, 158
Clinohumite, 306
Clintonite group, 49, 300
Cobalt compounds, 256, 292, 299, 306
Colemanite, 291
Colloidal properties of cements, 162
Colloids, 244
Colour of bricks and clay, 135
Combined water, 65, 321
Complex acid theory, 62
Complexes, 165
Composition of clays and melting point, 129
Conductivity, 227
Constitution of aluminosilicates, 7
Constitution of silicates, 3
Constitution of slags, 169
Co-ordination law, Werner's, 326
Copper ruby glass, 249
Cracking of cements, 175, 198
Cristobalite, 292
Cryophillite, 27
Crystalline form and chemical com-
position, 282
Crystallography, 282
Crystal molecule, 283
Crystals, angles of, 294
Crystals, optical properties of, 312
Crystals, structure of, 285, 289, 326
Cyanogen compounds, 256
D
Decolouration of glass, 246
Density, change in, 168
Dental cements, 199, 322
Dental stopping, characteristics of, 200
Dentistry, relation of H.P. theory to, 199
Depression of thermometer, 239
Desmine, 47, 48, 70, 71
Devitrification of glass, 241
Di-carbonic acid, 293
Diffusibility of A- and 2-cements, 235
Dimorphism of CaCO 3 , 293
Disdynamised compounds, 108
Dissociation theory, 266
Double salts, 11, 12, 16
Dualism, chemical, 305
Dyes, 246
Dye-stuffs, 212
Dynamisation theory, 168
Dynamised compounds, 108
E
Effective substances of cement, 157
Elaolite, 9
Elaolite-syenite, 59
Endlichite, 291
Enamels, 236
Enantiomorphism, 313
Enantiomorphous crystals, 313
Entpolymerisation, 170
Epidote, 46, 47, 53, 301
Epistilbite, 66, 68
Expansion of cements, 175
Faujasite, 66, 68
Felite, 158
Felspar, 5, 53, 58, 62, 64, 176, 294
Felspar group, 51
Felspars, formulae of, 297
Ferric sulphide, 292
Ferrocyanides, 257
Ferrosulphuric acid, 264
Fire resistant quotient (Bischof), 126
SUBJECT INDEX
453
Fire resistant quotient (Seger), 128
Fletcher's cement, 199
Fluorine compounds, 55
Forecite, 66, 69
Formulae, calculation of, 48
Formulae of porcelain cements, 215
Franklandite, 291
Free lime in cement, 155
G
7-hydroxyl, 65
Genetic relationship, 10, 14, 22, 40, 43, 47,
297, 298
Genetic relationship between Portland
and slag cements, 160
Geometrical constants, 305
Glass, Thuringian, 238, 240
Glasses, 236
Glasses, coloured, 243
Glasses, constitution of, 239
Glasses, formulae of, 254
Glazes, 236
Glazes, formulae of, 254
Granite, 47, 56
Gypsum, action of, on cement, 196
Hardening constituents of cements, 164
Hardening of cements, 153
Hardening of dental cements, 213
Hardening of porcelain cements, 205, 208,
212
Hardening of Portland cements, 173
Hardening of Portland cements, causes of,
177
Hardening, regulation of, 217
Hardening, secondary, of cements, 193
Heat development in hardening cements,
187
Heat on clay, effect of, 109 to 130
Heat resistance and composition, 126
Heulandite, 47, 66, 67, 70
Hexite, 30
Historical review of cements, 153
Historical review of ultramarines, 136
Historical survey, 3
Howlite, 77
Humite, 306
Hydrated limes, 183
Hydration of porcelain cements, 213, 216
Hydration of Portland cements, 181
Hydration phase, 173
Hydraulic binding materials, 153
Hydraulic limes, 153, 183, 188, 193
Hydraulic limes, action of acids on, 194
Hydraulic modulus, 168
Hydraulite, 153
Hydro-aluminosilicates, 106, 210, 261
Hydrobasic groups, 209
Hydrobasic salt, 166
Hydroborasite, 291
Hydroferrosulphates, 261
Hydrohexites, 32
Hydronephelite, 9, 65, 67
Hydro-pentites, 33
Hydrous aluminosilicates, 65
Hydroxide water, 194
Hydroxyl groups, 51, 52, 53, 72
Hygroscopicity of clay, 123
Ice, polymeric forms of, 259
Iron compounds, 78, 299, 301
Isomeric aluminosilicates, 64
Isomeric lime and magnesia, 175
Isomerism, 63, 113
Isomers of silicate cements, 195
Isomorphism, 294
