jp'fip ^ ?:!?-< ENGINEERING CHEMISTRY: A MANUAL OF QUANTITATIVE CHEMICAL ANALYSIS. FOR THE USE OF STUDENTS, CHEMISTS ENGINEERS. -BY- THOMAS B. STILLMAN, M.Sc., Ph.D., r| PROFESSOR OF ANALYTICAL CHEMISTRY IN THE STEVENS INSTITUTE OF TECHNOLOGY. WITH ONE HUNDRED AND FIFTY-FOUR ILLUSTRATIONS, EASTON, PA.: CHEMICAL PUBLISHING CO. 1897. COPYRIGHT, 1897, BY EDWARD HART, PREFACE. The preparation of this manual has resulted from many years of experience in the chemical laboratory, the work of which has been closely connected with engineering, and with the teaching of these subjects to students. A treatise of this character cannot be too comprehensive in the treatment of a subject, nevertheless better results are ob- tained, from students, by arranging the matter in such a way that the principles and methods of work are indicated and then references given for further study and research. Students commencing quantitative chemical analysis can with profit perform the first eleven exercises given in this work, with proper supervision, and then select a course of study suitable to their advancement : either for iron and steel chemistry ; railroad laboratory practice ; the technical application of water supply ; the chemical technology of fuels, etc., etc. It will be found conducive to thorough work, that each stu- dent before finishing any investigation, be required to write not only the analytical data, but also the references to the literature bearing upon the subject examined, following the plan outlined in the manual. The articles upon gas analysis and valuation, blast furnace practice, the heating value of fuels, the purification of water for technical purposes, lubrication, car illumination, and the ex- amination of Portland cement, have received especial attention, since these topics, at the present time, form a considerable por- tion of the work and investigations of engineers. The following articles have been contributed by experts in each line of study : "Blast Furnace Practice," by Edward A. Uehling, M.E. * ' Determination of the Heat Balance in Boiler Tests, ' ' and contributions of portion of the article upon "Pyrometry," by Wm. Kent, M.E. iv PREFACE. 11 Carbon Compounds of Iron," by G. C. Henning,M.K. "Practical Photometry," by Alten S. Miller, M.E. "Electrical Units," by Albert F. Ganz, M.E. "Energy Equivalents," by E. J. Willis, M.E. The author has endeavored to acknowledge every excerpt made by him, with the proper reference thereto, and his thanks are due to those chemists from whose experiences valuable methods of analysis have been incorporated in the manual. THOMAS B. STII^MAN. STEVENS INSTITUTE OF TECHNOLOGY, HOBOKEN, N.J.,Dec. 31, 1896. CONTENTS. Page. Determination of Iron in Iron Wire i Determination of Alumina in Potash Alum 2 Determination of Copper in Copper Sulphate 3 As copper oxide, by precipitation with sodium hydroxide, 3 ; Volumetrically with potassium cyanide solution, 4; As metal- lic copper by electrolysis, 5 ; Gulcher's thermo-electric pile, 7. Determination of Sulphur Trioxide in Crystallized Magne- sium Sulphate 8 Determination of Lead in Galena 9 Determination of Iron by Titration with Solution of Potas- sium Bichromate 10 a. Where the iron solution is in the ferrous condition, b. Where the iron solution is in the ferric condition, n ; The Bunsen valve, 12. Determination of Phosphoric Acid in Calcium Phosphate. 12 Determination of Chromium Trioxide in Potassium Bichro- mate 14 Analysis of Limestone 15 Scheme for analysis, 16 ; Determination of the carbon dioxide 17; Calculation of the analysis, 18; Phosphoric acid in lime- stone, 18. Coal and Coke Analysis 19 Determination of moisture, volatile and combustible matter, fixed carbon and ash, 19 ; Sulphur by fusion with sodium car- bonate and potassium nitrate, 20 ; Sulphur by the Eschka- Fresenius method, 21 ; Determination of CaSO 4 , 21 ; Determi- nation of phosphorus, 22; Analysis of "Bog Head Cannel " coal, 22; "Pittsburg Bituminous " coal, 23; Increase of ash with decrease of size of coal, 23 ; Analysis of ash of coal or coke, 23 ; Sample analysis, 24 ; Valuation of coke, 24 ; Thor- ner compression machine for coke, 24 ; Standard of strength of coke, 24 ; Apparent specific gravity of coke, 25 ; The true specific gravity, 25 ; The volume of pores in 100 volumes of material, 25 ; Method of making complete report upon a coke, 27; Weight per cubic foot of coke, 27; Fulton's standard table for coke, 28 ; References on the literature of coke, 28. Scheme for the Analysis of Hematite, Limonite, Magnetite and Spathic Iron Ores 29 Determination of silica, 30 ; of phosphorus pentoxide, 30 ; of iron, 30 ; of sulphur, 30 ; of alumina, 30 ; of manganese, 31 ; of lime, 31; of magnesia, 31 ; of water of hydration, 31 ; De- yi . CONTENTS. termination of ferrous oxide in FeO.Fe 2 O 3 , 32 ; Allen's method, 32 ; Method of fusion of iron ores insoluble in acids, 33 ; De- termination of chromium, 33 ; Genth's method, 33 ; Table of analyses of various chrome iron ores, 34 ; Determination of titanium, 35 ; Method of Bettel, 35 ; References on literature of iron ore analyses, 35 ; Table of the composition of various iron ores, 36. Scheme for the Analysis of Blast Furnace Slag 37 Form of blank used for reporting blast furnace slag analyses, 38 ; Examples of blast furnace slag analyses, 39 ; Analysis of open-hearth slags, refinery slags, tap-cylinder, mill-cinder and converter slags, 39 ; Calculation of the amount of material required for a furnace producing 300 tons of pig iron per day, 39-42 ; Heat energy developed, 42 ; The stopping of furnaces for repairs, 43 ; The charging of blast furnaces, 43-45 ; De- scription of the three different methods of reduction in the blast furnace, 46-48; Calculation of blast furnace slag, 48; Analyses of the iron ore, limestone and coal used, 49 ; Trans- formation of the three analyses into lime, 49-51 ; Examples of close coincidence between slags actually run from known cal- culated charges and the slag determined a priori, 52, 53 ; Table of types of slags, including acid, sesquiacid, neutral, sesquibasic, bibasic and tribasic, 54 ; Graphic method of cal- culating blast furnace charges, 55-57 ; References on the litera- ture of blast furnace slags, 57. The Analysis of Water to Determine the Scale- Forming In- gredients 58 The usual components of boiler scale, 58 ; The importance of the determination of the alkalies in water for boiler use, 58 ; Example of a boiler scale containing 72 per cent, of sodium chloride, 58; Scheme for water analysis for scale-forming in- gredients, 60; Determination of silica, alumina, oxide of iron, calcium oxide, magnesium oxide, sodium oxide, potas- sium oxide, carbon dioxide, sulphur trioxide, and chlorine in a sample of water with the quantitative results of each given, 61-65 5 Table showing the number of grains per United States gallon and Imperial gallon corresponding to milligrams per liter, 63, 64 ; Method of stating results of an analysis, 65 ; Analysis of a water not containing calcium sulphate, 66 ; Action of magnesium chloride as a corrosive agent in boilers, 66, 67 ; Statements in grains per gallon and not in parts per 100,000 or 1,000,000, 67 ; Example of a very corrosive water, 67 ; Determination of free acid, 68 ; Determination of the hardness of water, by standard sulphuric acid, 69 ; Determi- nation of the hardness by the soap test, 70, 71 ; The French standard of hardness, the German, the English, and the the American, 72 ; Table showing the hardness of water sup- plied to cities, 73. The Sanitary Analysis of Water 73 Determination of chlorine, 73 ; Amount of chlorine allowable in potable water, 74 ; Determination of the free and albuminoid ammonia, 74-78; Wolff's colorimeter, 76; Preparation of the standard Nessler solution, 74 ; Standard ammonium chloride, CONTENTS. Vll 74 ; Standard alkaline permanganate, 74 ; Amounts of free and albuminoid ammonia allowable in potable water, 79 ; Ap- paratus used by the New York City Health Department for determination of free and albuminoid ammonia, 80 ; Determi- nation of nitrates by the phenol method, 80 ; Preparation of standard potassium nitrate solution, 80 ; of phenolsulphonic acid, 80; Determination of nitrites, 81 ; Griess's method modi- fied by Glosway, 81 ; Preparation of sodium nitrite solution, 81 ; of 0-amido-naphthalene acetate solution, 81 ; Process of determination of nitrites, 81 ; Oxygen required to oxidize organic matter, 82 ; Conversion table, parts per 1,000,000 to grains per gallon, etc., 83 ; Table of analyses of thirty-nine American well and river waters, 84 ; Table of composition of various European lake and river waters, 85 ; Table of compo- sition of various ocean waters, 85 ; Description of the filter beds of city of Dublin, 86 ; Description of the Warren filters for rapid filtration of water, 88-91 ; References on the bacterio- logical examination of water, 92. The Composition of Boiler Scale 92 Analysis of boiler scale from boilers at Birmingham, Ala., showing that calcium and magnesium hydroxide may exist, replacing a portion of the calcium carbonate and magnesium carbonate, 92-94 ; Examination of boiler scale, layer by layer, shows where scale is in contact with red hot iron, carbon diox- ide is absent, 94 ; Change in method of analysis of boiler scale, if oil is present, 94 ; Amount of water evaporated by a 100 horse-power boiler per month, 95 ; Amount of loss of heat, fuel, etc., by scale in boilers, 95 ; Estimate of the Railway Master Mechanics Association of the United States of the loss of fuel, repairs, etc., for locomotive boilers due to scale, 95. Water for Locomotive Use 96 Results of experiments made by the Chicago, Milwaukee & St. Paul Railway, 96 ; For practical purposes water is classi- fied as incrusting and non-incrusting, 96 ; Foaming of alkali water in boilers, 97 ; Maximum residue allowable, 97 ; One to ten grains solid per gallon is classed as soft water, ten to twenty grains moderately hard water, above twenty-five grains very hard water, 97 ; Use of boiler compounds to prevent scale, 97 ; Formula for compound used by Chicago, Milwaukee & St. Paul Railway to prevent scale, 97 ; Washing out of locomotive boilers frequently with hot water necessary, 99; Reasons why good boiler compounds to prevent scale can be used profitably, 99. Feed Water Heaters 99 Feed water heaters as scale eliminators in boiler waters, 99 ; Boiler economizers, 99 ; Principle upon which feed water heat- ers operate, 100 ; Temperature required to precipitate calcium carbonate, 100 ; Temperature required to precipitate calcium sulphate, 100 ; The Goubert upright feed water heater, 100 ; Exhaust steam and-superheated steam in feed water heaters, 101; Exhaust steam precipitates calcium carbonate but not cal- cium sulphate, a temperature of 240 F. being required for the latter, 100 ; The Hoppes feed water purifier, 101 ; Example of composition of boiler water before treatment with the viii CONTENTS. Hoppes purifier and after treatment, 102 ; Table showing the yearly saving effected by the use of the feed water heaters for various horse-powers at different prices of coal, 103 ; Table showing percentages of fuel saved by heating feed water (steam pressure sixty pounds), 104; "Blowing off" as a means of prevention of scale in boilers, 105. Use of Chemicals and Filtration for Purification of Boiler Waters 105 The Dervaux water purifier, 105, 106; The Archbutt water purifier, 107-109 ; Table showing the cost of purification of boiler waters from the analysis of the same, by the Archbutt process, no; Use of sodium carbonate, no. Filter Presses for Rapid Filtration of Water in Description of the two varieties of, in, 112 ; Chamber presses and frame presses, 112 ; The Porter-Clarke process for soften- ing water, 112; Use of fibers of cellulose in filter presses to collect finely divided precipitates, 112 ; Description of a com- plete plant for water purification, using superheater, chemi- cal precipitation with sodium carbonate, and filter presses, 113 ; References on water analysis, boiler scale, purification of water, etc., 114. Determination of the Heating Power of Coal and Coke 114 Ignition of coal in a crucible with litharge, 115; Method of calculation of results, 115 ; Three methods available for the determination of the heating power of coal and coke : (i) Cal- culation of the heating power from an elementary analysis of the coal, (2) The useof calorimeters, (3)The combustion of large amounts of coal in specially designed apparatus therefor, 115; Determination of carbon and hydrogen in coal, 115-117; De- termination of nitrogen, 117, 118 ; Data for calculation of the heating power from the analysis, 120 ; Definition of a calorie, 120; Definition of a British thermal unit (B. T. U.), 120; For- mula for calculation of heating power when products of com- bustion are condensed, 121 ; When products of combustion es- cape in steam, 121 ; Calculation of the amount of air required for combustion of one kilo of coal, 122; Calculation of the amount of air required for combustion of one kilo of coke, 123 ; Calculation of the evaporation value of coal and coke, 123 ; Table showing the air required, the total heat of combustion, evaporative power, etc., of one kilo of carbon and one pound of carbon burning to carbon dioxide, to carbon monoxide, of hydrogen and of sulphur, 124 ; Cause of loss in actual evaporation in boiler practice, 125 ; Results of boiler evapora- tive tests made by J. E. Denton, 125 ; Ordinary boiler evapo- ration in less than eighty per cent, of the theoretical value, 125. Calorimetry 125 The Mahler calorimeter, description of, 125-127 ; Determina- tion of the water equivalent of the Mahler calorimeter, 128, 129 ; Detail of process of determination of the heating power of coal with the Mahler calorimeter, 129, 130 ; Example show- ing method of calculation, 130, 131 ; Results of tests upon five samples of coal, made in the laboratories of the Stevens In- CONTENTS. ix stitute, .131 ; References upon the Mahler calorimeter, 131 ; The Thompson calorimeter, 132 ; Method of determination of the water equivalent, 132 ; Determination of the heating power of a coal with the Thompson calorimeter, 133 ; Comparison of the theoretical heating value of a coal, as determined by analysis, and of the determination as made by the Thompson calorimeter, 134, 135 ; The Barrus coal calorimeter, 135-137 ; Results of tests, upon several coals, with the Barrus coal cal- orimeter, 138 ; The Fischer calorimeter, 139 ; Carpenter's coal calorimeter, 139, 140 ; References, 141 ; Description of the Kent apparatus for determining the heating power of fuels in large quantities, 141-143 ; Boiler tests of coal, 144 ; Table of the approximate heating value of coals, 145 ; Determination of the efficiency of a boiler, 147; Determination of the several losses of heat in boiler practice, 147 ; Method of making a "heat balance" in boiler tests, 147-149; Sources of error in making a " heat balance," 150; Estimations of radiations of heat by difference, 150. Determination of Sulphur in Steel and Cast- Iron 140 Bromine method, 151 ; Aqua-regia method, 152 ; The potas- sium permanganate method, 152-154 ; The iodine method, 154, 155 ; References on the determination of sulphur in steel and cast-iron, 156. The Determination of Silicon in Iron and Steel 156 References, 157. The Determination of Carbon in Iron and Steel 157 Report of the English, Swedish, and American committees upon the methods for determination of carbon, 157 ; Method of Berzelius, 158 ; Method of Regnault, Deville, and Wohler, 158; Ullgren's method, Eggertz, Langley, Richter, Weyl and Binks, Parry, McCreath, Boussingault, Wiborg, 159 ; Selec- tion of the best method, 160 ; Method as used by author, 160 ; Description of apparatus used in chromic acid process, 160-162; Method of Langley modified as used by author, with descrip- tion of apparatus, 163-165; Wiborg's method, 165-167; De- scription of Eggertz's method for combined carbon in steel, 168, 169 ; Stead's modification, 169. Carbon Compounds of Iron 170 Microscopical examination of iron, 170; Marten's and Os- mond's latest investigations, 170; Composition of unhardened steel, Fe 3 C ; Composition of ferrite and reactions of, 171 ; Cementite, 172; Perlite, 172; Martensite, 172 ; Sorbite, 172; Troostite, 173; Systematic microscopical examination, 174; Distinction between martensite and perlite, 174 ; Differences in reactions between ferrite, cementite, and troostite, 174; References upon carbon in iron, 174 ; References upon deter- mination of carbon in iron and steel, 175. The Determination of Phosphorus in Cast-iron and Steel. 176 The molybdate method, 176 ; Preparation of the standard solutions, 177, 178; Determination of phosphoric acid in the ammonio-molybdic phosphate, by direct weighing of the yel- low precipitate, 178 ; The agitation apparatus of Spiegelberg's X CONTENTS. for precipitation of phosphoric acid, 179; Volumetric deter- mination of phosphorus in iron and steel, 179; Apparatus and reagents required, 180 ; Calculations of analyses made by volumetric method, 182 ; References on the determination of phosphoric acid in iron and steel, 183. The Classification of Steel 183 Classification as made by the Midvale Steel Co., 183 ; Class O, carbon, o.i to 0.2 per cent. ; Class I, carbon, 0.2 to 0.3 per cent. ; Class II, carbon, 0.3 to 0.4 per cent. ; Class III, carbon, 0.4 to 0.5 per cent. ; Class IV, 0.5 to 0.6 per cent. ; Class V, carbon, 0.6 to 0.7 per cent. ; Class VI, carbon, 0.7 to 0.8 per cent. ; Class VII, carbon, 0.8 to 0.9 per cent. ; Class VIII, car- bon, 0.9 to i.o per cent. ; Class IX, carbon, i.o to i.io percent. ; Class X, carbon, i.io to 1.20 per cent., 183-184 ; Effect of other ingredients besides carbon or tensile strength, 184 ; Purposes for which the different classes of steel are recommended, 184 ; Phosphorus limit in machinery steel must be below 0.06 per cent., 185 ; Phosphorus limit in gun forgings, tool steel, and spring steel must be below 0.03 per cent., 185 ; Magnetic prop- erties of steel, 185 ; Effect of nickel on magnetic properties, 185 ; Experiments made by the Bethlehem Iron Co. on nickel steel, 185 ; Requirements of carbon, phosphorus, manganese, silicon, and sulphur for Jocomotive steel plates, 186 ; Kent's classification of iron and steel, 187 ; " Mitis" steel, 187. Determination of Aluminum in Iron and Steel 188 Brown's method, 188 ; Table of results of experiments on quantitative determinations, 189; Method of Carnot, 190; References, 190. Determination of Sulphuric Acid and Free Sulphur Triox- ide in Fuming Nordhausen Oil of Vitriol 190 Determination of Manganese in Iron and Steel 192 Initial treatment of the manganese for determination either gravimetrically, volumetrically, or colorimetrically, 192 ; Gravimetric method, 193 ; Preparation of standard solutions of ferrous sulphate and potassium bichromate for the volu- metric process, 193; Colorimetric method, as modified by J. J. Morgan, 194; Textor's method for the rapid determination of manganese in steel, 194, 195 ; References, 195. Technical Determination of Zinc in Ores 195 Preparation of standard solution of potassium ferrocyanide, 195 ; Of potassium chlorate and ammonium chloride, 196 ; Precautions to be observed in the process, 197. Sodium Cyanide as a Component of Potassium Cyanide. ... 197 The valuation of potassium cyanide for commercial purposes, 197; Composition of "ninety-eight per cent." cyanide, 197; Method to be used for analysis of the mixed cyanides, 198; Determination of method of manufacture from the analysis, 199 ; Comparison of the cost of manufacture of sodium cyanide and of potassium cyanide, 199, 200. CONTENTS. xi The Chemical and Physical Examination of Portland Ce- ment 200 Limit of variation in the composition of Portland cements, 200 ; Composition of, 200 ; Effect of magnesia, 201 ; Injurious effect of calcium carbonate, 201 ; Scheme of analysis of Port- land cement, 202 ; Determination, quantitatively, of the con- stituents with an example, 203, 204 ; Analyses of " Burham's," " Dyckerhoff's," and " Saylor's" Portland cements by the author, 205 ; List of analyses of German cements, 205 ; The mechanical testing, 205 ; Rules of the American Society of Civil Engineers for testing cements, 206, 207 ; Description of the " Fairbank's" cement testing machine, 208; Of the "Richie"," 209; Directions for testing cements according to the official German rules, 209, 210 ; Standard sand, 210 ; Pre- paration of Briquettes of neat cement, 210; Briquettes of a mixture of Portland cement and standard sand, 211 ; Descrip- tion of the " Michaelis" cement testing machine, 212 ; Of the " Reid and Bailey" machine, 213 ; The " Faija" and " Grant" machines, 213 ; Causes of variations in tensile strength in cements, 214; Experiments of Dr. Bohme, 214; The Bohme- Hammer apparatus, 216; Description of Jameson's automatic briquette molder, 217, 218 ; Table showing results of tensile tests on the same samples of cement, by nine different ex- perts, 218 ; Conditions required in France for a good cement, 219 ; Description of the Buignet cement machine, 220, 221 ; M. Durand-Claye's experiments on briquettes of Portland cement, 221 ; The crushing test of cements, 222 ; Ratio of tensile strength to crushing strength, 222; The "Suchier," the " Tetmajer," and the " Amsler-Laffon" machines for de- termination of crushing strength, 222-224 ; Variation in vol- ume of cements, 224 ; Hot water tests, 224 ; Porter's auto- matic cement testing machine, 225, 226 ; Resum6 of tests re- quired for Portland cements, 227 ; References : The Journal American Chemical Society, 16, 161, 283, 323, 374, contains an index, arranged by the writer, of the literature relating to Portland cement from 1870 to 1893. The Determination of Nickel in Nickel-Steel 227 Principles of the process, 227, 228 ; The electrolytic method, 229, 230 ; Volumetric method, 230 ; Special apparatus, 230 ; Preparation of the standard solutions of sodium phosphate, 230 ; of sodium acetate, 231 ; of potassium cyanide, 231 ; of nickel solution, 231 ; of cupric ferrocyanide solution, 232 ; Experiments show that the volumetric method gives results within 0.0003 gram of true nickel content in 2.222 grams of nickel-steel, 232. Analysis of Chimney Gases for Oxygen, Carbon Dioxide, Carbon Monoxide, and Nitrogen 233 Description of the Elliott apparatus, 233, 234 ; Method of col- lecting the gas, 234 ; Strength of potash solution for absorp- tion of carbon dioxide, 234 ; Preparation of alkaline pyrogal- late solution for absorption of oxygen, 235 ; Solubility of car- bon dioxide and carbon monoxide in distilled water, 235 ; Pre- cautions to be observed in the determination of carbon mon- Xli CONTENTS. oxide, 235 ; Preparation of cuprous chloride solution for ab- sorption of carbon monoxide, 236 ; Data for converting percen- tages by volume to percentages by weight, 237 ; Example of an analysis of a chimney gas, including all the requisite calcula- tions, 237. Analysis of Flue Gases with the Orsat-Miiencke Apparatus 237 Advantages of this apparatus for rapid analyses, 238 ; De- scription of the apparatus, 238, 239 ; Method of filling the ab- sorbing tubes with the different solutions, 239, 240 ; Composi- tion of chimney gases as an index of the fuel consumption under the boilers, 241 ; Method for determination of excess of air in furnace gases, 241 ; Table of ratio of carbon dioxide and air in furnace gases, 241 ; Amount of carbon dioxide as indi- cating heating efficiency, 241 ; The dasymeter of Messrs. Sie- gert and Durr, as described by W. C. Unwin, 242 ; Automatic indication of percentage of carbon dioxide in the flue gases, by the dasymeter, 242 ; Loss of heat in flue gases, as deter- mined by dasymeter and Siegert's formula, 243 ; Experiments on Ten-Brink furnaces, to determine the percentage of carbon dioxide as an index of maximum combustion, 244 ; Uehling and Steinbart's instruments for indicating automatically and continuously the percentages of carbon dioxide and carbon monoxide in furnace gases, 244. Analysis of Coal Gas, Water Gas, Producer Gas, Etc., by Means of the Hempel Apparatus 245 Description of the Hempel apparatus, 245-246; The " Wink- ler" burette, 247; Method of collecting the gas for analysis, 248 ; Example of an analysis of a gas containing carbon dioxide, oxygen, carbon monoxide, ethylene, methane, hydro- gen, and nitrogen, 251-256 ; Calculation of the percentages by volume into percentages by weight, 256 ; Determination of methane by explosion, 257. Heating Value of Combustible Gases 258 Calculation of calories per kilo to B. T. U. per pound, 258; Data required, 258; Method of H. L. Payne, 258; Liter weights of the gases, hydrogen, oxygen, nitrogen, air, carbon monoxide, carbon dioxide, methane, and ethylene, 258; Table of the heating power of combustible gases expressed in calo- ries per kilo, B. T. U. per pound, and B. T. U. per cubic foot, 259 ; Determination of heat units from analysis of the gas, 260 ; Illuminants, value of, 260 ; Standard temperature for gas measurements, 260, 261 ; Specific heats of the various gases, 261 ; Volumetric specific heats, 261 ; Calculation of heat car- ried away by the products of combustion of hydrogen at 328 F., 262 ; of carbon monoxide, 263 ; of marsh gas, 363 ; Table of B. T. TJ. per cubic foot, products of combustion condensed, and products of combustion at 328 F., of hydrogen, carbon monoxide, marsh gas, and illuminants, 263; Heating value of natural gas in B. T. U. per cubic foot, 263 ; Example, with calculations, of the heating value of a gas composed of carbon monoxide, carbon dioxide, illuminants, hydrogen, and marsh gas, stated in B. T. U. per cubic foot of each constituent, prod- ucts of combustion condensed, and products of combustion CONTENTS. Xlll escaping at 328 F., 264; Determination of calories per kilo, or B. T. U. per pound, from analysis of a gas stated in volume, 264. Manufacture of Water Gas and Calculation of Heating Power of Various Illuminating Gases 265 Description of plant, 266, 267 ; Operation, 267 ; Composition of uncarburetted water gas, 267 ; Composition of carburetted water gas, 268 ; Calculation of the heating power of the uncar- buretted gas in B. T. U. per cubic foot, from an analyses, 268; Of the carburetted water gas, 268 ; Analysis of a sample of London coal gas, 268 ; Calculation of its heating power in B. T. U. per cubic foot, products of combustion condensed, 269 ; The same, products of combustion in a state of vapor at 328 F., 269 ; Analysis of Heidelberg gas, 289 ; Konigsberg gas and Hannover gas, 289; Analysis of Wilkinson carburetted water gas, with determination of its heating power in B. T. U. from the analysis, 270 ; Analysis of "Tessie du Motay" gas, with calculation of B. T. U. per cubic foot, 270. Producer Gas 270 Constituents, 270; Analysis of Siemen's producer gas, with B. T. U. per cubic foot, 270 ; Analysis of anthracite producer gas, with B. T. U. percubic foot, 270 ; Analysis of soft coal pro- ducer gas, with B. T. U. per cubic foot, 270. Oil Gas 271 Method of manufacture, 271 ; Keith's oil gas, 271 ; " Pintsch" oil gas, 271 ; " Mineral Seal" oil, 271 ; Composition of " Pintsch" oil gas as determined from several analyses, by the writer, 271 ; Heating power per cubic foot, calculated from the analysis, 271 ; Tests of the production of oil gas, by the "Keith " process, and the " Pintsch" process, by W. Ivison Macadam, 271, 272 ; Oil gas compressed to atmospheres in iron cylinders as an illuminant for cars, 272 ; Loss in illuminating power of the gas by excessive compression, 272 ; References upon gas analysis and oil gas, 272. Natural Gas 272 Composition of the gas not uniform, 272 ; Chemists not in agreement as to constituents, 272 ; Analysis of Pennsylvania natural gas, by Dr. G. Hay, with calculation of the heating power per cubic foot, 272 ; Analyses of six samples of natural gas, by S. A. Ford, 273 ; Analysis of New Lisbon, Ohio, natural gas, by W. A. Noyes, with B. T. U. per cubic foot, 273 ; Inves- tigations upon the composition of natural gas by F. C. Phil- lips for the geological survey of Pennsylvania, 274 ; Analysis of Fredonia natural gas, by F. C. Phillips, 274 ; Also of the Sheffield natural gas, Wilcox natural gas, and the Kane natural gas, 274 ; Test of the fuel value of natural gas, under boilers, by the Westinghouse Air-brake Co., of Pittsburg, Pa., 274 ; References to literature on natural gas, 274. Practical Photometry 275 How the illuminating value of a gas is measured, 275 ; Stand- ard sperm candles, 275 ; Description of the standard Bunsen xiv CONTENTS. photometer, 275-278 ; Manner of using the photometer, 279- 281 ; Use of formula for correction for pressure and tempera- ture, 282 ; Table to facilitate the correction of the volume of gas at different temperatures and under different atmospheric pressures, 283. Hartley's Calorimeter for Combustible Gases 284 Description of the apparatus, 284 ; Method of use, 285 ; Re- sults of tests, with this instrument, upon the municipal gas of New York City, by E. G. Love, 285 ; Determination of the heating power of the London coal gas, 286 ; Average value in terms of B. T. U. per cubic foot, of the water gas of New York City, 286; Number of B. T. U. for |i.oo, gas costing $1.25 per cubic foot. Junker's Gas Calorimeter 287 Description of the instrument, 287 ; Method of operation, 288, 289 ; Table of resume of tests upon London coal gas, 291 ; Ex- periments made at the Stevens Institute with Junker calorim- eter upon Lowe process water gas, 291 ; Analysis of Lowe process water gas, 291 ; Heating value from calculation of analysis of the gas equalled 662 B. T. U. per cubic foot, deter- mination by calorimeter 668 B. T. U. per cubic foot, 292. Liquid Fuel 292 Evaporative power of petroleum as determined by Storer, 292 ; Heating power of various petroleums as determined by Deville, 292 ; Evaporative power of liquid hydrocarbons as determined by Dr. Paul, 292 ; Table of results, showing the evaporative power in pounds of water at 212 F., of C 6 H 6 O, C 7 H 8 0, C 10 H 8 , C M H 10 , C 8 H 10 , C 9 H 12 , C ]0 H U , 292 ; Calculation of effective heat, 293 ; The determination of the theoretical evap- orative efficiency of different combustibles, as given by Ran- kine, 294 ; Table of evaporation efficiency due to carbon, hy- drogen, etc., of charcoal, coke, petroleum, etc., 294; Formula representing the number of times its own weight of water a fuel will evaporate, 295 ; Formula for the loss of units of evaporation (Rankine), 295; The theoretical evaporative power of hydrogen and carbon, 295 ; Relative heating value of coal, gas, and petroleum, as determined by tests made by the En- gineer's club of Philadelphia, 296 ; Tests of the heating value of petroleum and block coal under the same boilers, at Chi- cago, 111., 296; Relative cost of oil $1-93, coal $2.15 for same evaporation performed, 296. Valuation of Coal for the Production of Gas 296 Method of T. Richardson, 296 ; Description of the apparatus, 296, 297 ; Determination of the amount of coke, tar, ammo- niacal water, carbon dioxide, hydrogen sulphide, and the gas produced, 297 ; Newbigging's experimental plant for the de- termination of the gas-producing qualities of coal, 297, 298 ; Method of using the apparatus, 298, 299 ; Average production of gas from New Castle coal, 299 ; Amount of gas that should be produced by a good variety of gas coal, 299. Analysis of Clay, Kaolin, Fire Sand, Building Stones, Etc. 299 Constituents to be determined, 299; Determination of total CONTENTS. XV silica, 299 ; The determination of combined silica, hydrated silicic acid, and of quartz sand, 300; Scheme for determina- tion of alumina, ferric oxide, manganese dioxide, lime, and magnesia, 301 ; Determination of potash and soda, sulphur trioxide, and titanic oxide, 302 ; Water of hydration, 303 ; Composition of various representative clays, 303. Physical Tests of Building Stones 303 1. Crushing strength, how determined, 304 : The Riehle"U. S. standard automatic and autographic testing machine, 304 ; Crushing strength of granite, trap-rock, marble, limestone, sandstone, and red brick, 304. 2. Absorptive power, 304 ; Method of determination, 304 ; Absorptive power of granite, marble, limestone, sandstone, brick, and mortar, 304 ; Freezing test, 306 ; The Tagliabue > * freezing apparatus, 306; Freezing test as required in "Uni- form methods of Procedure in Testing Building and Struc- tural Materials" by J. Bauschinger, (Mechanisch-technischen Laboratorium, Munchen), 307; The testing of bricks, 308; De- termination of soluble salts in bricks, 309-; Examination of unburnt clay for calcium carbonate, iron, or copper pyrites, mica, etc, 309; Use of Papin's digester with steam at one and one-quarter atmospheres, 310; Microscopical examination, 310 ; Determination of the character and structure of the stone, 310 ; Difference between sandstones and quartzites, 310; Method of H. Lynwood Garrison for microscopical examina- tion, 310; References to literature upon testing of building stones, etc., 311. Alloys 311 Classification of alloys into three classes, 311 ; First class comprise, brass, bronze, bell metal, gun metal, Muntz's metal, speculum metal, Delta metal, 311 ; Scheme for analysis of alloys of first class, 311 ; Example of analysis with weights ./ and calculations, 311-313 ; Alloys of the second class, Babbitt metal, Britannia metal, type metal, solder, white metal, camelia metal, Tobin bronze, ajax metal, car-box metal, mag- nolia metal, pewter, " Argentine," Ashbury metal, anti-fric- tion metal, phosphor bronze, deoxidized bronze, rose metal, Parson's white metal, " B" alloy, P. R. R., 313; Method for analysis of Babbitt metal, 313, 314; Preparation of sodium sul- phide solution, 314 ; Mengin's method for separation of tin and antimony in alloys, 314 ; Scheme for analysis of white metal containing Sb, Sn, Pb, Cu, Bi, Fe, Al, Zn, 315"; Volumetric determination of antimony in presence of tin, 315 ; Table of the composition of alloys of the second class, 316 ; Alloys of the third class comprising aluminum bronze, ferro-aluminum, ferro-tungsten, German silver, rosine, metalline, aluminum bourbounz, silicon bronze, Gutrie's "entectic," arsenic bronze, and manganese bronze, 316, 317; Method for analysis of alu- minum bronze, 317 ; Determination of manganese in manga- nese bronze, 317 ; Method for the analysis of ferro-aluminum, 318,319; The determination of phosphorus in phosphor-bronze, 319 ; Qualitative tests for lead, copper, tin, and antimony in alloys, 319 ; Thompson's method for determination of copper, tin, lead, and antimony, 320-322 ; References on analysis of alloys, 323. xvi CONTENTS. Analysis of Tin Plate 323 Method of analysis with use of dry chlorine gas, 324 ; Deter- mination in tin plate of tin, lead, iron, and manganese, 325 ; Table of analyses of nine different samples of tin plate, con- taining tin, lead, iron, manganese, carbon, sulphur, phos- phorus, silicon, 325 ; Iodine method for determination of tin, 326. Chrome Steel 3 26 Classification of the products of manufacture, 326; Determi- nation of chromium, 327 ; Table of mechanical tests of chrome steel, including limit of elasticity, modulus of elasticity, and breaking strength, etc., 328 ; Determination of manganese, 329; Silicon, tungsten, 339; Table of analyses of chrome steels made at the Stevens Institute, comprising "No. i steel," "No. 3 steel," "Magnet steel," and "Rock Drill steel," 330, 331. The Chemical and Physical Examination of Paper 331 Determination of the nature of the fiber, 331 ; Use of chemical solutions to detect fibers of pine, poplar, and spruce, 332 ; De- termination of the amount of mechanical fiber in a mixture of chemical fiber, linen fiber, cotton fiber, and mechanical fiber, 332 ; Action on wood pulp of solution of gold chloride, 332 ; Detailed instruction of procedure for examination of a paper, 333 ; Microscopical examination, 334 ; Description of poplar wood fibers under the microscope, 335 ; Description of spruce wood fibers under the microscope, 336 ; Description of linen fibers under the microscope, 335 ; Difference 'in appear- ance of fibers before and after manufacture into paper, 337; Quantitative determination of different fibers in a paper by means of the microscope, 337 ; Official German directions for the detection and estimation of the various fibers in paper, 337; Color reactions of the different fibers with solutions of iodine, 337) 338; Determination of the free acids in paper, 338; Process for the determination of chlorides, 338 : for sulphates, 339 ; Use of aluminum sulphate instead of alum in paper, 339; De- termination of the nature and amount of sizing used, 339, 340; Schumann's method for rosin, 340 ; Determination of the amount of starch, 340, 341 ; Tollen's formula for Fehling's solution, 341 ; Determination of the ash of paper, 341-343 ; Detection of Venetian red, Prussian blue, ochre, agalite, and clay, 342 ; Percentage of ash in commercial pulps, 342 ; Ash in the various fibers, 344 ; Determination of the weight per square meter, 344 ; of the thickness, 344 ; of the breaking strength, 345, 346 ; Description of the Wendler paper testing machine, 347 ; Method of using the instrument, 347, 348 ; The Schopper apparatus, 348 ; References to literature upon paper- making and paper-testing, 348, 349. Soap Analysis 349 Classification of soaps into toilet soaps, laundry soaps, com- mercial soaps, and medicated soaps, 349 ; List of adulterants used in soaps, 349 ; Manufacture of the common yellow soap, 349 I Use of recovered grease, 349 ; List of oils used in the manufacture of soaps, 349 ; Scheme for the analysis of soap, CONTENTS. XV11 350 ; Scheme for the analysis of unsaponifiable matters in soap, 351 ; Determination of water, 352 ; Determination of waxes, 352 ; Determination of total alkali and fatty acids, 353 ; Caprylic anhydride, 353 ; Determination of glycerine, 354 ; of silicates of the alkalies, 354; Factor to convert weight of fatty hydrates to anhydrides, 354; Free alkali, 353; Determination of resin, 355 ; Gottlieb's method, 355 ; Hiibl's method for resin in soap, 356 ; Twitchell's method for determination of resin in fatty acids, 356 ; Table for the physical and chemical inves- tigations of fats and fatty acids, 358 ; Determination of glyc- erine by titration, 359; Table of analyses of various kinds of soaps, 361 ; Washing powders, 362 ; References, 362. Technical Examination of Petroleum 362 Division into three classes by fractional distillation, 362 ; The method of Engler, 362 ; Variations in methods used by chemists, 362 ; Composition of crude petroleum as deter- mined by fractional distillation, 363; Composition of two sam- ples of crude Mexican petroleum as determined by the writer, 364 ; Technical divisions of the distillates of petro- leum, 364 ; First class, cymogene, rhigolene, petroleum ether, gasolene, naphtha, ligroin, benzene second class, the vari- ous varieties of kerosene and third class, residium, boiling- point 300 C. and above, 364, 365 ; Average percentage compo- sition of the products obtained from petroleum, 365 ; Classifi- cation of the products from petroleum by the oil trade, 365 ; Composition of valve oils, car oils, engine oils, spindle oils, dynamo oils, loom oils, 365 ; Formula of engine oil as used by the Pennsylvania Railroad, 365 ; Formula for cylinder oils, 366. The Examination of Lubricating Oils 366 The generally accepted conditions of a good lubricant, 366 ; Determination of the nature of the oil by saponification, etc., 367 ; Description of the process of saponification, 367 ; De- termination of fatty acids in vegetable and animal oils, 368 ; Method of determining the melting-point of fatty acids, 369 ; Table of melting-points and congealing points of fatty acids of the various animal and vegetable oils used in lubrication, 370; Specific gravity, 371 ; Baume" hydrometers, 371 ; Taglia- bue's hydrometer, 371 ; Table for converting Baume" degrees, liquids lighter than water, into specific gravities, 371 ; Table of Baume" degrees with correction for temperature, 372, 373 ; Formula for quantitative determination of two oils in a mix- ture, from the gravity, 374 ; Graphical method, 375 ; The Westphal balance, 376 ; The Araeo-picnometer, 376 ; Table for conversion of various hydrometer degrees into specific gravi- ties, 377 ; Table of specific gravity of oils, 377 ; The cold test, 377-379 ; Description of cold test apparatus for oils, as used by chemists of Chicago, Burlington, and Quincy Railroad, 379, 380 ; Table giving the cold test of the principal oils, 380, 381 ; Specifications for oils, with requirements of cold test stated, 381 ; Tagliabue's standard freezing apparatus, 382 ; Viscosity of oils, 383 ; Pennsylvania Railroad viscosity tests, 383 ; Engler's viscosimeter, 384, 385 ; Redwood's viscosimeter, 385 ; The septometer of Mr. Lepenau, 386; Davidson's viscosime- xviii CONTENTS. ter, 387 ; Tagliabue's viscosimeter, 389 ; Gibb's viscosimeter, 390, 391 ; Table of viscosities of valve oils and stocks, 392 ; Viscosities of car and engine oils, 392 ; Perkin's viscosimeter, 393 ; Stillman's viscosimeter, 394-396 ; Table of viscosities of forty-three of the principle oils used in lubrication, at 68 F., 122 F., 212 F., 302 F., 392 F., 397; Chart of above tests, 398; Conclusions deduced from viscosity determinations, 399; The Doolittle viscosimeter, 400, 401 ; Iodine absorption of oils, 401 ; of fatty acids, 402 ; Table of determinations of iodine ab- sorption of various oils, 403 ; Flash and fire test of oils, 403 ; The "Cleveland Cup" oil tester, 404; Tagliabue's open tester, 405 ; The Saybolt electric oil tester, 405 ; The Abel closed tester, 405, 406 ; The Pensky-Marten's closed tester, 407 ; Traumann's open tester, 408 ; Requirements for the flash and fire test, 408 ; Acidity of oils, 408, 409 ; Method for de- termining the acidity of oils as performed in railroad labora- tories, 409, 410; Maumene's test for oils, 410, 411 ; Table giv- ing the rise of temperature of oils, by Maumene's test, 412 ; Color reactions of oils with nitric and sulphuric acids, 412, 413 ; Heidenreich's test, 413 ; Massie's test, 413 ; Table of reac- tions of various oils with nitric and sulphuric acids, 414 ; Classification of oils used in lubrication into two classes, saponifiable and unsaponifiable, 414 ; Detection of fatty oils in mineral oils by method of I/ux, 414 ; Detection of rosin oil by the method of Holde or Valenta, 414 ; Scheme for the analysis of a lubricating oil containing mineral oil, lard oil, and cotton-seed oil, 415; Method of Salkowski for the de- termination of the amounts of animal and vegetable oils when mixed together, 415, 416; Wool grease, 416; Degras or sod oil, 416; Bone fat, 416 ; Coefficient of friction, 417; Descrip- tion of the Thurston, and the Henderson-Westhoven friction machines, 417-419 ; Description of the friction apparatus used by the officials of the Paris-Lyon Railway, 419-421 ; Descrip- tion of the Richie" lubricant tester, as used in many of the railroad laboratories in the United States, 422 ; Record blank used by engineers on Baltimore and Ohio Railroad for testing oils upon locomotives, 423 ; Detailed specifications for engine and passenger car oils, cylinder, and freight car oils, Balti- more and Ohio Railroad, 423, 424 ; Specifications for black engine oils and cylinder stock, Chicago, Burlington, and Quincy Railroad, 425, 426 ; References to literature of lubri- cation, 426. Oils Used for Illumination 426 Classification of illuminating oils into two groups : a, refined products of petroleum ; b, certain refined oils of animal and vegetable origin, 426; Kerosene, 426; Headlight oil, 426; Specifications for petroleum burning oils for railroad use, 427 ; 150 fire test oil, 427; 300 fire test oil, 427; Method of ma- king tests on 150 oil and 300 oil, 427, 428 ; The cloud test, 428 ; The "Wisconsin" tester for the flash and fire points of illu- minating oils, 429, 430; Rules and regulations for making the tests, 430 ; Law regulating the standard of illuminating oils and fluids, state of New York, 430-432 ; The grades of colors in classifying kerosenes, 432 ; The Stammer colorimeter for oils, 432 ; The Wilson colorimeter, 433 ; Colza and lard oil for illumination, 433 ; Different methods of car illumination, 434 ; Pintsch oil gas, method of manufacture and use for car CONTENTS. XIX illumination, 434 ; The Foster system, 435 ; The Frost system, 435 ; The electric system of car lighting, 436-438 ; Results of experiments made upon different railroads, 438; Relative ad- vantages and disadvantages of the various systems, 438, 439 ; Table showing the comparative cost of car lighting systems, 440. The Analysis of Lubricating Oils Containing Blown Rape- seed and Blown Cotton-seed Oils 441 Rape-seed oil as the standard lubricant in Europe, 441 ; Pro- portion of rape-seed oil added to mineral oils, 441 ; Method of duplicating an oil from the analysis, 442, 443 ; Comparison of the chemical reactions of blown rape-seed and normal rape- seed oil, 4/M ; Recognition in a mixture of the amounts of cot- ton-seed and rape-seed oil from the difference in the melting- point of the fatty acids, 445 ; Synthetical work, 445. The Analysis of Cylinder Deposits 445 Classification of deposits, 445 ; Composition of deposit taken from a locomotive cylinder, 446 ; Composition of a deposit containing scale-forming matter carried over by the steam, 446 ; Corrosive action of fatty acids on iron, copper, brass, etc., 449 ; Action of castor oil as a lubricant, 447 ; Method of pro- cedure in analysis of cylinder deposits, 449 ; Scheme for the analysis, 450 ; Composition of a deposit formed from mica grease, 452 ; References, 452. Paint Analysis 452 What should constitute a paint, 452 ; Qualities essential in a paint, 453 ; List of red pigments with their chemical for- mula, 453 ; brown pigments, 453 ; white, yellow, and orange, 453 ; green, black, and blue pigments, 454 ; Scheme for the analysis of white paint ground in oil, 455 ; Analysis of several representative paints, 456 ; Scheme for the analysis of lemon chrome paint, 457 ; Determination of water, volatile matter, and water extract in chrome paints, 458 ; Scheme for the analysis of chrome green, 459 ; Specifications for cabin car color, Pennsylvania Railroad, 460; Use of gypsum and cal- cium carbonate in red paints, 460 ; Specifications for freight car color, 461 ; Composition of paints used for iron work, Elevated Railroad, New York City, 462, 463 ; Asphalt paint, 463; Fire-proof paints, silicate paints, asbestos paints, etc., 463 ; Composition of the fire-proof paint used by the munici- pality of Paris, 494 ; Composition of ultramarine, commercial Prussian blue, and smalts, 464 ; Examination of the oil after extraction from the paint, 465; Detection of turpentine in presence of rosin spirit, 465 ; Petroleum, naphtha, and turpen- tine, 465 ; References on the literature of paints, 465. Pyrometry 466 Practical use of pyrometers, 466 ; Classification of pyrometers, 466 ; Principles upon which their operation depends, 466, 467 ; Air thermometers, 467 ; Air pyrometer of Siegert and Duerr, 467, 468 ; Wiborgh's air pyrometer, 468 ; Hobson's hot-blast pyrometer, 468; Bristol's recording thermometer for tempera- tures up to 600 F., 469; Brown's metallic pyrometer, 469; XX CONTENTS. The copper-ball or platinum-ball pyrometer, 469 ; The Wein- hold pyrometer, 470, 471 ; The Saintignon pyrometer, 472 ; Braun's electric pyrometer, 473 ; LeChatelier's thermo-elec- tric pyrometer, 473, 474 ; Uehling's and Steinbart's pyrometer for blast furnaces, 475-478 ; List of boiling and melting-points of metals as determined with pyrometers, 479 ; References to the literature of pyrometry, 479. The Electrical Units 480 The electrostatic and the electromagnetic systems, 480 ; The C. G. S. units, 480; Unit magnetic pole, 480; Unit current, 480; Practical units, 480; Ampere, 480; The ohm, the volt, the coulomb, the Farad, the Joule, the Watt, the Henry, 481 ; Kilo- Watts, 482 ; Relations between the international units of resistance and electromotive force to those of the older units, 482 ; Ohm's law, 482 ; Joule's law, 482 ; Measurement of elec- tric energy, 482 ; The Watt-meter, 483 ; Electro-chemical equivalents, 483. Energy Equivalents 483 Work in foot pounds, per second, per minute, per hour, 483; in B. T. U. per second, minute, hour, 484; in pounds of steam, in combustion, in electricity and light, 484 ; in rotary delivery, 484. Heat B. T. U. to work, light and electricity, 485 ; steam to work, light, and electricity, 485 ; one pound of carbon con- sumed in one hour, in terms of combustion, fuels to B. T. U., steam work, 486; one pound of kerosene consumed per hour in terms of light and electricity, 486 ; one cubic foot illumi- nating gas in terms of, 487. Light One candle power, in terms of light to work, B. T. U., electricity, steam and combustibles, 487. Electricity -One Watt, in terms of work, (H. P.), B. T. U., steam, light, and combustibles, 487. Tables 488-505 Index 506 List of Illustrations. Page. Figure I. Electrolytic apparatus for Ihe determination of copper 6 2. Gtilcher's thermo-electric pile 7 3. Bunsen valve 12 4. Apparatus for determination of CO 2 in limestone 17 " 5. Lychenheim's apparatus for determination of phosphorus in coal and coke 22 6. Thorner coke testing machine 24 7. Bunsen valve 29 8. Apparatus for determination of water of hydration in iron ores 32 9. Jenkin's scale for calculation of blast furnace charges 55 " 10. Bettendorf's automatic water-bath 61 " ii. Apparatus for determination of ammonia in water 75 " 12. Wolff 's colorimeter 76 13. Apparatus used by New York City Health Board for determination of ammonia in water 79 " 14. Filter-beds, water supply of Dublin 86 " 15-18. The Warren filter 87-92 " 19,20. The Goubert feed-water heater 100 " 21. The Hoppes feed-water purifier and heater 101 " 22,23. The Derveaux water purifier , 106 " 24-26. The Archbutt and Deely apparatus for purification of boiler waters 108 27. Filter press in " 28. Application of filter press for filtration of boiler waters 112 29. Apparatus combining chemical precipitation, feed-water heater and fil- ter press for purification of boiler waters 113 30, 31. Apparatus for determination of carbon and hydrogen in coal 116 32. Apparatus for determination of nitrogen in coal 117 " 33. Shell and connections of the Mahler calorimeter 126 34, 35. The Mahler calorimeter 127, 128 36. The Thompson calorimeter 132 37. The Barrus coal calorimeter 136 38-40. The Carpenter coal calorimeter 139, 141 41. Kent's apparatus for determining the heating values of fuels 142 42. Apparatus for determination of sulphur in iron 151 " 43. Apparatus for determination of sulphur in iron 153 " 44. Apparatus for determination of carbon in iron and steel ; chromic acid process 161 " 45. Apparatus for determination of carbon in steel and iron ; oxygen com- bustion process 164 46. Wiborg's apparatus for determination of carbon in iron and steel 165 47. Eggertz' apparatus for determination of carbon in steel 168 48. Spiegelberg's agitation apparatus for phosphoric acid determinations. . . 179 " 49.5- Agitation apparatus for determination of phosphoric acid, as used by chemists of the Pennsylvania Railroad 181 51. Picnometer 191 52. Fairbank's cement testing machine 208 " 53. Richie's cement testing machine 209 xxii LIST OF ILLUSTRATIONS. Fig. 54. Briquette mold 2I " 55. The Michaelis cement testing machine 211 " 56. The Faija testing machine 211 " 57,58. The Reid and Bailey testing machine 212,213 44 59. Curve of breaking strengths of cements (Faija) 215 " 60. The Bohme-Hammer apparatus 216 " 61,62. Jameson's briquette making machine 217 " 63. French modification of the Michaelis cement testing machine 219 " 64. The Buignet cement testing machine 220 41 65. The Suchier compression machine 223 " 66. The Bohme compression machine 224 44 67. The Porter automatic cement testing machine 226 68. The Elliott apparatus for analysis of chimney gases, etc > 233 " 69. The Orsat-Miiencke apparatus for analysis of flue gases 238 44 70. The dasymeter of Siegert and Duerr 242 14 71,72. Charts showing heat losses in boiler practice 243 " 73-83. The Hempel gas apparatus 246-250,252-254 41 84. The Humphrey water gas plant 267 41 85. The Bunsen photometer 276 44 86. The Hartley calorimeter for combustible gases 284 44 87,88. The Junker calorimeter 287-290 44 89. Newbigging's experimental plant for the determination of the gas-pro- ducing qualities of coal 297 " 90. The Riehle United States standard automatic and autographic testing machine 305 41 91. The Tagliabue freezing apparatus 306 44 92-99. Microphotographs of various fibers 33S.33 6 44 loo. Apparatus for determination of the thickness of paper 345 44 101. The Wendler paper testing machine 346 44 102. The Westphal balance with Reimann's plummet 357 14 103. Fractional distillation flask for petroleum 363 44 104. Separatory funnel for separation of oils 367 41 105-108. Apparatus for determination of melting-points of fatty acids 369, 370 44 109. Tagliabue's hydrometer for oils 371 44 no. Graphic method of determining percentages of oils in mixtures of oils.. 375 44 in. The Westphal balance 375 44 112. The Westphal balance modified for high temperatures 376 44 113. Eichhorn's araeo-picnometer 377 44 114,115. Cold test apparatus for oils 378,379 44 116. Sectional view, Tagliabue's freezing apparatus 382 44 117. Schubler's viscosimeter for oils 383 4 118. Engler's viscosimeter for oils 384 4 119. Redwood's viscosimeter for oils 385 44 120,121. lyepenau's septometer for oils 386 14 122. Davidson's viscosimeter for oils 388 4 123. Tagliabue's viscosimeter for oils 389 ' 124. Gibb's viscosimeter for oils 390 44 125. Chart of curves showing viscosity of oils as determined by the Gibb's viscosimeter 393 '* 126. Stillman's viscosimeter for oils 395 44 127. Chart of curves showing viscosity of oils as determined by the Stillman viscosimeter 398 14 128. Doolittle's viscosimeter for oils 400 4 129. Apparatus for determination of the 4l flash " and " fire " test of lubrica- ting oils 404 LIST OP ILLUSTRATIONS. Xxiii Fig. 130. Tagliabue's open tester 404 " 131. The Saybolt tester 405 " 132,133. The Abel closed tester 406 " I34.I35- The Pensky-Martens closed tester 407 " 136,137. The Treumann open tester 408 " I3 8 . 139- The Henderson-Westhoven friction tester for lubricants 417 " 140, 141. Apparatus used by the Paris-I,yon Railway for testing lubricants. 419, 420 " 142. The Richie machine for friction tests of lubricants 421 ' 143. The Wisconsin tester for illuminating oils 429 ' 144. The Stammer colorimeter 432 " 145. The Soxhlet apparatus 448 " 146. The air pyrometer of Siegert and Duerr 467 " 147. The Hobson hot-blast pyrometer 268 " 148. The Weinhold pyrometer 470 * 149. The Saintignon pyrometer 472 " !5<>i 151- Prof. Braun's electric pyrometer 473,474 4 152-154. Uehling and Steinbart's pyrometer 475~477 Page 80, line 14, for " NO 2 " read " NO 3 ." Page 81, line 19, add " with dilute acetic acid." Page 82, line 22, for " 1000 parts of salt " read " looo parts of water." Page 119, line 16, for " hydroscopic " read " hygroscopic." Page 125, line 10, for "hydroscopic" read "hygroscopic." Page 170, line 22, for " L,eduber " read " Ledeber." Page 187, line 12, for " fidelity " read "fluidity." Page 256, line 30, for " for carbon dioxide 24.2 per cent." read " carbon monoxide 24.2 per cent." Page 259, line 21, for " C 2 H 4 = 11900 calories" read "C 2 H 4 = 11911 calories." Page 263, line 3, for " (2.39 cubic foot of air) " read " (2.39 cubic feet of air)." Page 270, line 21, for "827.62 B. T. U." read " 754.6 B. T. U." Page 271, line 21, for " 1582. B. T. U." read " 1391. B. T. U." Page 273, line 36, for " 1000.52 B. T. U." read " 1115. B. T. U." Page 288, line 25, for " pressed " read " passed." Page 314, line 29, for " hydrogen oxide gas " read " hydrogen sulphide gas." Page 373, line 3, for "24 Baume at 60 F." read "24.7 Baume" at 60 F." Page 433, line 19, for " Wilson's calorimeter" read " Wilson's colorim- eter." ENGINEERING CHEMISTRY. QUANTITATIVE ANALYSIS. I. Determination of Iron in Iron Wire. Weigh two samples of bright iron wire (each sample 0.500 gram) ; transfer to beakers (No. 3), add twenty-five cc. hydro- chloric acid, five cc. nitric acid, cover the beakers with watch- glasses, and warm gently until solution is complete. Proceed with each sample as follows : Add 100 cc. water, then ammonium hydroxide gradually until the solution is faintly alka- line ; boil, filter upon a No. 4 ashless filter, 1 and wash precipi- tate with hot water until the washings no longer react alkaline. Dry at 105 C. Remove as much of the dry precipitate as possible from the filter paper to a piece of glazed paper and ignite the filter paper in a weighed porcelain crucible (Meissen No. 6), uncovered, until all carbonaceous matter is consumed. Add the precipitate from the glazed paper, cover the crucible, and ignite at a red heat for ten minutes, cool in a desiccator, and weigh. Heat the crucible and contents once more to a red heat for three minutes, cool as before, and weigh. Repeat until weight is constant. Example : Amount of iron wire taken = 0.500 gram. Crucible -+- Fe. 2 O 3 .............................. 9-43 2 grams. Crucible ...................................... 8.721 Fe 2 O 3 .................................. 0.711 gram. Then e 2 : : 0.711 : x. x = 0.4977 weight of Fe. -4977 X IPO _ cent. Fe in the wire. 0.500 References. Fresenius' " Quantitative Chemical Analysis" (London Edition), 703, I, a. ; "Hints to Beginners in Iron Analysis," by David H. Browne,/. Anal. Chem., 5, 325. 