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CHEMICAL CONTEIEUTIONS
TO THE
GEOLOGY OF CANADA.
Br
CHRLSTIAN KOFFMANN, P. I„st. Chem.
ON Canadian apatite.
Manner in which the Samples anabjzed were selected.
The sanipIoH were in hII cases ^^ood-.si.e.l hand specimens ; in seloctinff m r
the same such pieces were taken as were most free Lrnt^,^^"^
mmcra admixture, or, in other words, apparently the pure t of S ^'""'"^^•
h:Cr;r"""T" ^^^''-rC-uaHya veryL4 one!) from t f h
t was talcen As a rule, therefore, the various analyses may l,e s. id
in their greatest practically attainahle state of purity; such, indeed -J
might he secured by careful cobhi„g,-and not thetmpos tion^of a
average sample of any particular output, and the reader is cautioned
aga.nst accepting the .-esults in any other light. In some i.stZes
lep lesont a fair average of Uie vein ; in othei- cases, by the exercise of
vm- e v!;. ''.T" .^' '1"?' ^""•'^'^ '■'' l"**"""^' ''"•^- quantities of the
ya ety almost, 1 not equally, as pure as the sample examined. The
togetlior with others of a similar tenor, under the various analyses
!i
2 n
OEOLOOICATy SITRVEY OF CANADA.
Hrief allusion
to methods
employed in
the mialyiiis.
Brief allusion to some of the Methods emploi/ed in the analysis.
The fluorine \v!is dotorminctl in Jiccordjinco with Wiihloi-'H method,
as moditiod by Frosonius. (Frcscniiis' (Juiuititiitivo Choinical AnalysiH,
sixth (Jormaii edition, Vol. I., j). 431.) The apatite, reduced to an
impalpable powder and intimately mixed with finely ]>idvori'/ed quartz,
is deeomposed in a flask with eoneentratcd sulphurieacid. The fluorine
being estimated by colleelin;^ and weighing the fluoride of silicon
evolved.
The phosplioric acid was estimated by Sonnonschoin's process of
precipitation with molybdic acid — subsequently precipitating as phos-
phate of magnesia and amiixonia, and weighing as pyi'ophosphato of
magnesia.
Explanatory
remarks.
Explxnatory Remarks.
By the term " insoluble residue" is implied that portion of the apa-
tite left undissolved by the action of hy Irochloric acid ; the mineral
having been previously treated with hydrochloric acid, and evaporated
to complete dryness.
The term "variety" has not been employed in its strictest sense,
inasmnch as all the specimens here examined would, pro])erly speaking,
come under the one variety, fluor-apatite ; 1 have, however, permitted
myself its use in a wider sense, referring more particularly to texture.
It has been assumed, as is indeed most probable, that the whole of
the phosphoric acid is present in combintition with lime, and that any
excess of this latter beyond that required for the phosphoric and car-
bonic acids, may possibly— conjointly with the magnesia, alumina, and
in some instances a portion of the iron, — pertain to associated foreign
mineral matter.
Annlysis of
apatite from
Storrington.
Apatite, var. 1.
From the fourteenth lot of the sixth range of the township of
Storrington.
The sample was received from W. J. Morris, Esq., who informed me
that ho was disposed to regard it as representing a fair average oi a
quantity of some throe hundred tons extracted ; that about twenty tons
of the first two hundi'ed taken out contained some mica derived from
the foot-wall, but that this appeared to have since run out. The vein
ranged from seven to fourteen inches in width.
CANADIAN APATITE. 3 H
Massive, compact. . Lustre dull. Colour greyish to reddish-white,
witli reddisli-brown coloured stripes or bands, which impart to the
rock a stratified appearance (in some specimens those markings ai-c
less distinct). This variety of apatite may not ina])propriately bo said
to resemble, at a first glance, a tine-grained " variegated sandstone."
Tough. Fracture unove-.i. Colour of powder white with a faint
reddish tinge. Specific gravity 3'1393.
After drying at 100° C, its com])()sition was found to be as follows :
rhosphoiic iicid ' 40-373
BMuoiino « 3-311
Chlorine ■> 0-438
Carbonic atid ■• - 02G
Lime 47-828
Calcium 3 • 732
Magnesia 151
Alumina 0-(J09
Sesquioxiile of iron - 1 T) I
Alkalii'S ?