Isomorphous mixtures, 13, 26, 296
K
Kaliborite, 291
Kampylite, 291
Kaolin, 6, 7, 9, 10, 25, 44, 46, 47, 52, 90,
113, 139, 165, 181
Kaolin, acido- and baso-philism of, 212
Kaolin, amphichromatophilism of, 212
Kaolin, constitution of, 212
Kaolin lakes, 212
Kaolinates, 118
Kaolinic acid, 6, 111, 115
Kaolinisation, 117
Kaolinite, 110
Krypolite, 10
Labradorite, 295
Lakes, 212
Lardellerite, 291
Laumontite, 46, 47, 65, 66, 91
Leucite, 9, 46, 176
Lime, action on bond in cements, 194
Lime- clay mixtures, 181
Lime compounds, 306
Lime, free, in cement, 155
Lime, hardening of, 174
Lime, hydraulic, 193
Lime in cements, removal of, 193
Lime, isomeric, 175
Lime, proportion removable from cement,
160
Lime, separation of, in cements, 190
Lime-silica mixtures, hardening of, 176
Limes, hydraulic, action of acids on, 194
Lud wig's chart, 128
M
Magnesia compounds, 306
Magnesia, isomeric, 175
Magnesia, slaking of, 175
Magnesium silicate, 176
Manganese compounds, 299, 306
Marcasite, 292
Margarite, 10
Masonry, destruction of, 195
454
SUBJECT INDEX
Melting point, 168
Melting point and composition, 129
Melting point of clays, 109, 124
Melting point of silicates, 131
Mesolites, 57
Metal-ammonias, 256
Metal-ammonium salts, 17
Mica, 9, 58, 60, 300, 313
Mica group, 49
Mica ring, 325
Microcline, 64
Micrographic examination of cements, 158
Micrographic study of hardening, 178
Milarite, 78
Mimetesite, 291
Mix-crystals, 298
"Mixture," 112
Mixture theories, 6, 26, 62, 163, 253, 295,
298
Mixture theory of cements, 158
Modulus, hydraulic, 168
Molasses, 211
Molecular compound, 12
Molecular core, 298
Molecular volumes, 317
Molecular weight of slags, 171
Molecular weights of crystals, 285
Molybdates, 16, 300, 302
Molybdenum compounds, 78, 79
Mordennite, 78
Mortar, 156
Mortar, action of CO 2 on, 193
Muscovite, 9, 45, 46, 47
N
Natrolite, 9, 46, 47, 59, 66, 70, 91, 176
Nepheline, 6, 9, 25, 46, 52, 61, 62
Nepheline hydrate, 52, 58, 59
Neptunite, 48
Nerve-fibres and aluminophosphoric acids,
225
Nerve-fibres, chemical constitution of, 224
Nerve-substance, reactions of, 222
Neurotropism of aluminophosphoric acids .
222
Nickel compounds, 292, 299, 306
Nomenclature of silicates, 113, 114
Nontronite, 136
Nordenskioldite, 76
Norsean, 59
Nucleus, molecular, 298
Oligoclase, 295
Olivine, 47
Opals, 106
Optical properties of crystals, 312
Optically active crystals, 313
Orthochlorite group, 50, 300
Orthoclase, 9, 12, 27, 46, 64, 295
Oxygen, valency of, 109
Oxyphilism, 212
^andermite, 291
D araleucaniline, 246
Parameters, 307
Phakelite, 27
Pelinite, 128
Pentite, 32
Permutites, 210
Petalite, 23
Phillipsite, 47
Phosphates, 291, 294, 300, 307
Phosphoric acid, 294
Phosphorous compounds, 269, 271, 293
Phosphotungstates, 20
Pigments with hydraulic properties, 198
Plaster of Paris, action of, on cement, 196
Plasticity of clay, 133, 322
Polymerisation, 113, 168
Polymerisation of gas-molecules, 283
Polymorphism, 290
Polyspharite, 291
Porcelain cements, 199
Porcelain cements, chemical constitution
of, 209
Porcelain cements, formulae of, 215
Porcelains, 236
Porcelains, formulae of, 254
Porphyrexides, 277
Porpora glass, 248
Portland cement, 153, 322
Portland cement, action of water on, 197
Portland cement and sea water, 195
Portland cement formulae, 179
Portland cement, hydration of, 181
Portland cements, constitution of, 165
Portland cements, hardening of, 173, 177
Potash compounds, 306
Potash felspar, 53, 64
Potash mica, 58, 59, 60
Potash nepheline, 58
Potassium compounds, 300, 317
Potassium silicotungstate, 95
Prehnite, 45, 47
Prismatine, 10
Prolektite, 306
Pseudomorphous processes, 45
Ptiolite, 78
Puzzolans, 153, 176
Pyrite, 292