1 12 cm. diameter. (O QUANTITATIVE ANALYSIS. II. Alumina in Potash Alum. Press finely triturated potash alum between sheets of filter paper. Weigh out duplicate samples, each of two grams ; transfer to No. 4 beakers, and dissolve in about isocc. of water. Add ammonium hydroxide in slight excess, fifteen cc. solu- tion of ammonium chloride, and boil gently a few minutes, the liquid remaining alkaline. Allow the precipitates to settle, then decant the clear supernatant liquid upon No. 4 ashless filters. Pour boiling water upon the precipitates in the beakers, allow precipitates to settle, decant the liquid as before, and repeat the operation three times, finally transferring all of the precipi- tates to the filter papers, and washing with hot water until the reaction is no longer alkaline. Dry at 105 C., transfer to weighed porcelain crucibles, and ignite as directed for ignition of ferric hydroxide (I). Example : Amount of alum taken, 2.384 grains. Crucible -f A1 2 O 3 .............................. 17. 513 grams. Crucible ...................................... 17.258 " A1 2 O H ................................. 0.255 gram. O^XKX, = io ceut 2.384 Theoretical Percentage : K 2 SO 4 + A1 2 (SO 4 ), -f- 24H 2 O : A1 2 O 3 : : 100 : x. _r= 10.85 per cent. A1 2 O 3 . III. Copper in Copper Sulphate. (CuS0 4 + 5 H 2 0). About five grams of the crystallized salt are pulverized, pressed between folds of filter paper, and transferred to a small stoppered weighing tube, and the latter and contents accurately weighed. COPPER IN COPPER SULPHATE. 3 Pour out about one gram of the salt into a No. 3 beaker, and reweigh the tube. The difference between the two weights gives the weight of the salt taken. The salt is dissolved in about 100 cc. of hot water, and, if the solution is not clear, add a few drops of dilute sulphuric acid. Warm gently, and add gradually a clear solution of sodium hydroxide, with constant stirring, until the reaction of the cop- per solution is alkaline ; boil ; the copper is precipitated as dark brown cupric oxide. Thus : CuS0 4 + 2(NaOH) = C0 + Na,SO 4 + H 2 O. The precipitate is allowed to settle, when, if sufficient sodium hydroxide has been added, the supernatant liquid will be color- less. Filter by decantation upon a No. 4 ashless filter, wash with hot water until reaction of washings is no longer alkaline, and dry at 105 C. Remove the precipitate (as much as possible) from the filter- paper, and place it upon a piece of glazed paper. The filter-paper (which will contain some cupric oxide) is transferred to a weighed porcelain crucible (No. 6 Meissen), and ignited. A portion of the cupric oxide is reduced to copper by the in- candescent carbon of the filter-paper. Allow to cool, add two or three drops of nitric acid, warm gently to dissolve the copper, and, when solution is complete, evaporate to dryness, and heat to redness, converting all the copper nitrate to cupric oxide. Add the rest of the cupric oxide remaining upon the glazed paper to the crucible, and heat, at red heat, to constant weight. Example : First weight of weighing tube and CuSO 4 + 5H 2 O 7.0250 grams. Second weight of weighing tube and CuSO 4 -f 5H 2 5.9605 " Copper sulphate taken 1.0645 " Crucible + CuO 15-3744 " Crucible 15.0360 " o.33 8 4 gram. CuO : Cu : : wt. of CuO : x (=wt. Cu) 79-5 : 63.5 : : 0.3384 : x x-= 0.2702. 4 QUANTITATIVE ANALYSIS. Then, 0.2702 X IPO = 25 . 38 per cent . O f Cu . 1.0645 Theoretical Calculation : CuSO 4 + 5H 2 O : Cu : : 100 : x 249-5 : 6 3-5 : ' loo : x ^ = 25.45 percent. Cu. Found by Analysis : 25.38 per cent. Cu. Difference : 0.07 per cent. IV. Volumetric Determination of Copper by Potassium Cyanide Solution. Dissolve ten grains of potassium cyanide in 250 cc. of water and thoroughly mix. Weigh out two grams of pure copper wire, transfer to a one- fourth liter flask, add twenty-five cc. nitric acid, warm gently until the copper is all dissolved ; boil to expel oxides of nitro- gen ; cool, dilute with water to the mark, mix w r ell. Take fifty cc. of this copper solution, transfer to a No. 3 beaker, add ammonium hydroxide until the precipitate formed dissolves and the solution is alkaline. Fill a fifty cc. burette with potassium cyanide solution, and gradually drop the cyanide solution into the copper solution until the blue color disappears and the solution becomes color- less. Note the number of cc. of potassium cyanide solution required to do this, and mark upon the potassium cyanide bottle the value of one cc. in terms of copper. Thus : Suppose fifty cc. of the copper solution required 31.3 cc. of potassium cyanide solution : Then 31.3 cc. KCN=o.4o gram Cu. And i cc. KCN 0.0127 gram Cu. Having thus obtained the value of the potassium cyanide solution, it can be used for determining percentages of copper in alloys, bronzes, etc. For example Brass : DETERMINATION OF COPPER BY ELECTROLYSIS. 5 Two grams of brass are weighed out and treated with twenty- five cc. nitric acid, and the solution made up to 250 cc. Fifty cc. of this solution is made alkaline with ammonium hydroxide, filtered, and the filtrate titrated with the potassium cyanide solution. Having determined the number of cc. of potassium cyanide solution required to decolorize the fifty cc. of the brass solution, the percentage of copper is calculated from above data. Consult: Note on the use of potassium cyanide in the estimation of copper, by Geo. E. H. Ellis, F. C. S., /. Soc. Chem. Industry, 8, 686. V. Determination of Copper by Electrolysis. Weigh out five grams of crystallized copper sulphate, dis- solve in 500 cc. water (preferably in a half liter flask), mix well. Take fifty cc., transfer to a No. 2 beaker, and arrange the electrolytic apparatus as shown in Figure i, connecting the weighed platinum cone N with the negative element of a Bun- sen cell and the platinum spiral P with the positive. Add a few drops of dilute sulphuric acid and water enough so that the solution in the beaker covers two- thirds of the plati- num cone. Copper is deposited upon the platinum cone and the deposi- tion is generally complete in about four hours. To determine when all the copper is precipitated, takeout one drop of the colorless solution, in the beaker, by means of a glass rod, and place the drop upon a watch-glass. Bring in contact with this drop, one drop of a dilute solution of potassium ferro- cyanide. If copper is still unprecipitated, brown copper ferrocyanide will be formed. If, however, it is all precipitated, no brown coloration of the drops will form. When the copper is all deposited remove the platinum cone quickly, wash it several times by dipping it in distilled water, dry at 100 C., and weigh. QUANTITATIVE ANALYSIS. Fig. i. DETERMINATION OF COPPER BY ELECTROLYSIS. Example : Amount of copper sulphate taken = 5.000 grams. Solution 500 cc. Fifty cc. taken for electrolysis. Platinum cone -f- metallic copper 36.656 grams. Platinum cone 36.529 " Copper deposited 0.127 gram. Then, 0.127 X IPO Where many determinations of copper, by this method, are to be made, the apparatus described by W. Hale Herrick, /. Anal. Chem., 2, 67, can be used. A very convenient instrument for generating the current of electricity is Giilcher's thermo-electric pile, Figure 2. Fig. 2. t It consists of sixty-six elements and is equivalent to two large freshly filled Bunsen elements ; its electromotive force is equiva- lent to four volts, the inner resistance amounting to 0.65 ohm, so that with an equal outer resistance the thermo-electric pile gives a current of three amperes. The gas consumption is about 170 liters per hour (6.001 cubic feet). The amount of current should not be excessive, otherwise the deposit of copper upon the platinum cone will be granular and non-cohesive. 8 QUANTITATIVE ANALYSIS. References: " Bibliography of the Electrolytic Assay of Copper," by Stuart Croasdale,/. Anal. Chern., 5, 133-84. " Electro-Chemical Analysis," E. F. Smith, p. 48. " Quantitative Chemical Analysis by Electrolysis," by Dr. Alex. Classen, translated by W. Hale Herrick. 1894. "The Utilization of the Electric Light Current for Quantitative Chemical Analysis," by P. T. Austen and J. S. Stillwell,/. Anal. Chem., 6, 127. "On the Analysis of American Refined Copper," by H. F. Keller, /. Am. Chem. Soc., 16, 785. VI. Determination of Sulphur Trioxide in Crystallized Magnesium Sulphate. Weigh out one and a half grams of crystallized magnesium sul- phate. Transfer to a No. 3 beaker. Add 100 cc. water, a few drops of hydrochloric acid, and heat to boiling. Add a solution of barium chloride in slight excess. Stir well, and set aside for half an hour. Filter upon two No. 3 1 ashless niters, testing the nitrate with a few drops of barium chloride solution, to make certain that all the sulphur trioxide is precipitated. MgSO 4 + BaCl 2 = BaSO 4 + MgCl 2 . Wash the precipitate thoroughly with hot water until a drop of the nitrate placed upon a watch-glass and brought in contact with a drop of solution of silver nitrate shows no turbidity. Dry the precipitate, and ignite in a weighed porcelain crucible to constant weight. ist weight of tube -\- MgSO 4 -f- 7H 2 O 7.9040 grams. 2nd " " " " 6.5435 " MgSO 4 -f 7H 2 O taken 1.3605 '! Crucible + BaSO 4 23.502 grams. Crucible 22.214 " BaSO, 1.288 BaSO 4 : SO 3 : : 1.288 : x x = 0.442 gram SO 3 . 0.442 X ioo 1-3605 1 9 cm. in diameter. = 32.48 per cent. SO ;{ . DETERMINATION OF LEAD IN GALENA. 9 Theoretical : < MgSO 4 -f 7H 2 O : SO 3 : : 100 : x .r = 32.52 per cent. SO 3 . References : Fresenius, " Quant. Chem. Analysis," 132, i. "The Volumetric Estimation of Sulphates," by D. Sidersky J. Anal. Chem. ,.2, 417., VII. Determination of Lead in Galena, Transfer two grams of the finely powdered ore to a four-inch porcelain capsule ; add twenty-five cc. nitric acid, warm, then fifteen cc. sulphuric acid, and evaporate carefully until red fumes cease to be evolved, and the residue is nearly dry. Allow to cool, add a few drops of dilute sulphuric acid and seventy-five cc. water, bring to a boil, filter, and wash well. Neglect the filtrate. Wash the precipitate from the filter into a No. 3 beaker, using not over seventy-five cc. water ; add 100 cc. of a solution of sodium carbonate in water, (i to io)and boil the contents of the beaker for fifteen or twenty minutes. Solu- tion must be strongly alkaline. By this action the lead sulphate, formed by the nitric and sul- phuric acids upon the sulphide, is converted into carbonate. Filter, wash well with boiling water until reaction of washings is no longer alkaline. Neglect the filtrate. Wash the precipitate into a No. 3 beaker with about seventy- five cc. of water, add seventy-five cc. strong acetic acid, warm, and keep the contents of the beaker at boiling temperature for ten minutes, beaker covered with a watch-glass. The lead carbonate is thereby decomposed and soluble lead acetate formed, while any silica or gangue remains insoluble. Filter, wash well with hot water until the washings are no longer acid. Neglect the residue on the filter. To the solution of lead in the beaker, which should not ex- ceed 150 cc. or 200 cc., including the washings, dilute sulphuric acid is added in slight excess until no more precipitate is formed. After standing for half an hour the lead sulphate is filtered off 10 QUANTITATIVE ANALYSIS. upon a No. 3 ashless filter, and washed thoroughly with hot water. Dry at 102 C. Transfer the lead sulphate from the filter- paper to glazed paper, and ignite the filter-paper in a weighed porcelain crucible. After complete incineration, allow to cool ; add a few drops of nitric acid, and warm gently. (Any lead re- duced from lead sulphate by the burning paper will be dissolved, forming lead nitrate.) Add three or four drops of sulphuric acid and evaporate to dryness ; add the rest of the lead sulphate that is upon the glazed paper, and ignite contents of the crucible to redness ; cool in desiccator, and weigh ; repeat to constant weight. Example : ist weighing of tube and Galena 16.670 grams. 2d " " " " 14.503 " Galena taken 2.167 " Crucible + PbSO 4 17.576 grams. Crucible . . . 16.564 " i. 012 " PbSO 4 : Pb : : 1.012 : x x = 0.6914. 0.6914 X IPO 3I>9 pe r cent, lead in the sample of Galena. 2.167 VIII. Determination of Iron by Titration with Solution of Potassium Bichromate. a. Where the Iron Solution is in the Ferrous Condition. Take one and a half grams of crystallized ammonium ferrous sulfate ; transfer to a No. 3 beaker, and dissolve in 100 cc. of cold water ; add ten cc. hydrochloric acid. Make a solution of potassium bichromate by dissolving 14.761 grams of the " C. P." salt in 1,000 cc. water; mix well. Each cc. is equivalent to 0.0168 gram of iron. (Consult Fre- senius, "Quant. Analysis, London edition, 112 b.) IRON BY TITRATION. II Fill a fifty cc. burette with some of this solution, and drop the bichromate slowly into the beaker containing the iron solution until a drop of the latter placed upon a white porcelain slab and brought in contact with a drop of a very dilute solution of potas- sium ferricyanide no longer produces a blue or greenish colora- tion, showing the ferrous salt to be all oxidized to ferric salt. Note the number of cc. of the bichromate solution required to do this, and calculate percentage of iron in the ammonium ferrous sulphate. Example : Ammonium ferrous sulphate taken ............. 1.503 gram. 12.27 cc - bichromate solution required to oxidize. i cc. = 0.0168 gram iron. Then, 12.78 cc. = 0.2147 gram iron. ^ = J4 2g . Theoretical percentage : (NH 4 ) 2 SO 4 .FeSO 4 -f 6H 2 O : Fe : : 100 : x x= 14.28 per cent. b. Where the Iron solution Exists in the Ferric State. As the use of bichromate requires the iron to be in the fer- rous condition so as to be oxidized by the bichromate, the ferric salt is reduced to ferrous as follows : Take one and a half grams of ferric sulphate, 1 transfer to a 200 cc. flask, dissolve in fifty cc. water, add ten cc. hydrochloric acid, and a few pieces of "feathered " zinc. All the zinc must be dissolved and the solution colorless before it can be titrated with the bichromate. It is essential in this process, that all the ferric salt be reduced to ferrous, otherwise the number of cc. of the bichromate used would give too low a result for the percent- ages of iron. To keep the iron solution in the flask from [oxidizing while it is being reduced by the hydrogen from the reaction of zinc and hydrochloric acid, several methods are available : ist. Method described by Fresenius, in' which carbon dioxide is passed through the flask during reduction (see 112). 2d. The stopper of the flask is arranged to allow escape of the 1 Use ammonium ferric sulphate instead of ferric sulphate. 12 QUANTITATIVE ANALYSIS. hydrogen generated by the dissolving of the zinc by the hydro- chloric acid, but prevents inlet of air. The stopper is of rubber (one perforation) , through |- 1 ' which passes a glass tube. At the upper end of the glass tube a piece of rubber tube (closed at b with a glass rod), is adjusted, and at a an opening is made in the rubber tube, which, when the contents of the flask are heated, allows the exit of gas, but which closes and prevents the entrance of air when heat is removed, the so-called Bunsen valve. 3d. The method of Jones is the most expeditious FIG. 3. where a number of reductions are to be made./. Anal. Chem., 3, 124. Example : Ferric sulphate taken 1.520 gram. 18.01 cc. bichromate solution required to oxidize. Then, -' OI X - l68 x Io = 19.90 per cent, iron in ferric sulphate. 1.520 Theoretical Percentage : Fe 2 (SO 4 ) 3 -f 9H,O : Fe 2 : : 100 : ,r _r = 19.92 per cent, iron in ferric sulphate. IX. Determination of Phosphoric Anhydride in Calcium Phosphate. Weigh out one gram of finely pulverized calcium phosphate, transfer to a six-inch porcelain capsule, add twenty cc. nitric acid, ten cc. hydrochloric acid, and evaporate nearly todryness. Allow to cool, add twenty-five cc. nitric acid, seventy-five cc. water, boil, and filter into a one-fourth liter flask. Wash with water until reaction is no longer acid, and make solution and washings up to the containing mark by the addition of more water. The reading must be taken with contents of flask at a tem- perature of 15.5 C. to be accurate. Mix well, and take duplicate samples, each of twenty-five cc., transfer to No. 3 beakers, and treat as follows : PHOSPHORIC ANHYDRIDE. 13 Concentrate by evaporation to about fifteen cc. Cool some- what, and add carefully ammonium hydroxide until the solution is alkaline, then make reaction slightly acid with nitric acid. Add thirty cc. of standard ammonium molybdate solution, with stirring, and then some more ammonium hydroxide, but not enough of the latter to render the liquid alkaline. Add twenty cc. ammonium molybdate solution, and set aside two hours. Filter, test filtrate with a few drops of ammonium molybdate solution, to be certain all of the phosphoric acid is precipitated, and wash precipitate well on the filter with water containing one-eighth its volume of ammonium molybdate solution. The filtrate and washings are neglected. Fifteen cc. ammonium hydroxide are poured upon the yellow precipitate on the filter, and the solution formed caught in a No. 2 beaker. The filter-paper, free from the yellow precipitate, is washed thoroughly with hot water, and the filtrate made acid with hydrochloric acid. This produces a precipitation of the yellow ammonium phosphomolybdate. Ammonium hydroxide is added in quantity just sufficient to dissolve this and to form a col- orless solution again. Thirty cc. of standard magnesia mixture solution are now added gradually with constant stirring, and the beaker with the precipitated ammonium magnesium phosphate set aside for thirty minutes. Filter upon an ashless filter, wash with water containing one- eighth its volume of ammonium hydroxide, dry, ignite in porce- lain crucible to constant weight, and weigh as magnesium pyro- phosphate. Example : Amount of calcium phosphate taken = 1.157 grams. Solution = 250 cc. 25 cc. taken. Crucible -f- Mg 2 P 2 O 7 15.6037 grams. Crucible 15.5210 " Mg 2 P,0 7 0.0827 " Then, Mg 2 P 2 O 7 : P 2 O 5 : : 0.0827 : x x = 0.0529 gram. If the P 2 O 5 in 25 cc. = 0.0529 gram, in 250 cc. or entire solu- tion = 0.529 gram. ' ' 59OQ=45 - 7 per cent - P2 5 i 14 QUANTITATIVE ANALYSIS. References: A very complete article on "Mineral Phosphates and Superphosphates of Lime" will be found in the American Chemist, 7, 103-108; also Bulletin, No. 89 (Oct. 9, 1892), "New Jersey Agricultural Experi- ment Station, Analysis and Valuations of Complete Fertilizers, Ground Bone, and Miscellaneous Samples." J. Am. Chem. Soc., 15. 382. /. Anal. Appl. Chem., 5, 418. For method for complete Analysis of Phosphates and Superphos- phates consult Fres. Quant. Anal., p. 689. Also Principles and Practice of Agricultural Analysis, H. W. Wiley, 2, 101-141. X. Determination of Chromium Trioxide in Potassium Bichromate. Weigh out one gram of the finely crystallized salt, transfer to a No. 3 beaker ; add 100 cc. of water, and warm until com- plete solution. Take twenty-five cc. dilute hydrochloric acid, fifteen cc. alco- hol, add to the solution of bichromate, and heat the mixture nearly to boiling, until the chromium trioxide is entirely reduced to chromium sesquioxide, the solution becoming dark green in color, then boil out the alcohol, and add ammonium hydroxide to faint alkaline reaction. The mixture is exposed to a temperature approaching boiling, until the liquid above the precipitate is per- fectly colorless, presenting no longer the least shade of red. Filter, wash with hot water until the washings no longer react alkaline. Dry, ignite, and weigh as chromium sesquioxide. Example : ist weight tube and salt 10.942 grams. 2d " " " " 8.902 " K 2 Cr 2 O 7 taken 2.040 " Crucible and Cr. 2 O 3 43.270 " Crucible 42.230 ' ' 1.040 CHROMIUM TRIOXIDE. This weight of Cr 2 O 3 must now be converted into CrO 3 . Cr 2 3 :(Cr0 3 ) 2 : 11.044: x ^-=1.3705 grams. I.37I5 X I =67.23 per cent. CrO 3 . 2.040 Theoretical : K.,Cr.,O 7 : (CrO 3 ) 2 : : 100 : x 295 : 201 : : 100 : x .# = 68.13 per cent. References : Fresenius, Quant. Anal., 106, i a. Volumetric Determination of Chromic Acid,/. Anal. Chem., 5, 297. XI. Analysis of Limestone. Carbonate of lime is the principal flux used by the iron smelter, and as usually quarried, is called limestone. The composition of this varies greatly ; the pure crystallized variety may be designated as marble, which usually contains about ninety-eight per cent, calcium carbonate, the remainder being silica and iron oxide. Limestone, as distinct from marble, often contains organic matter (especially if very dark in color), alumina, ferrous or fer- ric oxide, ferrous sulphide, calcium sulphate, and magnesium carbonate, with the calcium carbonate. A small proportion of iron oxide is of advantage in the smelt- ing process, but an excessive amount of magnesium carbonate is objectionable, as it requires a higher heat for fusion than cal- cium carbonate, and more fuel is necessary in the blast furnace. . o cS S.^o o oS s a g a .a 2.2 O H3 4J C >-> 3 :ls to o ir-: o2.2 ti^ 'o ! v_, |^_O c -g jjCLi JC lisa Fin - o v O u ^* tf) " ** u pa O S3 tO w .^! 1 O !! ^U 5J u-o 2 ^J O "O s " s| a ; H 5 -5 - 53 ctf o> O > (- 1 t3 S ? . o -rt S -y O o -^ 0*1 ^ o iS 11 x S o o ? ^ ^ W c S fc 3 * ^ 'S C o o <*H O X 11 a I s ta^ -^ P. oc vo w a p 5 I. -2 9 x I CC i s o ^2 ~~ ooi X S X 5 ^h^5|| H g .S-o'~ ! * C ' C t'lO'O ?^ > " 100.00 " The analysis shows the limestone to be a dolomite or magne- sium limestone. The following is an analysis 1 of high grade limestone : Silica 0.87 per cent. Iron and aluminum oxides 0.12 " Calcium carbonate 98.60 " Magnesium carbonate 0.22 " 99.81 It is seldom that phosphoric acid is determined in limestone, since it usually amounts to less than two-tenths per cent. It is essential, however, in cases where the limestone is to be used in blast furnaces making Bessemer pig iron. 1 /. Anal. Appl. Chem., 6 ( 510. COAL AND COKE ANALYSIS. XII. Coal and Coke Analysis. Determination of Moisture, Volatile and Combustible Matter, Fixed Carbon, Ash, and Sulphur, Take a weighed platinum crucible (capacity about twenty-five cc.) weigh in it one and a half grams of the powdered coal. Transfer to a drying oven and heat to 103 C. for fifteen minutes ; cool in a desiccator, and weigh. Loss is moisture. Crucible -j- cover 4- coal 26.ii7grams Crucible + cover 24.617 " Coal taken 1.500 " f Crucible 4- cover + coal, before drying 26.117 " " Crucible -j- cover -f- coal, after drying 26.109 ' Moisture 0.008 0.008 X ioo = Q 53 per cent moisture . The crucible containing the dried coal is now heated over a Bunsen burner for three and a half minutes, then over the blast-lamp for three and a half minutes more, taking care that the cover of the crucible fits closely. Cool in the desiccator. Loss in weight equals volatile I and combustible matter plus one-half of the sulphur. J Crucible 4~ cover 4~ coal, before heating seven minutes 26. 109 Crucible 4~ cover 4- coal, after heating seven minutes 25.569 0.540 0.540 X ioo = 36. per cent. f The crucible and contents are now heated over a Bun- ! sen burner (lid of crucible removed) until all carbon- aceous matter is consumed. Where the combustion is extremely slow, it can be expedited by introducing into the crucible a slow current of oxygen gas so regulated that the contents of crucible are not disturbed. Replace cover of crucible when ignition is complete, cool in des- iccator and weigh. Crucible-(-cover-|-coal, before complete combustion 25.569 Crucible 4- cover -f- residue, after complete com- plete combustion 24.669 Fixed carbon + \ S 0.900 X ioo =60.00 per cent. 0.900 Fixed carbon 4- \ S. 20 QUANTITATIVE ANALYSIS. f Crucible + cover -\- residue of coal after complete combustion (Ash) .......................... 24.669 grams, Crucible and cover ............................. 24.617 " S.i 5 COAL AND COKE ANALYSIS. 27 The following is a report upon a sample of Connelsville coke : ANALYSIS OF THE .COAL FROM WHICH THE COKE WAS MADE. Per cent. Water 1.105 ^ Volatile and combustible matter 29.885 -g Fixed carbon 57-754 ** Sulphur 1.113 g Ash 9.895 ^ cc 100.752 *< ANALYSIS OF THE COKE. Per cent. Water 0.030 Volatile and combustible matter 0.460 Fixed carbon 89.576 _ Sulphur 0.821 ~ o Ash v-**.-s if* Total 100.000 < SPECIFIC GRAVITY, POROSITY, PER CENT OF CELLS, WEIGHT PER CUBIC FOOT, ETC. OF THE COKE. Apparent specific gravity 0.892 True specific gravity 1.760 Per cent, of cells by volume 49-37 Volume of cells ; cc. in 100 grams 55-73 Weight per cubic foot (Ibs.) 55-68 COKE. nethod of rianufacture. To be used for. Style of Bee-hive Size. iiX5'6" 12' X 6' Charge Yield Time in per of pounds, cent, coking. 4 8 and 72 Kind of furnace. Size of fur- nace. 7600 63 Iron blast. 7o'Xi6' John Fulton, M. E., gives the following as the standard for the chemical and physical properties of coke : 28 QUANTITATIVE ANALYSIS. FIT/TON'S TABLE EXHIBITING THE PHYSICAL AND CHEMICAL PROPERTIES OF COKE. REVISED SERIES. x - ! Locality. '"" O !f. ., C |:i a *j :j &% $ 2 a3"o o > ^f D o a a s2 ^a 5 |Il 5 8-1 4) u Sa T, * % u c gravity. ,a I ! Pk^" >X! U 'p! S 73 3 a< 3 Height o charge, s without c Ord< cellula "2 rt K Specific Dry. | Wet. Dry. | Wet. CokefCells. Standard Coke. 15.47! 23.67 58.98 87-34 49.96 50.04 301 120 i 2.5 1.89 Connellsville. v^Ji^iiii^cii ctiicti^nm. o : . X Locality. s t o V I J; Remarks. u "55 X 1 ft S| "O ** "5 s X t^ o C > s ix Standard Coke Connellsville. 87.46 0.49 11.32 0.69 0.029 O.OII References: "On the Density of Coke," by Wm. A.Tilden, F. R. S.,/. nd.i 3 610. "An Investigation Regarding the Differences Between Cokes," by Sir I. Lowthian Bell,/. Iron and Steel Institute, 1885. "The Physical and Chemical Properties of Coke," by John Fulton, Transactions American Institute of Mining Engineers,, 1885. Grundlagen der Koks-Chemie, von Oscar Simmersbach, Berlin, 1895. " A Method of Obtaining the Specific Gravity and Porosity of Coke," by W. Carrick Anderson,/. Soc. Chem. Ind., 15, 20. " An Investigation of Coals for Making Coke in Semet-Solvay Ovens," by J. D. Pennock,/. Anal. Appl. Chem., 7, 135. " ,+. . - x' i ~ 7C : ' ^ - -- S3 ff||i|10SS.! g 5* ^ S 2 WM d^aoS 4 w 2?S3?| r -t o . a,p 2'. 7=^ s 5- o ^C. M ^ M - --?r^ x r*o i.o-rt- - - ft ~ o o o^o o-o' 3iantr t ! ti a s! 5 a i r5 3 x--,_ p: ^r>o o S^|ffg. 1 gp3>. 8 S!?cgS3iss8S,ff?3~ ' =,, =cro=-^5- 23 ^ n n n '* n- * M a x a r* = 2 3 - ' xS. rt ' ? ?Of?5X 5- 3. n * x s & is g o. a < 30 QUANTITATIVE ANALYSIS. Example : Ten grams of iron ore taken. Insoluble residue and crucible Io -55i grams. Crucible 10.301 " 0.250 o.25Xioo__ 2 g C ent. insoluble matter. 10 Solution = 500 cc. Phosphorus pentoxide, (100 cc.) a. Crucible 4- Mg 2 P 2 O 7 8.923 grams. Crucible 8.919 " Mg 2 P 2 O 7 = 0.004 " b. Crucible + Mg 2 P 2 O 7 7.6140 grams. Crucible 7.6105 " Mg 2 P,0 7 = 0.0035 " Mg 2 P 2 O 7 : P 2 O 5 : : 0.0038 : x jr = 0.0024 0.0024 X 5 X zoo = 0.054 " P. Iron determination. Fifty cc. reduced with zinc required 34.65 cc. standard K 2 Cr 2 O 7 solution. One cc. K 2 Cr 2 O 7 corresponds to 0.0168 gram iron. 34.65X0.0168 = 0.58212 gram iron in fifty cc. of the iron solution. Then 0.58212X10X100 = 58 2I per cent Fe - n the Qre 10 = 83.16 " Fe 2 O 3 in the ore. Sulphur Trioxide (50 cc.) Crucible + BaSO 4 11.126 grams. Crucible 11.011 " BaSO 4 = 0.015 BaSO 4 : SO 3 : : 0.015 : x x =0.0051 0.0051 X io X IPO = per cent SOs 10 Alumina (50 cc. from 25oc.c. = 1-5 of 100 cc.) Crucible + Al 2 O 3 ,Fe 2 O 3 12.6614 grams. Crucible 12.3160 " Al 2 3 ,Fe 2 3 = 0.3454 " IRON ORE ANALYSIS. 31 Fifty cc. of the iron solution, by titration, gave 0.58212 gram of iron or 0.3326 gram of ferric oxide for fifty cc. of the 250 cc. solution of Fe 2 O 3 Al 2 O 3 in (4) scheme XIII. Subtract this weight (0.3326) from weight of alumina and ferric oxide, (0.3454) in the fifty cc. The remainder equals 0.0128 grams alumina. 0.0128x25x100 = 3 20 per cent Ala03 IO Another method of determination of alumina in presence of ferric oxide, where the aluminum oxide is in small amount, is to fuse the weighed oxides with potassium hydroxide in a silver capsule, and extract with water. The alumina forms a soluble salt whereas the ferric oxide remains undissolved. Filter off ferric oxide, wash, ignite and subtract weight from iormer weight of both oxides. Difference is weight of alumina. flanganese oxide (100 cc.) Crucible + Mn 3 O 4 12.166 grams. Crucible ' 12.131 " Mn 3 O 4 = 0.035 " 0.35 X 5 X ICQ = IJ5 per cent MnsCV 10 Lime (100 cc.) Crucible + CaO 8.936 grams. Crucible 8.929 " 0.007 " 0.0027X5 X IPO percent. CaO. 10 flagnesia (100 cc.) Crucible 4- Mg 2 P 2 O 7 8.929 grams. Crucible 8.919 " M g2 p 2O- =: o.oio Mg 2 P 2 7 : (MgO) 2 : : o.oio : x x = 0.0036 0.0036X5X100^,3 p Water of Hydration. Amount of ore taken .......................... 1.267 grams. CaCl 2 tube + H 2 ............................. 29.065 " CaCl 2 tube .................................... 28.963 " H 2 O=o.io2 0.102 Xjoo _ g Q5 per cent H ^ o ( hydrated ) 1.267 Carbon dioxide absent. QUANTITATIVE ANALYSIS. FIG. 8. Resume. Insoluble mineral matter 2.50 per cent. A1 2 3 3-20 Fe 2 O 3 83.16 Mn 3 4 1.75 P 2 5 0.12 S0 3 0.51 CaO * 0.35 MgO o. 18 H 2 O (hydrated) 8.05 Total, 99.82 If the ore is a magnetite, the iron exists as FeO,Fe 2 O 3 . There are several methods of determining theFeO in presence of Fe 2 O 3 . The one recommended by Whittlesay & Wilbur, 1 is frequently used, but the method of Allen is simpler and is to be preferred. It is as follows : One gram of the very finely powdered iron ore is heated in a small sealed combustion tube, half full of fuming hydrochloric acid (25 cc. of the acid being sufficient). The heating is first performed in the water bath for two or three hours, then in a hot-air oven at 150 C for four hours more. The ore is thus completely decomposed and after cooling the tube, it is broken under water in a beaker, and the ferrous oxide immediately determined by titration with standard solu- tion of potassium bichromate. The amount of ferrous oxide i Chemical News, 19, 270. IRON ORE ANALYSIS. 33 subtracted from the total oxides, determined in another sample of the ore, gives the amount of ferric oxide. Some iron ores resist solution in acids, in which case the scheme is modified as follows : Two grams of the finely pulverized ore are fused with fifteen grams of fusion mixture (Na 2 CO 3 + K 2 CO 3 ) in a large plati- num crucible for one hour. After cooling the fused mass is- treated with boiling water, the contents transferred to a four inch porcelain capsule, made acid with hydrochloric acid (carefully) , and evaporated to dry ness, twenty-five cc. hydrochloric acid, five cc. nitric acid are added, warmed until solution of iron is com- plete, then fifty cc. of water added, and the solution filtered from the silica, etc. The analysis can now be finished by scheme XIII. Determination of Chromium in Chrome Iron Ore. 1 Take a half gram of the very finely divided mineral and inti- mately mix it with twelve grams of a mixture containing equal parts of dry sodium carbonate and barium dioxide, transfer to a large platinum crucible and fuse over the Bunsen burner for one hour. At the end of this time a quiet fusion is obtained and the decomposition is completed. The crucible is then placed in a beaker, covered with water, and hydrochloric acid added, a lit- tle at a time, till the mass is completely disintegrated. The crucible is then removed, the solution made strongly alkaline with caustic potash, and ten cubic centimeters of a five per cent, solution of hydrogen dioxide added to oxidize the small amount of chromium sesqui-oxide that may be present. The solution is now boiled for twenty minutes to remove any excess of hydrogen dioxide, made acid with hydrochloric acid, and the amount of chromic acid determined by the aid of a standardized solution of ferrous chloride, one cubic centimeter of which corresponds to 0.015 gram Cr 2 O 3 . The usual method for the determination of chromium in chrome iron ores, is that of Genth's* which consists in the fusion of the finely divided ore with potassium bisulphate. In detail as follows : 1 Process of Donath modified by I,. P. Kinnicutt and G. W. Patterson. /. A nal. Chcm., 3, 132. 2 Chem. News, 6, 31. (3) 34 QUANTITATIVE ANALYSIS. A half gram of the pulverized ore is fused in a platinum cru- cible with ten grams of potassium bisulphate for one hour. This is allowed to cool when five grams of dry sodium carbonate and one gram of potassium nitrate are added and the mass sub- jected to fusion for one half hour. After cooling the crucible is transferred to a No. 4 beaker and the contents treated with water. Filter, wash well, and evaporate the filtrate to dryness in a porcelain capsule after acidulating with hydrochloric acid. Treat with hydrochloric acid, filter, wash with hot water, and reduce the chromium trioxide to chromium sesquioxide by the addition of ten cc. of alcohol and boiling (consult scheme X). Filter, dry and ignite the precipitate, which may contain some alumina, etc., with a small amount of sodium carbonate and potassium nitrate in a platinum crucible; cool, dissolve the fused mass in water and transfer to a platinum capsule and evaporate to a syrupy consistency. Add gradually crystals of potassium nitrate and continue this until effervescence ceases, add ammo- nia to alkaline reaction and filter. This precipitate contains the alumina, etc., that might have been present in the first precipi- tation of the chromium sesquioxide. The chromium trioxide in the filtrate is reduced to the sesqui- oxide by the addition of excess of solution of sulphurous acid. Boil, make faintly alkaline with ammonia and continue boiling for several minutes. Filter, wash well, dry, ignite and weigh as Cr 2 O 3 . The following analyses indicate the varying amounts of chro- mium sesquioxide in chrome iron ores : Place. FeO MgO Cr 2 3 A1 2 3 Si0 2 Analyst. 35-14 36.00 18.97 20.13 24.00 25.66 35-68 21.28 8.42 30.04 33-93 38.66 9.96 7-45 "5-36 15-03 18.13 6.68 51-66 39-51 44.91 60.04 53-00 54.08 45-90 49-75 64.17 63.37 42.13 63-38 9-72 13.00 13-85 11.85 II. OO 9.02 3.20 11.30 10.83 1-95 10.84 2.09 = 99.32 10.06 = 99. ii 0.82 = 98.15 Seybert. Abich. Rangier. Hunt. Moberg. Rivot. Bechi. Garret. 5. Siberia Mn. IO.OO, 1. 00 = IOO 4.83 = 78.95 = 99.81 = 100.46 O.gl = IOI.OI Ca. 2.21, 2.01 = 99.06 4-75 = 100.65 2.25 = 104.32 9. Lake Memphramagog, U.S.. ir. Baltimore 12. Voltena, Tuscany 13. Texas, Pa IRON ORE ANALYSIS. 35 Reference, " New process for the oxidation of chromium ores and the manufacture of chromates," by J. Massignon, /. Anal! 9 . Appl. Chem., 5, 465- Determination of Titanium in Iron Ores. The method of Bettel 1 is generally used. Fuse about half a gram of the finely powdered ore with six grams of pure potassium bisulphate in a platinum crucible at a gentle heat, carefully increased to redness, and continued till the mass is in tranquil fusion. Remove from the source of heat, allow to cool, digest for some hours in 150 cc. of cold distilled water (not more than 300 cc. are to be used, as it generally causes a precipitation of some titanic acid) ; filter off from the silica, dilute to i2oocc., add sulphurous acid until all the iron is reduced, then boil six hours, replacing the water as it evaporates. The titanic acid is precipitated as a white powder, which is now filtered off, washed by decantation, a little sulphuric acid being added to the wash water to prevent it carrying away titanic acid in suspension. Dry, ignite, allow to cool, moisten with solution of ammonium carbonate, re-ignite and weigh. The titanic acid is invariably obtained as a white powder with a faint yellow tinge, if the process has been properly carried out. The table on the next pa ge gives the composition of the principle varieties of iron ores. References. (Iron Ores.) " The Iron Ores of the United States. Pro- ceedings of the Iron and Steel Institute, special volume, 1890, pages 68-91. " Hints for Beginners in Iron Analysis," by David H. Brown, J. Anal. Appl. Chem., 5, 325- "Determination of Iron by Stannous Chloride," by R. W. Mahon, Amer. Chem. Journal, 15, 360. " The Volumetric Determination of Titanic Acid and Iron in Ores," by H. L. Wells and W. L. Mitchell, /. Am. Chem. Soc., 17, 878. "The Constitution of Magnetic Oxide of Iron," by W. G. Brown,/. Anal. Appl. Chem, 7, 26. 1 Crookes' " Select Methods," p. 194. QUANTITATIVE ANALYSIS. (0 a o O ^ : o\ : : : o\ : : : : : : o\ 00*^ONOOr < ~>OOOOO cv !'"1 * I '. ^T 1 j? 6 \ ': 6 \ : : : : j? : : \ | ^ ; i^ ; 2 ; ; ; ; ; j ; | M 1 M 6ooq60 d . rf . d - qdSl'l H 0.865 X ioo 2 Crucible + SiO 2 = 17.585 grams. C = 16.720 SiO 2 = 0.865 . SiO 2 . 3 "2. !* * Crucible + Mg 2 P 2 O 7 = 11.00935 grams. = 11.00879 Mg 2 P 2 O 7 = 0.00056 Mg 2 P 2 O 7 ; P 2 O 5 : : .00056 : x x = .0003594 .Q00359X5XIOO = ^ per ^ ^ 50 cc. require 0.058 cc. K 2 Cr 2 O 7 solution. i cc. K 2 Cr 2 O 7 solution 0.0168 gram Fe. 50 cc. solution of slag = 0.000974 ' 25occ. " " " =0.004870" " Fe : FeO : : 0.00487 : x x = 0.0062 0.0062 X 100 3 8.' c ?J n ^aoS "SSB. ?5"3 ^3 " " ' p S N ~w - >1 S2 r 2'-'7 -***dSa Mg 2 P a O 7 : (MgO) 2 : : 0.02353 = x x = 0.00843 5 3 * .00843 X5X ioo = 2i3pgrcent MgQ P||- ft a P. tion nearly oil and fil- inum The few drops urs, then Crucible -f BaSO 4 = 11.92356 grams. "8 = =11.879 " ^wS' BaS0 4 = 0.04456 S = 1.53 per cent. tr.a a g Jg-O e s m , warm, ext six-inch porc uated flask Fu nu wo grams of the finely powd ucible for fifteen minutes ov ract contents of crucible elain capsule and evapora Wh well with hot wate to n XIV. ered sla a Bun and 2 -0.31 per cent. H s e gr ts to a id care and fil m of sodium a No. 4 beaker a arefully, trans il a filter into a q ghly mix itra dd fer ua in a oo cc. tents liter 38 QUANTITATIVE ANALYSIS. Resume Lime (CaO ) 36.46 per cent. Magnesia (MgO) 2.12 " Silica (SiO 2 ) 43-25 Alumina (A1 2 O 3 ) 15-94 " Ferrous oxide (FeO) 0.31 " Sulphur (S) 1.53 Manganese Oxide (MnO 2 ) 0.09 " Phosphoric Acid (P 2 O 5 ) 0.09 " Undetermined 0.21 " Total, loo.oo FORM OF Bl,ANK USED FOR REPORTING BLAST FURNACE SLAG ANALYSES. SLAG. Lime ( CaO ) Oxide of Iron (FeO) Calcic Sulphide (CaS) Phosphoric Acid (P 2 O- ) SLAG ANALYSIS. 39 Examples of Blast Furnace Slags Analyses, No. i. 1 No. 2. 2 FeO 0.270 per cent. 0.436 per cent. SiCX 45-46o " 35-000 " A1 2 O 3 16.590 " 14.362 CaO 32-805 " 45.370 MgO 1.080 " 1.398 MnO 2 0.083 " trace Sulphur \ Sulphide of) 1.571 " I > 8 75 " Calcium./ Calcium > 1.963 " 1-500 " Phosphoric Acid (P 2 O 5 ) 0.008 " 0.059 " Undetermined Loss 0.070 " " IOO.OOO IOO.OO Some varieties of slag are soluble in hydrochloric acid, in which case the analysis can be made by scheme XIII. This applies also to open-hearth slags, refinery slag, tap-cinder, inill- cinder and converter slag. Basic slags, from the Thomas- Bessemer Process, often con- tain as high as thirty per cent, of phosphoric acid and require a somewhat different process of analysis. Thus : One gram of the finely pulverized slag is fused with excess of sodium carbonate in a platinum crucible. Extract with water, acidify solution with nitric acid and evaporate in porcelain capsule to dryness. Take up with hydrochloric, dilute to half a liter and precipitate the phosphoric acid by the Acetate process. 3 The precipitate is filtered, dissolved in hydrochloric acid, excess of nitric acid added, and the solution concentrated until the hydrochloric acid and acetic, acids are expelled. The nitric acid solution is diluted to half a liter and two portions are taken (each 250 cc.) and the phosphoric acid determined in these by the molybdate method ; see scheme IX. Blast furnaces capable of producing 300 tons of pig iron per day are becoming the rule rather than the exception, while an output of 400 tons in twenty-four hours is often reached. To show the amount of material required every twenty-four hours to keep such a furnace running, we will assume as follows : 1 Slag made during the run of Alice furnace, on mixture containing Enterprise ore. 2 Slag made at the Sloss furnace in June, 1886, on No. i foundry iron. (Consult "Transactions of American Institute of Mining Engineers," Vol. XVI, p. 148). 8 Fresenius Quant, p. 409, 134. 40 QUANTITATIVE ANALYSIS. Height of furnace, eighty feet ; internal diameters at the hearth, bosh and stockline respectively fourteen, twenty and seventeen feet; cubical contents, about 22,000 cubic feet. 1 To produce one ton of iron, would require, approximately, 160,000 cubic feet of air, engine measurement, which would be at the rate of 3 3,333 cubic feet per minute ( * 6 ' * 3 = 33,333-) \ 24 X oo / To deliver this quantity of air a blowing power of not less than 2,000 horse-power should be available and 200 horse-power more is required to hoist the stock and pump the water needed for cooling, etc. The blast should be heated from 1200 to 1400 F, and for this purpose four regenerative stoves twenty feet in diameter and seventy feet in height are employed. These stoves contain about 48,000 cubic feet of fire-brick, and are kept at such a temperature as will heat the blast to the de- sired degree, by burning in them the waste gases of the fur- nace. If we assume the ore smelted to contain sixty per cent. of iron and twelve per cent, of silica, it will require one and six- tenths tons of ore and 0.4 tons of flux to make a ton of iron, assuming that two per cent, of the silica be reduced and alloyed with the pig iron. It will further require one ton of fuel 2 to make a ton of iron, which, containing ten per cent, of ash, will require an additional amount of 0.15 ton of flux. Thus, for one ton of iron is required 1.6 + 0.40 + 0.15 + i. = 3.15 tons of solid material and - ^ - =5.81 tons of air. In one day 13.77 X 2000 therefore, there would be 300 X 8.96=2688 tons of material passing through such a furnace. Supposing the flux to be car- bonate of lime, and to contain two per cent, of silica and one per cent, of alumina, the furnace would produce (0.55 0.03 X -55) -5 6 + -3 X 0.55 + 1.6 X o.oi -j- i X o.oi =0.57526 ton of slag per ton of pig iron, or 0.57526X300=172.5 tons per day. 1 " The Modern Blast Furnace," E. A. Uehling, Steven's Indicator, 8, p. 17. 2 Well equipped and well managed furnaces using " lake ores" are making a ton of iron (2,240 Ibs.) with 1.800 Ibs. of coke, and in some instances the fuel consumption has been as low as i, 600 Ibs. of coke. BLAST FURNACE SLAG. 41 Summing up : Material charged into the blast furnaces per day : Ore 480 tons. Coke 300 " Flux 165 " 945 tons. Blast 1743 " Total 2688 " Tapped from bottom of furnace in molten state : Pig Iron 300 tons. Slag 172.5 " Total molten product 47 2 -5 " Gaseous product passing out at top of furnace : Total blast 1743.00 tons. Oxygen from ore r 144.00 ' ' Gasified Carbon, as CO and CO 2 , 246.00 " Carbon dioxide from flux 70.42 " Volatile matter in ore and fuel 12.08 " Total gaseous product 2215.50 tons. Thus it is shown that of the material charged into a blast fur- nace somewhat less than sixty-five per cent, is gaseous, while over eighty per cent, passes off in the form of gas. In addition to the 2215.5 tons f g as there must be added an equal weight of air, or nearly so, since considerable excess is required for combustion. Thus the chimney of a 3oo-ton blast furnace, when in full operation, discharges into the atmosphere every twenty-four hours about 4,450 tons of gaseous material, which is at the rate of over three tons per minute. The heat energy developed is enormous. In twenty-four hours fully 7,500,000,000 heat units are generated, which, if utilized in a first-class steam plant, would develop over 13,000 horse power. The average amount of solid and molten material contained in a 3OO-ton furnace is prob- ably not far from 900 tons. The temperature varies from 3000 F, in the hearth, to 300 at the stockline. If the heat varied regularly the average temperature would be 1650 F ; but since the stock becomes denser as it gets lower in the furnace, and also since a red heat reaches quite high up in the furnace, 42 QUANTITATIVE ANALYSIS. 2,000 is probably nearer the average temperature of the whole. The specific heat of such a conglomerate is not definitely known, but it will be between two-tenths and three-tenths ; assume it to be 0.25. Hence, is obtained, for the heat stored away in the incandescent furnace stock, 900 X 2000 X 2000 X 0.25 = 908,- 000,000 heat units. The lining of the furnace will weigh 800,000 Ibs ; its average temperature will not be less than 800 degrees ; the specific heat of fire-brick, at that temperature, is about o. 18 ; therefore the amount of heat stored away in the lining is 800,000 X 800 X o.i 8 = 115,000,000 heat units. The regenerative stoves contain something like 48,000 cubic feet of fire-brick, which, at 150 Ibs. per cubic foot, would make 48,000 X 150 = 7,200,000 Ibs. The average temperature of the brick- work in these stoves, when the temperature of blast is car- ried at 1400 may be taken at 1000 and the specific heat of the brick- work at that temperature, at 0.20. Upon this basis, the heat stored away in the regenerative stoves amounts to 7,200,000 X 1000 X 0.2= 1,440,000,000 heat units. Thus, in a blast furnace of 300 tons daily capacity, there are the follow- ing quantities of materials consumed and heat units developed : Charged into the furnace : Solid material at the top 945 tons. Gaseous material (blast) at tuyeres J 743 " Total charged 2688 " Discharged from furnace : Molten material from hearth 47 2 -5 tons. Gaseous materials, dust and fume 2215.5 " Total discharge 2688.0 " Heat energy developed : From fuel consumed in twenty-four hours, 7,500,000,000 heat units, ( Stored in the incandescent material ") ^ . , . , f 908,000,000 heat units. C contained in furnace J f Stored in regenerative stoves 1,440,000,000 " I Total heat energy stored 2,348,000,000 " Thus the stored energy is equal to 2l348>OOQ>OOQ X 778 = 2,000. 913,272,000 foot- tons of mechanical energy. CHARGING OF BLAST FURNACra= 43 The mechanical energy developed during twenty-four hours in the process of smelting is 7,500,000,000 X 778 = 5,835,000.000,000 foot pounds, or at the rate of 5,835,000,000,000 = mile . tons minute . 24 X 60 X 2000 X 5,280 When working well, a blast furnace gives but little evidence of the immensity of the force it contains ; it is only when ' ' run- ning off" that one realizes, in a measure, what a monster it is. It is furthermore quite evident that the process must be continu- ous, twenty-four hours a day and three hundred and sixty-five days in a year, from the beginning to the end of the blast, which may last from six weeks to as many years. When in good condition a furnace may be stopped for twenty- four or even forty-eight hours, without serious consequences, and when properly prepared may be "banked" for months and started up again. The Charging of Blast Furnaces. The process of smelting in a blast furnace is, of necessity, a continuous operation. The raw materials, ore, fuel and flux, are charged in at the top, keeping the furnace practically full, and the molten metal and slag are tapped out at the bottom at inter- vals as required. The time necessary for a charge to pass through the furnace varies from ten to forty hours according to the cubic contents of the furnace, the character of the ore, and the relative quantity of air driven through the furnace in a unit of time. Easily reducible ores require less time than those of a refractory nature. The average time in modern furnaces may be taken at twenty hours. In view of this fact, and of the further fact that the effects of bad fillings do not become positively manifest until the badly proportioned or irregularly distributed charges have entered the zone of fusion, and also that the correction for such irregularity can only become effective in the same zone, it be- comes very evident that serious consequences might result from bad filling before the remedy could have had time to act. The proper charging of a blast furnace is, therefore, of the utmost importance. This fact has long ago been acquired by practical experience, and the success of blast furnace manage- 44 QUANTITATIVE ANALYSIS. ment very largely depends on the proper proportioning and distribution of the fuel, ore and flux, in charging the furnace. Since the successful running of a blast furnace depends more directly upon proper charging than upon any other one thing, it may be profitable to inquire how a furnace should be charged to obtain the best results. To do this we must study the chemi- cal reactions as well as the physical changes which take place within a blast furnace. The first requirement is heat, which must not only be sufficient in quanity and intensity, but it must also be properly distributed. a. The temperature must be a maximum at the tuyere-line and a minimum at the stock-line. The former temperature must be higher than the fusing point of the iron and slag, and the latter should be below the point at which carbon dioxide is reduced to carbon monoxide by the fuel. b. Each horizontal layer of .the contents should have practically the same temperature through- out its whole area. c. The temperature of these horizontal layers should be fixed at fixed heights. The second requirement is an abundant supply of an efficient reducing agent. Since all the sensible heat in a blast furnace is due to the combustion of carbon to carbon monoxide at the tuyeres, except that brought in by the blast, and carbon monox- ide, as we shall presently show, being the most desirable reducing agent, it follows that if the first requirement is fulfilled the second must be also. The third requirement is that the ore and flux shall be so pro- portioned and mixed that the impurities of the former will assimilate with the latter and with the ash of the fuel and form a fusible slag. Of the sdlid material charged at the top, over fifty per cent, passes off in the form of gas first, by the evaporation of the hygroscopic and combined water ; second, by the volatilization of the hydrocarbons of the fuel and the carbon dioxide of the flux and air ; third, by the reduction of the ore, the oxygen combining with carbon, forming carbon monoxide, or with car- bon monoxide forming carbon dioxide ; and lastly, by the oxi- dation of the carbon of the fuel, which unites with the oxygen of the blast, forming carbon monoxide at the tuyeres, part of CHARGING OF BI> W u "o .2 '^'^ torC ID a gj: M^ - -^ is .2 in u in 88 S sg 5 UK .2 ^ H ..!' ^f "ii^ 1 1 -~'l! i " M ' o : o^l 3 .-&4i a ^__ -og O 'in I 'id "' r^H x^ ^ fl bi) psT rt o a. 2 : rt cc . ,-5; 5 ^-1 P, ^^0 v cd II be u 'I >> -2 : ^5 * ' s to ^ ^^ 5 b rt d" ^ 2 cd t/2 j, Cd to - ^8 * o H ^ O (^^ . a Su3 T3 O ^ ^ M f o '^'r cd cd /^ a O J^H *- 00 t-3" M o ^; in u ?5 5 c -^ be >> o in .. cd V3.2 5.s s hem. Denominat Sesquibasic. Disilicates. Oxygen Ratio of Silica : O of b = 4 -3 Composition : ilica ime Saturation; Lime 0.714 S Silica 1.400 I Fusibility: ' Very fusible," ' less than preced one. Grade of iron ikely to accompi such slag: Mottled and Lighter Grays u O CD t- M M 1-1 in c* oc cd u a u in **" r .0 g b m. Denominate Neutral. Metasilicic Monosilicates. Oxygen Ratio : : Silica ; O of ba = 2 : i Composition ; :a 5 e 4< Saturation ; me 1.071 Sil lica 0.932 Li Fusibility : Very Fusible.' Grade of iron ely to accompai such slag : White. ^ | ^ .. cd 2 - M 0! a : ..S" 1 ^ 3 - S 8 P* ^ 2 -*S ^ o M .2 O "vS >> 3 ^ S ba -^ i 1 1 tf .. '" ' '^"S o Zl >> H-t y f ) ^JO c s '^3 fl CO o 2 : : * "S U * JH "^ S 8 1 3 u cd || 2* 2 ' *tn -H> / j til >> 12 o "cd " to jj 2"^ 3 2 s o 5 O cd , " s P-.. . 1 * g a <-> ^ cd ^ H P< O a - * 1 : *2 3 1 1 i O cS o u cd || P< '. P ^ !S bC _o H G - 2 ^ in 3 to rt ^ 3 2 p ^ *^H o ^ ^ cd to - a O u- 2 p.y <5"cu u Js s 'ij'ol S! a '55 4 M M " CO OJ 5 l+H o CO a. BLAST FURNACE CHARGES. 55 Graphic Method for Calculating Blast Furnace Charges. The rule consists of two equal scales at right angles, Fig. 9, one of which (a) is fixed to a small board, while the other (b) is fixed at right angles to a upon a block, c, which is capable of sliding motion in a groove parallel to a. 1 0123456789 a 13 14 15 16 17 18 Fig. 9. The point A, given by the intersection of the zeros of the scales, is marked upon the board, and from it a line AB parallel to the groove is drawn. With A as a centre, lines AC, AD, AE, are also drawn, making with AB, angles whose tangents are 1 H. C. Jenkins, Iron and Steel Institute, 1891. 56 QUANTITATIVE ANALYSIS. equal to the ratios between the weight of the silica to weight of base in the respective silicates which it is desirable to produce in order to form the typical fusible slags ordinarily met with in blast furnace practice. The lines AC, AD, AE are marked with the names of the bases for which they have been calculated. Thus AC makes an angle of 28 10' with AB this angle having a tangent whose value is 0.5357, which is the ratio of the atomic weight of silica to twice the atomic weight of lime, and corres- ponds to calcium silicate : this .line, therefore, ismarked "lyime." Similarly the line AD makes an angle of 36 52' with AB, the value of whose tangent is 0.75, or the ratio of the atomic weight of silica to the atomic weight of 2 MgO : hence it is marked " Magnesia." Also the line AB is at an angle of 41 25', and this having a tangent corresponding to the ratio of the atomic weight of 3 SiO 2 , to that of 2A1 2 O 3 , makes the line correspond to the value of the component parts of silica and of alumina in aluminum silicate, and so it is marked " Alumina." With such a scale it is a very simple matter to at once read off either the excess of silica in any ore, or else the amount required to properly flux off the earthy bases present. As an example, take a spathic ore containing : Silica Required. FeO 50 per cent per cent. MgO 3 " 2.25 CaO 5 " 2-68 A1 2 3 3 " 2.65 Si0 2 3 " CO, 36 " Then setting the movable scale b against 3 on the fixed scale a and looking along b until the line marked " Magnesia" cuts it, we find the value 2.25 as being the amount of silica required to satisfy the magnesia. In like manner is found the amount (2.68) of silica required for the lime, and the amount (2.65) for the alumina respectively : adding all these together we find a total of 7.58 parts of silica required for every hundred of the ore. But as there are already three parts present, every hundred BLAST FURNACE CHARGES. 57 parts of the ore require 7.58 3. = 4.58 parts of silica added to flux it. Due allowance is also made for the ash of the coke, and any small quantity of sulphur in the mixture. In the treatment of several kinds of ores to be smelted together they should be mixed and divided into three classes, one having less and another more iron than is required in the final charge, and one should be acid and another basic after the correction for the ash of the coke is made, or one of these three may be a limestone or a siliceous flux : it need not necessarily contain iron. Then let it be required to have n parts of iron per hundred of the charge, and let a iy a n , a s be the percentages of iron in the ores, and #,, 2 , b z percentages of deficiency (or excess) of silica in the same, and x, y, 2, the number of parts required of the component ores per hundred of the charge FeO SiO 2 x K-M,) y (, + *,) * (, *,) then, (i) x+y + 2 100. (2} **> + y*, + **, = n IOO (3) ^^==^3 = By solving these simple equations there is obtained, at once, the number of parts of each component required to satisfy the conditions of the charge. If it is desired to produce a more acid or a more basic slag, it only requires that the scale b be replaced by one having a length of one-half (for bi-silicate slag), or twice (for bi-basic slag) that of the normal scale. References : ' ' Note on the Determination of Silica in Blast Furnace Slag, " by P. W. Shinier, y. Am. Chew. Soc., 16, 501. " Estimation of Metallic Iron in Slag" by G. Neumann, Ztschr. anal. Chem., 6, 680. "Estimation of Phosphoric Acid in Basic Slags" by V. Oliveri /. Anal. Chem. 5, 415. " The Determination of Phosphoric Acid in Basic Slags" by Adolph F. Jolles,/. Anal. Chem., 6, 625. 58 QUANTITATIVE ANALYSIS. XV. The Analysis of "Water to Determine Scale-Forming Ingredients. The scale- forming ingredients of a water are usually composed of calcium and magnesium carbonates and calcium sulphate, and though an analysis of a water for boiler purposes usually states the number of grains per gallon of the above constituents, the analysis should also comprise the determination of other ingre- dients, not scale forming, that are necessary to a proper estima- tion of the former. This is especially true of the alkalies, which are not always determined in a commercial analysis, of water, for boiler purposes ; the amounts of lime, magnesia, chlorine, carbon dioxide and sulphuric acids, being considered a sufficient index of the character of the water. The alkalies and their salts rarely form scale in boilers 1 and so cannot be classed as scale-forming, yet they play fully as im- portant a part in the relation they sustain to the sulphuric acid and chlorine. If all the sulphuric acid in a water were combined with the alkalies, there would be no sulphate of lime present, and the lat- ter would be eliminated as a part of the scale ingredients. This is a condition rarely occurring, however, since in most waters a portion of the sulphuric acid is united with the alkaline earths and the alkalies. The indirect estimation of the carbon dioxide would be changed also. That is to say, where the carbon diox- ide is estimated by uniting all the lime and magnesia (left un- combined with sulphur trioxide and chlorine), with carbon dioxide, it is evident that if all the sulphur trioxide is united 1 A sample of Boiler scale, from Charlestown S. C., analyzed by the author in 1887 had the following composition : Carbon i.oi per cent. SiO 2 1.52 A1 2 O 3 0.43 NaCl 72.12 CaCl.j 10.32 KC1 i.oi MgCl 2 1.71 CaSO 4 11.20 Undetermined 0.68 ANALYSIS OF WATER. 59 with lime, when a large portion belonged to the alkalies, the amount of calcium carbonate would be too small, and also that the proportion of the carbon dioxide would be deficient by the amount required to saturate the lime incorrectly united with the sulphur trioxide. There is nothing in the usual commercial analysis to indicate whether the sulphuric acid, as determined in the water, is all united with the lime to form calcium sulphate or not : but the custom has been so to unite it, with the result that calcium sulphate may be represented as a large component of the scale-forming material, when, in reality, none whatever may be present. In a report of a partial analysis of the Mouongahela River water, ( Transactions Amer. hist. Mining Engineers, Vol. XVII, P- 353) > the amount of objectionable substances, for boiler use, are given as follows : Total lime 161 parts per 100,000 = 94 grains per gallon. " magnesia 33 " " " = 19 " " " Sulphuric acid- 210 " " " =122 " " " Chlorine 38 " " " = 22 " " " It further states the amounts of carbonates of lime and mag- nesia precipitated upon boiling to be : Carbonate of lime 130 parts per 100,000 = 76. grains per gallon. " " magnesia. 