Insoluble refiidut' 3-890
100-509
1 Equal to 88-138 tribiisic piiosphate of lime,
i Equal to 6 79G fluoride of calcium.
3 Equal to 685 chloride of calcium.
4 Equal to 0-059 carbonate of lime.
Apatite, var. 2.
From the "(rrant Mine," situate on tlie south-half of the eighteenth Analysis of
lot of the twelfth range of the town.ship of Buckingham. The property luckinghanl.
of the Buckingham Mining C()m])any.
In the earlier stages of the working about two Imndred and fifty tons
of this variety were taken out; as the shaft increased in do])th, this
particular kind was not, nor has it so flir, since been met with ; it is
however inferred, that it will be found again with the other phosphate
which lies near the surface, and has yet to be removed.
Massive, vitreous. Brittle. Fi-acture uneven, angular; in some
specimens sub-conchoidal. Lustre sub-viti-eous. In thin splinters
translucent. Cohmr pale greenish grc}'. Colour of powder pale
greenish-white. This variety of apatite closely resembles in its aspect
" porcelain Jas])er." It is not unfrcquently penetrated by thin seams of
calcite. Hardness 5. Specific gravity 31493.
4 H OEOJ.OorcAT, SURVEY OP CANADA.
After drying at 100° ('., its coiupoHilion wuh iouiid to bo an follows:
Pliosphoric ncid i- 41 OSO
Fluorine* 3-474
ChloriiM" ' • 2G0
Carbonic aiid^ 0-370
Lime 49 • 1 Gl
Calcium 3 -80:!
Magnesia - 15H
Alumina 0-705
Sesquioxide of iron 0'126
Alkalies ?
Insoluble residue 0-370
99-506
1 Equal to 89-G82 tril)a8ic pliosplmte ol' lime.
2 Equal to 7-131 fluoride of calcium.
3 Equal to 0-40G chloride of calcium.
4 E<iiial to 0.84(1 carbonate of lime.
Apatite, var. 3.
Analysis of From the sixteenth lot of the third ranjjo of the township of North
apatite from -^ '
North BiirKess. RuriresH.
Massive, confusedly crystalline, weak-defined schistose te.xturc.
Fracture uneven. Lustre sub-vitreous, in parts dull. Colour dull
red. Colour of powder pale red. Specific gravity 3-l(J03.
After drying at 100° C, the composition was found to be as follows :
Phosphoric a(Jd' 39-04G
Fluorine 3-791
Chlorine' 0-476
Carbonic acid< - OiiG
Lime 4G-327
Calcium 4-2.^)8
Magnesia • 548
Almnin-i I - 190
Sesquioxide of iron 1 • 290
Alkalies ?
InsohiLle residue 3 • 490
100-512
1 Equal to 85-241 tribasic phosphate of lime.
2 Ecjual t<» 7-781 fluoride of calcium.
3 Equal to 0-744 chloride of calcium.
4 Equal to 0-218 carbonate of lime.
CANADIAN APATITE. 5 n
Apatite, var. 4.
Promtl.o "Kitcl.ioMino," situate on the seventh lot of the Hoventl, Anal.., of
lange ol tlie townshin of" Portland npatUo from
mi • ' Portland.
TluH specimen wa. collocteU by Br. B. J. Harrington, who informs
me hat at the spot whence it was taken, the mass, as exposed, mea-
sured nearly twenty feet across, and in the whole of this thickness the
only a],parent foreign mineral admixture consisted of n few crystals of
pyroxene and mica, and that, consequently, this specimen mi.-ht be
regarded as representing a large portion of said exposed mass.