Pyromorphite, 291
Pyrophillite, 46
Quartz, 176
Quicklime, slaking of, 174
R
Racemic acid, 313
Radio-activity, causes of, 279
Rational analysis, 107, 108
Red-burning clays, 135
Refractoriness and composition, 126
SUBJECT INDEX
455
Refractory index, 130
Regenerated cements, 186
Resistance to alkalies of slags, 160
Ring-isomerism, 64
Ring-prognoses, 74
Ring-water, 72
Roman cement, 153
Rosaniline, 246
Rubidium compounds, 317
Ruby glass, 249
S
2, 60, 152
2-aluminosilicates, 197
2-cements, 213, 227, 235
2-hydro-aluminosilicates, 142
2-sodalites, 153
2-ultramarines, 215
Saliva, action of, on cements, 218
Sapphirin, 23, 76
Scapolite, 62
Scapolite group, 50
Scolecite, 66, 69, 91
Sea water, action of, on cements, 195
Seger cones and temperatures, 129, 130
Setting of cements, 153
s-hydroxyls, 65, 165, 209, 210
Side-chains, 305
Silica, 3, 291
Silica-lime mixtures, hardening of, 176
Silica, precipitated, 7
Silica, soluble, 154, 156, 189
Silica, separation from ultramarine, 151
Silicate cements, 199
Silicate cements, isomers of, 195
Silicate- water, 186, 194
Silicic acid, 3
Silico-aluminic acid, 6
Silico hydrates, 8
Silico-molybdate, 16
Silico-tungstates, 94
Sillimanite, 110
Sintering point, 159
Skelezite, 47
Slag cement, 153
Slags, 160, 169
Slags, action of alkali on, 172
Slags, composition of, 170, 171
Soda felspar, 64
Sodalites, 12, 25, 42, 43, 46, 52, 59, 60, 65,
152, 153, 198
Sodium alumino-lactate, 226
Sodium aluminosilicate, 139
Sodium nepheline hydrate, 59
Sodium orthoclase, 64
Sodium phosphate, 293
Sodium s-kaolinate, 116, 118
Softening point and composition, 132
Softening points, 129
Softening water, 211
Solid solutions, 71, 157, 159, 253, 305
Soluble silica, 154, 156, 189
Spectrum analysis, 228
Spinels, 4
Steatite, 176
Stereo-chemical theories, criticism of, 281
Stereo-hexite and stereo-pentite theory,
286
Stilbite, 66, 68
Strontium carbonate, 291
Strontium carbonates, 306
Sugar, inversion of, 229
Sugar recovery, 211
Sugars, formation of, 271
Sulphides, 292
Sulpho-aluminates, 196
Sulphonate groups in ultramarines, 141,
151
Sulphonates, 141, 151
Sulphonates, action of, on cements, 196
Sulphonates as chromophores, 142
Sulphur, 292
Sulphuric acid ; action on clays, 107
Summary, 318
Syntagmatite, 300
Talc, 176
Tartaric acid, 313
Tellurium compounds, 317
Thermo-chemical studies of hydration, 187
Thermodynamics, law of, 71
Thermometer depression, 239
Thomsonite, 67
Tin compounds, 76
Titanic oxide, 292
Topaz, 54, 210
Topical parameters, 307
Tourmaline, 24, 47, 75, 295
Tourmaline group, 50
Toxic action of the .4 -cements, 219
Trass, 153, 176
Tri-calcium silicate, 158
Tridymite, 292
Tungstates, 18
Tungsten compounds, 20, 24, 78, 81
Type theory, 4
U
Ultramarines, 59, 136, 165, 322
Ultramarines and sodalites, 152
Ultramarines, composition of, 143
Ultramarines, constitution of, 212
Ultramarines, effect of heat on, 150
Ultramarines, isomeric, 147
Ultramarines, vitrification of, 150
Uranium compounds, 306
Urano -acetates, 306
Valencies, 275, 289, 294
Vanadates, 291
Vanadinite, 291
Vanadium compounds, 20, 75, 79
Vitrification of clay, 109
Vitrification of ultramarines, 150
456
SUBJECT INDEX
w
Water, combined, 65, 72, 109, 110
Water of constitution, 4, 51, 53, 65, 95,
104, 108, 109, 116, 134, 152, 305,
321
Water of crystallisation, 59, 65, 71, 103,
108, 186, 259, 305, 321
Water of hydration in cements, 181, 186
Water of silication (see Silicate-water),
186
Water-separation phases, 71
Water, softening, 211
Zeolites, 47, 65, 154, 210, 314
Zinc aluminophosphates, 226
Zinc compounds, 299, 306
Zinc phosphate cements, 199
Zinnwaldite, 26
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