21 " " " =12.2 " " " The alkalies not having been determined, the proportion of sulphuric acid combined with them becomes problematical : in fact, the inference is that there are not any present, when in all probability, they may amount to a large percentage. For this reason it is essential that the alkalies be included in the analysis, and the following scheme is so arranged as to include them : 3J s&i fc o rt OJ rH dl- | jilfll!!|ffii K P " SjiS J| = e 'O > > s 5 * S 5 S> S rs G ^ 7; > u v-i ru j* <* e i i | -. C 2 rt ? O >> o -' ^ fc * ^ ^ I O -S ctf fl 0)^1- S - X OJ cS i o -9 s u g o 2 S CO >- ex & w ^ *: K^ CTJ JH* cd 9 ^ c a- < S '5 u S ^ D 5 tJ J_l H chloric aining s Fo si II s "w a - - *** H- ^ ^ ?. Ill p~.2~ ^2 -M O "Q Uj T3 X c be 2| 2 ^W -- tn^ O tn CT . o ^ ^- .H ' ' 2 5O'S.S . *"^ M t* 3 fr Z 6 Z I I | 8 .5 PM fc H!, M ^ & O Parts per 100,000- . ---- 4.4 3.3 2.2 3.2 2.1 4.8 5.5 6.4 Grains per U. S. gallon 2.56 1.92 1.28 1.86 1.22 2.79 3.20 3.73 ANALYSIS OF WATER. 73 The Sanitary Analysis of Water. This comprises the determination of 1. Chlorine. 2. Free and albuminoid ammonia. 3. Nitrates. 4. Nitrites. 5. Total solids. 6. Organic and volatile matter by ignition of residue. 7. Oxygen required to oxidize organic matter. /. Determination of Chlorine. Standard Silver Solution. Dissolve five grams of pure crystallized silver nitrate in I'ooo cc. of distilled water. One cc. of the solution is equivalent to o.ooi gram chlorine. If the water to be tested shows by qual- itative analysis a small amount of chloride present, 250 cc. of the water should be evaporated to about fifty cc., allowed to cool, three drops of saturated solution of potassium chromate added, and the silver nitrate solution dropped carefully from a bu- rette until a faint permanent red color is produced in the water. This point indicates that all the chlorine has combined with the silver, and that any additional silver solution added forms sil- ver chromate. Thus : 250 cc. of the water used for examination. " " " " required 1.3 cc. silver nitrate solution, looo cc. " " '* " 5.2 cc. " Equivalent to 0.0052 grams of chlorine per liter. " " 0.52 parts chlorine in 100,000 parts of the water. " " 5.20 " " " 1,000,000 " " " " It is customary to state the amount of chlorine as ' ' chlorine as chlorids ' 'as NaCl. Thus : 0.0052 gram chlorine per liter = 0.0085 gram sodium chloride per liter. 0.52 parts chlorine per 100,000 = 0.85 parts sodium chloride per 100,000. 5.2 " " ''1,000,000=8.5 " " " 1,000.000. The amount of chlorine allowable in good drinking water can- not be stated positively, since the source from which it is derived must be taken into account. 74 QUANTITATIVE ANALYSIS. Results from a great many analyses of various waters would indicate the amount allowed as follows : Rain water Traces to one part per 1,000,000. Surface water One to ten parts per 1,000,000. Subsoil Two to twelve parts per 1,000,000. Deep well water Traces to large quantity. 2. Free and Albuminoid Ammonia. Solutions required are : a. Standard solution of ammonium chloride, made by dis- solving 0.382 gram dry ammonium chloride in 100 cc. of ammo- nia-free distilled water. One cc. of this solution is diluted to 100 cc. with distilled water, each cc. of the latter solution cor- responding to 0.000012 gram ammonia. b. Standard Nessler Reagent. Dissolve seventeen grams of mercuric chloride (pulverized) in 300 cc. of water, and thirty- five grams of potassium iodide in 100 cc. of water. Pour the mercuric chloride solution into the potassium iodide until a per- manent red precipitate is formed. Add a twenty per cent, solu- tion of sodium hydroxide until the volume of the mixed solution amounts to one liter. Add some more mercuric chloride solution until a permanent red precipitate forms and allow to settle. c. Alkaline potassium permanganate, formed by dissolving eight grams of potassium permanganate and 200 grams of potas- sium hydroxide in a liter of distilled water. This solution is concentrated by boiling to about 750 cc., then 250 cc. of ammonia-free water is added. When properly pre- pared this solution gives but traces of ammonia by distillation. In any event, however, it must be tested, and if an appreciable amount is found, it must be deducted from the determination of albuminoid ammonia in any sample of water under examination. Ammonia-free water is made by distilling water acidulated with sulphuric acid. Process. The apparatus shown in Fig. 1 1 is well adapted for this pur- pose. Place 250 cc. of the water to be tested in a flask, capacity ANALYSIS OF WATER, 75 7 6 QUANTITATIVE ANALYSIS. one liter, add one cc. saturated solution sodium carbonate, con- nect with the condenser and distil until no reaction for ammo- nia is shown in the distillate, (caught in one of the comparison tubes) 1 when two cc. of the Nessler solution is added thereto, a yellowish brown color being indicative of ammonia. The apparatus being free from ammonia, 500 cc. of the water are now added to the water remaining in the flask and one cc. of the saturated sodium carbonate solution (free from ammonia) added. Distillation proceeds until three distillates, each of fifty cc., have been received in the comparison tubes, when the distillation is stopped and the heat removed until the distillates can be exam- ined. The comparison tubes are protected by being enclosed in a glass vessel, with a movable top, as shown in Fig. n, at the base of which is an opening filled with cotton wool. #4 Fig. 12. These comparitor tubes have a mark indicating fifty cc., and i See Fig. n. ANALYSIS OF WATER. 77 when the distillate reaches that mark, the handle of the stand containing the comparator tubes is turned and another compari- tor tube placed under the outlet of the condenser. The revolv- ing stand contains seven comparitor tubes, sufficient for both the free and albuminoid ammonia determinations. C. H. Wolff's colorimeter, Fig. 12, has an extended use in water analysis for the purpose of comparing tints of color of the water, also in the de- termination of the difference in color in the estimation of free and albuminoid ammonia. One of the tubes contains the nesslerized standard ammonium chloride solution, the other tube a portion of the water distillate, nesslerized, to compare with the former. The contents of the tube containing the darker liquid are partially drawn off by means of the glass stop-cock at the base, and the remaining liquid diluted with distilled water until a uniform tint of color is obtained in both glasses. As these tubes are graduated, the calculations are simplified and rendered more expeditious. Ammonia Determinations. The first fifty cc. of distillate is now tested for ammonia, as follows : The tube is removed and placed in a comparitor and two cc. of the Nessler solution added. The color produced must be matched by taking another tube and filling to the fifty cc. mark with ammonia- free distilled water, adding two cc. Nessler solution and one cc. of the standard ammonium chloride solution. Allow to stand five minutes for full development of color, then compare the color of the liquids in the tubes. If the solution containing the ammonium chloride is too strong, divide it and add distilled ammonia-free water to fifty cc. mark and compare again, and repeat until the tints are identical. If, however, the solution containing the ammonium chloride is not deep enough in color, add one cc. more of the standard ammonium chloride solution and compare as before. The second and third distillate are treated in a similar man- ner, but if the third distillate shows over a trace of ammonia, a fourth distillate must be taken, or until no appreciable amount of free ammonia can be obtained. yg QUANTITATIVE ANALYSIS. Free Ammonia. 500 cc. of the water taken. First distillate (50 cc.) required 1.5 cc. ammonium chloride solution. Second " (SGCC.) " 0.3 cc. " Third " (50 cc.) " none Total for 500 cc. i.Scc. " " looo cc. 3.6 cc. One cc. ammonium chloride solution is equivalent to o.ooooi gram nitro- gen, or O.OOOOI2 gram ammonia. Then one liter of the water contains 0.000043 gram free ammonia. Equivalent to 0.0043 part ammonia per 100,000. " " 0.0430 " " " 1,000,000. Fifty cc. of the alkaline solution potassium permanganate are added to the contents of the flask, after the determination of the free ammonia. The contents of the flask must be cooled some- what before the addition of the alkaline permanganate solution. The latter is placed in the flask by means of the glass delivery tube, which passes through and is fused to the glass stopper of the flask. By this arrangement any solution can be added to the contents of the flask without removing the stopper. The distillation and comparison of distillates by known amounts of ammonium chloride solution are made in the same manner as for the determination of free ammonia. Album in o id A m mo n ia . 750 cc. of the water taken. First distillate required 3.2 cc. ammonium chloride solution. Second " " 0.7 cc. " " " Total " 3-9cc. IOOO CC. " 5.2 CC. " " " Equivalent to 0.000063 gram ammonia per liter. " 0.0052 part ammonia per 100,000 parts. "0.0520 " " 1,000,000 It must be remembered that the free ammonia was determined in the 500 cc. of water after the free ammonia was expelled from the 250 cc. of water first placed in the flask. As the albuminoid ammonia is not developed until the addi- tion of the alkaline permanganate solution, the determination of the albuminoid would be upon 750 cc. of water, as above stated. ANALYSIS OF WATER. 79 The amounts of free and albuminoid ammonia allowable in good drinking water are thus stated by Wanklyn : " If a water yield o.oo part of albuminoid ammonia per million, it may be passed as organically pure, despite of much free ammonia and chlorides; and indeed if the albuminoid ammonia amounts to 0.02, or to less than 0.05 parts per million, the water belongs to the class of very pure water. When the albuminoid ammonia amounts to 0.05, then the proportion of free ammonia becomes an element in the calculation, and I should be inclined to regard with some Q Fig. 13. suspicion a water yielding a considerable quantity of free ammo- nia along with more than 0.05 part of albuminoid ammonia per million. Free ammonia, however, being absent, or very small, a water should not be condemned unless the albuminoid ammo- nia reaches something like o.io part per million. Albuminoid ammonia above o.io per million begins to be a very suspicious So QUANTITATIVE ANALYSIS. sign ; and over 0.15 ought to condemn a water absolutely. The absence of chlorine or the absence of more than one grain of chlorine per gallon, is a sign that the organic impurity is of vegetable rather than of animal origin, but it would be a great mistake to allow water highly contaminated with vegetable mat- ter to be taken for domestic use." The apparatus for the determination of free and albuminoid ammonia, used by the New York City Health Department, is shown in Fig. 13, a description of which will be found in the Journal of the American Chemical Society, 16, 871. j. Determination of Nitrates by the Phenol Method. a. Standard potassium nitrate solution, formed by dissolving 0.722 gram potassium nitrate, C. P., in a liter of water. One cc. of this solution is equivalent to 0.00044 NO 2 . b. Phenolsulphonic acid, formed by adding three cc. of water, six grams pure phenol and thirty-seven cc. of concentrated sul- phuric acid together. The operation of determining the nitrate is as follows : Twenty-five cc. of the water are evaporated to dry ness in a No. 2 porcelain capsule, on a water bath. One cc. of the phenol- sulphonic acid is added and incorporated thoroughly with the residue. Add one cc. water, three drops of concentrated sulphuric acid and warm. Dilute with twenty-five cc. water, make alkaline with ammonium hydroxide and make solution up to 100 cc. with water. If an appreciable amount of nitrate is present, it forms picric acid with the phenolsulphonic acid, imparting a yellow color to the solution, when the ammonia is added by the forma- tion of ammonium picrate. The intensity of the color is pro- portional to the amount of ammonium picrate present. One cc. of the standard potassium nitrate solution is evapo- rated in a porcelain capsule, treated as above, and the solution made up to 100 cc. The two solutions are placed in comparitor glass tubes and distilled water added to one or the other until the colors agree in tint. Suppose twenty-five cc. of the original water after treatment and subsequent dilution to 100 cc. corres- ponded in color to the standard solution of one cc., which after ANALYSIS OF WATER. 8 1 treatment and dilution to 100 cc. was diluted to 200 cc. Then twenty-five cc. of the original water contained 0.00005 gram nitrogen, or 1000 cc. contained 0.0020 gram nitrogen or 0.009 gram NO 3 per liter, corresponding to 0.52 grains per gallon, or 0.9 part per 100,000, or 9.0 parts per 1,000,000. U pipieiwMvdiopJrorJo'dOo'Oi-id-'j-Odwpidfldi-idddwd OO vO 00 O ^ co covO w vo VO vo 00 MOO M MVO ^GOO PI t^M T^-TfO ^ COOO 00 vo co M vo ^-1 ^ri oo O oc vg K. M to ^,00 ^- 0_ r^co >Z oo _ PI Ov^ t^.vc_ o t^gg f^ 2 d d -: d d io cJ M pi M d 4 ro PJ d d d d d d d co d d d M M d d d d M d d d co P M P w d d d d d d d N d d d M d d d d o d d d d poq^ara v o v v v v jo o^oocoMi-iooiiaj 00 vd COOO t^.00 O 10 o S d d d g g lbumi ammo proce BTOOUIUIB pioutuinq^v gi ! d 6 d o* d d d d d d o* d o* d 6 d d o d d d d d d d o* d d d d d d d d d d d 21 BIUOUJUIB lOiOOOiOOOiOOoOiOOOiOOiOOOuOOOOrsOiOOOO r^O lOlON rj-Tj-t-^rolOi-i r^M-M rots M M M t^-( ^-T^-avMS rolO 8 to M o c< M o o (To M M o M b V lOOOiOiOO TtPJ corDCTM-i q q M q q q q q q q M d o* o* d d d o* o* d d d d d d d d d o* d d d d d d d d d d d d d o" d d d d d d Frankland's combustion d d d d d o" d d d d d d d d o' d d d d d d d d o* M o' d d d o" \o' M d d d d d noqjBD I/}VO ONM O - GNU O t^OvO l^t^OvO M Os^-OOO O\ ^-00 00 ro*Or^^M cot^t^ lOvO OOVO w cor^Ot^r> rt-oq Tj-vq Piq x o>OMp)Ti-t-.w 1 -.i>.qNqv rovq t-. co t M M t-Cvq q\ r^oq qvoq * q ~ to io N vdNroddddddMpJ^-dddrodo'diHfNMdwtJ g 2 &8 ^?>^8 8 IQ8 8 8 8 85 8 6 4d Pi ,00 4civd M M M 4jd 4jg COVN c^^ avtivovo doo g.^-g 8 8 uopraSi no ssoi '0 OOI }B SpTlOS Atlantic Ocean, 41 18' N., 36 28' M Pacific Ocean, 28" n' S., 93 24' U feet deep German Ocean, between Belgiun England Baltic Mediterranean, off Cette Black Sea, off southern coast of Ci Caspian Sea Dead Sea ANAI/S i 'SIS OF D to n CO O "h O o n P 3 nT 3 WATER. IflDIHp Source. Composition of European Waters. : <3 : : * : : : b b b b b b |!!{4f b bxii oj -*> to oo ? Constituents of solid contents ; parts by weight in 1,000,000. Total solid contents. Parts in 1,000,000. ^ b >b i ia ^i ox b b i. 00^ o\c/i Ox ** -^ " &zs<& ^ & K tmmm P Constituents of solid contents ; parts by weight in 1,000,000. tilfll 1 1 3 b p ; i -S P O> M a M :cn : 4,- -^ 5 s o - : : r : :^v;: : : 9 *. o n: *: : : s ^ . . . . b ' * ' 5 Cj . M 00 Cn 3 Constituents of solid contents ; parts by weight in 1,000,000. g|$||t|1^ o : 3$.3: : : O O oo^j-^Sw-^ wvpw to Ol U *** 300J ^J 10 M i . b> Ui vb * * -, ~ W (0 10 OJ M OOVO 10 ON 00 A. JO $ JO . pN<2* o O ::nB!hsi; O n 2 *:o,S:: S Cd b 1 8 M '^ ' b b ri 3 *vj . o Cn -ft oo I I I I ON " b bo io O O Gaseous con- tents cc. per liter. Organic On .... ? 86 QUANTITATIVE ANALYSIS Water supplied to large cities is usually filtered through sand filter beds. Fig. 14 shows the section of a well-arranged filter bed built for the city of Dublin. The bottom of the filter is com- posed of puddled clay three-fifth meter in thickness A, built in with stones one-fifth meter in thickness. The next layer, three- quarters meter thick, consists of coarse angular stones B, then fifteen centimeters of smaller stones C, followed by a layer fifteen centimeters in depth of coarse gravel D, then the same Fig. 14. depth of fine gravel E, and finally three-fourth meter of sand F, To collect the water there are two channels B, situated half in the bed of clay and half in the stratum of large stones. Each chan- nel is seventy-five centimeters in width and sixty centimeters in depth. The surface of sand in each meter is sixty-one by thirty- one meters ; the depth of this water is sixty centimeters. The speed of filtration varies in "the existing sand filters from one and four-tenths to fifteen meters per twenty-four hours. Each water requires, if it is to be well filtered by a given sand, a determined speed of filtration. Thus, under otherwise similar conditions, three and five-tenths cubic meters of Thames ANALYSIS OF WATER. 87 water may be filtered in twenty-four hours per square meter of filtering surface, but only one and seven-tenths cubic meters of Elbe water, as the latter contains much more finely divided dirt. In a well managed filtration the turbid water passes so slowly through the sand that each of the fine particles of dirt, though far smaller than the intervals between the grains of sand, has opportunity to attach itself to one of the grains. Therefore, the finer and more numerous the particles of dirt are, the finer must be the sand and the slower must be the rate of filtration. If this Fig- 15- rate is too great, the suspended particles flow simply through between the grains of sand. But if the sand is too fine, the fil- ter bed may easily become water tight, but if the sand is too coarse slower filtration is to some extent a remedy. The best size of the sand grains is from one-half to one millimeter, and the sand is the better the more uniform the grains are. A sand con- taining much finer grains cannot be used, as it is easily ren- dered too compact by the pressure of the water. Wagner's Chem. Tech., p. 236. 88 QUANTITATIVE ANALYSIS. A very complete description of the sand filter beds, constructed for the Massachusetts Water Works, will be found in The Engi- neering Record, 1895. These works represent the latest ad- vancement in this line of engineering. A very complete article on ' ' Purification of Sewage and of Water by Filtration," by H, F. Mills, C.E., will be found in the Transactions of the American Society of Civj,l Engineers, 1894. To show the methods in use for quick filtration as well as the general arrangement of the apparatus, the Warren filter is taken as an example. The filter plant usually consists of a settling basin, one or more filters, and a weir for controlling the head, together with the necessary pipe connections . Each filter contains (see Figs. 15 and 16) a bed of fine sand, C, two feet in Fig. 16. depth, supported by perforated copper bottom, B, and for cleaning this bed an agitator, D, is provided. This con- sists of a heavy rake containing thirteen teeth twenty- ANALYSIS OF WATER. 8 9 90 QUANTITATIVE ANALYSIS. five inches long, rotated by a system of gearing, K, and capa- ble of being driven into the bed by means of suitable screw mechanism, L, M, whereby the entire bed is thoroughly scoured. The process of filtration is as follows : The water enters the settling basin through a valve operated by a float, by which a constant level is maintained in the entire filter system. The water entering through this valve passes through an eight- bladed propeller of brass, from ten to sixteen inches in diameter, so arranged as to revolve freely with the passage of the water. This, by means of two small bevel gears and an upright shaft, operates an alum pump of unique design, consisting of six hol- low arms radiating from a chambered hub, and bent in the direc- tion of rotation. This pump revolves in a small tank containing a dilute solution of aluminum sulphate, or other coagulant, and by its revolution each arm takes up its modicum of alum water, passes it into the hub and to the deflector, which sends it down to the incoming water. The latter, having received its proper amount of coagulant, is then allowed to remain in the settling basin from thirty to forty minutes, to enable the chemical reaction between the coagulant and the bases and organic matter in the water to take place, and to permit of the heavier sediment, together with a portion of the coagulated matter, to settle by subsidence to the bottom of the tank, where it can be drawn off at intervals into the sewer. The water, with all the suspended matter, as well as practically all the bacteria present in the water, bound and held together by the insoluble hydrate of alumina resulting from the addition of the coagulant, passes on through suitable piping and valves to the filter A, and, filling the tank, passes down through the fine zinc sand bed, leaving all the coagulated matter upon it, and makes its exit from the filter through the main /, bright and clear and perfectly adapted in every way for domestic purposes. The main, collecting the filtered water from the various filters, passes along between them to the head box, or weir, over which the water is compelled to pass and which controls the operation of the filters. The top of this weir is twenty inches below the water level maintained in the filter system, and this head of twenty inches (equivalent to a pressure of three-quarters of a ANALYSIS OF WATER. pound to a square inch,) is the extreme pressure that can be brought to bear upon the niters, and it is evident that they can at no time be pushed beyond the rate which experience has shown to yield the best results. When the bed of a filter becomes clogged, and it seems best to FIG. 18. clean it, the inlet and outlet valves EF, are closed, and the washout G, opened, allowing the contents of the tanks to escape to the sewer, Fig. 16. The agitator, D, is then set in motion by means of the friction clutch with which it is equipped, and as the teeth on the rake begin to plough up the surf ace of the bed a slight amount of filtered water is allowed to flow back up through the bed, in order to rinse off the dirt loosened by the rake. This is kept up until the rake penetrates to the bottom of the bed, and thoroughly agitates every particle of material therein. As soon as the water following to the sewer is clear, the motion of the rake is reversed and it is slowly withdrawn from the bed. When the teeth are raised above the bed, the water pipe is closed the inlet valve E opened, and the filter tank allowed to fill. 92 QUANTITATIVE ANALYSIS. After waiting a few minutes the outlet valve, F, is slowly opened and filtration is resumed. A filter ten feetsixinch.es in diameter, net area, eighty-four square feet, will filter 375000. gallons of water per twenty-four hours. Bacteriological Examination. The bacteriological examination of water is dependent more upon the Microscopic than the Engineering Chemist. The following references, however, are inserted : " Micro-organisms in water" by Percy and G. C. Frankland, 1894. " Manual of Bacteriology," by Dr. George M. Sternberg, 1892. " A Bacterial Study of Drinking Water," by Dr. V. C. Vaughn, 1892. " Bacteriological Diagnosis," by Dr. James Eisenberg, Vienna, 1887. " Report of the Massachusetts State Board of Health for 1892. "Bacteria and other organisms in water" by John W. Hill, Transac. Amer. Soc. Civil Engineers, Vol. xxxiii pp. 423-467. " Practical Bacteriology" by Dr. W. Migula, London, 1893. The Composition of Boiler Scale. 1 The results of an analysis of boiler scale usually represent the lime and magnesia as carbonates with a portion of the former as sulphate on the general principle that the scale made continues to exist in the form in which it was precipitated. In those por- tions of the boiler where the direct heat does not come in contact with it, the scale remains unchanged after formation, but the conditions are altered where the scale is subjected to intense heat. In the latter case, while the deposition of the scale-forming material at first occurs as carbonate and sulphate, the gradual heating expels some of the carbonic acid, and the oxides of cal- cium and magnesium are formed. That portion of the scale nearest the iron and to the heat loses more of its carbonic acid, and becomes caustic so long as the fire continues. As soon, however, as the fires are drawn, the oxides of calcium and magnesium become hydrated by absorption of water. If now a sample of the scale were taken for analysis, the water of hydration becomes an important factor in the analysis. A sample of scale from some boilers at Birmingham, Ala., gave the following result : iThe scheme for analysis of Limestone, (XI), can be used in this analysis. Consult J. Anal. Chem. iv., Jan., 1890. COMPOSITION OF BOILER SCALE. f 93 Silica and clay 11.70 per cent. Fe 2 O 3 , A1,O 3 2.81 " " CaO 13.62 " " MgO 41.32 " " C0 2 6.92 " " S0 3 0.96 " " H 2 O (of hydration) 21.78 " " H 2 O (moisture at 212 F.) 0.69 " " Undetermined 0.20 " " Total, loo.oo " " An examination of this analysis shows an unusually small amount of carbonic and sulphuric acids, a large amount of water and of magnesia. The great excess of the latter over the lime indicates that the water from which the scale was formed is a magnesia water, but its presence in this amount does not in any way alter the conditions of the problem. With less than one per cent, of sulphuric acid and less than seven per cent, of carbonic acid, the oxides of calcium and mag- nesium could not exist in their entirety as carbonates or sulphates, for, combining the above acids to form carbonates and sulphates the result indicated over twenty per cent, lacking in the 100 parts. The large percentage of the oxides of calcium and magnesium left after combination with the acids suggested water of hydration. A sample of the scale (dried at 100 C.) was transferred to a platinum crucible and heated over the blast lamp to a constant weight. The loss of weight was over twenty-eight per cent, and, of course, included the carbonic, but not the sulphuric acid. To check this result, a sample of the dried scale was ignited in a combustion tube and the water collected in a weighed calcium chloride tube. The result was 21 .78 per cent, of water of hydra- tion. This satisfied the conditions existing, and the combinations gave as follows : 94 QUANTITATIVE ANALYSIS. Silica and clay 1 1 .70 per cent. Fe 2 3 , A1 2 3 2.81 " " CaSO 4 1.69." " CaCO 3 _ 5-45 " " MgC0 3 7-36 " " Ca(OK) 2 13.70 " " Mg(OH) 2 56.37 " " H 2 O (Moisture at 212 F.) 0.69 " " Undetermined 0.20 " " Total, 99.97 " " A section of the scale was subjected to examination, layer by layer, and the following results confirm the above. That portion of the scale next the iron and nearest the fire contained but traces of carbon dioxide, and was principally the hydrated oxides. The middle portion of the scale was a mix- ture of carbon dioxide and the hydrated oxides, while the upper portion of the scale contained carbonates, but no hydrated oxides. In other words, the composition of the scale will de- pend, in a great measure, upon what portion of the boiler the deposit is made. That deposited on the iron or shell not in con- tact w r ith the flame or not subjected to extreme heat, will remain as deposited as carbonates and sulphates, while the scale de- posited upon the iron subject to the flame or heat sufficient to drive out any carbonic acid from the scale, will vary in the amounts of carbon dioxide and water of hydra tion as indicated. Scale formed in which the lime all exists as calcium sulphate and in which no magnesium carbonate is present will be subject to but little variation. When oil has been indicated, by qualitative analysis, as pres- ent, the method of analysis requires the following modification : The sample of pulverized scale is dried at 98 C. to constant weight, and a portion of this, one and one-half gram, is trans- ferred, to a Soxhlet tube and the oil extracted with ether. The ether solution evaporated carefully in a platinum capsule and the amount of oil determined. The residue in the Soxhlet tube is dried again and the analysis made in the regular way. The following is an analysis of a boiler scale containing some lubricating oil : COMPOSITION OF BOILER SCALE. 95 SiO 2 7-36 per cent. Al 2 3 .Fe 2 3 1.91 " " CaCO 3 62.71 " " MgC0 3 18.15 " " Mg( OH) 2 *. 4.21 " " H 2 O. atuoC 2.51 " " Oil (lubricating) 3.53 " Undetermined 0.62 " " Total, 100.00 " " Nearly all waters contain foreign substances in greater or less degree, and though this may be a small amount in each gallon, it becomes of importance where large quantities are evaporated. 1 For instance, a 100 H.P. boiler evaporates 30,000 Ibs. of water in ten hours or 390 tons per month : in the comparatively pure Croton water there would be 88 Ibs. of solid matter in that quan- tity, and in many kinds of spring water as much as 2000 Ibs. The nature and hardness of the scale formed of this matter will depend upon the kind of substances held in solution and suspension. Analysis of a great variety of incrustations show that calcium carbonate and sulphate form the larger part of all scale, that from carbonate being soft and granular, and that from sulphate hard and crystalline. Organic substances, in connection with calcium carbonate will also make a hard and troublesome scale. The presence of scale or sediment in a boiler results in loss of fuel, burning and cracking of the boiler, predisposes to explo- sion and leads to extensive repairs. It is estimated that the presence of one-sixteenth inch of scale causes a loss of thirteen per cent, of fuel, one-fourth inch thirty-eight percent., and one- half inch sixty per cent. The Railway Master Mechanics' Association of the U. S., es- timates that the loss of fuel, extra repairs, etc., due to incrus- tation, amount to an average of $750 per annum for every loco- motive in the Middle and Western States, and it must be nearly the same for the same power in stationary boilers. When boil- ers are coated with a hard scale difficult to remove, it will be found that the addition of one-fourth Ib. of sodium hydroxide per horse power and steaming for some hours, just before clean- IG. H. Babcock, "Steam," p. 63. 96 QUANTITATIVE ANALYSIS. ing, will greatly facilitate that operation often rendering the scale soft and loose. Water for Locomotive Use. After many years of experiment upon waters for lyOcomotive use, by the chemists of the Chicago, Milwaukee & St. Paul R. R., the results obtained may be stated as follows : Varieties of water may be classified by either of two methods : 1. By their chemical composition. 2. By their effect in use. The second is manifestly what is wanted by master mechanics and superintendents. The following may be placed in the first class : a. Alkaline waters. b. Non-alkaline, bad and good. In the second class (2): a. Those causing foaming and corrosion, but non-incrusting. b. Hard, or incrusting. c. Soft non-alkaline and good. These two classes are related as follows : "# " of class i, " alkaline " waters, will produce the trouble mentioned in "#" of class 2 ; that is, foaming and in certain cases corrosion. "V the bad "non-alkaline," would be classed as hard or incrusting. "<:," "soft waters," would include all those having little mineral impurities of any kind. It is, however, impossible to set hard and fast limits for each class, one generally shading into the other, and what would be called good water in the West, for instance, would be thought poor enough in the Hast. In making an analysis all ingredients are grouped broadly under two heads, " incrusting" and " non-incrusting." Under the former are put such salts as are thrown out of solution by heat, and in the latter case those which do not precipitate until great concentration occurs a condition which hardly ever hap- pens with locomotives. WATER FOR LOCOMOTIVE USE. 97 In the " non-incrusting" group is found a variety of actions. A well known property of alkali in water is to cause foaming and priming, when sudden reduction of pressure occurs upon opening the throttle. At just what point this action begins to be apparent depends on a number of circumstances. With a boiler overworked and foul from mud, it appears sooner than in one having ample heating surface, with moderate train load, uniform resistance and consequent regular consumption of steam. For a maximum allowable with good results in service and in the West, where really good water, as before mentioned, is un- common, fifty grains per gallon of alkaline water are taken. When this figure is exceeded it certainly pays to institute a regular search for better water. With these non-incrusting salts are associated a few that are readily decomposed in contact with iron, and attack it, causing gradual corrosion. These are most commonly the magnesium chlorides and sulphates, a very small amount of which, say ten grains per gallon, should con- demn the water. Organic matter is supposed also to have this action, but in the presence of alkali the danger is not great and with frequent blowing out little attention need be given it. The water may be classified as follows : i to 10 grains of solids per gallon, soft water 10 to 20 " " " " " moderately hard water Above 25" " " " " very hard water. On this railroad " boiler compounds" are employed. Waters having thirty-five to forty grains of incrustating matter per gal- lon can be dealt with successfully, provided no alkali be present. The above reservation is made because the "compound" is itself an alkali ; so in adding it to a water care must be taken not to bring the total alkali above, say, fifty grains per gallon, or there will be trouble from foaming. In the " Report of Analy- sis" blanks, directions are given fixing the amount of compound to use in each case. 1 A few examples of the different kinds of water used on this road are here given, illustrating the distinc- tions above drawn. The best is surface water, in the forest 1 This compound is a mixture of one pound of caustic soda and one-half pound of sodium carbonate, dissolved in one gallon of water. The average cost for a run of 1,000 miles being about forty cents. (7) 98 QUANTITATIVE ANALYSIS. region of Wisconsin ; for example that from Wausau, as follows : Total solid residue .................. 6.78 grains per gallon. (Oxide of iron ---- 0.23 " " " Incrusting matter^ CaCO 3 .......... 2.26 " " " (CaS0 4 ........... 0.56 " Total ......................... 2.95 " Non-incrusting f Organic and volatile 3.15 " matter ...... \Alkalinechlorides-. 0.68 " Total ......................... 3.83 " For boiler ' purposes this water could not be better, the in crusting matter, about three grains, being inappreciable. For a good example of badly incrusting water, but non-alka- line, the following from Lennox Creek, Dakota, may be given : Total solid residue ................ 109.20 grains per gallon. Total ........................ 47.48 Non-iucrust- ing matter) ffi^^^s '. '. ^31 Total ....................... 61.72 " This water could not be properly purified by the addition of caustic or carbonated alkali without introducing an inadmissible amount of the latter, as above noted. It will be noticed that the magnesium sulphate is classed as " non-incrusting" matter. It is, however, much more hurtful than the lime salts on account of its corrosive properties. The organic matter is also high, but not more so than is usual for a surface water in that locality. For examples of absolutely worthless water, notice first, that from an artesian well at Kimball, D. T. Total solid residue ................ 182.06 grains per gallon. Incrusting / Calcium carbonate ---- 61.85 " matter. \ Calcium sulphate ..... 41-44 " Total ........................ 103.29 " Non-incrust-f Alkaline sulphates.. 64.83 " " " ing matter! Alkaline chlorides-. 13.94 " Total ........................ 78.77 " FEED WATER HEATERS. 99 And again, from a 130 feet driven well at Fargo, D. T. Total solid residue 416.84 grains per gallon. t Calcium sulphate 35-46 " Total 220.46 " " " f Magnesium sulphate 20.90 " Non-incrust- ! Alkaline sulphates.. 150.92 " ing matter j Alkaline chlorides.. 1.14 " " " L Organic and volatile 23.42 " Total 196.38 " ' " It is manifest!}' useless to attempt the purification of these waters practically. All the round-houses are provided with hydrants and high pressure steam connections for the purpose of obtaining a power- ful stream of hot water for wash-out use. On eastern divisions, locomotives having run from 1,500 to 2,000 miles are blown off at low pressure, cooled, and the stream of hot water thrown in at hand holes, front tube-sheet and back head, and scraper worked in and out. The sediment is found mostly loose and in the form of fine mud, to the amount of ten to fifteen buckets full. After thorough cleaning, the boiler is again filled with hot water, and is ready for service. On the western divisions the frequency of washing out is increased, doing so as often as once ever}- 300 or 400 miles run. As to the economy of using hot water always, there can be no question. Fully seventy-five per cent, in the number of cracked fire-box sheets are saved by this practice alone, and it materially reduces the force of repairers in round-houses, notwithstanding a very large increase of engine mileage. Many people are opposed to the use of chemicals in boilers, rightly upon general principles ; but when the proper ones are used, the experiments have failed to show the slightest injury therefrom, while the economy resulting, both in service and re- pairs, has amounted to an enormous sum on this system. Feed Water Heaters. Feed water heaters as well as boiler economizers are often used as eliminators of the scale-forming materials in water. This is 100 QUANTITATIVE ANALYSIS. due to the fact that waters containing much calcium and mag- nesium carbonates when heated to the usual temperature in feed water heaters (2OO-2ioF) , give up the excess of carbon dioxide that holds the calcium and magnesium carbonates in solution, and the latter are precipitated and removed before the water en- ters the boiler. Where calcium sulphate is a large constituent of the water, feed water heaters using exhaust steam do not precipitate the lime salt, but if the feed water be heated by live steam under pressure to a temperature of 2 40 F, then the calcium sulphate precipitates. The addition to the water of the necessary amount of sodium carbonate will precipitate the lime as carbonate, at ordinary temperatures, and it will thus be found more economical in this case to use feed waters heaters, using exhaust steam with sodium carbonate, than feed water heaters using live steam only. An example of an upright feed water heater heated by exhaust steam is the " Goubert." Fig. 19. The Goubert feed-water heater. Fig 20. (Vertical type.) The exhaust steam from the engine is admitted to the shell through the nozzle on one side and spreading between the brass FEED WATER HEATERS. IOI tubes, impinges upon them on its passage across to the outlet on the opposite side : the water of condensation being removed by the drain pipe. The cold water may be admitted at either top or bottom of the heater, passing out at the opposite end : but for bad waters the feeding should be at the top. This being a closed heater and the water being forced through against boiler pressure, the flow along the heating tubes will be the same whether the water moves in an upward or a downward direction, but in the latter case the separation and settling of sediment will be much more thorough, while the heating will be the same. Fig. 21. The Hoppes feed-water purifier. This purifier consists of a round shell of best boiler steel, hav- ing a solid pressed flange steel head riveted in the back end, and a solid pressed flange steel head bolted to a heavy ring on the front end, by studs and nuts. Within the shell are a number of trough-shaped pans or trays, placed one above another, and supported on steel angle ways, fixed longitudinally by means of brackets to the sides of the shell. These pans are formed from thin sheet metal, the heads or end pieces being malleable iron, whereby a very light, strong and durable construction is obtained, and a degree of elasticity secured to the pans, which permits the lime or other incrustations being easily removed. Six pans are placed in a tier, and from one to four tiers used, according to capacity required. The purifier is connected to the boiler by a 102 QUANTITATIVE ANALYSIS. large steam pipe A, and the exit pipe D. A blow-off pipe is also connected at C. The feed pipe from the pump or boiler feed is attached at B. In operating the purifier, the water is pumped in at B and distributed into the upper pans through the pipes leading into each pan. While the purifier is in operation, the pans remain full of water, and afford ample settling chambers for the heavier solids, such as mud, sand etc., etc., while the carbonates and sulphates (scale-forming) adhere to their under sides. An analysis of a sample of water before passing through one of these heaters at Rochester, N. Y., is as follows: BEFORE USE. Inorganic solids 128.74 grains per gallon. Organic matter 3.38 " " " Total solids 132.12 " " " AFTER PASSING THROUGH HEATER. Inorganic solids 8.44 grains per gallon. Organic matter 3.20 " " " Total solids 11.64 " " " C/i O ON 10 O GO****! O^Cn > O 5* U>OOK>-1K>ON'-'00 ON w ooc^i 1-1 GO** vj O*" COW ON O -P* ON ONCK) O 00 ONOi -p. C*i 0> O-pi. K)^J K) 00 O K) ^J U ONvO tn 1-1 ^j ONCn C/i4^G)IOK)tOiHMM _,. KiCn^l OOJ ONOOt/i K> OO-P OO^J Cn Oi ^ C*> O OJ t-i v) ONGJ - vO OJ O\U\ 4^Oi OsKi^J OCA> O\S O O 00^1 Oi ^4 OOvO ^1 C** O 00^1 ChCa IUJ O OO^J C^C^ 4^- OCa O\KJ '-i oo-t*. to o vo *vi-viC/ OsOOO -i^iai K) C 1 -^ N> 00 00 /iKi (O O\ (O IO Ki M M ^ vO ON KJ v) ONCA) HH O 00 ONC/i Oo CA> K) IO M 1-1 ~ KJ ON K) LnC^J O^I^ W OC*i i-HOitn NsO 10 O\K)vO ta OC/i OOO^I WvO^4^J "-I O OCa I-H-VJ^ ON M OOC/i 00-C. KJi-( 1-1 Cn vO U> ^J O -^ ONC>> (0 N) ^J OJ ON OOC/i M OO 00 O\Cn -H QvO^l ONO^O-P^ 00-P>. M v5 OO 00 00 OOvO v)vO-P* K>vOOJ^v> M^JOJvO "-i^^^lO M NC>i K) ONCa ^J OO 00 00 OC\O C^I -P* c>j oj to (o to t^j 4^. O ON H ^ -P>. ^J -P* O ^ 1.11 8 o 111 i"l ^L - S**5 a a K 5 a ? a > o M> " If HH O fi c/3 a p w w fo o ^ s? 2 'O 5 a M S a a M CO rOvO ON O O OM-1 TfVO 00 M OCO O M ONCO f^ i s- Tt Tt ro (N M O ONCO t^ o (L> to ^OO M fOVO CO O N f) !O 3 o rt ro rO t^ t^vO fOOO *-i lO O N ^'VO CO O N rO iO '& H^ M M M to *> ONCO MCSMOvocNior^ aocsiot^ONMCNTj- vnvo to ON t^-CO r^vO N t-> M CO Tt 1-1 10 t> ON 1-1 CO Tl-vO t^GO J ONCO t^vO \D ^n -^- CO CN M to ^"OO O CN ^* ^"vO CO ON 8 t^vOvO^^-coCNMO . utB3}s Sup -qB - qi J3d s}iun } OS B3JJ l>.vO lO Tf CO CS M O OOO j9}B9t{ Suu3}n a3}BAv jo aan^Baaduts; jsp 9 V^ R 5 42 USE OF CHEMICALS AND FILTRATION. 105 ' ' Blowing-off . ' ' The arrangement in a boiler for this purpose usually consists of one or two internal pipes extending along the bottom of boiler and connected with the blow-out tap. They are placed about one and one-half inches clear of the plates and are perforated on their under side. It is usual to blow-out the sediment every two or three days just before drawing the fires and the sediment in the water has had time to settle. Consult also "Wilson on Boilers," page 169-171. Use of Chemicals and Filtration. Dervaux Water Purifier for boiler use. This apparatus (Figs. 22, 23) is automatic in action, and is thus described. 1 The purifier is intended to act as an eliminator for both calcium sulphate and calcium and magnesium carbon- ates. It not only acts to precipitate the dissolved impurities, but also to collect those that are in suspension. These last are caught and held in the tower- shaped holder D. The water enters at H, passes 'down through^, and is made to rise through a series of fun- nels or inclined funnel-shaped walls. 2 On these walls the coarsest particles are caught and from them they flow down to the bottom of the tower, where they collect : the water then passes upwards % though the filters F, which are made of wood shavings, and flows off, freed from its mechanical impurities through the open- ing T. In the mean time, by the addition of lime and soda, the water has been chemically purified in the following way : The water first flows into the reservoir C, through the pipe H. In C, there is a float for regulating the flow of water. A portion of the water goes into E, through the pipe P, while the rest passes through the valve V into the lime saturator S ; Sis filled with lime : the water first meets the lime at the bottom of the saturator and passes up through it; the conical shape of 5 causes the rise to be slower and slower as the water nears the top, so that the milk of lime, at first formed, has plenty of time to clarify itself. The lime water usually contains some calcium carbonate in suspension : and as this is worthless for purposes of purification, it is eliminated by causing the water to flow over 1 Papier Zeitung, 34, 984. 2 The Chemistry of Paper Making, p. 345. io6 QUANTITATIVE ANALYSIS. m Fig. 22. Fig-. 23. into the cone K, which is closed at the bottom. In this cone the carbonate settles out, and may be drawn off through G. The clear, saturated lime-water, containing 1.3 gram of lime per liter, runs then directly into the mixing tube E. A solution of soda-ash is made by taking a known weight of the ash, which is placed in the tank Z, after which the tank K, is filled to a de- USE OF CHEMICALS AND FILTRATION. IOy finite mark with water. This solution slowly passes through the tube provided with strainers : a float in the tube keeps the water in E at a constant level. The siphon N, one end of which dips to the bottom of B, allows the alkaline solution to flow into B. The regulation of the flow in E is performed as follows: The siphon A^ is joined by a chain Q, to the float in C. In case the flow of water through //to C is cut off, the float sinks, rais- ing N and thus stopping the flow of the solution. At the same time the level in C sinks so low that the flow of water through P and F ceases : as soon as the flow of water through //"recom- mences, the apparatus is again set in operation automatically. The chemical operations may be stated as follows : The addi- tion of the lime softens the water by precipitating any bicarbon- ate which may be present, and the excess of lime is thrown down by the sodium carbonate. This, by its precipitation throws out much of the finely divided organic impurity. The apparatus may be easily modified to work with alum where desirable. This Derveax Purifier is extensively used in France and Ger- many. In England the apparatus devised and patented by L,. Arch- butt, F. I. 0., and R. M. Deeley, M. E., has an extensive use for the purification of boiler waters. The drawings (Figs. 24, 25, 26) show the construction and rep- resent a purifier suitable for the treatment of from 5,000 to 10,000 gallons of water per hour. It consists of a cast-iron tank, measur- ing 32 feetX 1 6 feetX 10 feet deep, divided into two equal parts by a transverse partition of cast or wrought iron. The two tanks are intended to be used alternately, so as to maintain a continuous supply of softened water. The water to be purified is admitted to either tank by means of the supply pipe, i, which is connected up to a pump or main. The water fills up nearly to the level of the top of the well, 4. While the tank is filling the proper amounts of lime and sodium carbonate are weighed out, with the addition, in some cases, of a very small quantity of aluminum sulphate, or alumina-ferric cake, and these are boiled up with water in the small chemical tank, 2, by means of steam from the steam pipe. The trajector, 3, is put into action by opening its steam valve 7 and then the io8 QUANTITATIVE ANALYSIS. PATENT HARD WATER PURIFIER. Fig. 26. USE OF CHEMICALS AND FILTRATION. IOQ chemical liquid is run out of the chemical tank into the well. The trajector creates a powerful current of water from the well, through the projecting pipe, across the tank, and into this cur- rent the chemicals pass. After the chemicals have thus been added and mixed with the water, and the trajector shut off, steam is admitted to the blower, 5, which causes air to be sucked down the orifice and forced out of the perforations in the pipes laid close to the bottom of the tank. After the blower has been in operation for fifteen minutes, the steam is turned off and the water is allowed to rest. The result is that in about thirty min- utes very nearly all of the precipitate will have settled to the bot- tom of the tank. The drawing-off and carbonating are opera- tions that are automatically and simultaneously effected by means of the floating discharge pipe, 9, of rectangular section. Fuel gas, from the coke stove, 7, constructed so as to produce a minimum of carbon monoxide and a maximum of carbon dioxide is forced continuously by means of a very small steam blower, 8. The gas and water pass together through the ball tap fixed over the small supply tank, 12, into which the softened and carbona- ted water falls, and from which it is drawn off for use, whilst the residual gas and nitrogen, etc., escape into the air. The mud is removed by extending the main blower pipe through the side of the tank where it terminates in a valve, 14, which by opening for a few minutes at intervals the accumulation of mud is prevented. The reasons for carbonating the softened water are fully ex- plained in a paper read before the Society of Chemical Industry in June, 1891. Uncarbonated softened water often forms a de- posit in pipes and especially in the feed apparatus of steam boilers, which may become very troublesome. This is not a pe- culiarity of w r ater softened in this apparatus. The output can be calculated as follows : u = the number of gallons of softened water supplied continu- ously per hour. .r = the working capacity, in gallons, of each tank. y= the number of minutes required to fill each tank. 2=: the number of minutes required for settling. = the cost. 25 no QUANTITATIVE ANALYSIS. ONOO -tf-vo VO . CO vO r/} ^ t-i if ON CM co CO r^oo vo O co ON j M M -4- CN 00 . . . vo O to (N M HH COOO M CN VO 10 . ' . 10 rf ^OCO VO CM vO Cg rOCO VO 00 ON M CM COCO O CJ CU CO CM O CM CN . C . vo' O rj- CM en CO M oo o CM VO CM . OH ^ co 1-1 O "-" o O CO to O TJ- Q ON ON * vo * O O ON J>-00 to -M N M .* M CO vO Tf ON O M IO O M en ctf vO -3- ^f- O CO . . t^ CN O ON cO I s * ON ... t^^o 5. vo'io ^ CJ PH H CO t^ ON ^ ON CM cO vg ONOO f^ CO Tf *^ M O CM CM' CM oo . . . to d to t^. IO VO CM o co ON M O CO > ' . 10 CM IO CO CO CM . C8 . O -3- ON VOOO ON QN *-o O^ . vd d -4 M . . S . co d M en ff 00 CM cu en IO CO VO O vO . VO ^ X vO w vo COOO M CJ Jo co O .MO . O I CM' ON t>. o to M - ^tCO VO . -^f . CN CO r^ t^.CM . rt . . . t^ Tj- CO- Tf CO O CM CO to en *-> 00 CN CO . M . . . CM O ON VO M Tj- M M * ^ 5 bJO . o 2 . . ^ softening estimate ...at $4-: Calcium carbonate Magnesium carbonate Calcium sulphate Magnesium sulphate Sodium sulphate Magnesium n itrate Sodium nitrate Magnesium chloride Sodium chloride Silica Total lime (CaO) Total magnesia (MgO) Total hardness ( = calcium < equivalent to total lime an sia) Cost of chemicals required for 1000 gallons NOTE. The above Quicklime FILTER PRESSES. Ill To remove calcium carbonate by chemical means from water costs very little, because lime alone is necessary, and is very cheap. To remove calcium sulphate, alkali must be used, which greatly increases the cost. Both lime and. alkali are necessary for the removal of certain magnesium salts, and the alkali must be used in greater relative proportion. Waters containing much magnesium salts are therefore the more costly to treat. The table on page no gives the analyses of nine typical samples of water, together with the cost of chemicals needed to soften each by this process, and reduce the hardness to 3 and not exceeding 5. Filter Presses. Filter presses are often used for rapid filtration of water. These presses consist of a number of filter chambers with solid separat- ing walls, which are held between two head pieces, one of which is fast and the other movable ; the latter as well as the filtering frames slide along two strong iron rods. Between the chambers the filtering cloth is hung and this also helps to make the outer edges fit closer together. The whole system is pressed together by a screw or lever or by hydraulic pressure and forms a num- ber of hollow spaces lying together and communicating with one another. Between these hollow spaces the liquid to be filtered is pressed by a pump or other means. During this- process the separation of the liquid and solids takes place, in that the liquid 112 QUANTITATIVE ANALYSIS. is forced through the cloth and runs out clear through channels to a common outlet, leaving the solids behind. We distinguish two varieties of filter presses. 1. Chamber Presses, (Fig. 27) by which the space for the cake i. e. y the solid matter remaining, is formed by the edges of each two filters plates, so that the cake falls out when the press is opened. 2. Frame Presses, by which the space for the cake is formed by frames that are placed between each two filter plates, so that the cake can be lifted out with the frames. In order to dry the cake completely and to wash it, when necessary, there are in most filter presses two extra canals in Fig. 28. each chamber, one in which the washing fluid enters and the other by which it is removed. There is also an attachment by which liquids can be filtered hot or cold. The Porter-Clarke process for softening hard water, largely used in England, makes use of filter presses to remove the pre- cipitated material in the water. Where this latter precipitate is very fine and small in amount, manufacturing establishments sometimes arrange a system as shown in Fig 28 in which fibers of cellulose are added to collect the fine precipitate. The ap- FILTER PRESSES. 113 paratus consists of a high horizontal reservoir H (Fig. 28) for reception of the w r ater to be filtered, another reservoir or tank M, in which the floating material (or fibers of cellulose or asbestos) is mixed with water, a reservoir R into which the purified water flows and the filtering apparatus proper F. The latter is com- posed, as are the filter presses, of a series of frames on which metal sieves are fastened. The filtration takes place in the following manner : The thin mass of cellulose or asbestos fibers are caught by the sieves and remain on them ; the water is then allowed to pass from the reservoir H through the sieves which now holds back all suspended matter, so that clear water flows in the reservoir R. Another method made use of in some large industrial plants, is to combine the action of a heater, chemical precipitation and filtration by filter-presses as shown in Fig. 29. Fig. 29. The water passes first through the heater A in which it is brought to the temperature of the heater, thence into the pre- cipitation tank B in \vhich it is mixed with the chemicals in solutions the latter being pumped into B from F by means of the pump D. The water then passes into the filter press C, in the chambers of which the suspended matter is retained, and is then pumped by the pump E either directly to the boiler or else to a reservoir. The water and chemicals are mixed in the propor- (8) 114 QUANTITATIVE ANALYSIS. tions shown to be necessary by analysis. This system of water purification has shown itself to be very successful, but the filter press must be cleaned every two to eight days according to the composition of the water. References : "Boiler Deposits," Vivian B. Lewes, F.C.S., Transactions Inst. of Naval Architects. Vol. XIV. " Boiler Incrustation," Treatise on Steam Boilers, Robert Wilson C.E., pages 158-187. " The Purification of Water for Domestic and Manufacturing purposes, {Hyatt System.} By J. S. Crone. Trans. Am. Soc. Mech. Engineers, 7, 617-630. " The use of Kerosene oil in Steam Boilers, as a preventative of scale. By Lewis F. Lyne, Trans. Am. Soc. Mech. Engineers, 8, 247-259 " Corrosion of Steam Boilers." By David Phillip, Proceedings Institu- tion of Civil Engineers, 65, 73. "On the Results of an examination of the Chemical Composition of steam-raising waters and of the incrustations formed from such, with notes on the action of the more common materials employed as " ante- incrustators" and of the various processes for softening water for steam purposes." By W. Ivison Macadam, F.C.S., J. Soc. Chem. Industry, 2, 12-21. ' The Porter-Clark Process" (for softening water.) By J. H. Porter. J. Soc. Chem. Industry 3, 51-55. " Suggestions on Boiler Management." By VeroC. Driffield. J. Soc. Chem. Industry, 6, 178-189. "The Analytical Examination of Water for Technical Purposes." By Alfred H. Allen, F. C. S.,/. Soc. Chem. Industry, 7, 795-806. " The Action of Water on Lead Pipes." By Percy F. Frankland, F.I.C., /. Soc. Chem. Industry 8, 240-256. " The Treatment of Hard Water." By L. Archbutt, F.I.C., and R. M. Deelay. /. Soc. Chem. Industry 10, 511. " The Purification of water, on the large scale, by means of Iron." By William Anderson. Proceedings of the Institution of Civil Engineers. 