Massive, lamellar; the laminro varying in thickness from one to eiffht
mdhmetre., the faces of the same are not unfrequently coated with a
more or less delicate film of calcite; the coherence between the indi-
vidual plates varies; when struck the rock has a tendency to split along
he hno of laminaticm rather than across. Brittle. Fracture across
the lam.na> uneven, angular. Lustre of this fracture vitreous, that of
•the clean surflice of the lan.ina. resinous. Colour bright sea-green
Co our of powder white with a faint greenish tinge. Semi-tran.par-
3"l884" «P'"'tei-8, transparent. Hardness 5. Specific gravity
The following interesting fact in connection with this apatite is
perhaps, not altogether unworthy of mention ; after a short exposure
to a low red-heat in a covered crucible it becomes perfectly colourless
Its lustre being not at all, and its diaphaneity very slightly affected. '
After drying at 100° C, its con. position was found to be as follows:
Pbospfioric acid' 4i • 139
*''"""»*'' "''.'.'.''''.''^'. 3-8G3
Chlorine' ^l.g'jg
Carbonic acid< ^ 223
^''"^ .'..'..'. 4i.-335
<''alcium 4. jgg
Magnesia o-\80
^''""'°'* ..'.'.'.'".'. 0-5G6 •
Scfiquioxide of iron . ^j,^
Alkalies o
Insoluble vesidue 0-060
»9-884
1 Equal to 89-810 tribasic phosphate of lime.
2 Equal to 7-929 fluoride of calcium.
3 E(iual to 0-358 chloride of calcium.
4 Equal to 0.607 carbonate of lime.
fi ir
OEOLOaiCAI, SCRVEV OF CANADA.
AniilyniM uf
iipat'tH from
lA>uiihborough.|
Apatite, luir. 5.
Krom the tenth lot of'tlio tenth vaw^o ofthe township ofLou«^hhomiii,'li.
VV. J. Morris, K..([., hy wiioui the speeimen was presented, stated thai
tho vein from which it was taken — and ofwliich, in his opinion, it might
be considered a lair sample, — had a width of about seven feet.
Massive, conipact. Lustre dull, in jtarls sul)-resinous. Hrittle.
Fracture uneven, angular. Colour dull-i-ed. Colour of jjowder
reddish-wliite. Interpenetrated by delicate tihuH of specular iron.
Specific gravity 31() U.
After drying at 100° t-., its 'composition was found to be as follows:
I'hoNphoiic acid ' 40-808
Fhioiine" 3-731
Chlorine' 0-428
Carbonic acid^ 0-105
J^ime 48-475
(Jttlcium 4-108
Magnesia 158
Alumina 0-835
Si'S(|uli)xi(le of iron o • 905
Alkalies ?
Insoluble residue 1 • 1 50
100-823
1 Equal to 80-219 tribasii; jjhoHpliate of lime.
2 Equal to 7C5H fluoride of c-alciuni.
3 E(iuiil to OCGO ililoridt' of calcium.
4 E(iual to 0-239 carbonate of lime.
Analysis of
apatite from
.Portland.
Apatite, v<(r. G.
From the " Watts Mine," situate on the sixth lot of tho tirst range
of the township of Portland. The propei-ty of the Buckingham Mining
Company.
About seventy per cent, of tho phosphate raised from tliis mine
consists of this variety, the balance is similar to that described below,
vv^herein tho compact ciystalline jihosphate preponderates, sometimes
to the almost total exclusion of the liue-gramilar.
Massive, crystalline-granular. Fi-iable. Fracture uneven, granular.
Prevailing colour greenish-white. Colour of powder M'hite. Lustre
glimmering. Specific gravity 31G7(J.
The texture of this variety varies from a verj- fine-granular crystal-
line, greenish to greyish-white, homogeneous, somewhat easil}' friable
rock, closely resembling a disintegrating sandstone, — to crystalline
granular, with imbedded rounded fragments of semi-ti-ausparent sea-
CANADIAN APATITE. 7 H
groon apatite, coiiHtituting what, jtorliaps, might not inaptly l»o
(loHignated a conglomorato — thonco j)assing on to a condition in which
the I'ragmcntH hccome nioro nunu'rous and hirger, to tlic almost total
exclusion of the tinc-granulai- matrix.
After drying at 100° C, its compoHition was found to be as I'oHowh:
I'hoBphoiicacid' 40 •MS
Fluorini'* :»-377
Cliloiiiio' (»()8G
Carbonic ncid^ • H55
Lime 40 • 04 1
( 'alciuin 3 • (jou
Magiic'Hia e • 205
Alumina o-'iOT
Sf8(|nioxi(lo itf iron 'J-08:t
Alkalies 7
Insoluble rusidue l-eso
l»9-C65
1 Equal to 88-455 tribasic pliOHpliatc of lime
2 Equal to 6-932 rtuoridc of cali-ium
3 Equal to 0-134 chloride of fiiKiuiu.
4 Equal to 1-943 carbonate of ^lime.
Apatite, oar. 7.