81, 279. XVI. Determination of the Heating Power of Coal and Coke. The simplest method, but which gives only approximate re- sults, is the ignition of coal with litharge in a crucible. In de- tail the process is as follows : one gram of the finely powdered coal is intimately mixed with thirty grams of litharge (PbO), transferred to a No. 3 Hessian crucible, twenty grams more of HEATING POWER OF COAL AND COKE. 115 litharge placed on top of the charge, the crucible covered and heated at a high heat in the furnace for fifteen minutes. The crucible is removed, allowed to cool, broken, and the button of metallic lead cleaned from the slag and carefully weighed. Duplicate results should not vary more than 0.025 gram. To calculate the result : One part of carbon reduces thirty-four times its weight of lead, and if one kilo, of carbon = 8140 calories, then each part of lead is equivalent to 8i4O_ =239 calories 34 Suppose the lead button from one gram of coal weighed 31.05 gram, then - X 3 1.05 = 7420.9 calories per kilo, or 13357.76. OT" T. U. per pound of coal, which represents the heating power of the coal. The heating power of coke, containing no volatile combustible matter, can be calculated from the analysis, thus Carbon 94-43 per cent. Ash 5-57 100.00 " " ^- X 8140 = 7686.6 calories^ 13837 B. T. U. per pound. Bituminous coals contain volatile combustible matter as well as varying amounts of water, for which reasons both of the above methods give very incorrect determinations of the heating power. Three methods are available (which include all varieties of coals :) i . Calculation of the heating power from the results of an ele- mentary analysis of the coal, viz. : determination of the percent- ages of carbon, hydrogen, nitrogen, oxygen, sulphur and ash. 2 The use of calorimeters in which a sample of coal is burned and its heating power determined directly from the experiment. 3. The combustion of large amounts of coal in specially de- signed apparatus therefor, and also boiler tests. Calculation of the Heating Power from the Results of an Elemen- tary Analysis of the Coal. a. Determination of the carbon and hydrogen. Select a Bo- hemian glass combustion tube about seventy cm. long, two cm. in diameter, open at both ends (Fig. 30). Place in it at j n6 QUANTITATIVE ANALYSIS. ll J X Fig. 30. granulated cupric oxide for a dis- tance of about thirty cm., and at k a plug of asbestos ; place the tube in a combustion furnace c, connect it at b with the drying apparatus a, and at d with calcium chloride tube e filled with CaCl 2 , granulated. The latter is connected with an aspirator, and air is very slowly drawn through the apparatus ; at the same time the furnace is gradually lighted and the heat increased until all the cupric oxide has reached a red heat. Main- tain this for fifteen minutes, turn off the gas, and continue the aspiration of air until the tube is nearly cold. M - This preliminary heating is necessary ^ to eliminate any moisture that may be in the tube or in the cupric oxide. Transfer five-tenths gram of the finely powdered coal to a weighed porcelain boat and place in the tube at h ; at" is a coil of platinum foil. The calcium chloride tube e (Fig. 31) is now accurately weighed, as well as the potash bulbs /, J and when all the connections are properly made, heat is turned on in the furnace at the end d, and oxygen gas is very slowly passed through the apparatus. At intervals of a few minutes the heat is turned on in the furnace until the cupric oxide is at a red heat, and finally the entire tube from k to g is also at that temperature. After the complete combustion of iThe latter one-third full of KOHisolution sp. gr. 1.27. HEATING POWER OF COAL AND COKE. 117 the carbon of the coal, which is indicated by the absence of black particles in the porcelain boat, turn off the heat in the furnace, but continue the slow current of oxygen until the appa- ratus is nearly cold. The hydrogen in the coal by its combus- tion is converted into water and absorbed by the calcium chlo- ride tube e ; the carbon of the coal, by its combustion with ex- cess of oxygen has produced carbon dioxide, and is absorbed in the potash bulbs/. From the increase of weights thus obtained the percentages of hydrogen and carbon are calculated, thus : Amount of coal taken = 0.500 gram. Calcium chloride tube -j- H 2 O = 36.5118 grams. = 36.4025 H 2 0= 0.1093 " 0.109 gram H 2 O = 0.0121 gram H. - 0121 X I0 = 2.42 per cent, hydrogen. 0.500 The potash bulbs and CO 2 = 34.9554 grams. = 33.3200 " 1-6354 " 1.6354 grams CO., = 0.4460 gram C. '4 46 X I0 = 89.20 per cent, carbon. 0.500 The ash is as follows : Remove the porcelain boat from the combustion tube care- fully and weigh ; the increase of weight is ash. Thus : Porcelain tube + residue (ash) = 8.9693 grams. = 8.9460 " Ash = 0.0233 0.0233 X IPO =66entash 0.500 b. The nitrogen determination is made as follows : Select a combustion tube about sixty cm. long and two and five-tenths cm. diameter, drawn to a point at one end and open at the other end (Fig. 32). ^^BSSSS^S^ti^SI^SSMS&^^SSSSSSSS^^^ a b c e Fig. 32- Il8 QUANTITATIVE ANALYSIS. At a place three grams of crystallized oxalic acid, then a few layers of freshly ignited soda-lime, and at b insert five-tenths gram of the powdered coal mixed with about twenty grams of soda-lime, fill the rest of the tube with soda-lime and finally some asbestos near the open end of the tube. Connect with a bulb tube d containing fifteen cc. of a standard solution of sul- phuric acid, each cc. of which contains 0.049 gram sulphuric acid. The combustion tube is now placed in the combustion furnace and heat is gradually applied under the tube at e and extended slowly towards a . The soda-lime between c and the coal must be at a red heat before heat is applied under the coal. Now heat the tube until the soda-lime and the coal are well heated and maintain this until no more gas is generated or passes into the standard acid ; being careful, of course, that none of the oxalic acid has yet been heated. Gradually heat the oxalic acid, which slowly vaporizes, and in passing over the soda- lime is converted into carbon dioxide. The nitrogen in the coal, by this ignition with soda-lime, is con- verted into ammonia and forced out of the tube into the stand- ard acid by the excess of carbon dioxide generated from the oxalic acid. After the operation is completed, disconnect the (J-tube con- taining the standard acid, transfer its contents to a No. 3 beaker, add a few drops of litmus solution and titrate with normal soda solution to determine the amount of ammonia united with sul- phuric acid. Thus : Coal taken = 0.500 gram (dried) H 2 SO 4 solution taken = 15 cc. Normal soda solution required to neu- "I /- tralize free acid }= 14.768 cc. (One cc. NaOH solution neutralized one cc. H 2 SO 4 ) 0.232 cc. of H 2 SO 4 solution neutralized by the ammonia. If one cc. H 2 SO 4 solution = 0.049 gram H 2 SO 4 : : 0.232 cc. = 0.0113 gram H 2 SO 4 . 0.0113 gram H 2 SO 4 = 0.00392 gram NH 3 . = 0.00322 " N. 0.00322 X IPO = Q 6 cent nit 0.500 HEATING POWER OF COAL AND COKE. 1 19 The method of Kjeldahl can also be used for the determina- tion of nitrogen in coal. Consult "Contribution a 1' etude des combustibles," P. Mahler, 1893, p. 19. The sulphur is determined as directed in scheme XII, and in this sample amounted to 0.19 per cent. Having determined all of the constituents in the dried coal but oxygen, the latter is estimated by subtracting the sum of the other constituents from 100. Thus : Carbon ...................................... 89.21 per cent. Hydrogen ................................... 2.43 " " Nitrogen .................................... 0.65 " " Sulphur .................................... 0.19 " " Ash ......................................... 4-67 " " Oxygen ..................................... 2.85 " " Total ................................. loo.oo " " d. We will now include in this analysis the hydroscopic water (the above analysis having been made upon the dried sample) . This moisture in the coal is a direct loss in the calorific power, since it absorbs heat. Amount of coal taken ........................ 2 grams. Watch-glass and coal before drying twenty minutes at 102 C ........................ 12.162 grams. Watch-glass and coal after drying twenty min- utes at 102 C ............................ 12.101 " Loss (moisture) 0.061 " 0.061 X IPO = 3 Q5 per cent moisture . The complete analysis of the coal will now be : Moisture .................................... 3.05 per cent. Carbon ................ ..................... 86.49 " " Hydrogen .................................. 2.36 " " Nitrogen ................................... 0.63 " " Sulphur .................................... 0.18 " " Oxygen ..................................... 2.76 " " 4.53 " ;t i - Total ................................ 100.00 " " The calorific power of the coal is calculated from the follow- ing data : I2O QUANTITATIVE ANALYSIS. A calorie is the standard heat unit, and represents the heat required to raise the temperature of one kilo of water from 4 C. to 5 C. A British thermal limit (" B. ^T. U.") is the heat required to raise the temperature of one pound of water iF., at its temper- ature of maximum density, (39. i ). 1 To reduce calories per kilo to "B. T. U." per pound, multiply by f . One kilo of carbon (from wood charcoal) in burning to car- bon dioxide produces 8140 calories. These figures, 8140, obtained by Berthelot and Bunte are probably nearer correct than the figures 8080 given by Favre a ad Silbermann. One kilo of sulphur in burning to sulphur dioxide produces 2220 calories. One kilo of hydrogen in burning to water (condensed) pro- duces 34500 calories. If the water produced by the burning of the hydrogen is not condensed, but remains in the form of steam, part of the 34500 calories, produced by the combustion of one kilo, appears as latent heat and as sensible heat in the steam. Thus, suppose one kilo of hydrogen and eight kilos oxygen, both at i5C. unite to form nine kilos of steam which escapes at 100 C. The total heat of one kilo of steam at 100 C., measured from water at 15 C. is 622.1 calories, and of nine kilos, 9 X 622.1 = 5599 calories, which subtracted from the 34500 calories pro- duced by the combustion of one kilo of hydrogen, leaves 28901 calories as the available heat of combustion of hydrogen at 15 C. when the product of combustion escapes as steam at 100 C. If the steam escapes at some other temperature, or if the ini- 1 One French calorie =3.968 British thermal units : one B. T. U. 0.252 calorie. The " pound calorie " is sometimes used by English writers : it is the quantity of heat re- quired to raise the temperature of one ponnd of water iC, one pound calorie = 2.2046 B. T. U. = $ calories. The heat of combustion of carbon, to CO a , is said to be 8140 calories. This figure is used either for French calories or for pound calories as it is the number of pounds of water that can be raised iC. by the complete combustion of one pound of carbon, or the aumber of kilograms of water that can be raised iC. by the combustion of one kilo- gram of carbon. [Kent]. HEATING POWER OF COAL AND COKE. 121 tial temperature of the hydrogen is other than i5C. the avail- able heat units will vary accordingly. In practical calculations of the heating value of fuel, it is gen- erally most convenient to take the total calorific power of the hydrogen it contains at 34500 calories per kilo, and after ob- taining the total heating value of the fuel on this basis to make the necessary corrections for the initial temperature of the hydro- gen and for the latent and sensible heat of the steam in the products of combustion. The heating value of coal is thus calculated from the analysis : Let C=the percentage of carbon in the coal. Let.//= " " " hydrogen " " Let O " " " oxygen " " Let S " " " sulphur " " Then: 8140 C + 345oo(/f o ) 4. 222 o S. Heating power = ]foo _(8i4o X 86.49) + 34500 (2.360.345) 4- 2220 X 0.18 TOO __704028 + 69517.5 -f 399.6 100 = 77394 calories per kilo of coal. Where the products of combustion of hydrogen escape as steam at iooC., the formula will be : 8140 C 4- 28901 (// O) -|- 22205 622W Heating power = ~~KKD W = moisture of the coal. Then: _ 8140 X 86.49-^28901 (2.36 0.345 )+2220X 0.18 622X3.05 100 ^ 704028.6 -f 58235.5 -f- 399.6 1897.3 100 = 7645.6 calories per kilo of coal. To calculate the amount of air required for complete com- bustion, the following data are required : 122 QUANTITATIVE ANALYSIS. i kilo of carbon burning to carbon dioxide requires 2.66 kilos of oxygen. [ " " hydrogen " " water " 8.00 " " " t " " sulphur " " sulphur dioxide " i.oo " " lt Air is composed of a mechanical mixture of oxygen and nitrogen in the proportion by weight, of 26.8 parts of nitrogen with eight parts oxygen ; that is, 3.35 parts of nitrogen with one part of oxygen; or in volumes 3.76 cubic meters of nitrogen with one cubic meter of oxygen. The volume of i kilo of oxygen is 0.74 cubic meter at i6.67C. nitrogen " 0.84 " " " " " " " hydrogen " 11.84 " " " " " " " sulphur dioxide " 0.36 " " " " " " carbon dioxide " 0.54 " " " " " (< air <. 0>82 (t One kilo of carbon requires n.6 kilos of air to produce car- bon dioxide. Thus, the oxygen required 2.66 kilos, which combined with 8.94 kilos of nitrogen (the proportion of oxygen and nitrogen in air) gives n.6 kilos of air or 9.5 cubic meters. i. o kilo carbon Carbon i.oo kilo "] f Total One kilo hydrogen requires for combustion 34.8 kilos of air, or 28.58 cubic meters: i. o kilo hydrogen Hydrogen i.o kilo 35.8" In a similar manner it it found that one kilo of sulphur re- quires 4.35 kilos of air to produce sulphur dioxide, or 3.6 cubic meters. The amount of air required for the combustion of one kilo of the coal will be : HEATING POWER OF COAL AND COKE. 123 COMBUSTIBLES IN THE COAI,. Carbon = 86.49 per cent. = 10.2 kilos of air or 8.32 cubic meters. Hydrogen = 2.36 " " = 0.82 " " " " 0.67 " " Sulphur = 0.18 " " = 0^007 " " " " 0.003 " One kilo of the coal requires 11.027 " " " " 8.993 " " or one pound of the coal would require 11.027 pounds or 144.9 cubic feet of air at 62 F. for its combustion. In a similar manner the amount of air required for the com- bustion of one kilo of coke (partial analysis given on page 115) would be : Carbon 94.43 X 11.6 = 10.95 kilos of air, or 8.97 cubic meters, equivalent to 144.4 cubic feet of air per pound of the coke! The evaporative power of a coal or coke expressed in kilos of water evaporated per kilo of coal, is determined by dividing the total heat of combustion of one kilo of the combustible by 620, which is the total heat (degrees C.) of one kilo of steam at atmospheric pressure, raised from water supplied at 62 F. or i6.67C., or by 536.5 (degrees C.) if the water is supplied at 100 C. If the results are stated in pounds of water evaporated per pound of fuel, it is obtained by dividing the total heat of com- bustion in " B. T. U." by 1116.6 F., which is the total heat of atmospheric steam raised from water supplied at 62 F., and by dividing by 956.7 F. when the water is supplied at 212 F. The evaporative value of one kilo of the coal will therefore be, theoretically, assuming the water to be supplied at i6.67C. (62 F.) , and the steam generated at atmospheric pressure : Carbon, 86.49 X 8140 -5- 100 = 7040.28 calories. Hydrogen, (2.36 | X 34500.) -5- 100= 695.17 Sulphur, 0.18 X 2220 -i- 100 = 4.00 " 7739-45 7739-45 ~*~ 620= 12.48 kilos of water evaporated per kilo of coal. 124 QUANTITATIVE ANALYSIS. . n s J&8 tt 8.-- a o a .2 S 3138. M 8. > C9 3J Slll^j | a*..t-.-- 2 VM&'i Js!cS*n Sit** I 8 ! s 2 11 1 f ** o o "3 <* o w HI VO O 00 TT o . ^ o 'a 2 a J72 S 3 S . s s o s.^: r * 10 ^ i-! .5 D 1 H 1 ^ I pq S = 2 Ov (5? - - cr, a s s o a, 10 8 rt rO rt M cj I OJ 3 o 4-1 V o _a> 3 t; 0) a t; c mete o s be a 'jj Ch 3 (S to hH 2 a CO 2 o 00 C( lO u ^ a o 1 | 1 1 pq & : : 1 o 8 | 2- en 3 o o 8" o O CJ 2 p O K 3 a w 3 .2 'S 0" o" 0} 3 V is in general p ." 22 S 25 5 -s S ? t 5 5 5 A *,- rt^ ^^SvC y O^^ 03 o'go'g'S'g'S'dl? O 3^3^ 3 3^ SaSs-SaSajr aaacaaca OO'OOOOOO HEATING POWER OF COAL AND COKE. 125 If the water be supplied at iooC., the evaporative value will be 7739.45-7-536.5= 14.42 kilos of water evaporated per kilo of coal. The actual evaporation is less, in boiler practice, than the theoretical as computed above, for the following reasons: 1. There may be a loss due to incomplete combustion. 2. There is necessarily a considerable amount of heat carried off by the chimney gases. 3. There is loss of heat due to radiation. 4. Heat is also lost, due to the evaporation of the hydroscopic moisture contained in the coal and to the heat in the vapor formed by the combustion of the hydrogen in the coal. For example, in a test of a standard type of boiler made by Prof. J. H. Denton, where the fuel, anthracite coal, was burned so thoroughly as to practically eliminate the loss due to incom- plete combustion, the remaining losses were as follows : Loss of heat by chimney JS-Ss per cent. " " " " radiation 2.64 " " mo i sture 0.08 " Total 16.55 " " These per cents being in terms of total heat per pound of combustible. 'Consult article on Boiler Tests. The total heat as determined by calorimetric measurements being 14302. "B. T. U." per pound of combustible. The heat imparted to the steam was 100 16.55= 83.45 P er cent, of the total heat. This is a high economical result. Ordinarily the heat imparted to the steam is not over 80 per cent, of the total heat, so that the available heat is usually less than 80 per cent, of the theoretical heat. Calorimetry. Of the many instruments in use in calorimetry for determining the heating power of coals, the Mahler, the Thompson, the Barrus, and the Carpenter are selected for description. For rapidity and accuracy, the Mahler is to be recommended. This apparatus consists of a modified form of Berthelot's bomb. Berthelot's instrument, which was originally made for the 126 QUANTITATIVE ANALYSIS. combustion of gases under pressure, consisted of a steel cylin- der lined with platinum. Mahler uses porcelain as a lining to the steel cylinder in place of the platinum, thereby materially reducing th'e cost of the ap- paratus. The accompanying sketches represent a vertical section of the calorimeter itself, showing all of the attachments, and also a ver- tical section of the shell to a larger scale. The shell is forged out of mild steel having a tensile strength of thirty-one tons to the square inch, and an elongation of twenty-two per cent. It is about eight millimeters thick and usually weighs about 3,500 grams, with a capacity of 814.6 cc. The capacity of the instru- ment was made much greater than that of M. Berthelot for two reasons : First, to insure complete combustion, and second, be- cause many gaseous fuels used for industrial purposes contain nitrogen and carbon dioxide. It is necessary to take a large quantity of them in order to obtain a measurable rise in tem- perature. The shell is coated on the inside with porcelain to protect it from corrosion or oxidation. The porcelain being very thin, does not inter- fere with the transmission of heat. The cover is fitted with a ferro-nickel cock R, with a conical screw and stuffing box K, for the introduction of oxygen under pres- sure. The cover is screwed down upon a ring of lead P, placed in a circular groove cut in the rim of the shell, making a tight joint. Through the cover passes an iso- lated electrode, to which a platinum rod is fastened by means of a clamp. Another platinum rod is fastened to the cover, and the pan which contains the substance to be burned is attached to this by means of an- other platinum rod and two clamps. At- tached to the platinum rods and passing through the substance to be burned is a small helix of fine iron wire. Ignition is produced by heating this wire white-hot by Fig- 33- CALORIMETRY. I2 7 means of a batter}-. The calorimeter, the outer vessel, and the various details of M. Mahler's apparatus differ from the analo- gous parts of M. Berthelot's instrument. The calorimeter is of thin brass and contains about 2.3 kilos of water. The large amount of water practically eliminates all error due to evapora- tion. The agitator S is worked by the lever L, which pushes Fig- 34- down the rod K, to which the agitator is attached. This rod has a spiral thread on it and moves through a nut, so that in pressing it down it also receives a revolving motion, thus very thoroughly stirring the water. The thermometer T should read to the one hundredth of a degree. For igniting the substance a battery capable of giving a current of two amperes with an E. 128 QUANTITATIVE ANALYSIS. M. F. of ten volts is required. The oxygen is supplied in cyl- inders of 125 cubic feet capacity at a pressure of 150 atmos- pheres. Such a cylinder will supply oxygen enough for about 140 determinations. Before this instrument can be used for determining calorific power, it is necessary to find the water equivalent of the shell and its appendages. This must be determined with the utmost care, as upon it depends the correctness of all the results after- 35- ward obtained. It may be calculated directly from the weights and known specific heats of the parts. It may also be obtained experimentally. The method by calculation can only be ap- proximate, because of the weight of the porcelain of the shell is not known and can only be estimated. This method gives the following results : Weight in Material. grams. Brass of calorimeter ........ 703.07 Steel of calorimeter ........ 3>3 2 3 2 5 Porcelain .................. 134.078 Platinum ................... 21.3 Lead ....................... 9.0 Glass of thermometer ...... 12.69 Mercury of thermometer . . . 25.03 Oxygen ............ ........ 29.1205 Specific Water equivalent heat. in grams. 0.094 66.088 0.1165 387.157 0.179 24.0 0.0324 0.68 0.0314 0.282 0.17968 3-II4 0.03332 0.833 0.155 3.513 485.657 CALORIMETRY. 1 29 In determining the water equivalent the following method is employed. The shell is charged with oxygen at twenty- five at- mospheres pressure. A known weight of water, about 2000 grams, is then placed in the calorimeter, the shell immersed in it, and the whole appa- ratus placed under the same conditions that would exist during an actual combustion. The water is then agitated until the temperature becomes constant, when about 300 grams of water at a much lower temperature are added, and the whole agitated until the temperature again becomes constant. Readings of the thermometer are taken every half minute. From the observed fall of temperature the water equivalent may be calculated by means of the following formula : Let X= water equivalent of calorimeter shell and appendages. / = final temperature of water in calorimeter. /, = initial " " " -" } " ^ =. initial temperature of cold water added. W= weight of water in calorimeter at beginning of ex- periment. w = weight of cold water added. Then we have : (/, t) W+ (/, t)X = (tt^w, Or, The results of twenty-five determinations gives a mean of 489.97, or practically 490. Method of Making a Determination with Coal. About ten grams of coal to be tested is finely powdered and passed through a sieve having 10,000 meshes to the square inch. It is necessary that the coal be very fine or it will not burn com- pletely. The powdered sample is placed in a glass weighing tube and carefully weighed. The platinum wires and pan are attached to the cover of the shell and the iron wire helix placed in position. A sample of the coal is now poured into the pan from the weighing tube, its weight determined, care being taken to see that none is spilled and that the iron (9) 130 QUANTITATIVE ANALYSIS. wire helix passes through the coal. The cover is then placed on the shell and screwed down firmly. The shell is now con- nected with the oxygen cylinder, and the oxygen allowed to flow in until the gauge shows a pressure of about twenty-five atmospheres . The stop-cock is then closed and the shell placed in the calorimeter, which has been previously partially filled with about 2,400 grams of water. The thermometer and agitator are adjusted, and the whole well stirred to obtain a uniform tem- perature. The temperature is then observed, from minute to minute, for four or five minutes, so as to determine its rate of change. The charge is then ignited by connecting one pole of the battery to the electrode F, and touching the other pole to any part of the shell. The temperature is observed each minute until it begins to fall regularly, and then each minute for five minutes in order to ascertain the law of cooling. The agitator should be kept going constantly during the whole period of the observation. The shell is now removed from the water, the stop-cock R opened to let out the gas, and then the shell itself is opened. The shell should be rinsed out with distilled water to collect the acid formed during combustion. The amount of acid carried out with the escaping gas is negligible. The calo- rific power of the coal may now be calculated as follows : L,et Q = calorific power of the coal. 4 = observed rise of temperature. x = correction for radiation. P =. weight of water taken in grams. /* = water equivalent of shell, appendages, and gas. p = weight of nitric acid found. p' = weight of iron wire helix. 0.23 calorie = heat of formation of one gram of nitric acid. 1.6 calories = heat of combustion of one gram of iron. Then Q = (* + x] (/>+ P') - (o.2 3 / + i.6/') . Example Showing Method of Calculation. 1.042 gram of coal was taken. The calorimeter contained 2,276.6 grams of water. The water equivalent of apparatus = 490 grams. CALORIMETRY. 131 The pressure of oxygen =25 atmospheres. The law of variation of temperature in the calorimeter before combustion is expressed by X Q = O. The law of variation during subsequent period is X l 27.46 27.395 = 0.065 C. Hence, during the period of combustion the system lost 0.065 degree by radiation. The apparent variation of temperature is 27.460 24.855 = 2.605 C. Actual variation = 2.605 + 0.065 = 2.67 C. The nitric acid formed = 0.15 gram. And the weight of iron wire = 0.025 gram. Hence, heat of formation of nitric acid = 0.15 X 0.23 = 0.0345 calorie, and heat of combustion of wire = 0.025 X 1.6 = 0.04 calorie. Heat of combustion of coal = 2.67 X (2, 276.6 + 490), = 7,386.8 calories. 7,386.6 (0.0345 + 0.04) = 7,386.72 " -r- 1.042 = 7,088.9 " 7088.9 calories per kilo. = 12760. B. T. U. per pound of coal. To show the accuracy with which this calorimeter works, five samples of willow charcoal were burned, with the following re- sults : Average of five determinations 7973 calories per kilo. Highest determination 7975 " " " Lowest determination 797 1 " " " Five determinations of a sample of bituminous coal from Cole- man County, Texas, gave as follows : Average of five determinations 6766.0 calories per kilo. Highest determination 6793.6 " " " Lowest determination 6720.3 " " " References. " On the Berthelot-Mahler Calorimeter for the Calorific Power of Fuels." Prof. A. M. Mayer. Steven? Indicator, April, 1895, p. 133-148. " Zur Werthbestimmung der Brennstoffe." (Verfahren und Calorime- ter von Mahler, Bunte, Fischer, Scheurer-Kestner), Stahl und Risen, 13, 52- Determination industrielle du pouvoir calorifique des combustibles. Mahler. La Sucrerie Indigene, 41, 443. 132 QUANTITATIVE ANALYSIS. THE THOMPSON CALORIMETER. This instrument, in general use in England for calorimetric determinations of solid fuels, is shown in Fig. 36. Fig. 36. Thompson Calorimeter. The water equivalent (theoretical) of the calorimeter is found by weighing each part carefully and multiplying by its specific heat. Thus: Weight. Part of glass cylinder in ) contact with the water / ^ Glass bell jar 75. 381 Brass base 99-853 Four copper disks 65. 100 Brass over top of bell jar. 21.307 Copper tube 30.800 Rubber cork 1-578 Rubber tube 1-784 Platinum crucible ....... 15.111 Mercury of thermometer. 9.583 Glass of thermometer .... 7.350 Specific heat. Water equivalent. grams X 0.19768= 182.245 X 0.19 = X 0.09391 = X 0.09515 = X 0.09391 = X 0.09512 = X 0.331 = X 0.33 [ = X 0.324 = X 0.333 = X 0.19 = I4-3I3 9-377 6.294 2.OOI 2.930 0-552 Q-59 1 0.490 0.319 1.396 Total 220.478 THE THOMPSON CALORIMETER. 133 This theoretical water equivalent should be checked by a de- termination by direct experiment, as follows : The calorimeter is taken and adjusted under the conditions of use. 2000 grams of distilled water are weighed out and the temper- ature taken : call this temperature t. Let /, = temperature of the apparatus. The 2000 grams of water are poured into the glass cylinder ab, Fig. 36, the other parts c, d, g, h, etc., placed in position in- side the cylinder, and the water kept well stirred by means of the discs K. K. on the side of the bell jar. After agitating it about fifteen minutes (about the time re- quired for a coal combustion) the temperature is taken ; this temperature call / . To correct for radiation it is necessary to continue this operation for an equal period of time, calling the last temperature c, from which we obtain the fall of temperature to be (4 c] =. r. Expressing this in a formula 2000 (t (/ + r} . \~^j = water equivalent r being the fall of temperature due to radiation. Thus: Temperature of apparatus = 14.6 C. " water = 19.5 C. Final " " " = 18.65 C. Correction (18.65 18.3) = 0.35. 2000(19.5 19.0) = 227>22 19 14.6 By calculation the water equivalent is 220.47. " experiment " " " " 227.22. The combustion with a sample of coal is performed as follows : An incandescent paper (about one mm. long) is dropped into the crucible (/) containing one gram of the very finely pulver- ized coal, the oxygen supply being slowly turned on and the in- verted bell jar (/) containing the crucible (/) is gently lowered into the 2000 grams of water contained in the glass cylinder (ad) . The combustion will be quite active : the gaseous products will bubble through the water and give up their sensible heat. After the fuel has been consumed the supply of oxygen is stopped and the glass tube c is opened, permitting the water to 134 QUANTITATIVE ANALYSIS. enter the bell jar and flow into and submerge the crucible so that the whole of the apparatus and water is raised to a uniform temperature. It will be noted that the coal burns gently at first. The oxy- gen introducing pipe (g li) should not be projected too low into the bell jar until the volatile hydrocarbons are consumed ; the residual fixed carbon is more difficult to burn. The oxygen supply tube should consequently be projected so as to deliver the oxygen immediately over the platinum cruci- ble, and to more effectually burn the fuel, the tube may be slightly rotated. Great care must be taken in reading the thermometer before and after the gram of coal is burned : the difference of these two readings gives the rise in temperature for the amount of coal taken, which when multiplied by 2000 plus the water equivalent of the calorimeter, gives the heating power of the coal. But since heat is being radiated to the air during the experi- ment, a correction must be made. To determine this, it is necessary to note the time required to burn the coal, and then agitate the apparatus for a corresponding period. During this last agitation the temperature will fall somewhat ; this fall, di- vided by two, will give tho proper correction. The figure obtained is an average of the whole radiation : should the fall be taken direct, it would give the correction for radiation when the water is at its maximum temperature. The following is the analysis of a sample of coal, the theoretical heating power calculated from the analysis, and calorimetric de- termination of the coal by means of the Thompson calorimeter, and a comparison of the number of calories per kilo derived by calculation and by direct experiment. Analysis : Carbon 84.80 per cent. Hydrogen 2.42 Sulphur 0.62 Nitrogen 0.93 Moisture 1.03 Oxygen 3.19 Ash 7.01 Total 100.00 THE BARRUS COAL CALORIMETER. 135 the theoretical heating value being : (8140 X 84.8) + (34500 X 2.42 0.4) + 2220 X 0.62 ~^o~ ' = calories per kilo of coal. The test of the coal by the Thompson calorimeter gave as fol- lows : Amount of coal taken = 0.445 gram. Temperature of water and apparatus (initial) J^.gs C. Maximum temperature " " 20.45 C. Final temperature (used for correction of radiation) 20.40 C. Correction for radiation j 2o -45 20.40 _ O-O25 o c Rise in temperature for 0.445 gram = 1.525 C. " " " " i.ooo " = 3.43 C. 2227 X 3.43 = 7638.6 calories per kilo of coal. THE BARRUS COAL CALORIMETER. 1 The complete apparatus is shown in the accompanying figure (37). The calorimeter itself consists of a glass vessel five inches in diameter, nine and a half inches high, which holds the water of the calorimeter. Submerged in the interior is a bell- shaped glass vessel two and a half inches in diameter, four inches high, having a long neck three-fourth of an inch in diameter, which is closed at the top with a stopper. The upper end of the neck stands five inches above the top of the outside vessel. The glass bell, or "combustion chamber," as it may be termed, rests upon a metal base, to which it is held by means of spring clips, the bottom of the chamber being pro- vided with an exterior rib by means of which the clips are made fast. The base is perforated, and at the center is mounted a short tube, for the reception of a crucible in which the combus- tion takes place. The crucible is made of platinum. It is sur- rounded by a layer of non-conducting material, which is placed between it and the outer metal. A small glass tube is inserted in the stopper at the top of the neck, and this is carried down to the interior of the combustion chamber. It is fitted somewhat loosely, so that a slight pressure will move it up or down, and thereby adjust its lower end to any height desired above the crucible. The tube has a slight lateral movement also, so that 1 Transactions American Society Mechanical Engineers, 14, 816. THE BARRUS COAI, CALORIMETER. 137 it may be directed, at the will of the operator, toward any part of the crucible. This tube is connected with a tank containing oxygen gas, and through it a current of gas is passed, so as to enable the combustion of the coal to be carried on under water. The pressure of the gas drives out the water which would otherwise fill the chamber, and keeps its level between the base. The products of combustion rising from the crucible pass down- ward through the perforations in the base, escaping around the edge of the base, and finally bubbling up through the water and emerging at its surface. A wire screen is secured to the neck of the combustion chamber, extending to the sides of the outer vessel, thereby holding back the gas and preventing its imme- diate escape to the surface of the water. In making the test the quantity of water used is 2000 grams and the quantity of coal one gram. The equivalent colorific value of the material of the instrument is 185 milligrams (0.185 gram). One degree rise of temperature of the water corresponds, therefore, to a total heat of combustion of 2185 B. T. U. The number of degrees rise of temperature for ordinary coals varies from 5.5 to 6.5 F. The thermometer used for determining the temperature of the water is graduated to twentieths of a degree ; and as the divi- sions are about one-thirtieth of an inch apart, they may be sub- divided by the eye so as to readily obtain a reading to hun- dredths of a degree. . The scales shown at the extreme left of the cut are used for weighing out the water, and the chemical scales shown in the center are employed in weighing the coal and ash. The process of making a test is as follows : Having dried and pulverized the coal, and weighed out the desired quantities of coal and water, the combustion chamber is immersed in the water for a short time, so as to make the tem- perature of the whole instrument uniform with that of the water. On its removal the initial temperature of the water is observed, the top of the chamber lifted, the gas turned on, and the coal quickly lighted, a small paper fuse having been previously in- 138 QUANTITATIVE ANALYSIS. serted in the crucible for this purpose. The top of the combus- tion chamber is quickly replaced, and the whole returned to its submerged position in the water. The combustion is carefully watched as the process goes on, and the current of oxygen is directed in such a way as to secure the desired rate and condi- tions for satisfactory combustion. When the coal is entirely consumed, the interior chamber is moved up and down in the water until the temperature of the whole has become uniform, and finally it is withdrawn and the crucible removed. The final temperature of the water is observed, and the weight of the re- sulting ash. The initial temperature of the water is so fixed by suitably mixing warm and cold water that it stands at the same number of degrees below T the temperature of the surrounding atmosphere (or approximately the same) as it is raised at the end of the process above the temperature of the air. In this way the effect of radiation from the apparatus is overcome so that no provision in the matter of insulation is required, and no allowance needs to be made for its effect. RESULTS OF TESTS WITH THE BARRUS COAL CALORIMETER. Cumberland Coals. Number for reference. Kind of coal : Mine or locality Percentage of asn. Ij ** 3 g H u I 2 3 4 5 6 I 9 10 ii 12 13 14 15 16 17 7 .6 8.2 6.1 6.6 8.6 6-5 7.0 5-0 5-i 5-7 6.1 5-i 7-5 5-i 5-4 8. 4-4 13,868 1 14,058 14,217 13,925 12,874 12,921 13,360 13,487 13,656 13,424 13,534 13,745 13,617 13,653 13,427 12,973 13,923 5. 1 \ 1 J. < ' ' (Md Coal Co ).. .. (G. C. Coal and Iron Co.) T^llTptfl CARPENTER'S COAL CALORIMETER. Fischer's calorimeter, while somewhat more complex than the Mahler or Thompson's, is an accurate instrument for the deter- mination of the heating power of fuels. Consult Chemische Technologic der Brennstqffe, von Dr. Ferdinand Fischer, p. 401- CARPENTER'S COAL CALORIMETER. R. C. Carpenter 1 has devised a calorimeter for the determina- tion of the heating power of coals, which is thus described. The general appearance of the instrument is shown in Fig. 38, a sec- tional view of the interior is shown in Fig. 39, from which it is 37 Fig. 38. Fig. 39. seen that, in principle, the instrument is a large thermometer, in the bulb of which combustion takes place, the heat being ab- sorbed by the liquid which is within the bulb. The rise in tem- perature is denoted by the height to which a column of liquid rises in the attached glass tube. In construction, Fig. 39, the instrument consists of a chamber, 1 Transactions Amer. Society of Mechanical Engineers, Vol. XVI, (June, 1895.) 140 QUANTITATIVE ANALYSIS. No. 15, which has a removable bottom, shown in section in Fig. 39 and in perspective in Fig. 40. The chamber is supplied with oxygen for combustion through tube, 23, 24, 25, the prod- ucts of combustion being discharged through a spiral tube, 29, 28, 30. Surrounding the combustion chamber is a larger closed cham- ber, i, Fig. 38, filled with water, and connecting with an open glass tube, 9 and 10. Above the water chamber, i, is a dia- phragm, 12, which can be placed in position by screw, 14, so as to adjust the zero level in the open glass tube at any desired point. A glass for observing the process of combustion is in- serted at 33 in top of the combustion chamber, and also at 34 in top of the water chamber, and at 36 in top of outer case. This instrument readily slips into an outside case, which is nickel plated and polished on the inside, so as to reduce radia- tion as much as possible. The instrument is supported on strips of felting, 5 and 6, Fig. 39. A funnel for filling is provided at 37, which can also be used for emptying, if desired. The plug which stops up the bottom of the combustion cham- ber carries a dish, 22, in which the fuel for combustion is placed ; also two wires passing through tubes of vulcanized fiber, which are adjustable in a vertical direction and connected with a thin platinum wire at the ends. These wires are connected to an electric current and used for firing the fuel. On the top part of the plug is placed a silver mirror, 38, to deflect any radiant heat. Through the center of this plug passes a tube, 25, through which the oxygen passes to supply combustion. The plug is made with alternate layers of rubber and asbestos fiber, the out- side only being of metal, which, being in contact with the wall of the water chamber, can transfer little or no heat to the out- side. The discharge gases pass through a long coil of copper pipe, and are discharged through a very fine orifice in a cap at 30. The instrument has been so designed that the combustion can take place in oxygen gas having considerable pressure, but in pressure it has been found that very excellent results have been obtained with pressures of two to five pounds per square CARPENTER'S COAL CALORIMETER. 141 inch, and these having been commonly used in the determinations. Two instruments have been built at the pres- ent time, which differ from each other some- what in detail, but principally in dimensions. The first instrument held about one pound of water, and was intended for use with about one gram of coal. In that instrument the entire bottom of the water chamber was removable and the whole of the combustion chamber. This form, while giving fully as good results as the one described, was more likely to leak, and, consequently, was difficult to keep in good con- dition. The first form built employed an ad- justing piston to regulate the initial heading of the water column, which, possibly, may have been as good as the diaphragm used at pres- ent. The instrument described, which is of later design, holds about five pounds of water, and is large enough for the consumption of two grams of coal. Full details for manipulation of the apparatus are given in Trans. Amer. Society Mechanical Engineers, Vol. XVI, (1895). Fig. 4 o. References. " Uber die Bestimmung des Heizwerthes der festen Brenn- materialien und Bericht iiber die wichtigere neure Ivitteratur dieses Gebietes ;" von Knorre, Die Chemische Industrie, 17, 93. " Etude sur les combustibles et la combustion," Vivien, La Sucrarie indigene, 44, 261. Determination of the heating power of coal by the use of large amounts of coal either (a) in specially constructed apparatus for the same, or (b) under boilers in actual practice. Apparatus for determining the heating value of Fuel, by Win. Kent, M.E., (Fig. 41). Its principal feature is that it is not a steam boiler but a water heater. It consists of two sheet-metal cylinders, each twelve feet long, the upper one four feet in diameter and the lower one three feet, and connected by a short neck at one end only. 142 QUANTITATIVE ANALYSIS. The upper cylinder is provided with a fire-box three and a half feet in diameter and six feet long, and its rear end is filled with about 100 two-inch tubes. The lower cylinder is com- g-a 3 S. ** u o M< *- > +> i ' !*.V f 11 _e S ^ > O ! I SrH O Hi | S? -M 1 5 pletely filled with two-inch tubes. The fire-box is lined through- out with fire-brick, and contains a grate surface two feet wide by two and a half feet long. A hanging bridge- wall of fire- brick is placed in the upper part of the fire-box in the rear of HEATING VALUE OF FUELS. 143 the bridge-wall proper, for the double purpose of presenting a hot fire-brick surface to the flame before allowing it to touch the heating surfaces of the tubes and tube-sheet, and of changing its direction so as to cause the gases to thoroughly commingle, and thus to insure complete combustion. In testing highly bituminous coals, it might be advisable to have more than one of these hanging walls, and to give the fire-box a greater length, to more certainly insure complete combustion of the gases. The gases of combustion pass through the tubes of the upper heater, then down through a fire-brick connection into the tubes in the lower heater, after leaving which they pass into the chimney. Air is fed to the fire, under the grate-bars, through a pipe lead- ing from a fan- blower. The air is measured by recording the revolutions of the blower, and the measurement is checked by an anemometer in the air-pipe. Its weight should be calculated from the barometric pressure, and its contained moisture should also be determined. Its temperature should be taken before it enters the ash-pit. The temperature of the escaping gases should be taken by sev- eral thermometers, the bulbs of which reach to different por- tions of the chimney connection. Cold water is supplied to the bottom of the lower heater, at the chimney end, its temperature being taken before it enters by a thermometer inserted in the pipe. The water supply pipe may be conveniently attached to the city main. The water passes through the two heaters in an opposite direction to that of the gases of combustion, and escapes at the outlet pipe at the top of the upper heater by which it is taken to two measuring tanks, which are alternately filled and emptied. The temperature of the outflowing water is taken by a thermometer inserted in the overflow pipe. The rate of flow of water through the apparatus is regulated so that the temperature of the outflowing water does not exceed 200 F. The measuring tanks have closed tops, which prevent evapora- tion, small outlet pipes being attached to the top of each, which serve both as indicators when the tanks are full, and to allow air to escape from the tank when it is being filled with water. The grate surface being only five square feet and the heating 144 QUANTITATIVE ANALYSIS. surface about 1000 square feet, the ratio of 200 to i, or more than five times the usual proportion in a steam boiler, and the water being much colder than that in a steam boiler, the gases of combustion should be cooled down to near the temperature of the air supplied to the fire, especially when, as is usually the case, the water supply is colder than the air. For extremely accurate tests, the water might be cooled before entering by a refrigerating apparatus or by ice. The whole apparatus being thoroughly protected by felting from radiation, the heat generated by the fuel is all measured in the increase of heat given to the water which flows through the apparatus, and in the increase of temperature of the gases of combustion as taken in the chimney, over the temperature of the air supplied to the fire. This increase, however, being in any case very slight, and the quantity of air being known, the amount of heat from the fuel which escapes up the chimney can be calculated with but small chances of error. Boiler Test. RESUME OF TESTS UPON BABCOCK & WILCOX BOILERS.* 8 re ,j l til 1 *&* Name of coal. Anthracite 1 tonfpa. Semt bitum . CS rt 6o> I2 ' 42 448 Jackson, O., nut 8 48.0 3358 9.6 32.1 4.11 8.93 9.88 262 460 Castle Shan'n | Pa. f nut. f > 42^ 69.1 4784 10.5 27.9 4.13 10.00 11.17 416 570 lump. J Cardiff, lump .. 6f 21.2 1564 11.7 26.7 3.69 10.07 H-4O 136 189 1 Trans. Amer. Soc. Mechan. Engineers, 4, 267. 2 The term "per pound of combustible" represents one pound of the heating con- stituents of the coal, viz. : ashes and moisture taken out. BOILER TEST. 145 APPROXIMATE HEATING VAI.UE OF COALS. (KENT.) I-< g E/*^ *S"a w " E.^* ~- 8 * IB " "2 a-'O w >e n * >> o >^ - ^ a mbustible matter in the boiler furnace. If a boiler efficiency sixty-five per cent, could be obtained, then the evaporation r pound of coal from and at 212 F. would be 14.42 X 0.65 = 1.37 pounds. (10) 146 QUANTITATIVE ANALYSIS. With best anthracite coal, in which the combustible portion is, say ninety- seven per cent, fixed carbon and three per cent, volatile matter, the highest result that can be expected in a boiler test with all conditions favorable, is 12.2 pounds of water evaporated from and at 212 F. per pound of combustible, which is eighty per cent, of 15.28 pounds, the theoretical heating power. With the best semi-bituminous coals, such as Cumberland and Pocahoutas, in which the fixed carbon is eighty per cent, of the total combustible, 12.5 pounds, or seventy-six per cent, of the theoretical 16.4 pounds may be obtained. For Pittsburgh coal, with fixed carbon ratio of sixty-eight per cent., eleven pounds, or sixty-nine per cent, of the theoretical 16.03 pounds, is about the best practically obtainable with the best boilers. With some good Ohio coals, with a fixed carbon ratio of sixty per cent., ten pounds, or sixty-six per cent, of the theoretical 15.9 pounds has been obtained under favorable conditions, with a fire-brick arch over the furnace with coals mined west of Ohio; with lower carbon ratios, the boiler efficiency is not apt to be as high as sixty per cent. From these figures a table of probable maximum boiler test results from coals of different fixed carbon ratios may be con- structed as follows : Fixed carbon ratio 97.0 80.0 68.0 60.0 54.0 50.0 Evaporated from and at 212 F. per pound combustible, maximum in boil- er tests 15.1 Boiler efficiency, per cent 80.0 Loss, chimney radiation, imperfect com- bustion, etc 20.0 The difference between the loss of twenty per cent, with an- thracite and the greater losses with the other coals is chiefly due to imperfect combustion of the bituminous coals, the more highly volatile coals sending up the chimney the greater quantity of smoke and unburned hydrocarbon gases. It is a measure of the inefficiency of the boiler furnace and of the inefficiency of heat- ing surface caused by the deposition of soot, the latter being primarily caused by the imperfection of the ordinary furnace 12.5 76.0 n.o 69.0 10.0 66.0 8-3 60.0 7.0 55-o 24.0 31.0 34.0 40.0 45.0 BOILER TEST. 147 and its unsuitability to the proper burning of bituminous coal. If in a boiler test with an ordinary furnace lower results are ob- tained than those in the above table, it is an indication of unfavorable conditions, such as bad firing, wrong proportions of boiler, defective draft, and the like, which are remediable. Higher results can be expected only with gas producers, or other styles of furnace especially designed for smokeless combus- tion. The efficiency of a boiler is the percentage of the total heat generated by the combustion of the fuel, which is utilized in heating the water and in generating steam. With anthracite coal the heating value of the combustible portion is very nearly 14500 " B. T. U." per pound, equal to an evaporation from and at 212 F. of 14500 -r- 966 = fifteen pounds of water. A boiler which when treated with anthracite coal shows an evaporation of twelve pounds of water per pound of combustible has an effi- ciency of 12 -7- 15 = 80 per cent., a figure which is approximate, but scarcely ever quite reached in the best practice. With bituminous coal it is necessary to have a determination of its heating power made by a coal calorimeter before the effi- ciency of the boiler using it can be determined, but a close esti- mate may be made from the chemical analysis of the coal. The difference between the efficiency obtained by the test and loo per cent, is the sum of the numerous wastes of heat, the chief of which is the necessary loss due to the temperature of the chimney gases. If we have an analysis and a calorimetric determination of the heating power of the coal, and an average analysis of the chimney gases, the amounts of the several losses may be determined with approximate accuracy by the method described below. Data given : i. ANALYSIS OF THE COAL. CUM- 2. ANALYSIS OF THE DRY CHIMNEY BERLAND SEMI-BlTUMINOUS. GAS BY WEIGHT. Carbon 80.55 per cent. c. o. N. Hydrogen 4.50 Oxygen 2.70 Nitrogen 1.08 Moisture 2.92 C0 2 13.6 3.71 9.89 CO 0.2 0.09 o.ii .... O II. 2 11.20 N 75-0 75-0 Ash 8.25 Total loo.o 3.80 21. 20 75.0 IOO.OO " 148 QUANTITATIVE ANALYSIS. The gases being collected over water, the moisture in them is not determined. Heating value by Dulong's formula = 14243 heat units. 3. Ash and refuse as determined by boiler test 10.25 per cent, or two per cent, more than that found by analysis, the difference representing carbon in the ashes obtained in the boiler test. 4. Temperature of external atmosphere 60 F. 5. Relative humidity of air, sixty per cent, corresponding to 0.007 pound of vapor in each pound of air. 6. Temperature of chimney gases = 560 F. Calculated results : The carbon in the chimney gases being three and eight- tenths per cent, of their weight, the total weight of dry gases per pound of carbon burned is 100 -7- 3.8 = 26.32 pounds. Since the carbon burned is 80.55 2 - = 7 8 -55 P er cent, of the weight of the coal, the weight of the dry gases per pound of coal is 26.32 X 78.55-^-100 = 20.67 pounds. Each pound of coal furnishes to the dry chimney gases 0.7825 pound C., 0.0108 N, and ( 2.70 - ~-~- j -f- 100 = 0.0214 pound O ; a total of 0.8177 or 0.82 pounds. This subtracted from 20.67 pounds leaves 19.85 pounds as the quantity of dry air (not including moisture) which enters the furnace per pound of coal, not counting the air required to burn the available hydrogen, that is, the hydrogen minus one-eight of the oxygen chemically combined in the coal. Each pound of coal burned contained 0.045 pound of hydro- gen, which requires 0.045 X 8 = 0.36 pound O for its combus- tion. Of this 0.027 pound is furnished by the coal itself, leav- ing 0.333 pound to come from the air. The quantity of air needed to supply this oxygen (air containing twenty-three per cent, by weight of O) is 0.333 ~i~ - 2 3 = l -45 pounds, which added to the 19.85 pounds already found gives 21.30 pounds as the quantity of dry air supplied to the furnace per pound of coal burned. The air carried in as vapor, 0.0071 pound for each pound of dry air, or 21.3 X 0.0071 = 0.15 pound for each pound of coal. Each pound of coal contained 0.029 pound of moisture, which was evaporated and carried into the chimney gases. The BOILER TEST. 149 0.045 pound of hydrogen per pound of coal when burned formed 0.045 X 9 = 0.405 pound of water. From the analysis of the chimney gas it appears that 0.09 4- 3.80 = 2.37 per cent, of the carbon of the coal was burned to carbon monoxide instead of carbon dioxide. We now have the data for calculating the various losses of heat, as follows, for each pound of coal burned : Heat units. 21. 3 pounds dry air X (560 60 F.) X sp. heat 0.238 2534.7 0.15 pound vapor in air X (560 60) X sp. heat 0.48 36.0 0.029 pound moisture in coal heated from 60 to 212 F. 4.4 " " evaporated from and at 212 ; 0.029 X 966 28.0 " " steam (heated from 212 F. to 560) X 348 X 0.48 4.7 0.405 pounds water from H in coal X (560 60) X 0.48 97.2 0.0237 pound carbon burned to carbon monoxide, loss by incomplete combustion, 0.0237 X (14544 4450 239.2 0.02 pound coal lost in ashes ; 0.02 X 14544 290.9 Radiation and unaccounted for by difference 712.1 3947-8 Utilized in making steam, equivalent evaporation 10.66 pounds from and at 212 per pound of coal 10295.7 Per cent. of heat value of the coal. 17.80 0.25 0.03 0.20 0.03 0.68 1.68 2.04 5.00 27.71 72.29 14243.0 100.00 The heat lost by radiation from the boiler and furnace is not easily determined directly, especially if the boiler is enclosed in brick work, or is protected by non-conducting covering. It is customary to estimate the heat lost by radiation by difference, that is, to charge radiation with all the heat lost which is not otherwise accounted for. One method of determining the loss by radiation is to block off a portion of the grate surface and build a small fire in the remainder, and drive this fire with just enough draught to keep up the steam pressure and supply the heat lost by radiation without allowing any steam to be discharged, weighing the coal consumed for this purpose during a test of _ several hours dura- tion. 150 QUANTITATIVE ANALYSIS. Estimates of radiation by difference are apt to be greatly in error, as in this difference are accumulated all the errors of the analyses of the coal and of the gases. An average value of the heat lost by radiation from a boiler set in brick work is about four per cent. ; when several boilers are in a battery and enclosed in a boiler house the loss by radiation may be very much less, since much of the heat radiated from the boiler is returned to it in the air supplied to the furnace, which is taken from the boiler room. An important source of error in making a "heat balance,'' such as the one given above, especially when highly bituminous coal is used, may be due to the non-combustion of part of the hydrocarbon gases distilled from the cold immediately after fir- ing, when the temperature of the furnace may be reduced below the point of ignition of the gases. Each pound of hydrogen which escapes burning is equivalent to a loss of heat in the fur- nace of 62500 B. T. U. XVII. The Determination of Sulphur in Steel and Cast Iron. Of the various methods described for this purpose, the follow- ing three are selected as giving the best results in general practice : (a). Bromine method. (). Aqua Regia method. (c). Potassium permanganate method. a. Bromine Method. Dilute hydrochloric acid is allowed to act upon the steel or iron ; the sulphur is expelled as hydrogen sulphide and is oxidized by the bromine to sulphuric acid. This latter is precipitated by barium chloride as barium sul- phate, filtered, washed and weighed as such, then calculated to sulphur. The apparatus used is as follows : ,In the flask A, capacity about 400 cc., is placed the steel or iron (five grams of steel or three grams of cast iron), and con- nection made with the absorption apparatus D? In the latter, 1 All stoppers are of glass. SULPHUR IN STEEL AND CAST IRON. 151 at E, is placed five drops of bromine and twenty-five cc. of hy- drochloric acid (sp. gr. 1.18). Seventy-five cc. of hydrochloric acid (sp. gr. 1.12), is placed in the delivery funnel B and about ten cc. allowed to run into the flask. The action is quite often violent, and care must be exercised that small amounts of acid only be admitted at a time from B until all action of the acid upon the steel or iron ceases. Heat is now gently applied, and contents of the flask brought to boiling ; continue the boiling two or three minutes ; remove Fig. 42. the heat, connect the delivery tube B with a " Bennert drying apparatus," and connect the absorbent apparatus with an aspi- rator. Gradually aspirate about one liter of the air through the asparatus. Between the aspirator and the absorbent apparatus there should be placed a wash bottle containing dilute ammonium hy- droxide, (250 cc. strong ammonia to 600 cc. water), to absorb any fumes of bromine that may pass out of the absorbent appa- 152 QUANTITATIVE ANALYSIS. ratus during aspiration. Transfer the liquid in the absorbent tube to a No. 3 beaker, washing the tubes with water and add the washings to solution in beaker. Bring to boil, expel any excess of bromine, add solution of barium chloride and set aside twelve hours. Filter upon two No. 3 ashless filters, wash with hot water, dry, ignite, and weigh as barium sulphate and calculate to sulphur. b. Aqua Regia Method. Five grams of the iron or steel (in fine turnings) are trans- ferred to a No. 4 beaker and the latter covered with a watch- glass. Introduce into the beaker (in quantities not exceeding ten cc. each time) some nitric acid, until the iron or steel is dis- solved. Warm gently and evaporate to dry ness on an iron plate, adding some sodium carbonate previously, so that no sulphuric acid may be lost by vaporization. Allow to cool, treat with hydrochloric acid, warm until solu- tion of iron is complete and filter off the silica. Wash well and to the filtrate containing the washings add a few cc. of solution of barium chloride, and set aside twelve hours. Filter, wash with hot dilute hydrochloric acid, then with water thoroughly ; dry, ignite, weigh as barium sulphate and calculate to sulphur. This method is preferred where the iron or steel contains any metals (even in minute amounts) that are precipitated by hydro- gen sulphide. Thus the presence of one-fourth percent, of cop- per would render the bromine or permanganate process unrelia- ble since hydrogen sulphide is generated, forming copper sul- phide, and the resulting amount of sulphur would be too low. In the ' ' aqua regia method ' ' the oxidation is performed at once upon the addition of the nitric acid, no hydrogen sulphide being formed. c. The Potassium Permanganate Method? a is a flask holding 300 cc., with pure rubber stopper, through the latter passing a thistle tube with stop-cock for the delivery of the acid, as required. Fig. 43. b is a flask with rubber stopper. The glass tubing must not reach below the neck of the flask. This flask should be large 1 Trans. Amer. Inst. Mining Engineers, a, 224. SULPHUR IN STEEL AND CAST IRON. 153 enough to hold the contents of the bottles in case back-suction should occur. The bottles c, d, and e contain a solution of potassium per- manganate, five grams potassium permanganate to 1000 cc. water, and are filled to the amount shown in the figure (about twenty-five cc. each) . / contains an ammoniacal solution of silver, and is used to 154 QUANTITATIVE ANALYSIS. test whether the hydrogen sulphide is all oxidized by the perman- ganate ; if not oxidized, the solution in / becomes black from the silver sulphide formed. The process is as follows : Three grams of cast iron or six grams of steel are placed in flask a and hydrochloric acid (sp. gr. 1.12) gradually added until seventy-five cc. have been used. Warm contents of the flask, observing that the evolution of gas is not too rapid. When the iron or steel is dissolved, bring the liquid to boil- ing, connect bottle f with an aspirator and slowly draw air through the apparatus ten minutes. Transfer contents of bottles c, d, e, to a No. 3 beaker, dissolv- ing any oxide of manganese that may have deposited in bottles with hydrochloric acid. Wash the bottles with hydrochloric acid, then with water, adding the washings to contents of the beaker. The solution in the beaker is warmed and enough hydro- chloric acid added that it becomes colorless or nearly so, and barium chloride added in sufficient quantity to precipitate the sulphuric acid. Allow to settle twelve hours. Filter upon two No. 2 ashless filters, wash with boiling water, dry, ignite, weigh as barium sulphate and calculate to sulphur. Great care must be exercised in this process, that the potas- sium permanganate is free from sulphurous or sulphuric acid before use. The iodine method for the determination of sulphur in pig iron and steel, as used by the chemists of the Duquesne Steel Works, is as follows : Five grams pig iron or steel are weighed off into a dry 500 cc. flask, provided with a double perforated rubber stopper, with a long stem four ounce funnel tube with a stop-cock, and a delivery tube bent at right angles, on which a short piece of one-quarter inch rubber tubing is placed, making connection with a delivery tube, also bent at right angles reaching to the bottom of a one inch by ten inch test tube, suitably supported. About ten cc. of the ammoniacal solution of cadmium chloride is introduced into the test tube, which is diluted with cold water, 1 J. M. Camp : Proceedings Engineers Society of Western Pa., n, 251, 1895. SULPHUR IN STEEL AND CAST IRON. 155 until the tube is about two-thirds full. Eighty cc. of dilute hy- drochloric acid one acid to two water is poured into the fun- nel tube, a file marked on the bulb indicating this amount, which is allowed to run into the flask, the stop-cock is then closed, and a gentle heat applied, till the drillings are all in solution, and finally to boiling by raising the heat, until noth- ing but the steam escapes from the delivery tube. The apparatus is then disconnected, and the delivery tube is placed in a No. 4 beaker in which the titrations are made, the contents of the test tube are then poured into the beaker, the test tube filled to the top twice with cold water, the sides of the tube rinsed down with about twenty-five cc. dilute hydrochloric acid and filled again with cold water. The total volume of the solution equaling about 400 cc., both acid and water being sup- >lied from overhead aspirator bottles and suitable rubber con- lections with pinch cocks ; the delivery tube is now rinsed off inside and out with dilute hydrochloric acid, and about five cc. starch solution added to the beaker. Without waiting for complete solution of the cadmium sul- >hide, the iodine solution is run in from a burette, stirring gen- ly, till a blue color is obtained, the solution is then stirred vig- rously, keeping a blue color by fresh additions of the iodine solution, till the precipitate of cadmium sulphide is all dissolved, and the proper permanent blue color is obtained. The amount )f iodine solution used in cc. is hundredths per cent, sulphur. Iodine solution is made by weighing off into a dry 500 cc. flask about thirty-five grams potassium iodide, and sixteen grams iodine, fifty cc. water added and shaken and diluted cautiously until all are in solution, and finally diluted to 3500 cc. This is standardized with steels of known sulphur contents, so that one cc. equals 0.0005 grams sulphur. Cadmium chloride solution is made by dissolving 100 grams cadmium chloride in one liter water, 'adding 500 cc. strong am- monia, and filtering into an eight liter bottle; two liters of water are now added, and the bottle filled to the eight liter mark with strong ammonia. Starch solution is made by adding to one-half gallon boiling water, in a gallon flask, about twenty-five grams pure wheat 156 QUANTITATIVE ANALYSIS. starch, previously stirred up into a thin paste with cold water; this is boiled ten minutes and about twenty-five grams pure granulated zinc chloride dissolved in water added, and the solu- tion diluted with cold water to the gallon mark. The solution is mixed and set aside over night to settle, the clear solution is decanted into a glass stoppered bottle for use. This solution will keep indefinitely. References : " Volumetric Method of Elliott," Chem. News, 23, 61. " Wiborgh's Colorimetric Method,"/. Anal. Chem., 6, 301. " Sulphur Determinations in Iron and Steel," by different methods. By L. S. Clynier, /. Anal. Chem., 4, 318. " Cadmium Chloride as an Absorbent of Hydrogen Sulphide"(Sulphur in Iron and Steel). By Frank L. Crobaugh,/. Anal. Chem., 7, 280. " The Reduction of Barium Sulphate to Sulphide on Ignition with Fil- ter Paper." By C. W. Marsh,/. Anal. Chem., 3, 2. " Duplicate Determinations of Sulphur in Iron and Steel Should Agree within 0.005 Per Cent." By C. B. Dudley,/. Am. Chem. Soc., 15, 514. " The Determination of Sulphur in Iron and Steel. By L,. Archbutt, F.I.C.,/. Soc. Chem. Industry, 4, 75. XVIII. Determination of Silicon in Iron and Steel. Five grams of steel or three grams of pig iron in fine borings, are transferred to a No. 3 beaker 1 and fifty cc. of dilute sulphuric acid added. When the action of the acid ceases and the iron is dissolved, twenty-five cc. nitric acid (sp. gr. 1.20) is cautiously added until effervescence ceases. Apply heat and evaporate until white fumes of sulphur triox- ide appear ; allow to cool ; add strong hydrochloric acid until the residue is thoroughly saturated with it, then add seventy- cc. boiling water. Filter, wash with dilute hydrochloric acid, then with hot water, dry, ignite, weigh as silicon dioxide and calculate to silicon. This method must be used in the determination of silicon in pig iron, but in wrought iron and steel the insoluble residue in the determination of phosphorus may be used for the silicon, if desired. 1 Porcelain beakers are to be preferred to glass beakers for this determination. CARBON IN IRON AND STEEL. 157 In all determinations of this element, the ignited and weighed silicon dioxide must be white in color and a fine non-coherent powder. References : "Irregular Distribution of Silicon in Pig Iron. 1 ' By J. W. Thomas, /. Anal. Chem., 2, 148. "Silicon in Pig Iron." By Clemens Jones,/. Anal. Chem., 3, 121. "The Influence of Silicon on the Determination of Phosphorus in Iron." By Thomas M. Drown,/. Anal. Chem., 3, 288. " Notes on Silicon in Foundry Pig Iron. By David H. Brown,/. Anal. Chem., 6, 452-467. XIX. The Determination of Carbon in Iron and Steel. The determination of carbon in iron and steel has probably received more attention in later years from chemists than any other subject in analytical chemistry. To secure a method at once complete and rapid whereby car- bon varying in amounts from four per cent to o.ooi per cent, in different irons and steels could be accurately determined has been a desideratum. Processes that are satisfactory for special grades of irons or steels rarely can be relied upon in general practice. So important has this subject become to the metallurgical world that committees acting in union from Sweden, England, and America 1 have been appointed to determine not only the best methods of iron and steel analysis, but also to analyze standard samples of iron and steel, compare the results, and select methods which should be uniform for the different coun- tries. The determination of carbon, as made upon the standard sam- ples, are thus reported : Standard. No. I. No. 2. No. 3. No. 4. Per cent. Per cent. Per cent. Per bent. English committee 1414 0.816 0.476 0.151 Swedish committee 1.450 0.840 0.500 0.170 American committee-... 1.440 0.807 -45 2 0.160 The English and Swedish committees have not yet selected *J. Am. Chem. Soc., 15, 449. 158 QUANTITATIVE ANALYSIS. the method to be adopted as standard in carbon determinations, but the American committee have rendered their report suggest- ing certain modifications in the use of solvents for the iron and the separation of the total carbon. The use of the double chloride of copper and potassium, as a solvent for iron, is recommended in place of the double salt of chloride of copper and ammonium, owing to the great difficulty in obtaining the latter salt free from pyridin and other tarry products. Of the many methods used to .obtain the amount of carbon from the iron, the following few are selected to indicate not only the variety of the processes, but a gradual improvement by com- bination of different methods : Berzelius 1 first suggested that the iron or steel be finely pul- verized and then ignited in a current of oxygen and the result- ing carbon dioxide weighed. Regnault 2 made use of combustion of the powdered iron with chromate of lead and chlorate of potash and the amount of car- bon dioxide weighed. Berzelius, however, in 1840, separated the carbon from the iron by dissolving the latter in copper chloride and igniting the carbon in oxygen. 3 From this period, the methods for total carbon can be included in two general classes : First class. Combustion of the carbon in the powdered iron directly. Second class. Separation of the carbon from the iron by chem- ical means and combustion of the carbon. Deville and Wohler 4 describe processes by which the iron can be separated from the carbon, by volatilization of the iron with chlorine or hydrochloric acid gas, and combustion of the remain- ing carbon. With the exception of a method described by Gmelin 5 by which the powdered iron is treated directly with chromium tri- 1 Ann. phys. chem., 1838. 2 Ann. chim. phys. t 1839, 107. / prakt. Chem., 1840, 247. 4 Ztschr. anal. Chem., 8, 401. 6 Oestericher Zeitschrift fur Berg und Huttenwesen, /&?j, 392. CARBON IN IRON AND STEEL. 159 oxide and sulphuric acid and the carbon oxidized to carbon dioxide, the methods of the first class, above given, are no longer used. Second Class. These methods give better results in general practice, and nearly all the advances and improvements have been made in this direction. Ullgren 1 dissolved the iron with solution of copper sulphate and oxidized the carbon to carbon dioxide by heating with chromium trioxide and sulphuric acid. Eggertz 2 dissolved the iron with bromine or iodine, and the separated carbon was ignited with chromate of potash. Langley 3 modified Ullgren' s method by ignition of the carbon in oxygen after solution of the iron by copper sulphate. Richter dissolved the iron with chloride of copper and potas- sium and burned the carbon in oxygen. Weyl and Binks dissolved the iron in dilute hydrochloric acid passing an electric current at the same time and ignited the carbon in oxygen. 4 Parry dissolved the iron in solution of copper sulphate, the carbon burned, mixed with copper oxide, in vacuo, and the volume of carbon dioxide measured. 5 Eggertz 's method for combined carbon 6 , in which the iron was dissolved in nitric acid and the amount of carbon (com- bined) determined by color of the solution formed. McCreath and Pearse dissolved the iron with chloride of cop- per and ammonium and ignited the carbon in oxygen. 7 Boussingault* decomposed with mercuric chloride and oxi- dized the carbon to carbon dioxide. Wiborgh 9 dissolved the iron with solution of copper sulphate, oxidized the carbon by heating with chromium trioxide and sulphuric acid, and measured the volume of carbon dioxide formed. 1 Ann. de Chem. u Phar., 124, 59. 2 Dingler's Polytechnish.es Journal, 170, 350. 3 American Chemist, 6, 265. * Ann.phys. Chem., 114, 507. 5 Chem. News, 25, 301. 6 Chem, Neius, 7, 254. 7 Engineering and Mining Journal, ai, 151. 8 Dingler's Polytech.J., 197, 25. 9 Dingier' s Polytech. /., 265, 502. l6o QUANTITATIVE ANALYSIS. Experience has shown that the methods of Ullgren, Lang- ley, Richter, and Wiborgh give the best results for the total amount of carbon in iron, and that the Eggertz method for com- bined carbon in steel can be relied upon as the best for the pur- pose. The determination of total carbon, as made in my laboratory, is either by the Ullgren or L,angley methods, somewhat modi- fied. The Ullgren method is thus performed : Six grams of the iron, in fine turnings, are transferred to a No. 3 beaker and 100 cc. of a solution of copper sulphate 1 (i to 5) added, the solution being first rendered neutral by a few drops of a very dilute solu- tion of potassium hydroxide. Digest at a gentle heat until all the iron is dissolved (no smell of hydrocarbon given off) , add loo cc. cuprous chloride solution (i to 2) and seventy-five cc. hydrochloric acid (specific gravity 1.2) and warm until the metallic copper is dissolved. Filter upon an asbestos filter, washing first with dilute hydrochloric acid, and finally with water until no reaction for hydrochloric acid is obtainable with a drop of silver nitrate solution. Transfer the asbestos filter containing the carbon to the flask A, Fig. 44, using not over twenty-five cc. water in the operation. Add ten grams chromium trioxide, and in the delivery flask place fifty cc. concentrated sulphuric acid, and connect the flask with the system of U-tubes. B contains water sufficient to cover the neck of the U-tube, and is made slightly acid with sulphuric acid. C and D contain granulated calcium chloride free from lime. E and .F contain soda lime, medium granulated, and are care- fully weighed before use. G contains granulated calcium chloride. Allow the sul- phuric acid in the delivery tube to enter flask A and close the stop-cock. Warm the contents of the flask gradually to boiling, and when no more gas passes through B open the side stop- cock of flask A and connect with the Trauber drying apparatus. The aspirator is connected with G and the air is slowly aspir- ated through the entire apparatus. Continue this until about five liters of air have been aspirated. 1 Copper chloride and hydrochloric acid can be substituted as recommended by American Committee on Standard Methods. 1 62 QUANTITATIVE ANALYSIS. After twenty minutes weigh tubes E and F\ the increase of weight represents the carbon dioxide produced by the oxidation of the carbon. Thus, six grams of cast iron taken : Tubes and F -f CO 2 65.700 Tubes E and F 65.002 C0 2 0.698 CO 2 : C : : 0.698 : x = 0.1904. 0.1904 X IPO = 3 Ig per cent carbon 6 The carbon in cast iron being generally a mixture of com- bined and graphitic carbon, it is essential to determine the graphitic carbon, and this amount being subtracted from the total carbon gives the combined carbon. In steels where the carbon is all combined the color test of Kggertz suffices. The graphite is thus determined : Add fifty cc. hydrochloric acid (specific gravity i . i ) to six grams of cast iron or ten grams of steel in a No. 3 beaker; warm gently until the iron is all dissolved, bring to boiling tempera- ture for five minutes, allow the graphite to settle, and decant the supernatant liquid upon an asbestos filter ; wash by decan- tation four times with hot water and treat residue in beaker with twenty-five cc. solution of potassium hydroxide (sp. gr. 1.12) and boil. Transfer to the asbestos filter, wash thoroughly with boiling water, then with alcohol and ether, and transfer the as- bestos filter to the flask A , Fig. 44, and oxidize the carbon to carbon dioxide with chromium trioxide and sulphuric acid, as in the process previously given for total carbon. Thus, six grams of iron taken : Tubes E and F + CO 2 = 66.053 grams. Tubes E and F = 65.621 " C0 2 = 0.432 " C = 0.1178 gram. Graphitic carbon = i .96 per cent. Combined carbon 1.22 " Total carbon 3.18 " CARBON IN IRON AND STEEL. 163 Method of Lang ley Modified. In this process the sample is treated in the same manner for solution of the iron as described for total carbon in the Ullgren method. After the carbon has been thoroughly washed upon the asbestos filter, it is dried and transferred to a porcelain boat which is placed inside of a combustion tube in the furnace C, Fig. 45- The tube D connected with the combustion tube contains granulated calcium chloride, and E and F soda lime ; another tube G containing calcium chloride (not shown in the figure), is also used. Oxygen under pressure in the tank A is allowed to pass slowly through the Trauber drying apparatus, which removes all moisture and carbon dioxide, into the combustion tube and through the tubes D, E, /''and G. Heat is gradually turned on in the furnace and increased until the carbon is completely burned to carbon dioxide. Turn off the heat, disconnect the oxygen tank and slowly aspirate air through the apparatus by means of an aspirator. After cooling thirty minutes weigh the tubes E and F and calculate the result as given previously. It will be noticed that no Liebig's potash bulbs are used. I have obtained better results by the use of soda lime in [J-tubes than by the potash bulbs, and in general practice they will be found much more convenient and less liable to variation in weight. The use of the double chloride of copper and ammonium as a solvent for the iron has been quite general in this country. The American Committee on Standard Methods of Iron Analyses found that, contrary to the usual practice, this solvent must not be neutral, but strongly acid with from five to ten per cent, of its volume of strong hydrochloric acid. T. M. Drown, in his report to the committee, describes his process as follows : ' ' Three grams of the steel were treated with 200 cc. of a solution of copper potassium chloride (300 grams to the liter) and fifteen cc. of hydrochloric acid (sp. gr. 1.2). After complete solution of the iron the carbon was filtered off on an asbestos lined platinum boat, thoroughly washed with hy- CARBON IN IRON AND STEEL. 165 drochloric acid, and then with water until the washings gave no reaction with silver nitrate. After drying the boat was put into a porcelain tube and the carbon burned in a current of oxygen." This is a modification of Richter's process. There does not appear to be much choice in the method of the combustion of carbon. Some chemists prefer oxidation with chromium trioxide and sulphuric acid, and others ignition in a current of oxygen gas. Fig. 46. For rapidity of execution and simplicity of apparatus (Fig. 44.), Ilprefer the former. Wiborg's method, 1 in which the carbon dioxide is measured instead of being weighed, consists as follows : The apparatus required is shown in Fig. 46. A test tube A, 140 mm. long by twenty mm. internal diameter, is surrounded by a cage of brass !/ Soc. \Chem. Industry, 6, 748. i66 QUANTITATIVE ANALYSIS. wire gauge, and fitted with a caoutchouc cork with two perfor- ations. Through one perforation passes the narrow end of the stop-cock funnel B, which should project for about fifteen to twenty mm. beneath the cork ; through the other, but not pro- jecting beneath the stopper, passes the connecting tube D. This latter tube consists of two portions, united by India rubber tub- ing ; the part more remote from A and carrying the stop- cock E is bent to pass through one of the perforations of another caout- chouc stopper in the graduated tube C, the other perforation serving to connect the latter with a stop-cock funnel F. The tube C should for the distance of seventy mm. downwards have an internal diameter of sixteen mm ; it should then be widened to a bulb G, of about twenty-five centimeters capacity, and be finally reduced for the remaining 200 mm. to about nine mm., this narrow portion being graduated into divisions of one- tenth, or preferably, one-twentieth of a cubic centimeter, denot- ing in each case the capacity of the whole of that portion of the tube above the respective graduations. Beneath this tube is- the stop-cock H, communicating by flexible tubing with the movable water reservoir /. The test tube A is warmed by a gas or spirit lamp, and the whole apparatus should be mounted on a suitable stand. The measuring tube is surrounded by a water jacket A' to preserve an even temperature. To conduct an analysis two-tenths gram of finely divided wrought iron or steel or one-tenth gram of cast iron is intro- duced carefully into the test tube A, taking care that none of the filings adhere to its sides. Four cc. of a saturated solution of pure copper sulphate are then introduced and allowed to act, with frequent stirring, during ten minutes, unless an apprecia- ble smell of hydrocarbon is observed, when the action must be suspended after three or four minutes. One and two-tenths grams of crystallized chromic acid are added to the solution. Meanwhile the tube C must have been filled with water by rais- ing the reservoir / until the liquid has risen above the bulb tube G, the remaining space up to the cock being filled by water in- troduced through F. The test tube is now corked and con- nected with the burette C. Eight cc. of sulphuric acid (sp. gr. 1.7) are introduced CARBON IN IRON AND STEEL. 167 drop by drop into A through B, the cock of the latter is closed, that marked E opened, and the liquid in the test tube gradually raised to boiling, the pressure having been diminished by previously lowering the water reservoir /. After ten minutes' boiling, during which the reservoir has been still further low- ered, if necessary, to maintain the diminished pressure, the tube is cooled somewhat, and, together with the connecting tube D, is carefully filled with water introduced through B. The cock E is then closed and the total volume of air and carbon dioxide read off after leveling with the reservoir. /is then once more lowered and the cock //closed in order to draw in a quantity of a ten 'per cent, potassium hydroxide solu- tion through F. After the carbon dioxide has been completely absorbed, //is reopened, the liquid leveled again and a reading of the residual air is taken. The difference between the two readings will be the volume of carbon dioxide evolved from the carbon in the iron. Evidently if two-tenths gram of substance were used, each cc. of carbon dioxide will correspond to 0.253 P er cent, of car- bon, and the factor 0.253 multiplied by the number of cubic centimeters of gas should give a direct reading of the percentage of carbon. But this is not quite correct, since a certain quantity of car- bon dioxide (to be found by experiment) is absorbed by the water in the tube. By treating pure anhydrous sodium carbon- ate in the apparatus instead of iron and comparing the actual with the theoretical yield of carbon dioxide, the factor may be corrected. Thus the true factor was found to be 0.28, and this was uni- versally correct for cast irons ; but for wrought irons or steels, which contain less carbon, it should be 0.29. When one-tenth gram of iron is used the factor must of course be doubled. Where the temperature of the operation differs much from the normal eighteen degrees, correction must be made by multiply- ing or dividing by ( i -\- 0.00367 X /) , where / is the variation in temperature, according as the solution is cooler or warmer than the normal. i68 QUANTITATIVE ANALYSIS. This process is expeditious, and a very delicate measurement of the carbon dioxide can be obtained, thus : One-twentieth cc. of carbon dioxide from two- tenths gram of iron represents 0.014 P er cent, of carbon, but weighs only o.oooi gram. G. Lunge 1 gives this process the preference where small quantities of carbon are to be determined in cast irons. Determination of Combined Carbon in Steel. Eggertz^ Method. This method depends upon the color given to nitric acid (sp. gr. 1.2) when steel is dissolved therein ; the carbon present pro- ducing a light brown or dark brown coloration to the liquid in proportion as the carbon is in small or large amounts. The ap- paratus, Fig. 47, is well arranged for this test. It consists of Fig. 47- a series of graduated tubes, of glass, each 27.5 centimeters long, fifteen mm. in diameter, and graduated to hold thirty cc. divided by one-fifth cc. The back plate of the appa- ratus is of white porcelain, 25.5 centimeters wide, twenty-seven centimeters high, and three mm. thick, and I have found it much better than the various cameras to obtain correct compari- 1 Stahl und Eisen, 13, 655. CARBON IN IRON AND STEEL. 169 sons of colors of solutions in the different tubes. Three stand- ard steels are required, one containing one per cent, combined carbon, for tool steels, etc., one containing four-tenths per cent, carbon, for tires, rails, etc., and two-tenths per cent, carbon, for soft steels ; these percentages of carbon having been very accu- rately determined by combustion. The process is as follows : Two-tenth gram of the standard steel is transferred to one of the graduated tubes, four cc. of nitric acid (sp. gr. 1.20) added, and the tube placed in cold water to prevent energetic action of the acid. After a few minutes inter- val the tube is placed in warm water, and the latter gradually raised to the boiling-point and maintained at that temperature about twenty minutes. The sample of steel, in which the amount of carbon is unknown, is treated in a similar manner, using the same amount of steel and acid. Suppose the standard steel contains 0.84 per cent, of carbon, the solution in the tube is diluted with water to 16.8 cc. Each cubic centimeter therefore contains o.oooi gram of carbon. Suppose that upon dilution of the test sample solution to four- teen cc., and placing the two tubes side by side in the frame (Fig. 47), that the test sample is somewhat stronger' in color than the standard sample ; upon diluting it, however, to fifteen cc. it is slightly lighter in color. This would indicate that the unknown or test sample contains more than 0.70 per cent, (o.i X V) f carbon, but less than 0.75 per cent, (o.i X l f). The steel can be thus assumed to contain 0.73 per cent, carbon. The use of Eggertz' color test for combined carbon requires that steels should have been subjected to a similar physical treat- ment to which the standard steels had been subjected in order to secure accurate results. A steel shows less carbon, by color, when hardened than when unhardened, and less unan- nealed than when annealed. Several modifications of the pro- cess have been submitted by various chemists, but they offer no special advantages. Stead 1 renders the nitric acid solution of the steel alkaline with sodium hydroxide, which dissolves the carbon, producing a solution about two and a half times stronger in color than the solution in nitric acid. The precipitated iron 1 Chem News, 47, 285. 1 70 QUANTITATIVE ANALYSIS. oxide is filtered off, and a measured quantity of the colored fil- trate is transferred to a Stead's chromometer and the color com- pared with a standard steel under similar conditions. Except where the carbon is present in minute quantity only is this pro- cess of any advantage over the Eggertz method. Carbon Compounds of Iron. Microscopical examinations of iron have led to remarkable developments of our knowledge of its structure. Recent inves- tigations by Osmond, Martens, Arnold and others have shown that eminently practical results are to be obtained from this microscopical examination. These microscopical examinations indicate that structure of iron depends upon a number of partially identified compounds which have been given the names of pearlite, cementite, mar- tensite, etc., and which are all compounds of carbon and iron. Marten's and Osmond's latest investigations, as well as those of Arnold, have demonstrated that the presence or absence of one or more of these compounds determines and identifies the qualities and properties of different kinds of iron and also de- termines the methods of manufacture and heat treatment to which they were subjected. Messrs. Abel, Mueller, and Leduber showed some years ago that carbon in unhardened steel exists chiefly as the definite carbide, Fe 3 C; but microscopical investigations have further proven the coexistence of many other carbides, especially after heat treatment. Professor Arnold claims to have proven the existence of : (a) Crystals of pure iron which remain bright upon etching. (b) Crystals of slightly impure iron which become pale brown on etching, probably owing to the presence of a small quantity of an intermediate carbide of hypothetical formula Fe 10 C. (c) Normal carbide of iron, Fe 2 C, which exists in three dis- tinct modifications ; each one conferring upon the iron in which it is found particular mechanical properties : ( i ) Emulsified carbide present in an excessively fine state of division in tempered steels. CARBON COMPOUNDS OF IRON. 1 71 (2) Diffused carbide of iron occurring in normal irons in the forms of small ill-defined striae and granules. (5) Crystallized Fe 3 C occurring as well defined laminae in annealed and in some normal irons. (d} Subcarbide of iron, a compound of great hardness exist- ing in hardened and tempered irons and possessing formula Fe 24 C. This substance is decomposed by the most dilute acids, and at 400 C. it is decomposed into Fe 3 C and free iron with evolution of heat. One of the most remarkable properties of this compound is its capacity for permanent magnetism. (e) Graphite or temper carbon. Chemists have heretofore identified only graphitic carbon, combined carbon, and carbide of iron. These alone are not sufficient to identify iron, and what must be done is to devise accurate methods for determining all of the above enumerated substances by chemical analysis. Professor Arnold says : ' ' The existence of Fe 24 C is proved by the fact that iron containing 0.89 per cent, carbon presents sev- eral co-relative critical points when examined by different methods of observation : ( i ) Well marked saturation points in micro-structure of normal annealed and hardened steels. (2) A sharp maximum in a curve, the coordinates of which are heat evolved or absorbed at Ar i (point of recalescence) and carbon percentage. (3) A point in the compression curve of hardened steels at which molecular flow absolutely ceases. (4) A sharp maximum in a curve, the coordinates of which are carbon percentage and permanent magnetism in hardened steels. ' ' The famous French micrographist, F. Osmond, defines and describes five distinct carbon compounds which can only be found and identified by the microscope, as existing in iron sub- jected to heat treatment. (i) The first he calls, with Howe, ferrite, because it is almost pure iron ; it at first retains a dull polish (poli speculaire) when relief polished ; after continued polishing, especially with precipi- tated chalk and water, it becomes more granular as it is less massive , but when forming large masses it finally shows as polyhedral crystals. Etch polishing with tincture of iodine produces no coloration. 172 QUANTITATIVE ANALYSIS. (2) The second is called cementite, which is distinguished by its hardness (felspar, No. 6, Mohr's scale). This hardness, which is greater than that of all other carbon compounds, per- mits its identification even when polishing with emery paper, pro- vided it is not so imbedded in softer particles, that the micro- scope is no longer able to identify it, and chemical analysis alone is able to prove its presence. This substance corresponds to that imagined by Karsten and Caron, and isolated by Dr. F. C. G. Mueller, Sir Fred. Abel, and Professor Ledebur as carbide, and of the probable formula Fe 3 C, and which Howe also calls cementite. Osmond believes that cementite of iron of cementa- tion (de 1'acierpoule) can now be identified with the hard com- ponent of cast and forged steels. (3) The third compound is called sorbite, after Dr. Sorby, which was first described as "pearly constituent," (Howe called it perlite) , which could be identified under a magnification of 800 diameters, as a subsjtance w 7 ith the sheen of mother-of-pearl. It is possible, with oblique light, to separate this in bands of alternating hard and soft flakes. Osmond questions the accuracy of the conclusion generally held that this is Fe 3 C, because he points out that etch polishing gradually changes the color from yellow to brown and then from purple to blue, and at a certain period there is great difference be- tween the colors in adjacent "islets" (ilots). The uncolored flakes (lamelles) may appear elevated or de- pressed. With tincture of iodine similar results are obtained. It must be remembered that neither ferrite nor cementite take such colors under similar conditions even when extract of liquorice root or tincture of iodine is used. He can offer no suggestion in regard to the chemical compo- sition of " sorbite." (4) A fourth compound always found after quenching iron, which is already well known, is " martensite," named after Pro- fessor A. Martens, the famous micrographer of Berlin. When iron with 0.45 per cent, carbon is heated to 825 C., and then at 720 C. quenched in a freezing mixture of 20 C., re- lief polishing produces no effect ; but etch polishing shows the structure. Groups of needles (fascicles) or groups of rectilinear CARBON COMPOUNDS OF IRON. 173 parallel fibers, which are separated or not by a scarry or vermi- form filling, and are shown in very slight depths. Three groups of fibers, parallel to the sides of a triangle, are often seen in one spot, as crystalline bodies of the cubicaj system. Etch polish- ing does not always color martensite, and then only takes a light yellow sheen. However, when applying tincture of iodine it takes a yellow, brown, or black color, according to the percent- age of carbon present. Because of the non-uniformity of color it is not quite certain whether martensite can be considered a fundamental compound. It does, however, retain its forms even in the quenched parts, in the softest as well as in the hardest iron, with the single difference that the fascicles, (needles) are sometimes longer, sometimes more varied, in accordance whether the iron is more or less carbonized. The shapes are character- istic and permit the determination of differences in hardness. Martensite is not positively a definite compound of iron and car- bon ; it represents rather the crystalline arrangement of an allo- trapic modification of iron under the influence of carbon. (5) A fifth well defined fundamental compound found in me- dium iron quenched while undergoing structural changes (into its allotropic modifications according to Osmond), is named troostite, after the famous French metallurgist Troost. When >n with 0.45 per cent, carbon is heated to 825 C. and then [uenched at 690 C., is relief polished, nodules in relief, de- >ressed tatters or tongues (lambeaux), and between the two intercalations of varying breadth and medium hardness are leveloped. Etch polishing proves that the hard nodules are la'rtensite, and the soft tatters or tongues are ferrite. The in- tercalated bands show temper colorations, but they harden less rapidly than sorbite under identical conditions, and these colors roduce an irregular marbleized appearance ; they are almost imorphous, slightly granular and wart}'. Tincture of iodine first and second application produces quite similar effects in this fifth fundamental compound, troostite. It is noticed that it is a transitory form between soft iron and hardened steel. But troostite is identified by 'the microscope alone, just like the sorbite ; its composite character is still to be 174 QUANTITATIVE ANALYSIS. determined. The systematic microscopic examination consists briefly in the application of three methods : (i) Relief polishing, (2), etch polishing, and (3) etching with tincture of iodine. In relief polishing it is sometimes advisable to use precipitated chalk as well as rouge, to preserve the ferrite. In etch polishing with precipitated chalk, the fundamental compounds, with the exception of martensite, are divided into two groups : (a) Not colored : ferrite, cementite, or martensite. () Colored: martensite, troostite, or sorbite. Martensite takes only a yellowish color and is distinguishable by its crystalline form. A novice might take martensite for per- lite, especially by oblique light, for both have irridescent sheen, and its structural elements may be of equal dimensions ; but they are easily distinguished, as the needles of martensite are straight and crossed, while those of perlite are curved and never cross each other. Ferrite and cementite are distinguished by their great differ- ences in hardness ; the former is low, the latter is high. Troo- stite takes less color and more slowly than sorbite, but the true distinctive mark is that troostite accompanies martensite, while sorbite goes with cementite in perlite. By etching with tincture of iodine two groups can be distin- guished, viz. : (a} Uncolored : ferrite and cementite. () Colored : sorbite, troostite and martensite. In group (b) the three compounds vary in color, in kind and depth in proportion to the percentage of carbon and of the quan- tity of tincture of iodine used. References : " Unification of Methods of Iron Analyses." By Prof. H. Wedding. Stahl und Risen, No. 21, 18^5. " Microphotography of Iron." By F. Osmond, Paris. /. Iron and Steel Inst., 7890, No. i. " Microphotography of Iron." By A. Martens, Berlin. Stahl und Eisen, No. 20, 1895. "On the Influence of Carbon on Iron." By John Oliver Arnold, Bir- mingham, England. CARBON COMPOUNDS OF IRON. 175 " Report of the French Commission on Testing Materials." Ministere des Travaux Publics, Paris, 1892 and 1895. " Testing of Materials." By R. A. Hadfield. /. Iron and Steel Inst., 1894, NO. i. " The Microstructure of Ingot Iron in Cast Ingots." By A. Martens. Trans. Am. Inst. Mining Engineers, 23,37-63, 1893. "Determination of Combined Carbon in Steel by the Colorimetric Method." By J. Blodget Britton. Chem. News, 26, 139. " On the Estimation of Carbon in Pig Iron." By Charles H. Pierce. Chem. News, 28, 199. 'Colorimetric Carbon Estimation." By Fred P. Sharpless. /. Anal. Chem., 2, 55. "A Funnel for Filtering Carbon." By Thomas M. Drown. J. Anal. Chem., 2, 330. " Determination of Carbon in the Irons of Commerce." By L. Blum. Chem. News, 60, 167. " Determination of Carbon in Iron and Steel." By L. I/, de Konick. Ztschr. anal. Chem., j888, 463. "A New Form of Apparatus for Determination of Carbon in Steels by Color." By C. H. Risdale. /. Soc. Chem. Ind., 5, 583. " International Standards for the Analysis of Iron and Steel." J. Anal. Chem., 6, 402. "Notes on Carbon in Experimental Standards." By P. W. Shimer. J. Anal. Chem., 6, 129. " The Determination of Carbon in Steel." By A. A. Blair. /. Anal. Chem., 5, 121. "Researches on the Carbon of White Cast Iron." By Isherwood. Engineer, 44, 461. "Determination of Combined Carbon in Cast Iron and Steel." By Townsend. Proceedings of the Engineers" Club, Philadelphia, Pa., 2, 31. " Determination of Carbon in Iron and Steel." By Zabudsky. Ber. d. chem. Ges., 16, 2318. " The Colorimetric Determination of Combined Carbon in Steel." By Alfred E. Hunt. Trans. Am. Inst. Min. Eng., 12, 303. "Apparatus for the Determination of Carbon in Iron and Steel by Measurement of the Evolved Carbon Dioxide." By Reinhart. Stahl und Eisen, 12, 648. "The Determination of Carbon in Iron and Steel." By C. B. Dudley and F. N. Pease. The American Engineer and Railroad Journal, 67, 347- " A Method for the Determination of Carbon in Steel." By Frank Julian. /. Anal. Chem., 5, 162. i 7 6 QUANTITATIVE ANALYSIS. XX. Determination of Phosphorus in Cast Iron and Steel. The molybdate method, as described by Troilius, 1 gives uniform and satisfactory results. It is as follows : Five grams of drillings are dissolved in a No. 4 Griffin's beaker, in nitric add (sp. gr. 1.20), using about fifty cc. of the acid. The solu- tion is then evaporated with excess of strong hydrochloric acid by rapid boiling on a large iron plate by one of Fletcher's solid flame burners. The plate is so heated that the heat gradually decreases from the centre towards the edges. The hottest part ought to be rather above than below 300 C. The evaporation is continued on the hottest part of the plate until signs of spattering are noticed. The beaker, or beakers, are then moved to a less hot part of the plate. When the tendency to spatter has ceased the beakers are moved back to the hottest part of the plate for at least half an hour. This heating is necessary in order to com- pletely oxidize and decompose the last traces of iron phosphide, which would otherwise remain insoluble with the silica. The presence of hydrochloric acid lessens the tendency to spatter, which is always less in high carbon steels than in low carbon steels. The beakers are now slowly cooled and strong hydrochloric acid added in excess. This acid is at once brought to a boil, which effects a solution of the residue, and the boiling is con- tinued until only a small bulk remains. This boiling serves two purposes : 1. To convert any pyrophosphoric acid (H 4 P 2 O 7 ), which may have been formed by the strong heating into orthophosphoric acid (H 3 PO 4 ). 2. To concentrate the solution and remove the excess of hydrochloric acid which would otherwise interfere with the pre- cipitation of phosphoric acid by means of molybdic acid. Hot water is added and the insoluble residue filtered off and thoroughly washed with dilute hydrochloric acid, and afterwards with hot water. 1 " Notes on the Chemistry of Iron," by Magnus Troilius, E. M. PHOSPHORUS IN CAST IRON AND STEEL. 177 The phosphoric acid in the filtrate is precipitated as the yel- low phospho-molybdate of ammonia. For this precipitation is used a solution of about one part by weight of molybdic acid in four weights of ammonia (0.96 sp. gr.), and fifteen parts of nitric acid (1.20 sp. gr.). The molyb- dic acid is first dissolved in the ammonia, and this solution slowly poured into the nitric acid, which must be shaken con- stantly in order to prevent the separation of molybdic acid, which redissolves with difficulty. After a few days' standing the solution may be siphoned off clear. Fifty to one hundred cc. of this solution are used for each phosphorus determination. To precipitate the phosphoric acid in the filtrate from the in- soluble residue (silica, etc.) sufficient ammonia is added to nearly neutralize the solution. The fifty cc. of molybdic acid solution are then added and the solution well stirred. If the yellow precipitate is slow in coming down, a little more ammo- nia may be added. If too much ammonia is added, a little strong nitric acid must be introduced to redissolve the iron pre- cipitate. As a rule the yellow precipitate comes down very quickly. By neutralizing the solution before adding the molyb- dic acid, as described, the yellow precipitate becomes granular and easy to filter. When precipitated in any other way it has a tendency to pass through and creep over the edges of the fil- ter. The yellow precipitate is allowed to settle over night at about 40 C, or during a few hours at 80 C. After settling the clear supernatant liquid is siphoned off and the precipitate washed with copious quantities of molybdic acid solution diluted with an equal volume of water. About 300 cc. of washing are not too much to insure the complete removal of the last traces of iron. The yellow precipitate is then treated on the fil- ter with six cc. hot ammonia (0.96 sp. gr.) and the filtrate al- lowed to run back into the beaker in which the precipitation was made . When all is dissolved the ammoniacal solution is thrown on the same filter again, butnow allowed to run intoa loocc. beaker. The filter is then washed well with small portions of cold water, so that the bulk of the ammoniacal solution will not exceed forty cc. This is now made faintly acid with hydrochloric acid, then (12) 178 QUANTITATIVE ANALYSIS. alkaline with a few drops of ammonia, enough to dissolve any yellow salt that may have separated. Add ten cc. of magnesia mixture and stir well until the white crystalline precipitate of phosphate of magnesia and ammonia appears; about six cc. of ammonia (0.96 sp. gr.) are then added. Allow to stand two hours, filter upon a No. 2 ashless filter and wash with diluted ammonia (one part ammonia, 0.96 sp. gr., with three parts water) . About eighty cc. of this mixture are sufficient for washing the precipitate. It is advisable not to use more than this amount, as the same has a slightly solvent action upon the precipitate. The white precipitate must be rubbed loose from the sides of the beaker with rubber tubing on a glass rod. The "magnesia mixture" is prepared by dissolving no grams of crystallized magnesium chloride together with 280 grams of ammonium chloride in 1300 cc. of water and adding 700 cc.'of ammonia (0.96 sp. gr.) to the solution. The filter with the well washed precipitate is ignited in a small weighed platinum crucible and weighed as magnesium pyro- phosphate, care being taken that the ignited precipitate when weighed is white and uniform in color. Calculate the weight of phosphorus from this magnesium pyrophosphate. If it be desired to estimate the phosphorus from the yellow precipitate (ammonio-molybdic phosphate) directly, proceed as follows: The yellow precipitate, when dried at 95 to 100 C., contains 1.63 per cent, of phosphorus. It must be washed with water containing one per cent., by volume, of nitric acid (1.2 sp. gr.) instead of the dilute molybdic solution. After drying it is transferred from the filter, by shaking and brushing, into a weighed watch-glass, or some other suitable vessel and weighed. When much phosphorus is present this method can be used with great accuracy, but when little the risk of loss is too great. Weighed filters must then be used. The magnesia method is, however, undoubtedly the better of the two in general working. When precipitating phosphoric acid with the molybdic acid solution it should be borne in mind that 100 cc. of the acid solu- tion are required for the complete precipitation of one-tenth PHOSPHORUS IN CAST IRON AND STEEL. I 79 gram of phosphorus pentoxide containing 0.044 gram of phos- phorus. Many forms of agitation apparatus have been devised for the thorough precipitation of the ammonio-magnesium phosphate. The apparatus of Spiegelbergs (Fig. 48), which is run by Fig. 48. water power, is well adapted for the purpose of continued and violent agitation of the liquids. Volumetric Determination of Phosphorus in Iron and Steel? Put one gram of the steel in a ten or twelve ounce Erlen- meyer flask and add seventy-five cc. of nitric acid (1.13 sp.gr.). When solution is complete, boil one minute and then add ten 1 Method adopted by Motive Power Department of Perm. R. R. Co., Dudley and Pease, J. Anal. Chem., 7, 108. i8o QUANTITATIVE ANALYSIS. cc. of oxidizing potassium permanganate solution. Boil until the pink color disappears and manganese dioxide separates, re- move from the heat and then add crystals of ferrous sulphate, free from phosphorus, with agitation until the solution clears up, adding as little excess as possible. Heat the clear solution to 185 F., and add seventy-five cc. of molybdate solution, which is at a temperature of 80 F., close the flask with a rubber stop- per and shake five minutes, keeping the flask so inclosed during the operation that it will lose heat very slowly. Allow to stand five minutes for the precipitation to settle, and then filter through a nine cm. filter and wash with acid ammonium sulphate until the ammonium sulphide tested with the washings shows no change of color. Dissolve the yellow phospho-molybdate on the filter in five cc. of ammonia (sp. gr. 0.90), mixed with twenty- five cc. of water, allowing the solution to run back into the same flask and thus dissolve any yellow precipitate adhering to it. Wash until the washings and filtrate amount to 150 cc., then add ten cc. strong C. P. sulphuric acid and dilute to 200 cc. Now pass the liquid through a Jones reductor or its equivalent, wash and dilute to 400 cc., and then titrate in the reduction flask with potassium permanganate solution. Apparatus and Reagents. The apparatus required needs no especial comment, except perhaps the shaking apparatus and the modification of the Jones reductor. Accompanying cuts represent these two. The shaking apparatus is arranged to shake four flasks at a time, which is about all one operator can manipulate without the solutions becoming too cold. The cut is about one-twelfth the actual size of the apparatus. The flasks containing the solutions rest on a sheet of India rubber -about one-quarter inch thick and are held in position by the coiled springs as shown. There is a recess in the spring arrangement to receive the cork of the flask. Of course during use the door of the box is closed, the cut showing it open so that the interior may be seen. The modification reductor seems to work equally as well as the more elaborate apparatus. The cut is about one-fourth the actual size. As will be seen the tube is fitted with two rubber corks, the top one of which holds the fun- nel and the bottom one a small tube which also fits into the rub- PHOSPHORUS IN CAST IRON AND STEEL. 181 her cork in the flask. Next to the bottom cork in the tube is a disk of perforated platinum ; then about three fourths of an inch of clean white sand, then another perforated platinum disk and then the tube is nearly filled with powdered zinc. At least half the zinc may be used out before it is necessary to refill. Fig. 49. Fig. 50. The oxidizing potassium permanganate solution is made as fol- lows : To two liters of water add twenty-five grams of C. P. crystallized potassium permanganate and allow to settle before using. Keep in the dark. The molybdate solution is made as follows : Dissolve 100 grams of molybdic acid in 400 cc. of ammonia (sp. gr. 0.96), 1 82 QUANTITATIVE ANALYSIS. and. filter. Add the filtrate to one liter of nitric acid (sp. gr. i. 20). Allow to stand at least twenty-four hours before using. The acid ammonium sulphate solution is made as follows : To one-half liter of water add 27.5 cc. of ammonia (sp. gr. 0.96) and then twenty-four cc. strong C. P. sulphuric acid and make solution up to one liter. The potassium permanganate solution for titration is made as follows : To one liter of water add two grams of crystallized po- tassium permanganate and allow to stand in the dark not less than a week before using. Determine the value of this solu- tion in terms of metallic iron. For this purpose 0.150 to 0.200 gram of iron wire or mild steel are dissolved in dilute sulphuric acid (ten cc. C. P. sulphuric acid to forty cc. water) in a long- necked flask. After solution is complete, boil five to ten min- utes, then dilute to 150 cc., pass the liquid through a reductor and wash, make the volume up to 200 cc. Now titrate with the permanganate solution. Several determinations should be made. The figures showing the value of the permanganate solution in terms of metallic iron should agree to the hundredth of a milli- gram. Calculations. An example of all the calculations is given herewith. The soft steel employed in standardizing the potas- sium permanganate solution contains 99.27 per cent, metallic iron. 0.1498 gram of this contains (0.1498 X 0.9927) 0.1487064 gram Fe. This requires 42.99 cc. permanganate solution or one cc.= 0.003466 gram Fe. But the same amount of permanganate solution used up in producing the characteristic reaction in this amount of metallic iron, will be used up in reaction with 90.76 per cent, of the same amount of molybdic acid. Hence one cc. of the permanganate solution is equivalent to (0.003466 X 0.9076) 0.003145 gram of the molybdic acid. But in the yellow precipi- tate obtained as above described, the phosphorus is 1.90 per cent, of the molybdic acid. Hence one cc. of permanganate solution is equivalent to (0.003145 Xo.oi9o), 0.0000597 gram of phosphorus. If, therefore, in any sample of steel, tested as above, the yellow precipitate requires eight and six-tenths cc. of permanganate, the amount of phosphorus in that steel is (0.0000597 X 8.6) = 0.051 per cent. CLASSIFICATION OF STEEL. 183 Ten cc. of the " magnesia mixiure " are required for the same quantity of phosphorus pentoxide. References. "Volumetric Estimation of Phosphorus in Iron and Steel." By Edward D. Campbell. /. Anal. Chem., i, 370. " Note on Percentage Composition with Table for Phosphorus." By William St. G. Kent. /. Anal. Chem., i, ^64. "The Elimination of Arsenic in Phosphorus Determinations." By F. D. Campbell. /. Anal. Chem., 2, 370. " Determination of Phosphorus in Iron and Steel." By Porter W. Shi- mer. J. Anal. Chem.> 2, 97. "The Influence of Silicon on the Determination of Phosphorus in Iron." By Thomas M. Drown. /. Anal. Chem., 3, 288. " Phosphorus in Pig Iron, Steel and Iron Ore." By Clemens Jones. /. Anal. Appl. Chem., 4, 268. "Phosphorus Determination by Neutralization of the 'Yellow Precipi- tate ' with Alkali." By C. E. Manby. /. Anal. Appl. Chem., 6, 242. "Note on the Precipitation of Phosphorus from Solutions of Iron and Steel." By Robert Hamilton. /. Anal. Appl. Chem., 6, 572. XXI. Classification of Steel. 1 Classification of Steel Made by the Midvale Steel Company. Class O. Carbon o.i to 0.2 per cent. Approximate tensile strength from 55,000 to 65,000 pounds. Class I. Carbon 0.2 to 0.3 per cent. Approximate tensile strength from 65,000 to 75>ooo pounds. Class II. Carbon 0.3 to 0.4 per cent. Approximate tensile strength from 75,000 to 85,000 pounds. Class III. Carbon 0.4 to 0.5 per cent. Approximate tensile strength from 85,000 to 95,000 pounds. Class IV. Carbon 0.5 to 0.6 per cent. Approximate tensile strength from 95,000 to 105,000 pounds. Class V. Carbon 0.6 to 0.7 per cent. Approximate tensile strength from 105,000 to 120,000 pounds. Class VI. Carbon 0.7 to 0.8 per cent. Approximate tensile strength from 120,000 to 135,000 pounds. Class VII. Carbon 0.8 to 0.9 per cent. On heats of this carbon and above, tensile strength is not con- sidered, as they are generally used for spring steel and tool steel, in which the fitness of the material for the purpose wanted can- not be decided by the tensile strength of a test bar. 1 Prof. Coleman Sellers : Stevens Indicator, n, 1894, 88. 1 84 QUANTITATIVE ANALYSIS. Class VIII. Carbon 0.9 to i.o per cent. Class IX Carbon i.oo to i.io per cent. Class X Carbon t.io to 1.20 per cent. It is of course understood that while this classification holds good in a general way, the other chemical ingredients besides carbon, as well as treatment, may so effect the tensile strength that, while the percentage of carbon would place it in one class, other chemical ingredients or physical treatment may bring it (as far as tensile strength goes) into one of the other classes. As a general thing, it has been found that a high percentage of manganese, say above seven-tenths per cent., up to and includ- ing one per cent., will exert a much greater hardening influence on steels of high carbon than of steel below five-tenths per cent, in carbon ; while the other chemical ingredients seem to exert a uniform hardening influence on all grades of steel. The purposes for which the different classes of steel are recom- mended by the Midvale Steel Company, taking into considera- tion the many different specifications for the same purposes that are received, are as follows : Classes I and II are used for propeller shafting, axles, and general machinery work. Also used for rifle-barrel steel, steel castings where toughness is the principal requirement, and finally, in the higher grades, where it approaches Class III, for gun tubes. Class III is principally used for Pennsylvania Railroad axle and crank pins, and for parts of machinery where a high elastic limit is required. This class is recommended for axles and crank pins, and, where the choice is left with the makers, they invariably use it for this purpose. It is a class which, in their opinion, is best suited for steel forgings of all descriptions, with the conditions, however, that the forgings should be thoroughly annealed. If this is not done, the lower class is preferable, as the strains left in the forging are not apt to be injurious in the lower carbon steel. This class is also used for gun forgings, jackets and hoops, the high requirements as to elastic limit making it necessary to have a good percentage of carbon. Class IV is used also principally for gun forgings and for large locomotive tires. CLASSIFICATION OF STEEL. 