From the " Gi-ant Mine," situated on the south-half of the eighteenth Analysis of
lot of the twelfth range of the township of Buckingham. The property Buokinglmm.
of the Buckingham Mining Company.
About five hundred tons of this variety have been taken out at this
mine ; it is still met with, but not in such large quantities.
Massive, crystalline, tine-granular, with occasional imbedded rounded
fragments of semi-transparent sea-gi-een apatite. Prevailing colour
greyish-green. Lustre glistening, due to the presence of intennixetl
grains of pyrrhotite. SomewhaL tough. Fracture uneven, granular.
Colour of powder greenish-grey. Specific gravity 3-2441.
In selecting the material for analysis the aforementioned imbedded
rounded fragments were excluded (as also in those specimens upon
which the specific gravity was determined), the object being to
ascertain the composition of the granular matrix ; it need hardly be
remarked that theii" presence would have raised the percentage of
tribasic phosphate.
I
8 It (lEOLOdlCAl, HIIUVEY (»F CANADA.
After dryni',' at 100° (-., itn comitoHition wan found lo bo an follows:
rhosplioiiim-id' 34-032
Fluorine'' 2 865
Chlorine' oKtl
CarlM.nic fU-iiH 2 HlH
iSulphur'* 3 • 507
Lime 44-198
Cftlciuin 3-0(!2
Magiiosliv O-t'22
Aliimiiift I!t79
Nickel, (■ol)alt iiiid coitper pii'Hont, hut were n()t<lc('(l
Iron 5;i70
SeH(|iiioxi«le of iron <»-l2()
Alkiilies ?
Insoluble rcHldun 2-000
100-544
1 K(|iinl to 74'2i)r) triliaHif i)hoR])linte of Hine.
2 K<nml to n-SOO fluoride of ciiliiutn.
3 K(|ual to Oins tliloride of caleium.
4 Kqiml to (! 473 carbonate of lime.
5 l';((ii(i! to 8-877 pyrrliotite.
Tho iiickol, cobiilt and <;()j)por kIiowii to l»o prowent, pertain to tlio
asHociutod ]»yri-liotitc. In ciilcnliUinjL? the jiniount of tho hitter (in
ac'cordanoo with tlic i'orniiiia Kc, S^) corroHpcnding to tho .sulphur
found, thoir presence has been ignored, as a conseciuonco, the total iron
found lias been somowhat too largely di-avvn upon, so that the balance,
whioh was a.ssiinied and calculated to bo ])resont as poroxi.le, is somo-
what, though pos.sibl3' very slightly below the actual amount })re8enl.
Analysis <if
apatite from
Templeton,
Apatite, var. 8.
Prom the "Doctor Pit," situat(^ on tho twolftli lot of tlio twelfth
rang(^ of the township of Temploton. Tho pi-oporty of tho Templctou
and North Ottawa Mining Company.
This specimen was colloctod by Dr. B. J. Harrington, who states
that so far as the working liad advanced, this particidar kind had not
been found in an}- great (piantity, l)ut formed a portion of a vein con-
sisting of a crystallino-griumlar, somewliat i'riablo variety, very similur
to that described under Ai)atite, var. 6, and a compact crystalline
vtiriety.
Ma.ssive, compact. ' racturo uneven. Lustre feeble, waxy. Trans-
lucent. Colour pal> 'onish-whito Colour of ])Owder white with a
faint greenish tinge. Jpecific gravity iM750.
OANAhlAN AVATtTlS. !• II
After drying at 100° C, tliu com|io,siti(>ii was I'ouiid to be a.s follows:
riioHphoric ncld' 40-812
Kliioriiic' .'l-fiO't
C'hloi iiio ■ • 040
Cailwnic at'icH o-SlS
Liiiic 4!t-102
Calcium 3-703
MannoBiii • (!20
Aliiminn i)MC>
S(!H(|iii()xido of iron 0.126
Alkalies y
Iimululile rcHiiliie 0-G3()
'.Ml -7 ■-'".»