185 Class V is used principally for tires for freight service and car wheels, and for forgings for air vessels for torpedoes, and also for steel castings where greater wear is desirable, such as ham- mer dies, roll pinions, etc. Class VI is used mostly for surgical instruments and grinding machinery. Class VII is used for spring steel. Classes VIII, IX and X are used for various grades of spring and tool steel, the highest grades being used for cutting tools and the lower grades for chisels, reamers, etc. It is necessary to remember in this classification, that while the carbon and tensile strength governs the classes, the chemical composition of the different heats that come under one class varies considerably. In the case of ordinary machinery steel and tires, the makers endeavor to keep the phosphorus limit below 0.06 per-cent. This is the case also with their steel cast- ings. In gun forgings, on the other hand, their phosphorus limit is below 0.03 per cent., as well as in tool steel and spring steel. At the present moment, the greatest interest is taken in the magnetic qualities of steel, as compared with the best Norway iron ; and from recenc experiments it will be seen that conclu- sions can not be drawn with safety from a few experiments, par- ticularly in regard to the alloys of various metals with steel. The statement has been broadly made that a large percentage of nickel introduced into steel castings destroyed the magnetic qualities of the steel to such an extent as to make this alloy par- ticularly desirable or useful for the bolts that clamp the punch- ings of the armature in the dynamo together, the general idea being that these foreign substances were all acting injuriously. Some recent experiments have been made by the Bethlehem Iron Company, bearing upon the dynamos that are to be made for Niagara, which seem to show that when a small quantity of nickel only is used, the magnetic qualities are improved to such a degree as to make its employment advisable, making nickel steel, properly prepared, higher in its capability of magnetiza- tion than even the best Norway iron. This statement does not hold good in all degrees of excitation, but is said to be particu- i86 QUANTITATIVE ANALYSIS. larly good at the amount of excitation to which field magnets are usually subjected. Mr. Iy. B. Stillwell, in his examination of this metal, con- cludes a report on the subject with the words : "I am emphati- cally of the opinion that no better material can be secured." The effect of the mixture of foreign substances with steel is one that is worthy of the most careful attention of the students of technical colleges, and would form an admirable subject for a thesis, as the experiments to be reliable need not involve great cost, and would give opportunity for a considerable display of ingenuity in devising methods of making the tests, and the man- ner of showing the results by graphical methods. Steel plate for locomotive use requires the carbon to be not under 0.15 per cent, nor over 0.20 per cent; 1 phosphorus 0.03 per cent, to 0.04 per cent. ; manganese 0.35 per cent, to 0.50 per cent. ; silicon 0.025 P er cent, to 0.04 per cent. ; sulphur 0.02 per cent, to 0.04 per cent. ; copper (if any) not over 0.04 per cent. 1 The Engineer, March 30, 1895. CLASSIFICATION OF IRON AND STEEL. 187 JB X p M S' S J n* ^ * rf M o 3 rr* 50 ^O t o ^ ^ o S 2 1'"- 5 3 .? O 2. o C B 1 i' 11 5' ^ - S o' j[ I* ? : ^ ? ft ft *.' 3O*^* O ? S 3 x Q > C S, 2. S - I S 1 1 ^- .' 0* 3i 3 3 8,1 g * "3. s 5 ^ f 82 ^ rc "1 ?> c ~ 2 P J- 3. a* 3 H "' JJ* ^ 3' ^ 3 r * oa . ^^ 5 " Q x^s ^ ^ ro "^ rt* DjP S "*a ^ r*-f- & 3 S w O JT" ^ P "~^ MI O ei-d K) - s ? I r O s sr f D P w 7? o ft o> ? Bb Q jf 9 ^ rt* o 51 y S- U> 5 0* -! - w 1 8 IS 3 ^ nf rt ^ w o O -h ~ g > !> W ^ hH a 3 2. a * ^ f> H ? 3 QfQ 3 x 2 JL J5- 2 ^5 o* HH M S 3 C/. f* W ^* o B C * ^ ^ i?5 P* 2- g w s 2. m to" * rt M ;s and produced I ind casting, whic ^ 3-g I S ?S 8 f 1 ?. i | CO g^ - , " Q - 21 r oo^ ' W P w ^.^5 5 Si s'iS ^ 3. \ 2. W A 3 r+ 3"< B* jSpOBWWp'rf- -H t ^^ OP^pPf ^W^Jfl ^Q p "*^ ^e 1 88 QUANTITATIVE ANALYSIS. XXII. Determination of Aluminum in Iron and Steel. The direct determination of aluminum in iron and steel is somewhat difficult, especially if the amount of aluminum be small. Drown 1 describes a process which gives good results, as fol- lows : Dissolve five to ten grams of iron or steel in sulphuric acid, evaporate until white fumes of sulphuric anhydride begin to come off, add water, heat until all the iron is in solution, filter off the silica and carbon, and wash with water acidulated with sulphuric acid. Make the filtrate nearly neutral with ammonia, and add to the beaker in which the electrolysis is to be made, about 100 times as much mercury as the weight of iron or steel taken. The bulk of the solution should be from 300 to 500 cc. Con- nect with the battery or dynamo current in such a way that about two amperes may pass through the solution over night. This is generally accomplished by using three lamps (thirty-two candle power) arranged in parallel on an Edison circuit. In the morning the solution is tested for iron, and, if necessary, the electrolysis is continued after adding enough ammonia to neu- tralize the acid that has been set free by the deposition of the iron. The progress of the operation may be observed by the changing color of the solution. At first it becomes darker in color near the anode ; after five or six hours it is nearly color- less, and finally becomes pink, from the formation of permanga- nate. When the solution gives no test for iron, it is removed from the beaker with a pipette while the current is still passing. When as much has been removed as possible without breaking the current, water is added, and the operation continued until the acid has been so far diluted that there is no danger of dis- solving iron from the mercury. The anode is now taken out and the mercur}^ washed with water until the last traces of the solution have been removed from it. After filtering, to remove any flakes of manganese dioxide l/. Anal. Appl. Chem., 5, 631. ALUMINUM IN IRON AND STEEL. 189 which may be suspended in the solution, sodium phosphate is added in excess and ten grams of sodium acetate. The solu- tion is now made nearly neutral with ammonia and boiled for not less than forty minutes. The precipitate of aluminum phos- phate is then filtered off, ignited, and weighed. It should be white after ignition. If it has more than the faintest shade of color it must be dissolved by fusing with acid potassium sul- phate, in a platinum crucible, and again electrolyzed for two or three hours. The second precipitate has been found to be always white without a trace of iron. The precipitate of alumi- num phosphate, produced as above, does not always have the composition A1 2 O 3 .P 2 O 5 . It is more nearly expressed by the formula 7A1 2 O 8 .6P 2 O 5 , containing 24.14 per cent. The following table gives the results obtained in determining by the above process the aluminum added in known amounts to solutions of steel : Steel taken. Per cent, of alumi- Per cent, of alumi- Grams. num added. num found. 5 0-39 0-36 5 o-39 o-38 5 -39 0.38 5 o-39 o-38 5 o-39 o-37 5 -043 0.045 5 0.043 0-041 5 0.043 0.049 5 o 043 0.048 10 0.027 0.015 10 0.200 0.160 10 0.046 0.044 5 0.085 0.088 A blank experiment with the same steel, without the addition of any aluminum, gave a precipitate of aluminum phosphate equivalent to 0.004 P er cent, of aluminum. Itinightbe thought that the process would be simplified by reducing the iron to the state of protoxide, and then precipitating alumina as basic ace- tate, subsequently removing by electrolysis the small amount of iron precipitated with the alumina. A number of experiments proved, however, that this modification not only gave less accu- rate results, but involved much more work than the precipitation of all of the iron by electrolysis. 190 QUANTITATIVE ANALYSIS. Method of Carnot. Treat ten grams of the iron or steel in a platinum dish covered with platinum foil, with hydrochloric acid, and when solution is complete, dilute and filter into a flask, washing the carbon, silica, etc., on the filter, thoroughly with distilled water. Neu- tralize the solution with ammonia and sodium carbonate, but see that no permanent precipitate is formed ; then add a little sodium hyposulphite, and when the liquid, at first violet, be- comes colorless, two or three cc. of a saturated solution of sodium phosphate and five or six grams of sodium acetate dissolved in a little water. Boil the solution for about three-quarters of an hour, or until it no longer smells of sulphurous acid. Filter and wash the precipitate of aluminum phosphate mixed with a little silica and ferric phosphate, with boiling water. Treat the pre- cipitate on the filter with hot dilute hydrochloric acid, allow the solution to run into a platinum dish, evaporate to dryness, and heat at 100 C. for an hour to render the silica insoluble. Dis- solve in hot dilute hydrochloric acid, filter from the silica, dilute to about 100 cc. with cold water, neutralize as before, add a little hyposulphite in the cold, then a mixture of two grams of sodium phosphate and two grams of sodium acetate, boil until all smell of sulphurous acid has disappeared, filter, wash, ignite, and weigh as A1 2 O 3 .P 2 O 5 , which contains 22.18 per cent, of aluminum. 1 References . " A Rapid Method for the Determination of Aluminum in Iron and Steel." Chem. News, 61, 313. "On the Determination of Minute Quantities of Aluminum in Iron and Steel." By John E. Stead, F. I. C.,/. Soc. Chem. Industry, 1889, p. 956. XXIII. Determination of Sulphuric Acid and Free Sulphur Trioxide in Fuming Nordhausen Oil of Vitriol. As this acid fumes immediately upon exposure to the air, also rapidly absorbing moisture, great expedition must be exercised in obtaining the samples for analysis. iy. Anal. Chem., 5, 178. NORDHAUSEN OIL OF VITRIOL. , Fig- 5i- Select a small picnometer (Fig. 51), weight about eight grams, and determine its weight with great accuracy. Insert a pipette into the Nordhausen acid, and with- out suction allow about two grams of the acid to run into the pipette. Remove the stopper of the picnometer, insert the lower end of the pipette into it, allow the acid to flow, remove the pipette and in- sert the stopper of the picnometer. Weigh the pic- nometer and acid carefully to the fourth decimal ; then drop it into a tall beaker (capacity 800 cc. ) containing about 500 cc. of distilled water and cover with a watch glass; remove the stopper of the picnometer at the moment the latter is dropped into the water. Too much acid should not be used, three grams being the maximum amount. Determine the amount of acid present by titration with a solu- tion of soda, which will give the total sulphur trioxide, but as Nordhausen acid is composed of varying amounts of a mixture of sulphuric acid and sulphur trioxide, it will be well to explain the method in detail. Picnometer and Nordhausen acid= 8.7210 grams. Picnometer =7.6320 " Nordhausen acid= 1.0890 " Amount of soda solution required to neutralize 1.089 grams of the acid = 28.7 cc. One cc. of the soda solution is equivalent to 0.0401 gram sul- phuric acid or 0.0327 gram sulphur trioxide. The acid therefore contains 86.2 per cent, of sulphur trioxide and 13.8 per cent, of water. To determine the proportions of sulphur trioxide and sul- phuric acid the following formulas are used : Let x = H 2 SO 4 in the acid. y SO 3 " " " x -\-y =. loo. . 98 x + 987 = 9800. 80 x -f- 98jy = 8447.6 1352.4 IQ2 QUANTITATIVE ANALYSIS. x 75.1 per cent, of H 2 SO 4 in the acid. 100 75.1 = 24.9 per cent, of SO 3 in the acid. y = 24.9 per cent of SO 3 in the acid. 75-1 + 2 4 -9_ I00 (x) + (y} - Nordhausen acid often contains small amounts of sulphur dioxide. This should be boiled out of the water before titra- tion with the soda solution. XXIV. Determination of Manganese in Iron and Steel. Manganese can be determined accurately in iron and steel colorimetrically, gravimetrically or volumetrically. The latter method is in general use as being expeditious. For the gravimetric and volumetric methods the initial treat- ment may be the same, that is, solution of the steel in nitric acid ; the precipitation of the oxide of manganese by means of the nitric acid and potassium chlorate, and its filtration and separation. Five grams of the steel are transferred to a No. 5 beaker and 150 cc. of nitric acid (sp. gr. 1.2) added. After solution of the iron and concentration to about 100 cc., there is added fifty cc. nitric acid (sp. gr. 1.42) and the boiling continued till the bulk of the liquid amounts to about 100 cc. To this is added crys- tals of potassium chlorate (not over three grams) gradually, and the boiling continued until no more fumes of chlorous gas are emitted. Allow to cool, add twenty-five cc. nitric acid (sp. gr. 1.42) and filter upon an asbestos filter, washing tw r ice with strong nitric acid and five times with cold water. Transfer the filter and contents to a beaker and treat a, for gravimetric de- termination, or b for volumetric determination of the manganese. a. Add seventy-five cc. hydrochloric acid (strong) and boil; the manganese dioxide is dissolved. The solution is diluted with water and the asbestos separated therefrom by filtration upon a No. 4 filter, and well washed. The filtrate is made faintly alkaline with ammonia, then to acid reaction with acetic MANGANESE IN IRON AND STEEL. 193 acid, and boiled. Filter off any basic acetate of iron that may be present, and to the filtrate add ammonium hydroxide to alka- line reaction and then bromine (not over one cc.); shake well, set aside two hours, then boil, filter, dry, ignite, and weigh as Mn 3 O 4 . Consult scheme XIII. b. Instead of dissolving the manganese dioxide in hydro- chloric acid, as in a, it is dissolved in a measured amount of standard acid solution of ferrous sulphate, and the excess of fer- rous sulphate determined by a standard solution of potassium bichromate. The ferrous sulphate solution is made by dissolv- ing twenty grams crystallized ferrous sulphate in i6oocc. water and adding thereto 400 cc. of sulphuric acid (sp. gr. 1.5). The bichromate solution is made by dissolving ten grams of potassium dichromate in 1000 cc. water. One cc. of the ferrous sulphate solution corresponds to o.on gram of iron, that is, it will oxidize the amount of ferrous sulphate to ferric sulphate that corresponds too. on gram of iron. One cc. of the bichro- mate solution corresponds to 0.0054 gram manganese. The manganese dioxide precipitate, obtained from the five grams of steel, is dissolved in 100 cc. of the acid ferrous sul- phate solution ; it is then titrated with bichromate solution until a drop of the liquid placed on a porcelain slab and brought in contact with a drop of fresh dilute solution of potassium ferricy- anide shows no blue or green color, but a faint brown color, (Scheme VIII) indicating complete oxidation. The amount of bichromate that would be required to oxidize the total iron in the 100 cc. would be 18.1 cc., but in this ex- periment 15.1 cc. were required, showing that the oxidizing action of three cc. of the bichromate solution had been sup- planted by the action of the manganese dioxide. Since three cc. of the bichromate corresponds to 0.0162 gram manganese dioxide, and this amount is obtained from five grams of the , ,, , ,. ., . , 0.0162 X 100 steel, the per cent, of manganese dioxide will be 0.324 per cent. Some chemists prefer the use of a solution of potassium permanganate instead of potassium bichromate. (Consult, Trans. American Inst. Mining Engineers, 10, 100.) The color method may be stated briefly as follows : In a test- 194 QUANTITATIVE ANALYSIS. tube, similar to that used for the estimation of carbon, place two- tenths gram of the sample to be tested, and in a like tube the same quantity of a standard steel, in which the manganese has been carefully determined by weight. To each add five cc. nitric acid (sp. gr. 1.20), and boil in a beaker of hot water until solution is complete. Cool the tubes, and to each add an equal bulk, about two cc. of water ; replace in the beaker, and, after boiling for a few minutes, add an excess of lead peroxide, which must be free from manganese, and ten drops of. nitric acid (sp. gr. 1.42.) After boiling for four minutes the tubes are with- drawn and placed in a beaker of cold water. When the per- oxide of lead has completely settled, transfer two cc. of the clear supernatant liquid of the standard solution to the graduated tube used in the colorimetric estimation of carbon, dilute to fivecc. with cold water, mix. In a similar tube place the same quan- tity of the solution of the sample which is being tested, diluting with water until its color is of the same intensity as that of the standard. Read off the number of cc. to which dilution is car- ried, from which, by a simple calculation, the percentage is easily determined. 1 Textor's Method for the Rapid Determination of Manga- nese in Steel. To one-tenth gram of steel, in a No. 2 beaker, add fifteen cc. of nitric acid (sp. gr. 1.20) ; boil until the brown oxides of nitro- gen are gone; add fifteen cc. of hot water, and while boiling introduce one-half gram of lead peroxide. Boil three minutes after the addition of the lead peroxide, filter through asbestos, and wash with water containing two per cent, nitric acid (sp. gr. i. 20). Titrate with a solution of arsenious acid till the pink color is gone ; each cubic centimeter of solution equals one- tenth per cent, of manganese. Precautions. The brown fumes must all be expelled before adding water, otherwise low results may be expected. Before filtering, the asbestos must be treated with nitric acid. For steels containing 0.75 per cent, of manganese, one-half gram or more lead peroxide should be added, and the solution, after the 1 J. J. Morgan : Chem. News, 56, 82. ZINC IN ORES. 195 addition of the lead, should be boiled not less than three minutes, otherwise low results may be obtained. To secure rapid filtra- tion, a special filter is required. It may be constructed as fol- lows : Fill a two and one-half inch funnel one-third to a half full with pieces of glass rod one-quarter to one-half inch long ; on this place a disk of platinum foil fitting the funnel at the point where the disk rests on the broken glass. The platinum disk is perforated by means of a pin, over its whole surface; the rough side is turned down. Pour suspended asbestos upon the foil till a layer is formed one-half inch in thickness. When the filter becomes clogged and works slow r ly, the thin layer of lead peroxide can be removed by carefully scraping with a wire, a fresh surface of asbestos thereby becoming exposed. For the arsenic solution, twenty grams of arsenic trioxide in powder and sixty grams of sodium carbonate are dissolved in 750 cc. of hot water, filtered and diluted to 2000 cc. An equiva- lent amount of sodium arsenite may be conveniently taken. Of this solution, 87.5 cc. are diluted to 2500 cc. and tested with a steel containing a known percentage of manganese. 1 References: " Colorimetric Estimation of Manganese in Steel." By B. \V. Cheever,/. Anal. Chem., i, 88. "Volumetric Determination of Manganese." By J. Pattison,y. Chem. Soc., 35, 365. " Method for the Rapid Determination of Manganese in Slags, Ores, Etc." By F. G. Myhlertz,/. Anal. Chem.. 4, 267. XXV. Technical Determination of Zinc in Ores. Prepare a solution of potassium ferrocyanide by dissolving torty-four grams of the pure salt in distilled water and diluting to one liter. Standardize as follows :' Dissolve 200 milli- grams of pure zinc oxide in ten cc. of strong pure hydro- chloric acid. Add seven grams of C. P. ammonium chloride, and about 100 cc. of boiling hot water. Titrate the clear liquid with the ferrocyanide solution until a drop, tested on a porcelain plate with a drop of a strong aqueous solution of uranium acetate, shows a brown tinge. About sixteen cc. of 1 Engineers' Society of Western Pa., Trans., 1892. - Method of von Schulz and Low. 196 QUANTITATIVE ANALYSIS. ferrocyanide will be required, and accordingly this amount may be run in rapidly before making a test, and then the titra- tion finished carefully by testing after each additional drop of ferrocyanide. As soon as a brown tinge is obtained note the reading of the burette, and then wait a minute or two and ob- serve if one or more of the previous tests do not also develop a brown tinge. Usually the end-point will be found to have been passed by a test or two, and the proper correction must then be applied to the burette reading. Finally make a further deduc- tion from the burette reading of the amount of ferrocyanide re- quired to produce a brown tinge under the same conditions when no zinc is present. This correction is about two drops, or 0.14 cc. Two hundred milligrams of zinc oxide contain 160.4 milligrams of zinc, and one cc. of the above standardized sol- ution will equal about o.oi gram of zinc, or about one per cent., when one gram of ore is taken for assay. Prepare the following solutions for the assay of ores : A saturated solution of potassium chlorate in nitric acid, made by shaking an excess of crystals with the strong acid in a flask. Keep the solution in an open flask. A dilute solution of ammonium chloride containing about ten grams to the liter ; for use heat to boiling in a wash bottle. Take exactly one gram of the ore and treat in a three and one-half inch casserole with twenty-five cc. of the above chlorate solution. Do not cover the casserole at first, but warm gently until any violent action is over and greenish vapors have ceased to come off. Then cover with a watch-glass and boil to com- plete dryness, but avoid overheating and baking. Cool suffi- ciently and add seven grams of ammonium chloride, fifteen cc. strong ammonia water, and twenty-five cc. hot water. Boil the covered mixture one minute and then, with a rubber-tipped glass rod, see that all solid matter on the cover, sides and bot- tom of casserole is either dissolved or disintegrated. Filter into a beaker and wash several times with the hot ammonium chloride solution. A blue colored solution indicates the pres- ence of copper. In that case add twenty- five cc. strong pure hydrochloric acid and about forty grams of granulated test-lead. Stir the lead about in the beaker until the liquid has become SODIUM CYANIDE. 197 perfectly colorless and then a little longer to make sure that all the copper is precipitated. The solution, which should be quite hot, is now ready for titration. In the absence of copper the lead is omitted and only the acid added. About one-third of the solution is now set aside, and the main portion is titrated rapidly with the ferrocyanide until the end-point is passed, us- ing the uranium indicator as in tjie standardization. The greater part of the reserved portion is now added, and the titration con- tinued with more caution until the end-point is again passed. Then add the remainder of the reserved portion and finish the titration carefully, ordinarily by additions of two drops of ferro- cyanide at a time. Make corrections of this final reading of the burette as in the standardization. Gold, silver, lead, copper, iron, manganese, and the ordinary constituents of ores do not interfere with the above scheme. Cad- mium behaves like zinc. When known to be present it may be removed, together with the copper, by the proper treatment with hydrogen sulphide, and the titration for zinc may be made upon the properly acidified filtrate without the removal of the excess of gas. XXVI. >dium Cyanide as a Component of Potassium Cyanide. The valuation of potassium cyanide for commercial purposes, dependent upon the amount of cyanogen present, the salt being rated from "thirty percent, cyanide" to "ninety-eight percent, cyanide " the former selling for twenty cents and the latter for sixty cents per pound. The determination of the percentage of cyanogen is usually made by titration with semi-normal silver solution, and in chemical manufactories where potassium cyan- ide is made, generally constitutes the entire analysis. Potas- sium cyanide, when pure, contains forty per cent, of cyanogen ; "ninety-eight per cent." would, therefore, indicate 39.2 per cent, of cyanogen, and "thirty per cent.," twelve per cent, of cyanogen. An analysis of a sample of the former gave by titra- tion 42.33 per cent, of cyanogen, or a rating of 105.87 per cent, of potassium cyanide. This result immediately showed that another base than potassium was present, and one also whose 198 QUANTITATIVE ANALYSIS. combining weight was less. Sodium being indicated by quali- tative analysis, a quantitative analysis of the sample was neces- sary to determine the proportions of potassium and sodium com- bined with the cyanogen. The method adopted was as follows : The cyanide was weighed, transferred to a platinum capsule, sufficient water added for solution, then dilute sulphuric acid in excess and con- tents evaporated to dryness and ignition to constant weight. This represented sulphates of potassium and sodium, and after solution in water and acidifying with hydrochloric acid, the sulphuric acid was precipitated and weighed as barium sulphate and calculated to SO 3 . These determinations gave a method of obtaining the propor- tions of potassium and sodium in the weighed alkaline sulphate as follows : 94.2 parts K 2 O require 80 parts SO 3 for K 2 SO 4 62.0 " Na,0 " 80 " S0 3 " Na 2 S0 4 Let G = weight of sulphates. " x = '" " K 2 O. " Na 2 O Or, G x + y -\- 0.85 x + 1.29 y x + y = G SO 3 1.85803 0.85 G 0.4387 Having obtained the values of potassium oxide and sodium oxide, they are calculated to potassium and sodium. These weights are multiplied by 100 and divided by the weight of cyanide taken, the results being the percentages of potassium and sodium respectively in the cyanide. If to these results is added the per- centage of cyanogen, as determined by titration with semi-nor- mal silver solution, the analysis is completed. A sample of the cyanide above mentioned as containing sodium as well as potassium, gave the following : SODIUM CYANIDE. 199 Amount of salt taken for analysis, 1.519 grams. Platinum capsule and alkaline sulphates 46.625 grams. 44-573 K 2 S0 4 4- Na^O, 2.052 Crucible and BaSO 4 25.165 " 22.306 " BaSO< 2.859 " Equivalent to 0.981 gram SO 3 . Cyanogen by titration was 42.33 per cent. Na 2 = 1.85 (o.98i) -0.85(2.05*0 = O . l6l gram . 0.4387 = o.i 20 gram sodium, or 7.90 per cent. K 2 O = 2.052 (0.981 + 0.161) = 0.910 gram. = 0.755 gram potassium, or 49.70 per cent. Resulting : Sodium 7.90 per cent. Potassium 49-7 " " Cyanogen 42.33 " " Undetermined 0.07 " " Total loo.oo " " Equivalent to : Sodium cyanide 16.90 per cent. Potassium cyanide 82.83 " " Difference - f 0.20 " " Undetermined 0.07 " " Total loo.oo " " This cyanide of potassium and sodium (though marked * ' pot- assium cyanide, ninety-eight per cent. ") is sold at a lower rate than the " ninety-eight per cent, potassium cyanide," and for many purposes is superior, as it contains a higher percentage of cyanogen. An examination of the formula for its manufacture shows that it can be made at a less cost than the potassium cyanide alone. Potassium ferrocyanide, or sodium ferrocyanide when heated in covered crucibles is converted into potassium or sodium cyanide, iron carbide and nitrogen : 2K 4 Fe(CN) 6 = 8KCN+ 2 FeC 2 + N 4 2Na 4 Fe (CN) 6 8NaCN+ 200 QUANTITATIVE ANALYSIS. ioo pounds of potassium ferrocyanide, at thirty cents per pound, produces 70.63 pounds of potassium cyanide, ninety-eight per cent., at a cost of forty-two cents per pound ; and ioo pounds of sodium ferrocyanide, at twenty cents per pound, produces 64.47 pounds of sodium cyanide, ninety-eight per cent., at a cost of thirty-one cents per pound. If a mixture composed of 1 1 7 pounds of potassium ferrocyan- ide and twenty-six pounds of sodium ferrocyanide be heated in covered crucibles, the resulting compound, weighing loopounds, will closely approximate, in composition, the sample submitted. XXVII. The Chemical and Physical Examination of Portland Cement. The enlarged consumption of Portland cement in this country during the past few years has caused the subject of its chemical and physical properties to receive increased consideration. Not only has the consumer been directly interested, that the cements used should stand special tests, but the attention of the manu- facturer has been drawn in the same direction, resulting in im- provements in methods of production. A number of causes have prevented the use of American Port- land cements in the home market, one of the chief being that the imported German cements always give higher physical tests when made by the German methods of testing than the American cements under the American system of testing. There are a number of American Portland cements fully as good as the best German cements, and have shown fully as high ten- sile strength when tested by the same methods. These differences in results are not due entirely to the cements, but rather to the methods in use in the different coun- tries for testing them, for Portland cements cannot vary much in their chemical composition without losing their value. The limit of variation is as follows : CaO 58.0 to 67.0 per cent. 1 SiO 2 20. o to 26.0 A1 2 O 3 5.0 to 10.0 Fe. 2 O 3 2.0 to 6.0 MgO 0.5 to 3.0 SO 3 0.510 2.0 1 E. Candlot: tude practique sur le Ciment de Portland, (Paris, 1886 PORTLAND CEMENT. 2OI After manufacture it is practically Ca 3 SiO 5 , and is quite dis- tinct from another product made and largely consumed here called " hydraulic cement." Experience has shown that Portland cements containing over two per cent, of magnesia (MgO) are inferior in lasting quali- ties, and by the gradual absorption of water produce cracking and disintegration. 1 Calcium carbonate (CaCO 3 ), formed by the absorption of carbon dioxide by the lime in the cement after manufacture, is another injurious compound found in cements containing more lime than sufficient to unite with the silica to form tri-silicate of lime. This carbonate of lime gradually produces seams and fractures after the setting of the cement. The " Ecole Nation- ale," of Paris, rejects all cements containing over one and five- tents per cent, of sulphuric acid. Thus, if upon chemical analy- sis, magnesia is found present in amounts over two per cent, carbonic and sulphuric acids in amounts over one and one-half per cent. , the cement can be condemned at once without any mechani- cal tests. Therefore, it is evident that a careful test of a Port- land cement requires : ( i ) a chemical analysis to determine the proportion of the ingredients, and (2) the mechanical or physi- cal tests to determine fineness, tensile strength, and resistance to crushing. The following scheme is arranged to show the method of making a cement analysis : 1 Compt. rend., May, 1886. *i X SI ll o J4 o b U be W.2 8'J e> IB I" j. a a o re '.w u s e "o s3 111 Si! C ^* JS ol o ^ ;; OU 3 5g VM S O - u "re ,ti *W ^ IT S o I! c si T3 03 V U 84 :* "3 o be N U T3 .SP S C 3 XI ^1 8? ?s p re ^^ S5 Is i\ 8 *o a ffi.S l 5. x > MI;? 1 s ' VJ Cd x_^ S -^ .SfS s *. ^ ^ Q *i _I Tri ' > ^ ^ 15 V co , 3 /i i u 1 >? ** *"^ T f? 1 ! ll-" 2 a is 11 ll 'x - o x l! * 1 3 O tS y >> s a a- S a H * 2-2 n 111 ij 111 - s-g PORTLAND CEMENT. 203 Weight of SiO 2 X 100 = per cent. SiO 2 . (i) Crucible + SiO 2 11.205 grams. Crucible 10.721 " SiO 2 = 0.484 0.484 X ico 2 = 24.20 per cent.SiO). Weight A1 2 3 X IPO = per cent AljQs . n the insoluble residue (i) Crucible -r- A1 2 O 3 10.743 grams. Crucible 10.721 A1 2 O 3 = 0.022 " O.O22 X IOO 2 Weight of Fe 2 O 3 X 2.5 Xioo 2 = 1.10 per cent. A1 2 O 3 . per cent. Fe 2 O 3 . (2) Crucible + Fe 2 O 3 10.745 grams. Crucible 10.721 Fe 2 O 3 = 0.024 ' 0.024 X 2.5 X IPO = 3>oo percent peA Weight of A1,0 3 X 2.5 Xioo_ pr cent ^ (2) Crucible -f A1 2 O 3 10.762 grams. Crucible 10.721 " A1 2 O 3 = 0.041 " 0.041 X 2.5 X loo - = 5.12 per cent. A1 2 O 3 . 5.12 + 1. 10 == 6.22 per cent. A1 2 O 3 . Weight of CaO X 2.5 X 100 = per cent. CaO. (5) Crucible -f- CaO 11.2223 grams. Crucible 10.7210 " CaO = 0.5013 " 0.5013 X 2.50 X loo = 62.67 P er cent. CaO. (7) Crucible -j- MgO 10.725 grams. Crucible 10.721 " MgO = 0.004 " 204 (8) QUANTITATIVE ANALYSIS. Platinum dish ........................ =33.7550 = 0.0500 (Total sulphates) " (MgS0 4 ,K 2 S0 4 ,Na 2 S0 4 ). Crucible + Mg 2 P 2 O 7 = 10.729 grams. Crucible = 10.721 0.008 " Mg 2 P 2 O 7 =o.oo8gms. =0.008 MgSO 4 X 2= 0.0176 (MgSO 4 ) " 0.0324 (K 2 SO 4 -f-Na 2 SO 4 ) " K 2 PtCl 6 = 0.0232 = 0.0082 K 2 SO 4 X 2 = 0.0164 (K 2 SO 4 ; o.oi6o(Na. 2 SO 4 ) 0.0176 MgSO 4 = 0.0058 MgO and is added to MgO in (7) MgO from (7) .......................... 0.004 MgO from (8) ........................... 0.0058 0.0098 0.0098 X 2.5 X ioo = 1.22 per cent. MgO. 0.0164 K 2 S0 4 = 0.0088 K 2 then ' O 88 x 2 -5 X ioo = Itloper ceut KzO> 0.0160 Na 2 SO 4 = 0.0069 Na 2 O then~ 69 X *' 5 X = 0.86 per cent.Na 2 O. (SO S ). Crucible + BaSO 4 ............................ 10.729 grams. Crucible ................... . .................. 10.721 BaSO 4 = 0.008 SO 3 = 0.0027 " 0.0027 X 5 X ioo = 0.67 per cent. SO 3 . RESUME). SiO 2 ........................................ 24.20 per cent. A1 2 3 ....................................... 6.22 " Fe 2 O 3 ....................................... 3.00 CaO ........................................ 62.67 MgO ........................................ 1.22 K 2 O ....................................... . 1. 10 " Na 2 ........................................ 0.86 " SO 3 . ..................................... 0.67 Total ................................. 99.94 " The following well known brands of Portland cements were analyzed in iny laboratory by above method. PORTLAND CEMENT. 205 Burham's. Dyckerhoff's. 19 05 per cent Saylor's. 21 25 per cent A1 Oo . 6 82 ' ' 700 " 4 21 " PP O 4 48 '* 8 25 " OaO 62 26 " 63 62 " \TcrO .. r 48 " i 87 " i 50 " K O - i SA " o 88 " I OI " XS^V./ AJo O o 98 " i. 20 " O.QA " 0.99 C0 2 . 99.95 " 100.00 " 99.84 " In some cements quartz is a constituent in amounts varying from five-tenths to six per cent. It can be separated from com- bined silica by the method of Fresenius. 1 Where carbonic acid has been indicated by the qualitative analysis the quantitative analysis, for this constituent, should be made upon at least eight grams of the cement. The carbonic acid rarely reaches one per cent., and while it is generally absent in well burned cements, it is by no means an uncommon constituent to the amount of 0.15-0.30 per cent., as the following table of analyses of German cements will show : 2 CaO I 2 Q Q 3 4 5 6 7 8 fin RT 22 09 80 J ' 7 1 27 3< 80 5o9 22 85 59-9 D4.51 22 28 p e O o/ 2 76 Al O 82Q 1 O' C Q r\ T ofi Mg-O . . O A7 2O 3 1 73 5 1 9-45 7.00 , OQ Alkalies 8/1 18 2.O9 -, 0- SOs Q 71 Q .04 87 J 40 08 T 6Q o 88 2.03 CO . '/* / i.uy 1.44 u-47 T o 78 o 8r> -33 Mechanical Testing. The method recommended for use in this country by the American Society of Civil Engineers is as follows : (1) Determination of fineness. (2) Liability to checking or cracking. (3) Tensile strength. 1 Quant. Chem.AnaL, p. 259. 2 Der Portland-cement und seine Anwendungen im Bauwesen, Berlin, 1892, p. 18. 206 QUANTITATIVE ANALYSIS. Fineness. Tests should be made upon cements that have passed through a No. 100 sieve (10,000 meshes to the square inch), made of No. 40 wire, Stubb's wire gauge. The finer the cement the more sand it will unite with and the greater its value. Liability to Checking or Cracking. Make two - cakes of neat cement two or three inches in diameter, about one-half inch thick, with thin edges. Note the time in minutes that these cakes, when mixed with water to the consistency of a stiff, plastic mortar, take to set hard enough to stand the wire test recommended by General Gillmore, one-twelfth inch diameter wire loaded with one-fourth pound , and one twenty-fourth inch diameter wire loaded with one pound. One of these cakes, when hard enough, should be put in water and examined from day to day to see if it becomes contorted or if cracks show themselves at the edges, such contortions or cracks indicating that the cement is unfit for use at that time. In some cases the tendency to crack, if caused by too much lime, will disappear with age. The remaining crack should be kept in the air and its color observed, which, for a good cement, should be uniform throughout. Tensile Strength. One part of the cement mixed with three parts of sand 1 for the seven days and upward test, in addition to the trials of the neat cement. The proportions of cement, sand and water should be carefully determined by w r eight, the sand and cement mixed dry, and all the water added at once. The mixing must be rapid and thorough, and the mortar, which should be stiff and plastic, should be firmly pressed into the molds with the trowel without ramming and struck off level, the molds in each instance, while being charged and manipu- lated, to be laid directly on glass, slate or other non-absorbent material. The molding must be completed before incipient setting begins. As soon as the briquettes are hard enough to bear it, they should be taken from the molds and kept covered with a damp cloth until they are immersed. For the sake of uniformity, the briquettes, both of neat cement and those con- i White crushed quartz, which passes through a No, 20 sieve, but remains upon a No, 30 sieve, is standard. PORTLAND CEMENT^ 207 taining sand, should be immersed in water at the end of twenty- four hours, except in the case of one day tests. Ordinary clean water having a temperature between 60 F. and 70 F. should be used for the water of mixture and immersion of sample. The proportion of water required is approximately as follows : For briquettes of neat cement, about twenty-five per cent. For briquettes of one part cement, one part sand, about fifteen per cent, of total weight of cement and sand. For briquettes one part cement, three parts sand, about twelve per cent, of total weight of cement and sand. The object is to produce the plasticity of plasterer's stiff cement. An average of five briquettes may be made for each test, only those breaking at the smallest section to be taken. The bri- quettes should always be put in the testing machine and broken immediately after being taken out of the water, and the tem- perature of the briquettes and of the testing room should be con- stant between 60 F. and 70 F. The following table shows the average minimum and maxi- mum tensile strength per square inch which some good cements have attained. Within the limits given the value of a .cement varies closely with the tensile strength when tested with the full dose of sand. AMERICAN AND FOREIGN PORTLAND CEMENTS. NEAT. One day, (i hour, or until set, in air, the rest of the 24 hours in water,) from 100 to 140 pounds per square inch. One week, (i day in air, 6 days in water), from 250 to 550 pounds per square inch. One month, 28 days, (i day in air, 27 days in water), from 350 to 700 pounds per square inch. One year, (i day in air, the remainder in water), from 450 to 800 pounds per square inch. AMERICAN AND FOREIGN PORTLAND CEMENTS. i PART OF CEMENT TO 3 PARTS OF SAND. One week, (i day in air, 6 days in water), from 80 to 125 pounds per square inch. One month, 28 days, (i day in air, 27 days in water), from 100 to 200 pounds per square inch. One year, (i day in air, the remainder in water), from 200 to 350 pounds 1 per square inch. 1 In regard to modification of these conditions required for tensile strength, consult Trans. A met'. Soc. of Civil Engineers, August, 1891, p. 285. 208 QUANTITATIVE ANALYSIS. The machines for determining the tensile strength of Portland cements in use in this country are the "Fairbanks," Fig. 52, the " Riehle," Fig. 53 and the Olsen. The Fairbanks machine is automatic and is operated as follows : Hang the cup on the end of the beam ; see that the poise is at the zero mark and balance the beam by turning the ball. Place the shot in the hopper. Place the briquette in the clamps and adjust the hand wheel so that the graduated beam will be Fig. 52. inclined upward about 45. Open the automatic valve so as to allow the shot to run slowly. When the specimen breaks the beam drops and closes the valve through which the shot has been pouring. Remove the cup with the shot in it and hang the counterpoise weight in its place. Hang the cup on the hook under the large balance ball and proceed to weigh the shot, using the poise on the graduated beam, and the weights on the counterpoise weight. The result will show the number of pounds required to break the specimen. PORTLAND CEMENT. 2O9 The '' Riehle," while not automatic, is accurate, and responds to differences as slight as one pound in 2,000. The distinctive features are : (a) The poise moves quietly and smoothly on the weighing beam. () The weighing beam is long and the marks not too close together. The slightest movement of the beam is promptly and plainly observed by the motion of the indicator. (c) The levers are tested and sealed to U. S. standard weight. ) The arrangement of the "grips" to hold the briquette is such that they are always swung from pins, thus giving the test Fig- 53- ipon the cement when the briquette is on a dead straight line. Directions for Testing Portland Cement According to the Official German Rules. 1 The quality of a mortar made with cement depends not only on the strength of the cement itself, but also 1 Portland Cement, by Gustav Grawitz. 210 QUANTITATIVE ANALYSIS. on the degree of sub-division of the same. It is therefore neces- sary to make the tests both with neat cement and with a mixture of the same with ''standard sand." This latter as used at the Royal It sting Station at Berlin, is produced by washing and drying quartz sand, which must be clean as possible, and after- wards be sifted through a sie-re of sixty meshes per square cen- timeter (387 meshes per square inch), by which process the coarsest particles are separated. The sand is again sifted through a sieve having 120 meshes to the square centimeter (774 meshes per square inch). Trie residue remaining in this sieve is the standard sand for experiments, the coarsest and finest particles having been eliminated. It is absolutely neces- sary in order to obtain uniform results to use only the "standard sand," as the size of the%rain has a material influence on the results of the testings The sand must be clean and dry, and all earthy and other substances previously removed by washing. Preparation of Briquettes of Neat Portland Cement. Upon a slab of metal or marble are laid five sheets of filtering paper, which have been previously saturated with water, and upon these are placed five brass molds (Fig. 54) thoroughly cleaned and moistened with water. One thousand grams of cement and 250 grams of water must be thoroughly mixed, well worked up, and when the resulting mass has been rendered perfectly homogen- eous, it is poured into the molds. The latter must be gently tapped by means of a wooden hammer with Fig 54. equal force on both sides during ten to fifteen minutes to insure the escape of confined globule^ of air. The molds must be carefully filled up until the mass becomes plastic, the superfluous mortar is then struck off, and the mold carefully withdrawn. The samples, after remaining twenty-four hours exposed to the air, at a temperature of about 60 F., must be immersed in water having the same temperature, and care must be taken that they remain covered with water until the time ar- rives for breaking them. In order to obtain a proper average at least ten briquettes should be prepared for every examination. Preparation of Briquettes from a Mixture of Portland Cement and Standard Sand. Place the molds on metal as described in PORTLAND CEMENT. 211 preparation of neat cement briquettes. The quantities (by weight) specified of cement and sand are thoroughly mixed and to this Fig. 55- is added the requisite quantity of water. The whole mass is then worked up with a trowel or spatula until it becomes uni- Fig. 56. 212 QUANTITATIVE ANALYSIS. form. In this manner is obtained a very stiff mortar. The molds are filled and mortar heaped up. The latter is then beaten into the molds with an iron trowel, at first lightly, and afterwards more heavily, until it becomes elastic and water ap- pears on the surface. The superfluous morter is then scraped off with a knife and by means of the same the surface is leveled. The further treatment of these briquettes is the same as for neat Fig. 57- cement briquettes. The average of ten breaking weights fur- nishes the strength of the mortar tested. The machine in general use in Germany for determining the tensile strength of cements is the Michaelis (Fig. 55), and from this is derived, with modifications, the "Reid and Bailey/' PORTLAND CEMENT. 213 machine in use in England, and the "Fairbanks" previously described. Xo standard specifications for the testing of Portland cement are required in Great Britain, the determination of fineness, ten- sile strength and variations in volume, being considered suffi- cient to determine the value of a cement. The machines for ten- sile strength are the "Faija," (Fig. 56), the "Reid and Bailey," (Figs.57and58),or the "Grant," similar to the Riehle, and de- Fig. 58. scribed in Proceedings of the Institution of Civil Engineers, 62, 113. The "Reid and Bailey " is essentially the " Michaelis " (Fig. 55), excepting that water is used instead of fine shot for the breaking power. It is readily seen that the " Faija " and "Grant " machines, not being automatic, require the application of the power at a certain uniform speed to obtain comparable results, since a dif- ference of twenty-five per cent, of tensile strength may be ob- tained by applying the strain very quickly or very slowly. 1 1 Proceedings of the Institution of Civil Engineers, 75, 225, 226. 214 QUANTITATIVE ANALYSIS. Faija has determined this variation with extreme care, there- suits being indicated in the curve shown in Fig. 59. To over- come these variations a uniform speed of 400 pounds per min- ute has been accepted as the standard. Not only are comparable methods required in the use of the machines to obtain uniform results, but the briquettes must also be constructed under similar conditions. It is manifestly unjust to compare the tensile strength of two cements (even when the briquettes are broken upon the same machine) unless the briquettes have the same weight of water for mixing ; the same pressure with the trowel when being formed in the molds, and the same length of time of exposure under water before submitting the briquettes to the tensile strain. For instance : Comparing tests made upon the Dyckerhoff Portland cement by Dr. Bohme, Director of the Royal Commis- sion for testing building material, at Berlin, and by E. J. DeSmedt, General Inspector Engineering Department, District of Columbia, we find that the German method gives a much higher tensile strength than the method in use in this country. DR. BOHME. Average tensile strength Age of briquettes. per square inch. Number of tests.. 7 days 767 pounds 10 28 " 895 " 10 E. J. DESMEDT, C. E. Average tensile strength Age of briquettes. per square inch. 5 days 250 pounds. 30 " 700 Showing : 109 pounds increase per day (7 days), Dr. Bohme. 59 " " " " (5 days), DeSmedt. or over 100 per cent, difference upon the same cement on the seven days test. These variations are undoubtedly due principally to the dif- ferent pressures upon the cement during the making of the bri- quettes, and to overcome difficulties of this nature the Vereins deutsche Portland Cement Fabrikanten have modified the rules I I I I JO. 1 I I l-l- 1 I I I I I I 216 QUANTITATIVE ANALYSIS. in the construction of the briquettes so that two methods are ac- ceptable : First, the normal method, above given, with the trowel, etc. (" Handarbeit".) Second, the use of the Bohme-Hammer apparatus or " ma- chine method," by which the cement in briquette form (after PORTLAND CEMENT. 2iy mixing with proper amount of water) , is submitted to a pres- sure of 150 blows from a hammer weighing two kilos (Fig. 60). The briquette of cement is then removed from the mold and treated for tensile strength as usual. This subject is receiving considerable attention at the pres- ent moment, the evident purpose being to render the tests of tensile strength as uniform as possible by making the working of the apparatus automatic and the production of cement bri- quettes with the least possible variation in the pressure in the molds. In this case, no matter how careful the experimenter may be, Fig. 62. Fig. 61. the ' ' personal equation ' ' enters largely into the results of test- ing hand-made briquettes, for which reason the manufacture of the briquettes should be as automatic as possible. In no other way can results obtained by different experimenters be compared. Prof. Charles D. Jameson describes an apparatus for this pur- pose (Figs. 6 1 and 62).' The method of operating is as follows : The lever being raised so that the lower end of the piston or main plunger is above the hole in the side of the cylinder communicating with the hopper, cement is put in the hopper and pushed down into the cylinder. The molding plate is pushed against one of the stops, so that 1 Transactions of the American Society of Civil Engineers, 15,302. CH W iu B *o S ^ S ^ S toW g O og *c o ^ ^ 4-1 to i u cr 'C rt S3 35 i 35 3535 55 a^osbfi * ^ ..a be^,^ s a a . 3 a . j ,0 "3 a 13 { -w OJ rt,j2 . a) rt tn to' II r'i "- |1 II II II III! "3 a 1* ss a-S JS ! li li X '-n ^3* ^3"5 Xx "*-J3 tfi -^. K a rt 55 W 'S w W X m * W tn W w ^ ^ w ^ t/j V aj * w w cj-^- ' "o bo 3 rt O bo bobo bo a a a '55 55 55 bo o bo be^bc^Q 1 ^ .2 | ^.5 So "rt ^ li 6 o o o 000 ^ 5?.2: 2 2 2 2 ^ a ^ be u Ift r> r B! g 1 * a. j ? d o vO 1 5S : : : : : a a 6 00 s H 1 w ON oo oj r- r>* CM 10 rt u ,24 2 6 R : 53 S s * s ff tn I s 2 a* SS 5 -I r cs cT S 5 i R S a gg, a i & j t 1 00 VO - 2 22 ? ID 1-1 O O &" If ON > ON S S S S Laboratory. Name. R. W. Hildreth & Co., New York. Washington University, St. Louis, Mo., Prof. J. B. Johnson. u I >> |i Columbia College, New York, Prof. W. H. Burr. Chas. F. McKenna, New York. & o ci ' cs .* * Ja r3 bo . ^ c' .3 S a 2 | W ^|1 5^ 3 3 =* y 6 M N to Tf UO VO t^ 00 O> PORTLAND CEMENT. 219 one of the openings is beneath the bore of the cylinder. The long lever is forced down, causing the plunger to force the ce- ment into the opening of the molding plate. After this,' the molding plate is swung against the other stop, cutting off the briquette, placing it over the plungers, throwing the other opening in the molding plate directly beneath the cylinder. The smaller lever is lifted, raising the plunger, and forces the bri- quette out of the mold, after which it is removed. The plunger is then pressed down, the main lever also, the molding plate swung back to the first position, the other plunger lever lifted, and another briquette is ready to be taken away, and so on. Fig. 63. After making three briquettes, the main lever is lifted and more cement placed in the cylinder. The machine is best operated by two men, one to feed and operate the long lever, and the other to swing the molding plate, remove the briquettes and lower the plungers. The pressure on the briquette is 175 pounds per square inch. The conditions required in France for a good cement are : l First. Analysis to determine the chemical composition. Second. The determination of density. Third. The determination of fineness. 1 E. Candlot, Ciments et Chaux Hydrauliques , Paris, Baudry & Co. 1891. 220 QUANTITATIVE ANALYSIS. Fourth. The determination of tensile strength. Fifth. The determination of crushing strength. Sixth. The determination of variations in volume. The tensile strength is determined by the use of a Michaelis machine, Fig. 63, or the use of a Buignet apparatus, Fig. 64, this latter being upon an entirely different principle than any yet in use, and is thus described by the designer, M. Buignet, Conductor des ponts et chaussees au Havre : It is composed of a basin A and frame B. The basin A, filled with mercury and water, closes up by a Fig. 64, diaphragm of rubber covered with a metallic disk, and is in direct communication with : (a) Manometrique tube D. (b} With a movable reservoir R, filled with mercury, by means of a thick rubber tube T. The grips G G, in which are to be placed the briquettes to be tested, are fastened, one to the frame B by the support V, the other to the support M, which rests upon the center of the PORTLAND CEMENT. 221 metallic disk over A. It is operated as follows : The briquettes are placed in the grips G G, and the support V moved up or down until equipoise is established, and then firmly secured by a crank in frame B. The support Mis adjusted until the point at its lower end just touches the metallic disk in A. By gradually lowering the reservoir R an upward pressure is given to the metallic disk in A, which is transferred to the sup- port M y until when sufficient pressure is exerted the briquette is broken. The moment rupture of the briquette takes place, the pressure required to do this is indicated by the float z" in the manometer tube D. By a comparison of the various machines used in Germany, England, France, and the United States, we find practically but two in general use: the "Michaelis" and the "Grant." While nearly all engineers require cements to be subjected to the tensile strength test, in fact relying more upon this one test than any of the others, it might be well to include here the opinion of H. Le Chatelier, professor at the Ivcole des Mines, Paris, France, as given in a paper presented at the last meeting of the American Institute of Mining Engineers, August, 1893, entitled "Tests of Hydraulic Materials," p. 44. "The method of tension is at present most widely used, but the preference for it is not well founded. Here, as in rupture by bending, only the surface of the briquettes acts in a really useful way, and its inevitable irregularities and alterations so greatly affect the precision of the results that they can in no case be trusted nearer than about twenty per cent. "This preponderant influence of the superficial parts was first shown by the fact that the resistance of briquettes of differ- ent sizes increases, not with the section, but, on the contrary, with the perimeter. Finally, M. Duraud-Claye has shown that the interior of a briquette may be removed without notably diminishing its resistance to rupture by tension, and has given a complete theoretical explanation of the phenomena which seemed at first sight paradoxical." 222 QUANTITATIVE ANALYSIS. The Clashing Test, This test is not official in this country and is seldom required by our engineers, who, however, have confined their^experiments in this direction mainly to crushing tests of concrete, formed by mixing Portland cement, sand, and broken stone. Tests upon cubes of neat cement and of mortar composed of one part cement and three of standard sand, are generally in- cluded in reports given upon the examination of cements in Europe, the ratio being that the crushing strength is about ten times greater than the tensile strength. Thus, a cement of good quality should show the following resistance per square centimeter : TENSILE STRENGTH. 7 days, 28 days. Neat cement 25 kilos. 35 kilos. ipartcement) IQ lg 3 parts sand - CRUSHING STRENGTH. 7 days. 28 days. Neat cement 250 kilos. 350 kilos, ipartcementj IQQ ,, igo 3 parts sand > To convert kilos per square centimeter to pounds per square inch, the equivalents used are : one kilo = 2.204 pounds English; 6.451 square centimeters = one square inch, English. The hydraulic presses made use of for this purpose, a few years since, gave very discordant results, as it was impossible to distribute the pressure evenly over the surface of the cubes. This has been overcome, and there are now several machines upon the market whose results are comparable, viz. : The "Suchier," Fig. 65, the "Bohme," Fig. 66, the " Tet- majer," as improved by Prof. Amsler-Laffon, 1 the " Brink and Hubner," 2 the "Riehle," the "Fairbanks," the "Olsen" and the "Bailey." Variation in volume (expansion or contraction) The method of Faija, 3 the one generally used for this purpose, is as follows : 1 Consult : Schweizer Bauzeit, January 12, 1889. 2 Description of the " Suchier," " Bohme," and " Brink and Huber " machines will be found in Der Portland Cement und seine Anwendungen im Bauwei>en, Berlin, 1892. 8 The determination of liability to ''checking" or "cracking" (variation in vol- ume) in Portland cements as recommended by American Society Civil Engineers, is not as complete as Faija's method. See J- Am. Chem. Soc., 15, 184. PORTLAND CEMENT. 223 Three pats should be made on pieces of glass or other non- porous substance, and their behavior watched under the follow- ing conditions : Pat No. i may be left in the air, and No. 2 should be put in Fig. 65. water as soon as it is set hard. Pat No. 3 should be treated in the apparatus for determining the soundness of cement. The apparatus consists of a covered 224 QUANTITATIVE ANALYSIS. vessel in which water is maintained at an even temperature of 110 C.; the space above the water is therefore filled with the vapor rising therefrom, and is at a temperature of about 100 C. Immediately the pat is gauged, it should be placed on a rack in the upper part of the vessel, and in five or six hours it may be placed in the warm water and left therein for nineteen or twenty hours. If, at the end of that period, the pat is still fast to the Fig. 66. glass and shows rib signs of blowing, the cement may be consid- ered perfectly sound ; should, however, any signs of blowing appear, the cement should be laid out in a thin layer for a day or two, and a second pat made and treated in the same manner, as the blowing tendency may only be due to the extreme new- ness of the cement. If pat No. 3 shows the cement to be unsound, pats Nos. i and 2 will eventually prove it, but it may be weeks or even months before they develop the characteristics. If pat No. 2 blows, it may be because it was put in the water before it was set. A cement is considered set hard when it can no longer be marked by the pressure of the thumb nail. CEMENT TESTING MACHINE. 225 An Automatic Cement Testing Machine. To promote convenience and rapidity and secure uniformity, regularity, and a standard method of work as free as possible from the irregularities coming under the head of ' ' personal equation," Prof. J. M. Porter has devised the adjustable auto- matic loading and balancing attachments which are illustrated by the accompanying elevation and details of the special mechan- ism added to the 2,ooo-pound Olsen machine of standard pat- tern. Fig. 67. The load is applied by filling with water a tank suspended from the long arm of a 15 to i lever, the con- nection of which has a pin bearing on a cylindrical surface which rests on the adjustment screw 7 of the lower grip. Neither the tank nor its contents are weighed, but the exact rate of loading per minute is accurately known from previous tests. Water is admitted to the tank from a large reservoir on the roof, where a practically constant height of surface level is maintained, so that there is no sensible variation of pressure in the stream admitted through a carefully fitted gate valve. The position of this valve at "open," "closed," and all intermediate points is shown by an index attached to the stem and registering on a dial marked off with the number of pounds per minute applied to specimen as determined and verified by previous experiments. When the specimen breaks, the load lever drops and permits the load tank to fall a few inches, so that the chain is brought into tension and arrests the descent of the valve before its seat stops descending. Thus the bottom of the tank is opened and the contents quickly escape into the hopper of the receiving case, and are carried off through the waste to the sewer. The actual load can be applied at from zero to eighty pounds per minute, thus giving an increase strain of zero to 1,200 pounds per min- ute on the specimen. A small electric motor is belt-connected to the pulley that continuously drives a friction disk and its engaged wheel. The wheel is feathered to a sleeve that runs loose on its shaft, and carries a coned clutch that is nominally disengaged from its cone, which is feathered to shaft, and can be moved slightly longitudinally on the shaft into contact with the wheel by the action of a lever. DETERMINATION OF NICKEL. 227 When the scale beam rises, it makes a contact which com- pletes the electric circuit and sends a current through the elec- tromagnet and causes it to attract its armature (here shown not in contact) , which moves to the right about a pivot a sufficient distance to make the friction clutch with the coned wheel and drive shaft. This shaft in turn operates the sprocket wheel and chain, which draw the weight out on the scale beam until the latter falls, and breaking the electric circuit, releases the arma- ture and allows the friction clutch to disengage. By turning the capstan-head nut, the friction wheel is set at a greater or less distance from the center of the disk, and the chain is overhauled faster or slower accordingly. .The arrangement was constructed in the college laboratory and is positive and simple. It does not get out of order and is considered accurate and satisfactory, and to enable more rapid and better comparable tests to be made more than twenty specimens per hour have been broken by its use. Resume ': The determination of the value of Portland cement therefore requires the following tests : First. Chemical analysis. Second. Determination of fineness. Third. Determination of tensile strength, including the use of automatic briquette machines as well as an apparatus for mix- ing the cement with water, as " Faija" mixing machine. Fourth. Determination of crushing strength. Fifth. Determination of variation of volume. References : J. Am. Chein. Soc., 16, 382-386, contains an index, ar- ranged by the writer, of the literature relating to Portland cement, from 1870 to 1893. XXVIII. Determination of Nickel. The principles involved in the processes are the following : l /**>$/. The iron is precipitated as ferric phosphate in cold, strong acetic acid solution, under which condition it precipitates perfectly free from nickel, although retaining a small amount of copper. 1 E. D. Campbell : J. Am Chem. Soc., 17, 125. 228 QUANTITATIVE ANALYSIS. ^ Second. The copper is separated from manganese and nickel in hydrochloric acid solution by means of granulated lead. Third. The manganese and lead, which displaced the copper, are separated from the nickel by means of cold ammoniacal solu- tion of sodium phosphate. Fourth. The nickel is determined in the ammoniacal filtrate from the phosphate of manganese and lead, by titration with standard potassium cyanide, or by electrolytic deposition. In case the nickel is accompanied by cobalt the latter metal remains with the nickel and may be separated from it by any of the well-known methods after dissolving off the electrolytically deposited nickel. The two methods described below are identical up to the point where a portion of the nitrate from the phosphates of man- ganese and lead is taken. The description of that part of the methods common to both will be first given, and then the two ways of treating the above filtrate for the final determination of nickel will be added. Take 2.2222 grams of nickel-steel, place in a 500 cc. gradu- ated flask, add twenty cc. nitric acid, sp. gr. 1.20, and five cc. hydrochloric acid, sp. gr. 1.21. Boil until the solution is clear, which will usually require not more than from five to ten min- utes. Remove from the plate and add 155 cc. sodium phos- phate solution. If a slight precipitate should form which does not dissolve upon shaking, add carefully a few drops of hydro- chloric acid until the solution clears up. Add twenty-five cc. acetic acid, sp. gr. 1.04, then 100 cc. sodium acetate solution, shake, dilute with water to 502.5 cc., shake again, and allow to stand fifteen minutes. Filter through a dry twenty-five cc. fil- ter, catching the filtrate in a dry beaker. As soon as enough of the filtrate has run through, which requires about ten minutes, draw off with a pipette 250 cc. of the filtrate, transferring to a No. 4 beaker. This will give one-half of the solution, since it was found by experiment that the ferric phosphate from the amount of steel taken occupies two and a half cc. Bring the solution to a boil and add twenty grams potassium hydroxide previously dissolved in forty cc. of water. Boil five minutes, then keep just below boiling-point until the precipitate has set- DETERMINATION OF NICKEL. 22Q tied and the solution is clear. This precipitates copper, man- ganese, and nickel so completely that the filtrate gives no color with hydrogen sulphide. Filter through asbestos, using a pump, decanting as much of the solution as possible before al- lowing the precipitate to get upon the filter. Wash with water. Dissolve the precipitate on the filter in a hot solution of six cc. strong hydrochloric acid with an equal volume of water. Wash the filter, using only as much water as is necessary. To the solution in the flask, \vhich should not exceed fifty cc. and should have a temperature of 40 to 50 C., add fifteen grams of granulated lead and agitate at frequent intervals for five or ten minutes. This will completely precipitate the copper, a small amount of lead going into solution. Filter through a small glass wool filter, catching the filtrate in a No. 2 beaker ; wash the granulated lead with a small amount of water and boil the solution down until it does not exceed sixty cc. Add ten cc. of sodium phosphate solution, then ammonium hydroxide until a precipitate begins to form, then hydrochloric acid suffi- cient to clear the solution, cool until cold, and transfer to a cylin- der or flask graduated to ui.i cc. Add five cc. strong ammo- nium hydroxide, sp. gr. 0.90, dilute to the mark, shake well, and allow to stand fifteen minutes. Filter through a dry nine cm. filter, receiving the filtrate into a dry beaker. Draw off, by means of a pipette, 100 cc. of the filtrate, which is equivalent to one gram of the original steel, and treat by one of the two fol- lowing methods : Electrolytic Method. Transfer the 100 cc. of filtrate, above mentioned, to a large platinum dish having a capacity of about 200 cc. Add twenty- five cc of strong ammonium hydroxide, sp. gr. 0.90, and dilute to 175 cc. Electrolyze for at least four hours, using a current yielding four cc. of electrolytic gas per minute. This strength of current can be easily obtained by connecting three medium- sized cells. The end of the precipitation of the nickel is indi- cated when a drop of the solution placed in contact with a drop of ammonium sulphide gives no color due to nickel sulphide. When the nickel is completely precipitated, disconnect the bat- 230 QUANTITATIVE ANALYSIS. tery, wash the nickel thoroughly with water, then finally twice with alcohol, and, after draining off as much as possible, heat for a few minutes in an air bath at 110 C. Cool and weigh. After getting the combined weights of the platinum dish and nickel, dissolve off the latter by warming with five to six cc. of nitric acid (sp. gr. 1.20), then wash the platinum dish by means of water and alcohol, and dry and weigh as before. The differ- ence in the two weighings gives the nickel. It is more satis- factory to weigh the empty dish after the precipitated nickel has been dissolved off than before electrolysis, since in this way a shorter time will elapse between the two weighings and conse- quently less error will be introduced from variations in atmos- pheric conditions. Volumetric Method. Take 100 cc. of the filtrate from the phosphate of manganese and lead, add hydrochloric acid very carefully until the blue color of the double ammonium nickel chloride disappears, then add ammonium hydroxide, drop by drop, until the blue just re- appears, add an excess not exceeding one cc. Dilute to 200 cc., add five cc. of cupric ferrocyanide indicator, and run in standard potassium cyanide until the solution turns from the purple color of the indicator to a perfectly clear light straw-yellow. Sub- tract from the number of cubic centimeters of potassium cyanide used, the correction for the indicator. The difference gives the amount necessary to convert the nickel into the double cyanide of potassium and nickel. Multiplying this by the factor of the potassium cyanide, expressed in metallic nickel, gives the amount of nickel in one gram of the original sample. Special Apparatus and Reagents. Five hundred cc. graduated flask with an additional mark at 502.5 cc. ; 250 cc. drop pipette ; 100 cc. drop pipette ; glass stoppered cylinder or flask graduated to m.i cc. The gradu- ated apparatus should be carefully calibrated and compared be- fore using. Sodium phosphate solution, made by dissolving 200 grams of the ordinary crystallized disodium hydrogen phosphate in 1860 cc. of water. Ten cc. of the solution contain one gram of the DETERMINATION OF NICKEL. 231 crystallized salt, and it requires seventy cc. to precipitate one gram of iron as ferric phosphate. Sodium acetate solution, made by dissolving 250 grams crys- tallized sodium acetate in 820 cc. of water. 100 cc. of this solu- tion contain twenty-five grams of sodium acetate, which is a slight excess over that which is necessary to convert the nitric and hydrochloric acids to sodium nitrate aud chloride, with the liberation of the corresponding amount of acetic acid. Granulated lead is of the same quality as that used in assay- ing. In size it should be that which passes through a sieve with twenty meshes to the inch, but remains upon a sieve with forty meshes. Before using, the lead should be washed with dilute hydrochloric acid (one part of acid to two parts of water) in order to dissolve any oxide that may be present. Standard nickel solution. This may be made from chemically pure nickel by dissolving two and a half grams nickel in fifty cc. nitric acid, sp. gr. 1.20, adding an excess of hydrochloric acid, evaporating on a water-bath nearly to dryness, then dilu- ting to one liter. One cc = 0.0045 gram of nickel. Standard potassium cyanide solution. Take twelve grams of C. P. potassium cyanide, dissolve in water, dilute to one liter. This must be standardized against a standard nickel solution. Since the presence of ammonium salts interferes somewhat in the titration with potassium cyanide, necessitating the use of a slightly greater amount of potassium cyanide than would be re- quired if there were no ammonium salts present, it is better that the potassium cyanide be standardized under the same conditions as are met in analysis. To standardize the potassium cyanide, take fifteen to twenty cc. of the standard nickel solu- tion, add six cc. of hydrochloric acid, sp. gr. 1.20, ten cc. sodium phosphate solution, ammonium hydroxide until the solu- tion turns blue and then five cc. in excess. Now add hydro- chloric acid until the blue color of the double nickel chloride disappears, then ammonium hydroxide until the blue color just reappears, and an excess not exceeding one cc. Dilute to 200 cc., add five cc. cupric ferrocyanide indicator and run in potas- sium cyanide until the solution changes from the purplish color 232 QUANTITATIVE ANALYSIS. imparted by the indicator to a perfectly clear light straw-yellow. Divide the amount of nickel in the standard nickel solution taken, by the number of cubic centimeters of potassium cyanide used, less the correction for the indicator. The result will give the strength of the potassium cyanide expressed in metallic nickel. Cupricferrocyanide indicator. Take two and a half grams of crystallized cupric sulphate, dissolve in twenty-five cc. of water, add to this a solution of ammonium oxalate until the precipitate first formed just redissolves, then dilute to 500 cc. Dissolve two and a half grams of potassium ferrocyanide in 500 cc. of water, then slowly pour this solution into the cupric sulphate solution, stirring constantly during the operation. This will give a deep purplish brown solution of cupric ferrocyanide which may pre- cipitate partially on standing ; but the precipitate so formed will be so fine that it will easily remain in suspension for a long time, upon shaking the bottle, thus insuring uniform composi- tion. To find the correction for the indicator take 200 cc. of water, add six to eight drops of ammonium hydroxide, then five cc. of indicator, taken after shaking the bottle well, and then run in potassium cyanide until the characteristic change of color is obtained. Five cc. of cupric ferrocyanide of the above strength require from 0.15 to 0.20 of potassium cyanide, one cc. of which is equivalent to 0.0025 nickel. If a stronger'end reac- tion is desired, ten or even fifteen cc. of the indicator may be used and a suitable correction made. Repeated analyses of steel have shown that the nickel may be determined, by the volumetric method, within from 0.0003 to 0.0005 gram of the true nickel content, duplicate determinations being made in three hours. The electrolytic method requires three hours to the time the solution is ready for electrolysis. XXIX. Analysis of Chimney Gases for Oxygen, Carbon Dioxide, Carbon Monoxide, and Nitrogen. The determinations usually made are the percentages, by ANALYSIS OF CHIMNEY GASES. 233 volume, of oxygen, carbon dioxide, carbon monoxide, and nitro- gen. The apparatus used (a modified form of the Elliott) is shown in Fig. 68, and consists of two glass tubes, ib and ah, the tube ib Fig. 68. having a capacity of about 125 cc. and is accurately graduated from o cc. to 100 cc. in one-tenth cc. At d and e are three-way 234 QUANTITATIVE ANALYSIS. glass stopcocks, connected by means of rubber tubing to the water-supply bottles, /and g. 1 The manipulation of the appa- ratus is as follows : Remove the funnel cap r, and connect in its place a glass tube of small diameter, but of sufficient length to reach well into the flue from which the gases are to be taken. Open the stop-cocks a and b and slowly raise g and / until both tubes are full of water including the glass tube in the flue. It is necessary in this operation to be certain that no air is in the tubes and that the displacement by water is complete. Now gradually lower the bottle /whereby the gas is drawn into the tube ah. As soon as sufficient gas has been obtained for the analysis, the lower portion of the tube containing water two or three inches above the point h, the stop-cock a is closed, the small glass tube con- necting a w r ith the flue removed, and the funnel cap c replaced. After allowing the gas to stand in the tube ah fifteen minutes to secure it the temperature of the room, and thus insure correct measurements, the bottle is slowly lowered until the surface of the water therein is on an exact level with o on the tube ib y the stop-cock b opened and the bottle / gradually raised until suffi- cient gas from ah has been transferred to bi, indicated by the volume taken reading from the mark o on the graduated tube ib to the mark 100 cc. immediately in contact with the stop-cock b. Having thus obtained 100 cc. of the gas, the stop-cock b is closed and/ is raised until all the remaining gas in ah and ab is displaced by the water. The first constituent of the gas to be determined is the carbon dioxide (CO a ). The gas is now transferred to the tube ah by raising g and opening b, keep- ing a closed and/ lowered. When the water reaches b the latter is closed. Fifty cc. of a solution of caustic potash are placed in the funnel cap c. (The solution being made by dissolving 280 grams of potassium hydrate in 1000 cc. of distilled water.) Open the stop-cock a only partially, so that the solution of caustic potash in c may slowly drop down through the gas in the tube ah and absorb the carbon dioxide in so doing. 1 The water used in this apparatus should contain 100 grams sodium, chloride in, each liter of distilled water. ANALYSIS OF CHIMNEY GASES. 235 When all the caustic potash in c (with the exception of two or three cc.) has passed through a, the latter is closed, thus pre- venting entrance of any air ; b is opened, /is slowly raised and g lowered. Continue the raising of /until the water in the tube ha reaches the stop-cock b and immediately close the latter. Allow the gas to stand in the tube ib five minutes before taking the reading of the volume on the tube, bearing in mind that the level of the water in g must be on a level with the water in ib to obtain equal pressure. The difference between o and the point indicated by the water in the tube ib will give the amount of carbon dioxide absorbed from the gas by the caustic potash. Thus: Original volume indicated at o.o After removal of carbon dioxide 11.2 or ii. 2 per cent, carbon dioxide by volume. To obtain the oxygen the gas is forced from ib into ah, as be- fore, and in c is placed fifty cc. of an alkaline solution of pyro- gallic acid. This latter solution is formed by dissolving ten grams of pyro- gallic acid in twenty-five cc. of distilled water, placing it in c and adding thirty-five cc. of the caustic potash solution. This is allowed to pass slowly through a and gradually absorbs the oxygen in the gas. a is closed before all the liquid passes out of c. Repeat with the same quantity of alkaline pyrogallic solution. Transfer the gas in the usual manner to ib, and after allowing to stand five minutes, take the measurement thus : Previous reading 1 1 .2 cc. After absorbing oxygen 19.6 ' ' Oxygen 8.4 " or 8.4 per cent, by volume. Before transferring the gas to ah for the determination of the carbon monoxide, all the water in/ and ah must be replaced by distilled water; 1 to do this, open the three way cock e, open , and all the water can be caught in a large beaker at e. Wash 1 Carbon dioxide is much more soluble in distilled water than carbon monoxide or nitrogen. For this reason the water used in the apparatus at the commencement of the gas analysis contains sodium chloride. After the determination of carbon dioxide dis- tilled water can be used. 236 QUANTITATIVE ANALYSIS. out /and ah three times with the water, then close e in the prop- er manner so that the water placed in/ will rise in the tube ha to a, then close a, lower/, raise g, open b, placing the gas in ah for treatment with a solution of cuprous chloride to determine the carbon monoxide. The cuprous chloride solution is made by dissolving thirty grams of cuprous oxide in 200 cc. hydrochloric acid (sp. gr. 1.19), and using fifty cc. as soon as the solution has reached the temperature of the room. Experience has shown that a freshly made solution acts much better as an absorbent of carbon monoxide than one that has stood several days. Fifty cc. of this solution are placed in c and allowed to slowly drop through a and absorb the carbon monoxide as it passes through the gas. This absorption should be repeated at least three times. The heat generated during this absorption often causes such an increase in the volume of the gas that when the latter is transferred to the tube ib for meas- urement, the reading may prove minus. To insure accuracy proceed as follows : The gas, after fifteen minutes, is transferred in the usual way to bi, and the water in /and ah is replaced with distilled water. The gas is now returned to ah and a solution of potassium hy- droxide is placed in c and allowed to pass through the gas in ah, absorbing all traces of hydrochloric acid gas. Repeat with this once. Return the gas to bi, allow to stand fifteen minutes, then take the reading : Previous reading ................................... 19.6 cc. After using Cu 2 Cl 2 solution ......................... 20.7 ' CO The nitrogen is determined by subtracting the total amounts of carbon dioxide, oxygen and carbon monoxide from 100. Thus the analysis will read : Carbon dioxide ................... 11.2 per cent, by volume. Oxygen .......................... 8.4 " " " " Carbon monoxide ................ i.i " " " " Nitrogen ......................... 79-3'" " " " Total ...................... 100.0 " " " ANALYSIS OF FLUE GASES. 237 In this analysis no corrections are required for the tension of the aqueous vapor, since the original gas is saturated with moisture, and during the analysis all measurements are made over water. 1 To convert percentages by volume to percentages by weight proceed as follows : i liter of oxygen gas weighs 1.430 grams, i " " hydrogen *' " 0.0895 " i " " nitrogen " 1.255 " i " " air " 1.293 " i " " carbon dioxide " 1-996 " i " " carbon monoxide " " 1.251 " i " " methane " " 0.7151 " i " " acetylene " " 1.252 " Then 11.2 cc. carbon dioxide gas weighs 0.02202 gram. 8.4 " oxygen " " 001201 " i.i " carbon monoxide " " 0.00138 " 79.3 " nitrogen " " 0.09952 " loo.o " 0.13491 If the 100 cc. of gas weighs 0.13467 gram, then The carbon dioxide = - 2202 X Io = l6 . 32 per cent, by weight. 0.13491 The oxygen = - OI2o x IO - 8 . 97 per cent, by weight. 0.13491 The carbon monoxide = = 1.02 per cent, by weight. 0.13491 The nitrogen = ' 9952 = 73.69 per cent, by weight. 0.13491 Total loo.oo per cent, by weight. Analysis of Flue Gases with the Orsat-Muencke Apparatus. Where the determinations to be made are the percentages of carbon dioxide, carbon monoxide, oxygen and nitrogen, this 1 The solubility of these four gases, at normal temperature and pressure, are as follows : i volume of air-free water at 15 C. absorbs 1.002 volume of carbon dioxide, i " " " " " " " " 0.024 " " carbon monoxide, i " " " " " 0.030 " " oxygen, i " " " " " " " " 0.015 ' " nitrogen. 238 QUANTITATIVE ANALYSIS. apparatus offers many advantages over any other. It is shown in Fig. 69, and is thus described: The measuring burette A, of 100 cc. capacity, is surrounded by a large cylinder filled with water, in order to free the gas from changes of temperature, and the first forty-five cc. are Fig. 69. divided into tenths cc., the remaining fifty-five cc. into cubic centimeters. The thick capillary glass tube is fastened at both ends, at i in a cut of the dividing panel, and at o by means of a small brace, attached to the cover of the case. The capillary tube is bent at its further end and connected with the y tube B, containing cotton, and at the bend is filled ANALYSIS OF FLUE GASES. 239 with water in order to retain all dust and to saturate the gas thorough!}* with moisture before measuring takes place. The rear end of the three way cock c is connected by means of a rubber tube a with the rubber aspirator C, which fills the tube with the gas to be analyzed. The absorption takes place in the " U " formed vessels Z>, E, and F, which are connected with the stoppers by short rubber tubes. For the enlargement of the absorbing surface, D, E and Fare filled with glass tubes. Since the mark m is above the place of connection, the latter is always moistened by the re- spective liquid and therefore can easily be maintained air tight. The other end of the [J tube vessel is closed by a rubber cork, which contains the small tube x ; the small tubes are all con- nected to one rubber bulb of about 200 cc. capacity in order to keep out the atmospheric oxygen. The entire apparatus is en- closed in a wooden case fifty centimeters high and twenty-five centimeters wide. Its use is indicated as follows : The glass cylinder surrounding the burette A as well as the bottle L are filled with distilled water. In order to fill the three absorbing cylinders, the stoppers are removed as well as glass tubes x and the rubber bag G, and. no cc. potassium l^droxide solution (sp. gr. 1.26) poured into the vessel D, so that the latter is about half full. This is for the absorption of the carbon dioxide. E contains a solution of eighteen grams of pyrogallic acid in forty cc. of hot water, which is poured into E, and then seventy cc. of potassium hydroxide solution (sp. gr. 1.26) added, whereby the oxygen is absorbed in the gas under examination. The carbon monoxide is absorbed in the cylinder F, which contains a solution of cuprous chloride made as follows : Thirty- five grams of cuprous chloride are dissolved in 200 cc. hydro- chloric acid (concentrated), fifty grams of copper clippings added and the mixture allowed to stand in a glass-stoppered bot- tle for twenty-four hours. Each glass tube in F contains a spiral of copper wire. 100 cc. of water is added to the solution (no precipitate forming) , and enough is transferred to F to fill to the required point. The solutions in the rear section of D, E, and F are transferred to the front sections, where the absorp- tion of the gas takes place as follows : The three glass stoppers 240 QUANTITATIVE ANALYSIS. are closed, the stop-cock c turned horizontal and the bottle L y containing distilled water, raised so that the water fills the bu- rette A, give a quarter turn to the left to the stop-cock r. so that the second passage leads to the tube B, open the stop-cock of the vessel D, lower the bottle L and carefully open the pinch- cock placed on the tube s, so that potassium hydroxide solution rises to the mark m, whereupon the stop- cock is closed. The fluids of the two other absorbing vessels are raised in the same way to the mark m. The three stoppers with the glass tubes x are then attached. About one cc. of water is placed in the tube B, loose cotton placed in both sides, the stopper reinserted and connected with the tube n. After filling the burette A with, water to the 100 cc. mark by raising the bottle L, the stop-cock is turned so that the connection of the rubber aspirator C with, the chimney, containing the flue gases, is brought about through, the tube B. Aspiration of the gas into the apparatus is now performed by compressing C ten or fifteen times till the whole conductor is filled with gas. This is easily done by compress- ing C with the left hand, closing the attached tube r with the thumb of the right hand, and then upon opening the left hand allowing Cto expand, raising the thumb again, compressing C, etc., till the object is obtained. To fill the burette A with the gas, the stop-cock c is turned horizontal, the pinch-cock of the tube s opened, and the bottle L lowered until the gas reaches the zero point in A, whereupon c is closed. To determine the carbon dioxide, the stop-cock of D is opened and L raised with the left hand, so that on opening the pinch- cock of 5 with the right, the gas enters the cylinder D ; L is lowered again until the potassium hydroxide solution in D reaches to about the tube connection under m, and once again drives the gas into the potassium hydroxide vessel by the raising of L. This is repeated two or three times, and the gas returned to the burette A by opening the pinch-cock of s and raising L, and closing the glass stop-cock of D. To measure the amount of absorbed carbon dioxide, the bottle L is held next to the burette in such a way that the water stands at the same level in both vessels, the pinch-cock of s closed, and the remaining volume of gas read off. This amount subtracted from 100 cc. gives the ANALYSIS OF FLUE GASES. 241 amount of carbon dioxide. The gas is now passed into the ves- sel E in the same manner as in D, the oxygen being absorbed by the alkaline pyrogallate solution. This absorption must be re- peated three or four times or until no diminution of volume takes place. The gas is then returned to the measuring burette A and the amount of absorption measured. The gas is then passed into the vessel F for the absorption of carbon monoxide. After repeating for a number of times the absorption in .Fthe gas is passed into D before measurement in A of the absorbed carbon monoxide. This is necessary on ac- count of the vapors of hydrochloric acid retained by the gas after contact with the cuprous chloride solution in hydrochloric acid. After passing the gas into D three or four times, it is then meas- ured as usual in A, the remaining gas being nitrogen. The composition of the chimney gases is an index of the working of the furnaces under the boilers. When the fuel is properly consumed, the furnace gases should contain only nitro- gen, oxygen, steam, and carbon dioxide, and to secure this re- sult, excess of air is required, but this excess must not exceed a certain amount, otherwise too great a volume of air is heated and the heat wasted. This excess of air can be determined by finding the amount of carbon dioxide in the furnace gases ; thus the percentages of carbon dioxide, herewith given, show the amount of air used in the furnace. 1 4 per cent, carbon dioxide indicates 4.9 times the theoretical amount of air required was in the gases. 5 per cent, carbon dioxide indicates 3.5 times the theoretical amount of air required was in the gases. 6 per cent, carbon dioxide indicates 3.0 times the theoretical amount of air required was in the gases. 7 per cent, carbon dioxide indicates 2.5 times the theoretical amount of air required was in the gases. 8 per cent, carbon dioxide indicates 2.3 times the theoretical amount of air required was in the gases. 9 per cent, carbon dioxide indicates 2.0 times the theoretical amount of air required was in the gases. 10 per cent, carbon dioxide indicates 1.7 times the theoretical amount of air required was in the gases. 1 Experiments at Munich : Bayrisches Industrie und Gcuxrbcblatt, 1880. 242 QUANTITATIVE ANALYSIS. 12 per cent, carbon dioxide indicates 1.5 times the theoretical amount of air required was in the gases. 17 per cent, carbon dioxide indicates i.o times the theoretical amount of air required was in the gases. It is customary in boiler trials to make analyses of furnace gases and calculate the amount of air required for combustion from the percentage of carbon dioxide found in the furnace gases. Prof. W. C. Unwin, F.R.S., 1 states that this method is accu- rate in principle, but the samples analyzed are a very minute fraction of the total chimney discharge, and the samples may not be the average samples. What is wanted is an instrument as Fig. 70. easily read as a pressure gauge, and giving continuous indica- tions, such as the dasymeter of Messrs. Siegert & Durr, of Munich. (Fig. 70.) This is a fine balance in an enclosed case, through which a current of the furnace gases is drawn. Atone end of the balance is a glass globe of large displacement, at the other a brass weight. Any change of density of the medium in the chamber disturbs the balance. A finger on the balance moving over a graduated scale gives the amount of the altera- tion of density. An air injector draws the furnace gas from the flues, and it is 1 Nature, (May 23, 1895), p. 89. ANALYSIS OF FLUE GASES. 243 filtered before entering the balance case. An ingenious mer- curial compensator counterbalances any effect due to change of temperature or barometric pressure. The dasymeter is usually combined with a draught gauge, and an air thermometer or pyrometer in the flue is required if the amount of waste heat is to be calculated. The losses through sensible heat in the escape gases can be easily determined with the assistance of the dasymeter and Siegert's approximate formula in the following way : Let the carbon dioxide = x in per cent. temperature of discharged gases = T (Celsius scale), temperature of draught at grate = t, then the loss of T with the coals as fuel equals : T t . C0 2 in per cent, of the heat value. With lignite, peat, wood, etc., the coefficient varies accord- ing to the contents of water and the coefficient of heat of the fuel and is so much the greater, the less valuable the combustible is. With coal furnaces the loss of heat can immediately be ob- tained from the following diagrams without any calculation : m m vf Fig. 71- Fig. 72. In Fig. 71 look up the carbon dioxide = contents of carbon dioxide in the lower horizontal (abscissa row), follow the ver- tical line appertaining thereto till it intersects the curve of the surplus temperature, draw from this point of section a horizon- tal line to the left and it will give the amount, per cent, of the loss of heat as indicated by that point on the scale at which it was intersected. 244 QUANTITATIVE ANALYSIS. In Fig. 72 look up the amount, per cent, of the surplus tem- perature on the bottom abscissa line, raise a perpendicular line from the point till it intersects the line drawn diagonally for that amount of carbon dioxide indicated by the dasymeter. The hori- zontal line through this point of section indicates, on the scale for the loss of heat on the left, the loss to be determined. Points lying between two given abscissa can easily be assumed on both diagrams by eye measurement. Experiments show that when using horizontal and step grate furnaces, as also the Ten-Brink furnaces, the most profitable combustion is obtained when about ten to fourteen per cent, of carbon dioxide is contained in the escaped gases, and in the use of gas furnaces about seventeen to eighteen per cent. The dasymeter requires, initially, exceedingly delicate adjust- ment, and its indications must be checked from time to time by analysis of the gas. It is set to read zero with pure air, and then any increase of density due to carbon dioxide is read as a percen- tage on the scale. When in adjustment, it is as easy to read the percentage of carbon dioxide in the furnace gases as to read the pressure on a pressure gauge. When the dasymeter is fitted to a boiler, the stoker has directions to adjust the supply of air, so that the furnace gases have about twelve per cent, of carbon dioxide. With practice he learns what alterations of the damper or fire- door, or thickness of fuel on the grate are necessary, or whether an alteration of grate area is desirable. After a little practice the percentage of carbon dioxide can be kept very constant. Uehling & Steinbach describe an instrument they make use of to determine the composition of furnace gases, and which in- dicates automatically and continually the percentages of carbon dioxide and monoxide present in furnace gases. It is fully de- scribed in United States patent No. 522746. GAS ANALYSIS. 245 XXX. Gas Analysis. COAL GAS, WATER GAS, OIL GAS, PRODUCER GAS, ETC., BY MEANS OF THE HEMPEL APPARATUS. In technical analysis of gases the most complete experiments may be conducted with the aid of the Hempel apparatus. The essential feature of this apparatus consists in the fact that meas- urements and absorptions may be conducted separately and in special apparatus. Gas burettes serve the first purpose and for the latter gas pipettes. 1 The gas burette, as shown in Fig. 73, consists of two parts, the calibrating tube b and the levelling tube a. The first has a constant diameter and ends above in a capillary tube about one-half millimeter in diameter and three centimeters in length ; at* the bottom it tapers into a small tube bent at an angle and passing through and protruding from the wooden stem^-, supported by an iron base. t The calibrating tube is divided from the capillary part down to a little above the wooden support into two-tenths cc., the total graduation comprising 100 cc. A rubber tube about 120 cm. long, having a short length of glass tubing inserted at about the middle, as shown in Fig. 73, serves to connect the glass tube projecting at g with the levelling tube a, which at the bottom is similarly fastened into the base at e. The tube a at h widens into a funnel to facilitate pouring in the water. Over the capillary tube c of the measuring tube a short piece of heavy rubber tubing is fastened by means of wire. A strong " Mohr" pinch-cock/ enables one to close the measuring tube directly above the capillary tube. The rubber tube at d has a i i shaped capillary glass tube leading from it (see E Fig. 75), to provide for a' connection with the various gas pipettes. Since in this simple gas burette water is used as a sealing fluid, it is not adopted for the analysis of gases containing con- stituents easily soluble in water. In such cases Winkler's gas burette, Fig. 74, is used. The capillary tube b is closed below 1 Chemisch-technische Analyse, Post, pp. HJ.et. seq. 246 QUANTITATIVE ANALYSIS. Fig- 73- GAS ANALYSIS. 247 by a three-way cock c and above by means of a simple stop-cock d. Similarly to the Hempel burette both the measuring tube b and levelling tube a are fastened into iron stands and are connected by a rubber tube. The space between the stop-cocks c and d is divided into 100 cc., and each of these into fifths of cc. Before use the ' ' Winkler' ' burette must be thor- oughly dried, by rinsing with alco- hol and ether, and thereupon pass- ing a current of dry air through it. In order to admit a sample of gas to be analyzed, e is connected by rubber or glass tubing with the source of gas, and the length-bore of the three-way cock c, which communicates with the inside of b, is attached to an aspirator or rub- ber pump. Gas is drawn through till all the air has been displaced, thereupon closing c and d. In order to transfer the gas into the [jj ! pipettes, the levelling tube a and the rubber tube are filled with water till the latter commences to flow from the stop-cock c, which at this moment communicates with a through its length-bore. The flow of water is checked by closing with a rubber tube and glass rod, or a pinch-cock. At Winkler's suggestion the calibrating tube b of Hempel's simple gas burette is surrounded by a water jacket in order to reduce the effect of atmospheric changes of temperature upon the gas in the burette. 248 QUANTITATIVE ANALYSIS. Fig. 75- The larger glass tube serving as a water jacket, Fig 75, is closed above and below by two rubber corks, through which the calibrating tube passes, and has also above and below two small projecting glass tubes, used for filling or discharging the water ; they are either simply closed by rubber corks or have attached to them rubber tubes to produce a continuous flow of water in the jacket. GAS ANALYSIS. 249 On the working table there rests a stand G upon which the pipettes are placed and whose height is so adjusted that the entrance to the pipette and the capillary tube of the burette are at one level. These pipettes, which must be equal in number to the various absorptions which are to be executed (since each one remains charged with one liquid and always serves for the determination of only one gas constituent), have according to the purpose which they serve, different attachments. The simple absorption pipette, Fig. 76, consists of two glass Fig. 76. globes a and b r connected by means of a bent glass tube d, and fast- ened to a wooden stand to prevent breakage. A capillary tube c passes from the globe b before a plate of milk glass m, which is let into the wooden stand, in order to easily trace the move- ments of the liquid thread in the capillary tube c. The exit tube /of the globe a and the capillary tube e extend above the wooden frame ; a small rubber tube e is connected to the protruding tube c and fastened by means of wire. The reagent to be used in the pipette is poured in at /, entirely filling the globe b, a only partially, and the capillary tube c to the junction with the rubber tube near e. When not in use, /is closed by a cork and e by a glass rod, which during use is displaced by a pinch-cock. 250 QUANTITATIVE ANALYSIS. A label designating the contents of the pipette is attached to the wooden frame. The gas is transferred into these pipettes, brought into intimate contact with the reagent by shaking and thus freed from the constituent gas under consideration. The simple burette, containing caustic potash solution (i to 2) is used for absorption of the carbon dioxide. The pipette contain- ing fuming sulphuric acid, Fig. 77, is so modified that shaking is avoided. Above the globe b, filled with disulphuric acid, the smaller globe g also filled with the fuming sulphuric acid and pieces of broken glass (the lat- ter placed there by the glass-blower). When the gas passes into the pipette it comes into contact with large surfaces of the broken glass, which are covered with the absorbing liquid. Passing the gas through g three or four times suf- fices for complete absorption. The Fig. 77. heavy hydrocarbons in the gas are ab- sorbed in the pipette by the disulphuric acid. Fig. 78 shows the compound pipette, two* of which are used: Fig- 7 GAS ANALYSIS. 251 one for the determination of oxygen in the gas, the other for the determination of the carbon dioVide.^ DOsM.Clfiu ODtn 30* JSvoiiS^j^. o^Jt^ O OsUJ >C ON _ r - r r r r r r r r r r P P P P P P P P P P P P P P P r r r r r r r r r r r r P P P P P P P P P P P P P P P P p P O O p p O O O O P O SO vC ooooooooooo p p p p p p p ? p p p p p p p p p p p p - - - ""^ B O^t p p p p p p p p p p p p p p p p p p p p p p p i jpt 4k 3^ & & 2* to w to i ^O Osi*J O ON to \C ON td - ~ - 1 P P P P P P P P P P P P P P P P P P P P P P O O O jb O Q444 ^. < c.c_Nb voivb'iNb>ONC>b'NpCi^>CNb>bv'-:; j c X'-Ji rr , rr ppppppopppppppppopppppppppp O O C : -: - ~ - - C>CvC*C^\O*DvD\CvD>C'C^ Osii vB 0^ VO O.UJ VD OsMvO 0\wv0 OsWVD OxJ>D OstJO OskJ^D Osw p p p p p p p p p o p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p o p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p poop p p p p p P P P P P P P P P P P P P P P P P P P P P P P P P P P P : - - - ; ; ; ; ; ; ; ; - . . r r r .- . . - --- -. On W 3Din i>CW> w Vi * OskJvC Ov 2 5 2 O * S3 "3 ft 284 QUANTITATIVE ANALYSIS. XXXIII. Hartley's Calorimeter for Combustible Gases. The conditions of use are as follows : From a small cistern A (Fig. 86) water flows over a sensitive thermometer j5 thence into a case surrounding the stem of a suitable burner C, onwards to a metal casing or jacket enveloping the calorimeter D, then Fig. 86. makes it way to the upper part of the latter, descends after traversing a series of shelves which present a very large surface, and finally passes out to the collecting tank/, at the base of the instrument. The burner is passed upwards into the center of a cylindrical chamber at the bottom of the calorimeter ; and, as already stated, the burner stem is surrounded by a casing through CALORIMETER FOR COMBUSTIBLE GASES. 285 which the supply water flows. Loss by radiation from the bur- ner is thus prevented. The gas is measured by a special meter M ': and its rate of consumption and the rate of water flow are regulated until the issuing water is found to be a few degrees higher in temperature than that at which it enters : and the temperatures, as indicated by the four thermometers employed, are found to be steady. During these adjustments, water runs to waste through a by- way cock. When all is^ready, and with the meter index, the bye-way cock is instantly turned, and the passage of the out- flowing water diverted to a collecting tank. The quantity of gas usually burned per experiment is one-fourth cubic foot ; and the time occupied with ordinary coal gas ten to twelve minutes. During the experiment, the temperatures of the inlet and outlet water should be frequently observed, and now and then also the temperature of the jacket. When the desired quantity of gas has been burned, the water flow is promptly turned to waste. The collected water is next measured, and its weight calculated, or better, weighed directly. The weight in pounds multiplied by the number of degrees the water has been raised gives the heat- ing power due to the quantity of gas burned. Thus, if tw r enty pounds of water have been raised 8 F, by one- fourth cubic foot of gas, we have 20 X 8 = 160 pounds, Fahr. units for one-fourth cubic foot, or 640 for one cubic foot. Note. The products of combustion are so completely reduced to the temperature of the inflowing water that, without aspira- tion, they would not rise through the instrument. The aspirator is simply a copper chimney F, heated at its upper part by a ring gas-burner G. Prof. E. G. Love, School of Mines Quarterly, 13, 97, gives the result of an analysis, with this instrument, of a sample of the Municipal Gas Co. gas, of New York City, as follows : Barometer 29.886 in. Temperature of gas burned 66.00 F. Temperature of the air (a) 65.98 " Temperature of the water, inlet (b) 61.605 " Temperature of the water, outlet (c ) 69.275 " Temperature of the water, raised 7.670 " 286 QUANTITATIVE ANALYSIS. Temperature of the " body"- (d) ". 6 3-795 F. Temperature of the escaping gases 64.43 " Duration of test 12.78 minutes. Gas burned 0.25 cubic feet Gas burned, corrected to 60 F. and 30 in Bar. 0.2452 " " Pounds of water heated 23.228 " " Corrections (ad) 2.185 X 0.025 X 1278 = 0.698 gain. (ca) 3.295 X o.oi X 12.78 : 23.228 -f- 7.67 0.28 = 177.88 -5- 0.2452 = 725.3 heat units at 6o c F. and thirty inches barometer. The coal gas of London, Eng., with an illuminating power of sixteen to seventeen candles, has a colorific power of about. 668 B. T. U. per cubic foot, and costs from sixty to seventy cents per thousand cubic feet. The average of numerous tests, made with the Hartley calori- meter, upon the New York City water gas, gives 710.5 B. T. U. per cubic foot* One thousand cubic feet of this gas, costing $1.25, would therefore yield 710,500 heat-units, which would be equivalent to 568,400 B. T. U. for $1.00. JUNKER'S GAS CALORIMETER. 287 XXXIV. Junker's Gas Calorimeter. Another form of gas calorimeter is the Junker, (Fig. 87 )/ The above sectional drawing shows the instrument to- consist Cold water inlet. Strainer. Overflow to calorimete Upper container. Waste overflow. 6 and 7. Fall pipe and^joint. 8. Drain cock. 9. Adjustment cock. 12. Cold water thermometer. 13. Air jacket. 14. Perforated spreading ring. 15 and 16. Water jacket. 17. Baffle plates with cross slots. 18. Lower overflow. 19. Lower container. 20. Hot water overflow. 22. Gas nipple. 23. Air supply regulator. 24.. Gas nozzle. 25. Clamp for burner. 26. Burner holder. 27. Burning cap. 28. Combustion chamber. 29. Roof of combustion chamber. 30. Cooling tubes. 31. Receiver for combustion gases. 32. Outlet for combustion gases. 33. Throttle for 34. Brass base ring. 35. Condensed water outlet. 36.) 37. V Air jacket. 38.J 39. Test hole in air jacket. 43. Hot water thermometer, } Qa3 Supply. Fig. 87. of a combustion chamber surrounded by a water jacket, the latter filled with a great many tubes. To prevent loss by radiation !/. Soc. Chem. Ind.July, 1895, 632. 288 QUANTITATIVE ANALYSIS. the water jacket is surrounded by a closed air space. The whole apparatus is constructed of copper as thin as is compatable with strength. The water enters the water jacket at the bottom, and leaves it at the top, while the hot combustion gases of the flame of the gas that is on trial enter the tubes at the top and leave them at the bottom. There is therefore not only a very large surface of thin copper betwej^he gases and the water, but the two move in opposite directions, during which process all the heat generated by the flaml^JK-ansferred to the water, and the water gases leave the apparatus approximately at atmos- pheric temperature. The gas to be burned is first passed through a meter, and then to insure constant pressure, through a pressure regulator. The source of heat in relation to the unit of time is thus rendered stationary, and, in order to make the absorbing quantity of heat also stationary, two overflows are provided at the calorimeter, making the head of the water and the rate of flow of the same constant. The temperatures of the water entering and leaving the appratus can be read at the respective thermome- ters ; as shown before, the quantities of heat and water passed through the apparatus are constant. As soon as the flame is lighted the temperature of the exit thermometer will rise to a certain point and will nearly remain there. All data for ascertain- ing the heat given out by the flame are therefore available. All that is required is to measure simultaneously the quantity of gas burned and the quantity of water pressed, and the differ- ence in temperature between the entering and leaving water. Centigrade thermometers and two-liter flasks are required. The meter shows one-tenth of a cubic foot per revolution of the large hand ; the circumference being divided into 100 parts, so that o.ooi can be read accurately. The water supply is so regulated that the overflow is working freely, and the water- admission cock is set to allow two liters of water to pass in about a minute and a half. The colorimeter is now ready to take the reading. The cold water as a rule has a sufficiently constant temperature that we note it only once : it is now 17.2 C. As soon as the large index of the meter passes zero, note the state of the meter and at the same time transfer the hot-water tube from the funnel into the measure glass, and while that is being JUNKER'S GAS CALORIMETER. 289 filled note the temperature of the hot water at say ten intervals, to draw the average. The temperatures are 43.8, 43.5, 43.5, 44.2, 44.1, 43.9, 43.8, 43- 7> 43-8, and 43.7, making the average 43.8. The measure glass is now filled ; turn the gas out. Find from the readings of the meter at the beginning and the end of the experiment that there was burned 0.35 cubic foot, by means of which the temperature of the two liters of water was raised 26.6 C., viz., 43.8 17.2 = 26.6 C. The calculation is as fol- lows : WT H= G~> where H the calorific value of one cubic foot of gas in calories. W= the quantity in liters of the water heated. T= the difference in temperature between the two thermome- ters in degrees C., and G^the quantity in cubic feet of gas used, then H ^L 6 I52 calories or 604 (152X3.968) " B. T. U." * oO per cubic foot. It is mentioned before that the effect of the cooling water is such that the waste gases leave the calorimeter at about atmos- pheric temperature. All hydrocarbons when burned form a considerable quantity of water, which in all industrial processes escapes with the waste gases as steam. The latent heat of this steam is therefore not utilized when fireing a stove or driving an engine with gas ; in the above result, however, the latent heat is included, because in the copper tubes the steam is condensed, and its heat is transferred to the circulating water and measured with the rest. The condensed water runs down the tubes which are cut off obliquely to allow the drops to fall off easily, and is collected in the lower part of the apparatus from where it runs through the little tube into a measure glass. In condensing steam gives off six-tenths calorie for every cubic centimeter of water formed. If therefore a graduated (cc.) cylinder be placed under the little tube the amount of water generated by burning say one cubic foot of gas, can be directly measured. From burning one cubic foot of gas, we have collected 27.25 cc. 290 QUANTITATIVE ANALYSIS. of condensed water, and must therefore deduct 16.35 calories from the gross value found above, which gives the net calorific value of the gas tested as 135.65 calories or 538 B. T. U. per cubic foot. Fig. 88. The calorimeter is placed so that one operator can simulta- neously observe the two thermometers of the entering and esca- ping water, the index of the gas-meter, and the measuring glasses. No draught of air must be permitted to strike the exhaust of the spent gas. JUNKER'S GAS CALORIMETER. 291 The water supply tube is connected to the nipple in the center of the upper container ; the other nipple is provided with a waste tube to carry away the overflow. This overflow must be kept running while the readings are being taken. The nipple, through which the heated water leaves the calor- imeter, is connected by an india-rubber pipe with the large measure glass, and the water must be there collected without splashing. The smaller measure glass is placed under the tube to collect any condensed water. After the thermometers have been placed in position with their india-rubber plugs, the water supply is turned on by the cock, and the calorimeter filled with water until it begins to discharge. No water must at this period exude from the smaller pipe or from the test hole under the air jacket, otherwise this would prove the calorimeter to be leaking. TABLE OF RESUME OF TESTS UPON LONDON COAL GAS. Is I'i H ** !!,; llf JS2 s s-i s g| i .s! 3-sg g|,|oi|IL s| "o "o "o a 65 '"'S 8 . 'C "3 P. First day.. 21.0 15.322 26.113 10.790.0407 ... 25.7 165.3 l 5-4 149-9 Second" .. 22.5 12.9 27.68 14.780.0584 ... 27.4 165.9 *6-4 148.5 Third " .. 17.5 13.71 28.6 14.89 0.1103 1 7-S 26.43 164.8 15.86 148.94 Fourth" .. 17.5 13.75 28.53 I4-78 0.1103 17.4 26.43 * 6 5-6 15.86 149.74 Experiments made with this calorimeter at the Stevens Institute, are recorded in the Stevens Indicator, October, 1896. The gas used was carburetted water gas " Lowe Process" composed as follows : CO 2 2.20 per cent, (by volume). Illuminants^ C 3 H 6 \ 12.80 IC 6 H 6 J O o.oo CO 24.20 CH 4 17.83 H 37-95 N 5.02 100.00 292 QUANTITATIVE ANALYSIS. The theoretical heating value of this gas, is 662 B. T. U. per cubic foot. The heating value as determined with the Junker calorimeter is 668. B. T. U. per cubic foot. XXXV. Liquid Fuel. Petroleum containing eighty-six per cent, of carbon has an evap- orative power, as estimated by Storer, of eighteen pounds of water per pound of petroleum. Deville has determined the heating power of various petroleums, by calorimetric tests, with the fol- lowing results : Heavy oil from West Virginia 10180 calories per kilo. Light " " " " 10223 " " " Heavy " " Ohio 10399 " " " Light " " Penn 9963 " " " Petroleum from Java 10831 " " " Petroleum from Alsace 10458 H H (Cymol) 89.55 10.45 16.94 14.55 The effective heat he calculates as follows, using twice the amount of air required by theory for the combustion. LIQUID FUEL. 293 COMBUSTION OF ONE POUND OF CARBON. Equivalent evaporation B. T. U. of water. Heat units. At 100 C. At 15.5 C. Total heat of combustion 14500 15.0 Ibs. ..Ibs. Available heat 14500 . .. " . . " Waste of furnace gases at 315 C 3480 3.6 " . . " Effective heat 11020 11.4 " 9.8 " COMBUSTION OF ONE POUND OF HYDROGEN. Equivalent evaporation of water. B. T. U. At 100 C. At 15.5 C. Total heat of combustion 62032 64.2 Ibs. ..Ibs. Latent heat of water vapor 8695 " .. " Available heat 53337 Waste heat of furnace gases 11520 11.9 ,, .. " Effective heat 41817 43.3 " 38 " The effective heat of two hydrocarbons (containing respectively carbon eighty-six per cent., hydrogen fourteen per cent., and carbon seventy-five per cent., hydrogen twenty-five per cent.) are thus tabulated : HYDROGEN CONTAINING CARBON EIGHTY-SIX PER CENT., HYDROGEN FOURTEEN PER CENT. Total heat Equivalent evaporation of com- Of W iter. bustion. At 100 C. At 15.5 C. C o 86 X 14500 , .. 8684 " 21154 21.9 Ibs . 18.8 Ibs. Heat units in fur- Furnace gases. nace gases. CO 2 316 Ibs 411 B T U T. CQ ' ' NTT AH " I68 3 212 A " 2 2 Ibs 4.8 " 30.24 " 4577 Latent heat of water vapor ... 1217 " 1,3 Ibs. Available heat ... 19937 Waste in furnace gases 4577 4.8 Effective heat ... 15360 15-8 " 13.6 Ibs. Theoretical evaporating power . 21.9 " 294 QUANTITATIVE ANALYSIS. HYDROCARBON CONTAINING CARBON SEVENTY-FIVE PER CENT., HYDRO- GEN TWENTY-FIVE PER CENT. C =o-75 X H = 0.25 X 62032 Furnace gases. CO 2 2.75 Ibs. Water vapor 2.25 " N 13-39 " Surplus air !7-39 " Total heat of com- bustion. 10775 B.T. U. 15508 " 26283 Heat units in fur- nace gases. 