1 KiiUftl to 8!! 098 tiiliiiHicr plioRplinto of lime
2 Kt I mil to 7'2!»,f) Huoiidti ot'ciilciimi.
3 K(|iuil to 0'(l(i'J ciiloi'ldt' of cakiuiii.
4 K(jual to I 177 taiiionatt! of lime.
The roHultH of thoforoffointj analysoH have hooii ombodied in Table 1. Expianafory
With the objeet ol ailoriiin^i^ oiwy reieronce, and laciiitatin^ C(>in])ans(>n, TaMoii.
not only the one with the other, but alike with those contained in Table
II., which embraces analyses of fluor-apatitcs from some of the })rinci))al
p]uropean localities. In selectincj these latter analyses I have only
availed myself of those wherein the Huorine lias been determined by
direct estimation; further, in transcribinii; them, I have taken the
liberty of prcsontiiiif them in a .soinewliat different form to that in
which they appeareil, — that is to hay, in analyses A. K C. where the
amount of tribasic phosphate of lime, tluoride and chloride of calcium
was given, the amount of j)liosphoric acid, fluorine, chlorine, lime and
calcium thus representeil has been calculated and atated separately.
In liko manner in analysis H. where the amount of fluoride of cah^ium
was given, the amount of Huorine and calcium thus represented has
been calculated and stated separately. In the other anal}ses vi/,., I).
F. G. and n. the total lime found was given and stated as such; in
these instances the amount of lime corresponding to the calcium (now
stated as such) required for the fluorine or fluorine and chlorine, as the
ca.se might be, has been deducted from the total (juantity given : as a
result of this altered representation, the analyses do not now foot up so
high as in the originals.
10 ir
UEOLOaiCAL 8UBVLY OF CANADA.
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OKOLOOrCAL SimVEV OK CANADA.
Iodine and Bromine in Apatite.
Iodine anil iodiiio hu8 been hIiowu to be present in certain varieties of upatite
apatite? from the (lepartniciits of Lot Jinil Turn-ot-Garonno : P. Tliil»ault lias
found it ill Nassau phosjihato, in Spanish phosphorite from the vicinity
of Cogues (Kslramaiiura) and has also established its presence in co-
prolites found in the Valley of the Rh(»ne, near Bellegardo (Ain) close
to the Swiss frontier : Petersen also found it in apatite from Diez,
Nassau, and that from Amberg, Bavaria, afforded II. Iveinsch in addi-
tion to iodine a trace of bromine.
aiMifito'from According to an analysis by P. Thibault, a sample of apatite from
oflor'""'*"' *'*^ department of Lot, contained :—
Phospliori'' acid ' 33 . 05
Limu 47.0!)
Silica 2.71
Aliiniiiia, oxide of iron, niiif^iicsia, )
chlorine, lluoriiK', iodine ( I „i„'||y), I 12-HG
carbonic acid (by dill'erence). J
Wator 4.20
100.00
1 Equal to 72-151 triliasic phonphate of lime.
It has been suggested tliat the apatite from the departments of Lot
and of Tarn-ct-Ciaroniic might jtossibly be utilized as a commercial
source of iodine, and etforts have been made in this direction by JL P.
Thibault at the Supei-i>hosphate Works of MM. Maxime Michclet ct
Paul Tliibault, (;ila Villetto-Paris). The phosphates employed at these
works consist ot apatite from the de[tartment of Jiot, coprolites from
the Ardennes and Sj)anish jdiosphorito.
The i^lant at this factory may be briefly describe<l as follows : —
Brief descriii- Two yudless belts, the one of leather with wooden scoops or cups
.xiii'tcrpliosphato lor raising the i)owdcreil phos[)hate, the other of gutta-percha with
Mil-h'ei'ct and Hcoops or Clips of the same material for raising the acid. On motion
Tnjaut. being communicated to these bolts, the powder and acid are raised
simultaneously and dropped into an horizontal, cylindrical, cast-iron
mi.xer where the powder and li(iuid arc thoroughly intermixed by the
revolving spindle oi" the mixer and its blades, after which the majs
passes down through a shoot into brick chambers where it solidi'ios
Roniovalof the and whence it is afterwards withdrawn. The acid vapours geneiated
n(ixiiiiis).'ases ... . , , . i i i
guncraicd in m the mixcr and chambers are withdrawn troin these vessels ny means
llm pniocss of ,, .■ i • i i i . ■ i- i
siiporphos- 01 a powerlul asj)iratf>r and made to traverse a sheet-iron cylin<lcr
'' " ""^' lined with lead and tilled with fragments of cokf, upon which a con-
stant stream of water is kept trickling from above, and pass tinally
into the factory chimney. By this arrangement the acid vapours
generated on mixing the powdered phosphate with the acid and which
CANADIAN ATATrTE.
13 H
Di-olitos i'roiii
are at all times cliBComforting and often (especiiiUy when fluor-apatites
are being worked) po.sitively injurious to those exposed to their in-
fluence, a!"0 carried ort' and completely absorbed. When phosphates
containing i(xline are enipIoj)C(l, the iodine disengaged during their
conversion into yuperpliosphate and carried a "V in the slate ol' vapour
or as iiydriodie acid, is completely absorbed and by allowing the same
liquid to retrn.vorse the coke, the solution may contain a** much as
eight grammes of iodine to the litre. It vill be thus seen that it is
quite possible to collect all the Iodine which is disengaged in tiic
gaseous condition ; the amount thus disengaged however is very tar
from representing the total amount originally contained in the apatite,
the greater part unfortunately remaining in the superphosphate; and,
so far us I am aware, a method has yet io be discovered whereby that
port'on of the iodine may be profitably extracted.
If, howovci', the method devised by M. P. Thibault does not so far
permit of the recovery of all the iodine it nevertheless possesses other
i:nportant advantages, such as a continuous process of manufacture,
considerable saving ol' manual labour, and complete absence oi noxious
vapours.
Fi'om its usually high content of phosjihate of lime Canadian apatite
may be regarded as a most eligible material for the manufacture of a
concentrated 8uperpIios])Iiate. (ienerally speaking it contains (as will
be seen on reference to Table I.) only sui II (juantities of oxide of iron,
and not unfrequently the amount is altogether (juitc insigniticant: it is
to be remembered that No. 7 is a very exceptionally occurring variety,
has oidy been met with at this mine, and ihci e )nly, as stated, in small
quantity.
All the Canadian apatite hitherto met with belongs to the variety
fluor-a])atite, and is very similar in composition to that derived from
many European localities, as will be seen on C(ini]»aring Table 1. with
II. A great deal of the phosphatie material at present extensively
employed in the manufacturo of superphosphate, contains more or less
fluoride of calcium, this maybe said of Spanish phosphorite, German
or Nassau jjliosjihato and niost coprolitcs : when such material are
treated with sulphuric acid in the process of suporplios{)hatiiig, hydro-
fluoric acid is evolved, which not only causes discomfort, but is in-
jurious to the woi'kmen. Kor this reason, at works where no special
precautions are taken to ell'ect the removal of the noxious gases evolved
in the mixing j)rocess, any phosphatic material containing much
fluorine is apt to bo looked upon with some disfavour : its i)resence,
however, can be a matter of very little moment when the very simple
ami etfectivo device, for drawing off and absorbing these gsvses, as car-
Ci)llection of
the iudine.
AdvimtiiKCS of
P. Tliibault's
method,
Canadian
apatite as a
material for the
inaiiufacture of
mipcriihos-
|)hate.
On the presence
of fluoride of
calcium in
phosphatic
material
oniployeil in the
manutacturc of
gupcrphoa-
phato.
14 H
GEOLOGICAL SURVEY OF CANADA.
ConciudinK
remarks.
ried out at tho works of MM. Michelet and Thibaiilt (afore briefly
described) is julopled.
It was originally contomplutcd to make some practical and coin-
parativo cxporimonts with Kuropean and Canadian phosphate in order
to ascertain tho relative facility with which they admitted of being
reduced to a fine powder; sufficient time could not be found to carry
out this intention. There is, however, no reason for supposing that in
this respect they compare at all unfavourably with foreign apatites.
In the manufacture of superphosphate from mineral phosphates it is
almost impossible in practice to render tho whole of the phosphate of
lime soluble, more or less (according to iho skill and care bestowed in
tho manuft'cture) of the latter remaining in its original unch. nged
state. In order to employ the mineral phosphates to tho best advantage,
it is requisite that they shoidd be reduced to an almost impalpable
powder, and that the mixing of this latter with the acid should bo most
thorough.
bre briefly
I and com-
ito in order
d of boin^
lid to cany
ing that in
iipatitcs.
pliatoH it is
losphato of
ostowcd in
unch: ngod
advantage,
impalpable
dd bo most