358 B. T. U. 641 " 1968 2483 Equivalent evaporation of water. At 100 C. At 15.5 C. 27.1 Ibs. 23.1 Ibs. 2.6 Ibs. 35.78 5450 Total heat of combustion 26283 Latent heat of water vapor 2174 Available heat 24109 Waste in furnace gases 545 2.2 Ibs. 5-6 Effective heat 18659 Theoretical evaporating power 19.3 " 16.5 Ibs. 27.1 The theoretical evaporative efficiency of different combustibles is estimated by Rankine from their chemical composition as fol- lows: = 150 + 64!! 8O, and to calculate the quantity of air required for combustion, A = I2C + 36H 4^0, from which the following table is derived. Chemical composition. Description of fuel. C. H. 0. Coke "yo o 88 Rock Oils{^ 18 ^ 20 I C 26 H., 8 Coal 0.84 0.85 o 87 0.16 0.15 O.OO o.oo Coal Ethylene, C 2 H 4 ... Acetylene, C 4 H 2 .. u -75 0.75 0.85 0.25 0.14 o.oo 0.00 o.e:8 n n? 0.31 n /in A. H'5 10.6 15.75 15-65 12.0 10.6 18.8 15-43 7-7 6.0 E. 14.0 13.2 22.7 22.5 15-9 I4.I 27.3 22.1 10.0 7-5 Evaporation due to C. o 14.0 0.00 13-2 o.oo 12.7 IO.OO 12.66 9.84 13.02 2.85 11.25 2.85 11.25 16.05 12.9 9.2 8-5 1.5 7-5 o.oo LIQUID FUEL. 295 Rankine adopts as his unit, the weight of fuel required to evaporate one pound of water at 100 C. under a pressure of 14.7 pounds per square inch this being equivalent to 966 B. T. U. The results were reduced as follows : L,et E be the corrected and reduced evaporation. e = the weight of water evaporated. 7", = the standard boiling point (212 F.). T { = the temperature of the feed water. T b = the actual boiling point observed : then r 966 F. This represents the number of times its own weight of water that a fuel would evaporate if there were no waste of heat, as however there is always a loss of heat, the efficiency of a furnance , , ^(available) would be ^ TT- E (total) The loss of units of evaporation by waste gases Rankine gives ; Loss by chimney = I ~' T c (F.) where i + A ' equals the weight of burnt gas per unit of fuel and T c (F) the temperature of the chimney gases above that of the atmosphere. For ordinary coal i -f- A' ranges from thirteen to twenty-five, and hydrocarbon oils it is 16.3 if no excess of air is necessary above what is required for the combustion of the fuel. Rankine gives the theoretical evaporative power of hydrogen and carbon as follows : Oxygen per Air per units Units unit of weight. of weight. evaporated. H ......................... 8 36 64.2 Carbon, solid (charcoal). 2f 12 15.0 Carbon gas in 2 1 parts CO-. i 6 10.5 Carbon, gaseous ........... 2f 12 21.0 In 1892, from tests made for the Engineer's Club of Philadel- phia, the relative heating value of coal, gas and petroleum are thus stated : 296 QUANTITATIVE ANALYSIS. Lbs. of water, from aud at 212 F. i lb. anthracite coal evaporated 9.7 i " bituminous " 10.14 i " oil 36 B 16.48 i cubic foot gas, 20 C. P 1.28 E. C. Potter, (Trans. Am. Inst. Mining Engineers, Vol. xvii, p. 807), states results of tests, at South Chicago Steel Works, of heating value of petroleum and block coal, as follows : With coal, fourteen tubular boilers, sixteen feet by five feet, required twenty-five men to operate them : with fuel oil, six men were required, a saving of nineteen men at $2.00 per day or $38.00 per day. For one week's work 2,731 barrels of oil were used, against 848 tons of coal required for the same work. With oil at sixty cents per barrel and coal at $2.15 per ton, the relative cost of oil to coal is as $1.93 to $2.15. XXXVI. Valuation of Coal for the Production of Gas. Take 100 grams of the coal in small lumps, so that they may be readily introduced into a rather wide combustion tube. This is drawn out at its open end (after the coal has been put in) so as to form a narrow tube, which is to be bent at right angles ; this narrower open end is to be placed in a wider glass tube, fitted tight into a cork fastened into the neck of a somewhat wide-mouthed bottle serving as tar vessel. The cork alluded to is perforated with another opening wherein is fixed a glass tube bent at right angles, for convejdng the gas, first through a cal 1 cium chloride tube, next through Liebig's potash bulbs con- taining a solution of caustic potash, having lead oxide dissolved in it. Next follows another tube partially filled with dry caus- tic potash and partly with calcium chloride ; from this last tube a gas-delivery tube leads to a graduated glass jar standing over a pneumatic trough, and acting as gas-holder. Before the igni- tion of the tube containing the coal is proceeded with, all the portions of the apparatus are carefully weighed and next joined by means of india-rubber tubing. After the combustion is fin- ished, which should be carefully conducted so as to prevent the VALUE OF COAL FOR PRODUCING GAS. 297 bursting or blowing out of the tube, the different pieces of the apparatus are disconnected and weighed again. The combus- tion tube has to be weighed with the coal after it has been drawn out at its open end, and with the coke after the end of the combustion when it is again cold, and for that reason care is re- quired in managing it. We thus get the quantity of coke, tar, ammoniacal water, carbon dioxide and hydrogen sulphide (as lead sulphide), and the gas is measured by immersing the jar in water, causing it to be at the same level inside and out. Empty the Liebig's bulbs into a beaker and separate the lead sulphide by filtration, wash well, dry and weigh. From the lead sulphide the hydrogen sulphide present is calculated. This pro- cess, devised by the late Dr. T. Richardson, of Newcastle-on- Tyne, was found by him to yield very reliable results, so as to be suitable for stating what quantity of gas a ton of coal thus analyzed would yield. 1 Newbigging's Experimental Plant for the Determination of the Gas-Producing Qualities of Coal. Fig. 89. 1 Crookes' Select Methods in Chemical Analysis, p. 607. 298 QUANTITATIVE ANALYSIS. A description of the apparatus and method of use are thus given : Retort Cast iron : five inches wide, four and one-half inches high, two feet three inches long outside, and one-half inch thick. Ascension pipe Two inch wrought tube. Connections One and one-half inch wrought tube. Condenser Twelve vertical, one and one-half inch wrought tubes, each three feet six inches long. Washer One foot long, six inches wide, six inches deep. Purifier One foot two inches square, twelve inches deep, with two trays of lime. Gas-holder Capacity twelve cubic feet, with graduated scale attached. Amount of coal to be taken for each test is y^Vir part of a ton, or 2.24 pounds. Care should be taken to obtain a fair average sample of the coal to be operated upon. For that purpose at least fifty pounds of coal should be broken up into small pieces and thoroughly intermixed, and from this three different charges are to be taken. The retort should be at a bright red heat before the introduction of the coal and maintained at that tem- perature during test. If from any cause the temperature is much reduced, the test will not be satisfactory. The time required to work off the charge of 2.24 pounds will range from forty to sixty minutes, according to the character of the coal. The illumina- ting power of the gas given out from each charge should be as- certained by the Bunsen photometer, no other being sufficiently trustworthy for that purpose. The average of the three is then taken, both for yield of gas and coke and for the illuminating power of the gas, and this fairly represents the capabilities of the coal. The further conditions to be observed are that the holder be emptied of air or of the previous charge of gas, and that the condenser be drained of its contents. The test charge may be continued until the whole of the gas is expelled, or otherwise, depending on circumstances. In comparing two coals, an equal production from both may be obtained, and the comparative illuminating power then ascertained. The coke and " breeze " should be carefully drawn from the retort into a water-tight receptacle made of sheet iron closed by VALUE OF COAL FOR PRODUCING GAS. 299 a lid. This is then placed in a bucket or other vessel of cold water, and when sufficiently cooled, the coke is weighed. For ascertaining the quantity of tar and ammoniacal liquor produced, drain the yield of three charges from the condenser and washer and measure this in a graduated liquid measure. The number of fluid minims in a gallon (English) is 76,800. Then Pounds. Pounds per ton. f The weight of ) f The nun-berof 1 [ , 75 { thr ee cha.es} : ton of | coal. and this amount divided by 76,800 gives the gallons of tar and liquor produced per ton. 1 A good variety of gas coal should produce from 2,240 pounds of coal 12,000 cubic feet of gas, illu- minating power twenty sperm candles. Newcastle coal on an average produces 12,700 cubic feet of gas per ton of coal, illuminating power of fifteen sperm candles. XXXVII. Analysis of Clay, Kaolin, Fire Sand, Building Stones, Etc. To be Determined. Silica, (total), (combined), (free), (hy- drated), alumina, lime, magnesia, potash, soda, ferrous or ferric oxide, manganous oxide, titanic oxide, sulphur trioxide and combined water. 2 The total silica is determined by fusing one gram of the clay (previously dried at 100 C.) with ten parts of an equal mixture of sodium and potassium carbonates, in a large platinum cru- cible. Fusion must be complete and maintained at a red heat thirty minutes. Allow to cool, treat with an excess of boiling water, make acid with hydrochloric acid, transfer solution to a four-inch porcelain capsule and evaporate to dryness. Take up with twenty-five cc. hydrochloric acid, add water, boil and filter upon ashless filter. Wash well with boiling water, dry, ignite and weigh as silica (total). INewbigging's Handbook for Gas Engineers, p. 57. 2 For analysis of limestone consult Scheme xi, page 16. 300 QUANTITATIVE ANALYSIS. The forms of combination of the silica in the clay are deter- mined as follows : l Let A represent silica in combination with bases of the clay. Let B represent hydra ted silicic acid. Let C represent quartz sand. Dry two grams of the clay at a temperature of 100 C., heat with sulphuric acid, to which a little water has been added, for eight or ten hours, evaporate to dryness, cool, add water, filter out the undissolved residue, wash, dry and weigh A + B -\- C. Now transfer it in small portions at a time to a boiling solution of sodium carbonate d : 10) contained in a platinum dish, boil for some time, filter off each time, still very hot. When all is transferred to the dish, boil repeatedly with strong solution of sodium carbonate, until a few drops of the fluid, passing through the filter, finally remains clear on warming with ammonium chloride. Wash the residue, first with hot water, then (to en- sure the removal of every trace of sodium carbonate which may still adhere to it) with water slightly acidified with hydrochloric acid, and finally with water. This will dissolve A + B, and leave a residue C of sand, which dry, ignite and weigh. To determine B boil four or five grams of the clay (previ- ously dried at 100 C.) directly with a strong solution of sodium carbonate, in a platinum dish as above, filter and wash thor- oughly with hot water. Acidify the filtrate with hydrochloric acid, evaporate to dryness and determine this silica. It repre- sents B or the hydrated silicic acid. Add together the weights of B and C thus found and subtract the sum from the weight of the first residue A + B + C. The difference will be the weight of A or silica in combination with bases in the clay. If the weight of A -\- B -\- C found here be the same as that of the silica found by fusion, in another sample of the clay of the same amount, the sand is quartz, but if the weight of A + B + Cbe greater, then the sand contains silicates. The weight of the bases combined with silica to silicates can be found by subtracting the weight of total silica found in one gram, by fusion, from the weight of A + B -\- C in one gram. 1 From Fresenius, Quant. Anal., Cairn's, p. 68. ANALYSIS OF CLAY, KAOLIN, FIRE SAND, ETC. 301 E ?! * JB S O^ jS. s " - re ? * s o ^ <*- \l i S'i =' n o o ~ H 3 "^ B c > ^ X rt M ft Sis- III s w s w' gig ^> 3 g" cr VJ Q. and washed then ex S 3 2.3 f 30 Q 3 3. C cr % ni *i* 1-1 f? S* ^' w 5t ' ^ S ft 3 ^ 302 QUANTITATIVE ANALYSIS. Potash and Soda. Take one gram of the dried clay, transfer to a three-inch plati- num capsule, add ten cc. sulphuric acid and twenty cc. hydro- fluoric acid and heat gently until the silica is completely dissi- pated and the excess of acid added driven off. Allow to cool, add twenty cc. warm hydrochloric acid, then twenty-five cc. water, transfer contents of platinum capsule to a No. 3 beaker, add two cc. nitric acid and boil. Add ammonia to alkaline re- action, boil, filter off the alumina and ferric oxide, and to the filtrate add ammonium oxalate to precipitate the lime ; allow to stand four hours, then filter ; the magnesia is separated in the filtrate by ammonium phosphate, and the filtrate from the mag- nesium phosphate precipitate is evaporated to dryness and ignited to expel ammonium salts. The residue is treated with hydrochloric acid and the potash precipitated by solution of platinic chloride as usual, and weighed as K 2 PtCl 6 on counter- poised filters. The alcoholic washings and filtrate is evaporated to dryness, the platinum compound decomposed by heating to redness with oxalic acid, boiled with water, filtered, a few drops of sulphuric acid added, then evaporated to dryness, ignited to constant weight as sodium sulphate, and then calculated to Na 2 O. Sulphur Trioxide Is determined by fusing one gram of the clay with sodium and potassium carbonates, separating the silica as usual, and precipitating the sulphur trioxide by solution of barium chlo- ride in the acid filtrate. (Consult Scheme XIII). Titanic Oxide. Fuse five grams of the dried clay with an excess of a mixture of sodium fluoride and sodium bisulphate, in a platinum cruci- ble for thirty minutes at a red heat. Treat the cold mass with cold water, about 200 cc., add potassium hydroxide in excess, filter off the titanic oxide, wash, dry and ignite and fuse this titanic oxide with about twelve times its weight of acid sodium sulphate ; alldw to cool, and treat with concentrated sulphuric acid. This is now added to 600 cc. of water, boiled for one hour, and the precipitated titanic oxide filtered, dried and weighed. (Consult Scheme XIII, Determination of Titanium). ANALYSIS OF CLAY, KAOLIN, FIRE SAND, ETC. 303 Wa ter of Hydra tion . Take two grams of the clay, dried at 100 C., transfer to a cov r ered platinum crucible and ignite over a blast-lamp at a red heat to constant weight. The loss represents the combined water. Clays or fire sands that are to be used in the manufacture of fire bricks, retorts, etc., should contain only small amounts of easily fusible materials, such as potash, soda or iron ; less than one per cent, of either alkali, or two per cent, of iron oxide be- ing allowable in the best fire clays. . COMPOSITION OF SOME REPRESENTATIVE FIRE CLAYS. i. 2. 3. 4- 5- 6. 7. 8. 9. SiO 2 (com'd) 50.46 50.15 56.42 65.10 39.94 40.33 29.67 44.20 A1 2 O 3 35.90 35.60 26.35 22.22 36.30 0.72 38.54 20.87 39-H H 2 O 12.74 13.61 10.95 7.10 14.52 0.35 13.00 8.61 14.05 K 2 O 0.48 0.18 0.42 0.14 0.66 1.55 0.25 Na 2 O 0.07 CaO 0.13 o.n 0.60 0.14 0.19 0.22 0.08 .... MgO 0.02 0.16 0.55 0.18 0.19 0.38 0.30 Fe 2 O 3 1.50 0.83 1.33 1.92 0.46 0.18 0.90 1.45 0.45 SiO 2 (free) 4-9 98-3 1 5^5 3 6 4i 0.20 Moisture 2.80 2.18 3.26 0.90 TiO 2 1.15 1.14 1.05 SO 3 0.14 Org. matter 0.58 Total 100.75 100.67 100.63 99.60 99.18 99.92 99.24 loo.oo 100.24 No. i. Mt. Savage fireclay, Md. No. 2. Fire clay, Clearfield Co., Pa. No. 3. Glenboig clay, England. No. 4. Stourbridge clay, England. No. 5. Saaran clay, Germany. No. 6. "Dinas," 1 England. No. 7. Zettlitz clay, Bohemia. No. 8. Stoneware clay, N. J. No. 9. Paper clay, N. J. Building stone, such as granite, limestone, sandstone, slate, brick, etc., are generally subjected to certain mechanical or phys- ical tests in addition to a chemical analysis to determine their relative value. i Used iu making the celebrated "Dinas" Fire Bricks, noted for their endurance at high heats and for swelling and making tight roofs for furnaces. 304 QUANTITATIVE ANALYSIS. These physical tests generally comprise : 1. Crushing strength. 2. Absorptive power. 3. Resistance to the expansion of frost, by saturating the stone with water and freezing a number of times to produce an effect similar to frost. 4. Microscopical examination. /. Crushing Strength. The crushing strength is generally determined by applying a measured force to one-inch or two-inch cubes of the material until they are crushed. These compression tests are comparative only and give no idea of the crushing .strength of the material in large masses. A Riehle U. S. Standard Automatic and Autographic Testing machine is used for this purpose. 2 (Fig. 90). CRUSHING STRENGTH OF VARIOUS BUILDING STONES. Ultimate crushing strength. Pounds per Tons per square inch. square foot. Kinds of stone. Minimum Maximum. Minimum. Maximum. Granite 12000 21000 860 1510 Trap rock of N. J 20000 24000 1440 1 730 Marble 8000 20000 580 1440 Limestone 7000 20000 500 1440 Sandstone 5000 15000 360 1080 Common red brick 2000 3000 144 216 2. Absorptive Power. This is determined by drying the sample and weighing it, then soaking it in water for twenty-four hours and weighing again. The increase of weight represents the amount of water absorbed. A close fine-grained stone absorbs less water than a coarse-grained one, and generally the less the absorption the better the stone. ABSORPTIVE POWER OF STONE, BRICK AND MORTAR. Ratio of absorption. 1 Kind of material. Maximum. Minimum. Granite i 150 o Marble I 150 o Limestone i 20 i 500 Sandstone i 15 i 240 Brick 15 150 Mortar I 2 i 10 1 Thus, if 150 units of dry granite weigh after immersion in water 151 units, the ab- sorption is one in 150 and stated 1150. 2 For description of this apparatus consult The Digest of Physical Tests and Laboratory Practice, Vol. i, p. 248 (July 1896). 306 QUANTITATIVE ANALYSIS. j. Freezing Test. Samples of the weighed material, preferably cut in two-inch cubes, are saturated with water, then placed in a Tagliabue freez- ing apparatus (Fig. 91) and maintained at a temperature of 10 F. Fig. 91. for four hours. They are then removed, allowed to thaw gradually to a temperature of about 65 ; then moistened with water and placed again in the freezing apparatus and maintained at a tem- perature of 10 F. for four hours. This process is repeated at least ten times, when, after the samples have acquired the tem- perature of the room, the moisture is wiped from them, then dried, and their weight carefully determined. The loss of weight represents the material broken off by the expansive action of freezing the contained water. The following method of making the frost test of building stones, is from "Uniform Methods of Procedure in Testing Building and Structural Materials" by J. ANALYSIS OF CLAY, KAOLIN, FIRE SAND, ETC. 307 Bauschinger (Mechanisch-technischen Laboratorium, Miin- chen). 1 The examination of resistance to frost is to be determined from samples of uniform size, inasmuch as the absorption of water and action of frost are directly proportional to the surface exposed. The test sample should be a cube of seven cm. (2.76 inches) length on edges. The frost test consists of : a. The determination of the compressive strength of saturated stones, and its comparison with that of dried pieces. b. The determination of compressive strength of the dried stone after having been frozen and thawed out twenty-five times, and its comparison with that of dried pieces not so treated. c. The determination of the loss of weight of the stone after the twenty-fifth frost and thaw : special attention must be had to the loss of those particles which are detached by the mechan- ical action, and also those lost by solution in a definite quantity of water. d. The examination of the frozen stone by use of a magnifying glass, to determine particularly whether fissures or scaling oc- curred. For the frost test are to be used : Six pieces for compression tests in dry condition, three normal and parallel to the bed of the stone, six test pieces in saturated condition, not frozen however ; three tested normal to, and three parallel to, bed of stone. Six test pieces for tests when frozen, three of which are to be tested normal to, and three parallel to, bed of stone. When making the freezing test the following details are to be observed : a. During the absorption of water, the cubes are at first to be immersed by two cm. (0.77 inch) deep, and are to be lowered little by little until finally submerged. b. For immersion distilled water is to be used at a temperature of from 15 C. to 20 C. c. The saturated blocks are to be subjected to temperatures of from 10 to 15 C. 1 Standard Tests and methods of Testing Materials : Trans. Amer. Society Mech. Engi- neers, 14, 1294. 308 QUANTITATIVE ANALYSIS. d. The blocks are to be subjected to the influence of such cold for four hours, and they are to be thus treated when com- pletely saturated. e. The blocks are to be thawed out in a given qiiantity of dis- tilled water at from 15 C. to 20 C. The Testing of Brick. i. When testing bricks as found in a delivery, the least burnt are always to be selected for investiga- tion. 2. Bricks are to be tested for resistance to compression in the shape of cubical pieces, formed by the superposition of two half bricks, which are to be united by a thin layer of mortar consisting of pure Portland cement, and the pressure surfaces are also to be made smooth by covering them with a thin coat- ing of the same material. At least six pieces are to be tested. 3. The specific gravity is to be determined. 4. In order to control the uniformity of the material, the porosity of the bricks is to be determined ; for this purpose they are to be thoroughly dried and then submerged in water until saturated. Ten pieces are to be thoroughly dried upon an iron plate and weighed ; then these bricks are to be immersed in water for twenty-four hours, in such a way that the water-level stands at half the thickness ; after this they are to be submerged for another twenty-four hours, then to be dried superficially and again weighed ; thus the average quantity of water absorbed is determined. The porosity is always to be calculated by volume, though the per cent, of water absorbed is always to be stated in addition. 5. Resistance against frost is to be determined as follows : a. Five of the bricks, previously saturated by water, are to be tested by compression. b. The other five are put into a refrigerator which can produce a temperature of 15 C. at least, and kept therein for four hours ; then they are removed and thawed in water of a temperature of 20 C. Particles which might possibly become detached are to remain in the vessels in which the brick is thawed until the end of the operation. This process of freezing is repeated twenty- five times, and the detached particles are dried and compared by weight with the original dry weight of brick. Particular ANALYSIS OF CLAY, KAOLIN, FIRE SAND, ETC. 309 attention, by using a magnifying glass, is to be given to the possible formation of cracks or laminations. c. After freezing, the bricks are to be tested by compression. For this test they are dried, and the result obtained is to be com- pared with that of dry brick not frozen. d. Thus, freezing the bricks does not give a knowledge of the absolute frost-resisting capacity ; the value of the investigation is only relative, because by it can only be determined which brick can be most easily destroyed by the action of frost. 6. To test bricks for the presence of soluble salts y five are selected , and again those which are least burnt, and then such which have not yet been moistened. Of these, again, the interior parts only are used, for which reason the bricks are split in three direc- tions, thus producing eight pieces, of which the corners lying innermost in the brick are knocked off. These are then pow- dered until all passes through a sieve of 900 meshes per square centimeter (about 5,840 per square inch), from which the dust is again separated by a sieve of 4,900 meshes per square centi- meter (about 31,360 per square inch), and the particles remain- ing on the latter are examined. Twenty-five grams are lixivi- ated in 250 cubic centimeters of distilled water, boiled for about an hour, however replenishing the quantity evaporated, then filtered and washed. The quantity of soluble salts present is then determined by boiling down the solution and bringing the residue to a red heat for a few minutes. The quantity of soluble salts present is to be given in per cent, of the original weight of brick. The salts obtained are to be submitted to a chemical analysis. 7. Determinations of the presence of calcium carbonate, py- rites, mica and similar substances are to be made on the un- burned clay, for which purpose unburned bricks are to be fur- nished. These are soaked in water and the coarse particles are separated by passing the whole material through a sieve having 400 meshes per square centimeter. The sand thus obtained is to be examined by the magnifying glass and with hydrochloric acid to determine its mineralogical composition. When im- purities, such as carbonate, pyrites, etc., are found, then pieces of brick, such, for instance, as remained from the determina- 310 QUANTITATIVE ANALYSIS. tion of soluble salts, are to be examined in a Papin's digester for their deleterious influence. They are to be so arranged in a Papin's digester that they are not touched by the water directly, but are subjected to the action of the generated steam alone . The pressure of steam shall be one-quarter atmosphere, and the duration of test three hours. Possibly occurring disintegration is to be determined by means of the magnifying glass. 4. Microscopical Examination. This consists in examining under the microscope their sec- tions of the building stone. Important results are often obtained, especially so if the substances used as matrix are indicated the presence and amount of injurious substances, such as iron py- rites, mica, etc. Nearly all reports upon samples of building stones now in- clude the microscopical examination. The first and most essential test applied to building stone is to determine the structure and character of a stone, to know whether it be a granite, syenite, sandstone, quartzite or some- thing else. Although an expert can usually determine at a glance to which, if any, of these groups a particular stone be- longs, it is frequently possible to determine the precise litholog- ical character only by a microscopical examination. Thus, for instance, there is a class of Cambrian rocks commonly called Potsdam sandstone, that are not sandstones at all, but are hard, compact rocks known as quartzites, which have been derived from sandstones by metamorphic action. The essential differ- ence between a sandstone and a quartzite lies in the presence of secondary silica between the quartz granules comprising the latter ; the presence of this secondary silica or quartz can be determined for a certainty only by microscopical means. The microscope is not only useful in determining the structure of a stone, but it has an even greater practical value in making it possible to detect the presence of deleterious substances, such as pyrite and marcasite, or other minerals whose chemical compo- sition is affected by atmospheric agencies and thus exert a dele- terious effect upon the stone. 1 1 H. Lynwood Garrison, Trans. Amer. Soc. Civil Eng., 33, 88. ALLOYS. 311 Consult : Tenth Census U. S., 1880. " Building Stones and Quarry Industry." Stones for Building and Decoration. By G. P. Merrill, 1891. Building Stone in New York. By Prof. J. C. Smock, in Bulletin of the New York State Museum, 1890. The Testing of Material of Construction. By W. C. Unwin, pp. 410- 440. A Treatise on Masonry Construction. By I. O. Baker, C.E., 1893. A complete description of the methods of determining the fusibility of Fire Clays will be found in Trans. Amer. Inst. Min. Eng., 24, pp. 42-67. XXXVIII. Alloys. This subject may be divided into three classes : 1 . Alloys composed principally of copper and zinc, or of cop- per, tin and zinc. 2. Alloys or compositions in which copper, tin, lead or anti- mony are constituents. 3. Alloys not included in the first two divisions. Alloys of the first class may comprise brass, bronze, bell metal, gun metal, Muntz's metal, etc. The analysis may be performed as follows (if composed of copper and zinc only): Transfer one gram of the brass to a No. 3 beaker covered with a watch-glass, and add gradually twenty-five cc. nitric acid ; when solution is complete, remove watch-glass, after washing, allow solution to cool, transfer it to a one-quarter liter flask and add water to the containing mark. Mix thoroughly (the solu- tion being at 15 C.) and transfer fifty cc. of the solution to a No. 3 beaker, dilute sufficiently with water and precipitate the copper electrolytically, as in Scheme VI, page 5. Upon complete precipitation of the copper, the platinum cone and spiral are removed from the solution, washed with water, the washings added to the solution in the beaker. Add a few drops of nitric acid to the solution, boil and precipitate the zinc with a slight excess of sodium carbonate. Boil, filter, wash well with hot water, dry, ignite and weigh as ZnO. Example: One gram brass turnings taken. Solution 250 cc. Fifty cc. of solution taken : 312 QUANTITATIVE ANALYSIS. Platinum cone + Cu 28. 175 grams. Platinum cone 27.995 ' ' Cu = 0.160 " 0.160 X 5 X ioo J = 80 per cent. Cu. i Porcelain crucible -f- ZnO 17-655 grams. Porcelain crucible 17.605 " ZnO = 0.050 0.050 X 65 0.040 X 5 X ioo ^-5 = 0.040 Zn, = 20 per cent. OI I Cu 80 per cent. Zu 20 " Total ioo " Where tin is also a component, the above method is varied as follows : Take one gram of the fine turnings and digest with nitric acid as above. Evaporate nearly to dryness, add fifty cc. warm water, filter by decantation into a one-quarter liter flask, wash- ing the precipitate thoroughly with hot water, dry it, ignite and weigh as SnO 2 and calculate to Sn. The filtrate is made up to 250 cc. ( 15 C.), thoroughly mixed, and fifty cc. taken for copper and zinc as before. Porcelain crucible 4- SnO 2 16.6743 grams. Porcelain crucible 16.5221) " SnO 2 = 0.1523 Sn = 12 per cent. Platinum cone -f- Cu 28. 1 15 grams. Platinum cone 27.995 ' ' Cu = o.i 20 " Cu = 60 per cent. Porcelain crucible + ZnO 17.6750 grams. Porcelain crucible 1 7.6052 ' ' ZnO = 0.0698 Zn 28 per cent. ALLOYS. 313 Resume : Sn 12 per cent. Cu 60 " " Zn 28 " " Total 100 " " EXAMPLES OF ALLOYS OF THE FIRST CLASS. Tin. Copper. Zinc. Bell metal 22 78 . . parts. Brass 72 28 " Brass (yellow) 60 40 " Bronze for bearings 16 82 2 " Speculum metal 33.4 66.6 .. " Delta metal 1 or "Sterro" .. 60 38.2 (i.SFe)" Muntz metal 60 40 " Alloys of the second class may comprise Babbitt metal, Britan- nia metal, type metal, solder, white metal, camelia metal, Tobin bronze, ajax metal, car-box metal, manganese bronze, magnolia metal, etc. Analysis of Babbitt Metal. 2 Five grams of drillings in an eight-ounce beaker are treated with thirty cc. nitric acid (1.20 sp. gr.) and heated till decom- position is complete and the free acid nearly all evaporated. When about five cc. of the solution remain, add fifteen cc. of water, and then add concentrated sodium hydroxide solution till nearly neutral ; fifty cc. of sodium sulphide solution are then added, the mixture well stirred, then boiled gently for half an hour. The solution then contains the tin and antimony. The precipitate, which contains the sulphides of lead and copper, is filtered on a nine cm. Swedish filter, and washed thoroughly with water containing one per cent, of the above sodium sulphide solution. The filtrate is received in a 300 cc. beaker. Tin and Antimony. The filtrate is diluted to 200 cc. and boiled. Crystals of oxalic acid, C. P., are cautiously added till the sodium sulphide is all decomposed and a milky separation appears, mixed with a precipitate which is usually at first black. Boil for twenty minutes. Pass hydrogen sulphide for ten min- utes. Filter rapidly on a Gooch crucible and wash with hot 1 Some varieties of Delta metal contain one to two per cent, of tin. 2 Method of E. M. Bruce, modiSed. 314 QUANTITATIVE ANALYSIS. water. Dry, and heat crucible and contents in a stream of car- bon dioxide to a temperature above 300 C. for one hour. Cool in carbon dioxide, remove crucible and weigh as Sb 2 S 3 . The Gooch crucible containing the Sb 2 S 3 + S may be treated with alcohol, then carbon disulphide, then alcohol (in order to re- move the sulphur), dried and weighed, instead of igniting in carbon dioxide. Sb 2 S 3 X 0.71390 Sb. The filtrate from the Sb 2 S 3 is treated with thirty cc. concen- trated sulphuric acid and boiled down till all oxalic acid is decom- posed and strong fumes of sulphuric acid come off. Cool. Dilute cautiously to 200 cc., mix well and filter quickly. Dilute fil- trate to 300 cc., warm slightly and pass hydrogen sulphide. Filter stannous sulphide and wash with hot water. Dry, ignite and weigh as stannic oxide in porcelain crucible. SnO 2 X 0.788 = Sn. The copper and lead sulphide precipitate is washed off the filter, treated with dilute nitric acid, warmed till decomposed, and the sulphur filtered off. The lead is then separated as sul- phate by evaporation with sulphuric acid. The lead sulphate is filtered on a Gooch crucible, washed with water containing five per cent, sulphuric acid, dried and ignited over a Bunsen bur- ner. PbSO 4 X 0.68298= Pb. The copper is separated from the filtrate by hydrogen sulphide. The sulphide is decomposed by nitric acid, and the resulting solution titrated or electrolyzed. Sodium sulphide solution for Babbitt analysis is made up as follows : One pound sodium sulphide crystals are dissolved in two liters of water. Portions of this are from, time to time satu- rated with hydrogen oxide gas and filtered for use. Separation of Tin and Antimony in Alloys. Mengin treats the alloy (for instance, anti-friction metal) with nitric acid (1.15), collects the insoluble oxides of tin and antimony, washes, carefully ignites and weighs them. M. The mixed oxides are next suspended in hydrochloric acid and water and a ball or plate of pure tin added, whereupon the anti- mony is reduced to metal and the tin converted into chloride ; the reaction is best accelerated by heat, about three hours being ALLOYS. 315 .. '' 5 5o" I J* ^"s.^ o Isfll^^? JT < '_ - S- r* " M o " s ^--c- s. tfl'liFfl^llSt^i 2r s -5^0 s.^22 K! rt 2 5 s : o" < o ? I188S, x-v"-t ii o n |pIl5fwS?M&?^P|fM^55 s s llll&llll 5'S 3-i I ^ ' ni > Va^' I! 2.3*0:3 Mil I ill -P * .1 p? 5 t i! Is > IS QUANTITATIVE ANALYSIS. necessary for two grams of the oxides. The precipitated anti- mony is washed by decantation with water, then with alcohol, dried and weighed A. There is no appreciable [oxidation of the antimony and the method is very exact. The tin is esti- mated by difference. M A X 1.262 = weight of tin oxide; the latter multiplied by 0.7888 gives the weight of tin in the alloy. An alternative method for the estimation of the tin is to precipitate the latter by zinc. The following figures (indicating grams) of an analysis, show the accuracy of the method : Samples taken. Sn Sb Oxides found. Sn Sb Metals found. I-I54 1.309 1.162 1.312 EXAMPLES OF ALLOYS OF THE SECOND CLASS. Iron. Tin. Antimony. Lead. Copper. Zinc. Bismuth. Phos. K>'0 90.0 89.3 85.5 77.8 50.0 40.0 0.9 10.0 12.40 4-75 22.90 4-25 10.98 86.00 8.00 10.00 7-i 14-5 19.4 5-0 15.0 14.38 1. 00 ^\j A O i 8 i 8 8 Soft solder Anti-friction metal Tobin bronze Phosphor-bronze 1 . . . Deoxidized bronze.. 0.2 0.20 50.0 55-0 0.4 9-5 2.27 80.0 27.10 14-75 7-37 84.33 2.00 TC.OO .... ... 61.2 79.70 82.67 trace 70.20 81.28 2.00 77.OO 37- 2. 10. 3 45 .... .. 0.25 .. 50.0 20 0.8 0.005 0-37 trace Rose metal 0.55 0.61 Ajax metal Car-box metal Parson's white metal " T5 " allov. P. R. R. 2 0.68 .... 27.00 THIRD CLASS COMPRISES : Aluminum bronze Al 7.3, Si 6.5, Cu 86.2 or Al 10, Cu 90 Ferro-aluminum Al i .23, Fe, etc. 99.73 or Al 12.50, Fe, etc., 87.50 Ferro-tungsten Fe 43.4, W 53.1, Mn 3-5 3 German silver Cu 50, Ni 14.8, Sn 3.1, Zn 31-9 Rosine Ni 40, Ag 10, Al 30, Sn 20 1 Detailed instructions for the determination of phosphorus in phosphor bronze will be found in The American Engineer and Railroad journal, 68, 128. 2 This alloy, according to C. B. Dudley (/. Franklin Inst., March, 1892, p. 168), is the best bearing metal known. 8 Consult experiments on ferro-tungsten ; J. S. DeBenneville. / Am. Chem. Soc., 16, 302. ALLOYS. 317 Metalline Co 35, Al 25, Cu 30, Fe 10 Aluminum " bourbounz " Al 85.74, Sn 12.94, Si 1.32 Silicon bronze Fe, etc. 86.59, Si 13. 4I 1 Guthrie's " Entectic " Cd 14.03, Sn 21.10, Pb 20.55, Bi 50 Arsenic bronze Cu 79.70, Sn 10, Pb 9.50, As 0.80 Manganese bronze Cu 88, Sn 10, Mn 2 Aluminum bronze can be analyzed as follows : Take one gram of bronze in fine turnings, transfer to a No. 3 beaker and add gradually twenty-five cc. of aqua regia. Evaporate to diy- ness, to render the silica insoluble, take up with twenty-five cc. hydrochloric acid, twenty-five cc. water, warm and filter. Wash well. The residue is dried, ignited and weighed as SiO 2 , and calculated to Si. The filtrate from the silica is diluted to 250 cc. thoroughly mixed and 100 cc. transferred to a No. 3 beaker and the copper precipitated with hydrogen sulphide, filtered, washed with hydrogen sulphide w r ater, the cupric sulphide dissolved in nitric acid, and the copper determined by electrolysis (Scheme VI). The filtrate from the cupric sulphide is boiled to expel hydrogen sulphide, a few drops of nitric acid added, the solution made alkaline with ammonia, and the alumina determined as in Scheme III, and calculated to Al. Determination of Manganese in Manganese Bronze? Dissolve five grams of drilling in nitric acid of i.2osp. gr., using a large beaker to avoid frothing over. An excess of acid must be avoided as it interferes with the precipitation of the copper by hydrogen sulphide. When solution is complete, transfer to a 500 cc. cylinder w r ij:hout filtering out the precipitated stannic oxide. Make up to 300 cc. and pass a rapid current of hydrogen sulphide from a Kipp's apparatus until the supernatant liquid is colorless. Decant off through a dry filter, 180 cc. corresponding to three grams of sample, and boil rapidly down to about ten cc. Transfer to a small beaker and add twenty-five cc. of strong nitric acid. Boil down one-half, make up with strong nitric acid, boil, and add one spoonful of potassium chlorate. Boil ten minutes and add another spoonful of potassium chlorate. Boil till free from chlorine, cool in water, and filter on asbestos, 1 Consult Determination of Silicon in Ferrc-silicons ; its Occurrence in Graphitoidal Silicon, by H. J. Williams, Trans. Amer, Inst. Min. Eng., 17, 542. 2 Jesse Jones, J. Am. Chem. Soc., 15, 414. 318 QUANTITATIVE ANALYSIS. using filter pump. Wash with strong nitric acid through which a stream of air has been passed. When free from iron, wash with cold water until no acid remains. Place the felt and pre- cipitate in the same beaker and dissolve in ferrous sulphate, using five cc. at a time. Titrate back with permanganate until a pink color remains. Deduct the number of cc. used in titra- ting back, from the number of equivalents of ferrous sulphate used, and the remainder shows the manganese in the amount of sample taken. Permanganate Solution. Dissolve 1.149 grams of potassium permanganate in 1,000 cc. water: one cc. equals o.oo igram manganese; check by dissolving 0.1425 gram ammonio-ferrous sulphate in a little water and acidulating with hydrochloric acid. This should precipitate ten milligrams of manganese. If not, apply factor of correction. Ferrous Sulphate Solution. A solution of ferrous sulphate in two per cent, sulphuric acid so dilute that five cc. corresponds to ten cc. permanganate solution. This is best made by trial and solution. Analysis of Ferro- Aluminum. Five grams of the ferro-aluminum are transferred to a 500 cc. beaker and dissolved in seventy-five cc. sulphuric acid (sp. gr. 1.30), then evaporated to dryness. The residue is treated with fifty cc. dilute sulphuric acid diluted to 300 cc. and mixed well. 100 cc. of the solution (= 1.666 grams) are filtered off into a graduated 100 cc. measure ; this is then poured into a 250 cc. beaker ; about five grams of pure iron wire are now added and the solution boiled, so as to reduce any ferric salt formed ; the excess of acid is carefully neutralized with solution of sodium carbonate and the mixture gradually poured into 150 cc. of a boiling solution containing thirty grams of potassium hydroxide and sixty grams of potassium cyanide ; the mixture of potas- sium hydroxide and potassium cyanide with iron precipitated as hydroxide is diluted up to 500 cc. in a graduated measure, and 300 cc. (= i gram of sample) filtered off into a six-inch evap- orating dish ; 200 cc. of a standard solution of ammonium ni- trate are now added and the mixture heated forty minutes ; ALLOYS. 319 filter and wash the precipitated alumina with hot water, re- dissolve in twenty-five cc. of dilute hydrochloric acid, dilute to 200 cc., neutralize with ammonium hydroxide, add a slight ex- cess, boil, filter and wash with hot water, dry, ignite and weigh as A1 2 O 3 . The weight obtained multiplied by 0.534 X loo = percentages of Al. This amount subtracted from 100 per cent, gives the percentage of iron. (Phillips.) German silver, Rosine, Aluminum " bourbounz." Guthrie's "entectic" and arsenic bronze all require solution innitric acid to render the tin insoluble, which is then separated by filtration from the other components. The determination of phosphorus in phosphor-tin presents some difficulty on account of the insoluble compound which phosphoric acid forms with stannic oxide. Hempel, 1 states as follows : The ordinary way of analyzing phosphide of tin by dissolving it in aqua regia and precipitating with hydrogen sulphide is not satisfactory, as a considerable quantity of phosphorus is thrown down with the precipitated sulphide as a basic phosphate of tin. It is easily analyzed according to Wohler's method, by treating with chlorine, the chlorides of tin and phosphorus formed being collected in about ten cc. of concentrated nitric acid. If the apparatus be rinsed with a solution of one part concentrated nitric acid and two parts of water, no trace of stannic oxide is precipitated. The phosphoric acid is now easily precipitated in the usual way by molybdic acid. If dilute nitric acid is taken, a part of the phosphorus separates with the stannic oxide and the result will be too low. This also applies to the determination of phosphorus in phosphor-bronze. Qualitative Tests of Alloys of Lead, Copper, Tin and Antimony ? For lead, dissolve in aqua regia. If much lead be present, it will separate on cooling as chloride ; if only a small amount is present it will be detected by the addition of four volumes of ninety-five per cent, alcohol. For tin, dissolve in hydrochloric acid, concentrated, and be- fore the portion of alloy taken is completely dissolved, pour off 1 Ber. d. Chem. Ges., 22, 2478, /. Anal. Chem., 4, 83. 2 Communicated to the author by G. W. Thompson, Chemist National Lead Co., N.Y. 320 QUANTITATIVE ANALYSIS. the supernatant solution, cool to separate lead as chloride, add four volumes of alcohol, filter and to filtrate add slight excess of bromine to convert stannous to stannic chloride ; heat to expel free bromine, dilute and pass hydrogen sulphide gas, when if tin is present it will be obtained as yellow stannic sulphide. For antimony treat alloy with concentrated hydrochloric acid . Almost all the antimony is left undissolved. Decant, wash the residue with water, after which dissolve in hydrochloric acid with potassium chlorate, boil to expel free chlorine, pass hydro- gen sulphide, obtaining a precipitate of Sb 3 S 6 , if antimony is present. If copper is also present, it will be precipitated as cop- per sulphide and may obscure the color of the antimonic sul- phide ; if so, filter and treat the precipitate with potassium hydroxide solution, which will dissolve the antimonic sulphide. Filter and acidify filtrate, when the pure color of antimonic sulphide will be observed if antimony is present. P v or copper, treat the alloy with dilute nitric acid in a porce- lain dish and evaporate to dry ness ; if copper is present, it will show as a green ring where it crystallizes out as nitrate on edge of the residue. For arsenic, dissolve alloy in hydrochloric acid, with addition of potassium chlorate, in an Krlenmeyer flask, boil to expel chlorine, add some more concentrated hydrochloric acid and two grams of sodium thiosulphate, connect flask with a condenser and distil, following in principle the method first proposed by Fischer. Arsenic, if present, will be found in the distillate by passing through it hydrogen sulphide gas. Quantitative Analysis of Alloys Containing Copper, Lead, Anti- mony and Tin 1 . One gram of the finely divided alloy is dissolved by boiling in from seventy to 100 cc. of the following solution, in a covered beaker. The solution is made by dissolving twenty grams of potassium chloride in 500 cc. of water, adding 400 cc. concentrated hydro- chloric acid, mixing, and then adding 100 cc. nitric acid of 1.40 sp. gr. No decomposition between hydrochloric acid and nitric acid takes place in this solution in the cold. If complete solu- i Method of G. W. Thompson. ALLOYS. 321 tion of the alloy is difficult in the amount of solution taken, more is added as required. Continue boiling until solution is evaporated to about fifty cc. Cool by placing beaker in cold water until the bulk of the lead has crystallized out as chloride and then add slowly, with constant stirring, 100 cc. ninety-five per cent, alcohol. Allow to stand about twenty minutes, filter through a nine cm. filter paper into a No. 4 beaker; wash by decantation three times with mixture (4 to i) of ninety-five per cent, alcohol and hydrochloric acid, concentrated, and wash filter paper twice with the same mixture. Wash the lead chloride on the paper into a beaker, and wash filter paper several times with hot water, allowing washings to flo\v into the beaker with rest of the chloride. Finally wash twice with solution of ammonium acetate, hot, (the ammonium acetate solution is made by taking one volume of ammonia water, 0.900 sp. gr., adding to it one volume of water and then eighty per cent, acetic acid until the reaction is slightly acid to litmus) , heat until the lead chloride is dissolved, then add fifteen cc. of a saturated solution of potassium bichromate, and warm until precipitate is of good orange color. Filter on weighed Gooch crucible, wash with water, alcohol and ether, dry at 110 C. and weigh. Evaporate filtrate from lead chloride by heating on hot plate and finally to dryness on water-bath ; add ten cc. solution potas- sium hydroxide (one gram to five cc.) and after a few minutes twenty cc. peroxide of hydrogen ; heat on water-bath for twenty minutes, add ten grams ammonium oxalate, ten grams oxalic acid and 200 cc. of water. Heat to boiling, pass hydrogen sul- phide with solution near boiling for forty-five minutes ; filter at once and wash precipitate with hot water. Boil filtrate to expel hydrogen sulphide, concentrate if necessary and electrolyze over night, using a current of about one-half ampere. Usually by morning the solution will have become alkaline, in which case it may be taken for granted that the tin is all precipitated on the cylinder. The cylinder is removed, washed twice with water and then with ninety-five per cent, alcohol, dried and weighed. The precipitate of antimony and copper sulphides on paper is washed back into beaker with the least amount of 322 QUANTITATIVE ANALYSIS. water possible, and treated with ten cc. potassium hydroxide solution (1-5), heated on w r ater-bath until undissolved matter is distinctly black ; then filtered through the same paper it was washed from into a twelve-ounce Erlenmeyer flask, washed, etc. On the filter the copper is obtained as sulphide with a small amount of lead which failed of precipitation as chloride. If it is desired to determine this lead, it can be done by separation from the copper as usual ; if not, dry and ignite precipitate in a small casserole, dissolve in nitric acid, boil to expel nitrogen dioxide, neutralize with sodium carbonate, add a few drops of ammonia, and determine volumetrically with potassium cyanide standardized against pure copper. The solution of antimony sulphide in potassium hydroxide should not amount to over forty cc. Add one gram potassium chlorate, fifty cc. concentrated hydrochloric acid, boil until solution is colorless and free chlo- rine is driven oft ; filter through mineral wool ; if sulphur has separated into similar flask, wash out original with concentrated hydrochloric acid, cool, add one gram of potassium iodide, one cc. carbon disulphide, and titrate for antimony with tenth-nor- mal sodium thiosulphate, one cc. of which equals 0.0060 gram antimony. This systematic method assumes the absence of other metals than lead, tin, antimony and copper. For the determination of other metals we offer the following suggestions : If arsenic is present it will be separated with the antimony and will liberace iodine, as does antimony. One cc. of tenth-normal thiosulphate equals 0.00375 gram of arsenic. Arsenic is prefer- ably determined on a separate portion by dissolving in hydro- chloric acid and potassium chlorate, boiling to expel free chlorine, and distilling after the addition of sodium thiosulphate as a reducing agent, passing hydrogen sulphide through the distillate, and weighing as As 2 S 3 , or dissolving in potassium hydroxide and determining volumetrically as in the case of anti- mony. Bismuth and cadmium sulphides would remain with copper after treatment with potassium hydroxide this renders this method very suitable for fusible metals. Zinc would interfere with this method, but as zinc does not alloy with lead, we will not speak of it further. Nickel and cobalt alloy but slightly ANALYSIS OF TIN PLATE. 323 with tin, and if present, should be sought for both in the pre- cipitate left by potassium hydroxide and in the tin precipitated on a cylinder. Iron will also be precipitated with tin if present in an oxalic acid solution. Phosphorus is best determined by Dudley's method. 1 In alloys containing only lead and tin, with the tin under twenty per cent., the two constituents can best be determined by treatment with dilute nitric acid in a porcelain dish, evaporating to dryness on a w r ater-bath, etc., and determining lead as chro- mate and tin as stannic oxide. In samples free from iron and copper, antimony may be determined directly by solution in hydrochloric acid and potassium chlorate, boiling to expel chlorine, and titrating as with pure antimony. Antimony in solders ma}' be determined very accurately by dissolving in hy- drochloric acid without access of air and filtering out the un- dissolved antimony on a weighed Gooch crucible. I have not found that a weighable amount of antimony was lost as stibine by this treatment. In the analysis of alloys of lead and tin, Richards' scales," which are accurate within one per cent., may be used. In the examination of the various classes of alloys described at the beginning of this paper, various steps in their analysis may be left out with the absence of the respective metals. References : " Phosphorus in Phosphor Bronze." By F. Julian., /. Am. Chem. Soc., 15, 115. " Analysis of American Refined Copper (determination of Cu, Ag, Se, Te, Bi, Sb, As, Fe, Ni, Co, Pb)."/. Am. Chem. Soc., 16, 785. " The Commercial Valuation of Tin-lead and Lead-antimony Alloys." By J. \V. Richards,/. Am. Chem. Soc., 16, 541. " Materials of Engineering." By R. H. Thurston, Part III. "The Testing of Materials of Engineering." By \V. C. Unwin, p. 342. " Das mikroskopische Gefiige der Metalle und Legirungen." By H. Behrens, Hamburg, 1895. XXXIX. Analysis of Tin Plate. From two to three grains of the tin plate, cut into strips two to three cm. long by three to five mm. wide, are placed in a dry 1 Consult Am. Engineer and R. R. Journal, 8, i&)4 128. 2 Consult/. Am. Chem. Soc., 16, 541. 324 QUANTITATIVE ANALYSIS. bulb tube. A current of carefully dried chlorine gas is then passed through the tube, at first in the cold ; it is then warmed gently by a Bunsen flame at most three cm. high and placed at least fifteen cm. beneath the bulb, the object being the complete chloridization of the tin, without any attack upon the iron. If the temperature be unduty high, the iron will be violently acted upon and the experiment spoiled. The excess of chlorine, laden with stannic chloride is passed successively through two Peligot tubes and a small Erlenmeyer flask containing water, in which the tin is retained, partly as the tetrachloride, partly as metastannic acid. The connections of these t'ubes should be entirely of glass and cork, unjointed with rubber and the delivery tube of each part of the apparatus should reach nearly to the bottom, to prevent undue crystallization of the tin salt upon the moist upper walls of the condenser. The current of chlorine must be so regulated that, on the one hand, no stannous chloride is formed, whilst on the other hand, no tin is lost by the chloride being swept through the washing tube ; it is con- tinued until the surfaces of the strips are uniformly brown with- out white spots. Stannic chloride condensing in the narrow portion of the bulb tube is carried forward by the application of gentle heat. The essentials for success are dry chlorine and the minimum temperature possible. -J. Soc. Ghent. Ind., 1895, p. 822. The Analysis of Tin Plate for Tin, Lead, Iron and Manganese. The following volumetric method, depending on well known reactions, has given very satisfactory results : Dissolve five grams of tin or terne plate in 100 cc. hydrochloric acid, i.io sp. gr., in a 500 cc. graduated flask, with exclusion of air. When dissolved, cool and fill up to the mark. Transfer fifty cc. to a beaker, and after adding starch paste titrate the tin with standard iodine solution. A convenient strength of iodine is made by dissolving 5.38 grams of pure iodine in strong potassium iodide solution and diluting to one liter. For the iron determination add mercuric chloride in excess to ANALYSIS OF TIN PLATE. 325 fifty cc. of tin plate solution, and titrate the iron with standard bichromate. The determination of manganese is quite important, since it shows whether iron or steel has been tinned. Treat four grams of tin plate, cut into small pieces, with hot dilute sulphuric acid for about fifteen minutes. When the iron has dissolved, leaving the layers of tin and lead, add a little zinc and let stand for about two minutes. Fil- ter and dilute to twenty cc. Take one-half of this filtrate, add five cc. nitric acid of 1.20 sp. gr., and treat in the ordinary way with lead peroxide. The lead in tin plate is best determined as sulphate after first separating the tin by nitric acid. However, for ordinary work, it is sufficiently accurate to take lead by difference, allowing 0.25 per cent, for phosphorus, carbon, sulphur, silicon, etc., in addi- tion to the tin, iron and manganese previously determined. In order to test the accuracy of the iodine method for tin, a weighed quantity of pure tin, together with about forty times as much iron, was dissolved and the tin titrated. The result was as follows : Amount taken, 0.1255 gram tin. Amount found, 0.1266 gram tin. The following are a few analyses that were made of British terne plate used for roofing : Tin . I. n. 1.58 2.08 in. 2.40 IV. 3-37 V. 1. 60 VI. VII. VIII. 1.96 IX. T r\ 7-97 1 7-I3 1 8.89 ii. 98 2.48 1 7. 48 1 8.I2 1 7> ,09 10.23 l^Cd. L Iron 89.84 90.23 88.10 84/18 95.31 89. 35 89.29 86.64 Manganese 0.36 0.31 0.31 0-35 0.36 0.38 0-37 o. 32 0.32 Carbon 1 Phosphorus Sulphur [-0.25 0-25 1 0.25 o. 25 0.25 0, 25 0.25 25 0.25 Silicon, etc- loo.oo 100.00 99.95 100.13 100.00 loo.oo loo.oo 100.17 100.00 The iodine method may be used for determining tin in all alloys which contain no metals that affect iodine. However, when the percentage of tin exceeds ten per cent., 1 By difference. 326 QUANTITATIVE ANALYSIS. as in the case of solder, the following method, although not quite so simple or rapid, is somewhat more accurate. In principle the scheme is simply a revision of the well known stannous chloride titration method for iron. Dissolve five grams of the tin alloy in strong hydrochloric acid in a 500 cc. graduated flask, as in the case of tin plate. After diluting to the mark, fill a fifty cc. burette with the solution. Transfer ten cc. of a standard ferric chloride solution (ten grams iron in one liter) to a four-ounce flask and heat to boiling. While boiling run the tin alloy solution cautiously into the ferric chloride until the yellow color disappears. Cool and determine the excess of stan- nous chloride with standard iodine solution (Fe,Cl 6 + SnCl 2 = 2FeCl 2 + SnClj. Proceedings Eng. Society of Western Pa., 82, 182. XL. Chrome Steel. 1 The Chrome Steel Company designate its products as fol- lows : No. i . For turning, planing and other tools used for pur- poses requiring a steady cut. No. i A. Special for punches, heaters, etc. No. 3. For all kinds of fine-edged tools, chipping chisels and machine shop tools ; a grade well adapted for general purposes. No. 2. Milder than No. 3, for heavy or drop dies of all descriptions, and best quality sledges, etc. Mill Picks. Special for mill picks, points, etc. Rock Drill. Special for mining, quarry and stone cutting, etc. Tap and Die Steel. For tap and dies of all kinds. Hammer Steel. Cast Spring Steel. Machinery Steel. Of extra toughness and strength, capable of enduring great friction and resisting heavy strains ; especially adapted to mandrils, shaftings for rotary pumps, and other pur- poses where great strength is required. Round Bars for Prisons or Burglar-Proof Gratings. These bars consist of alternate layers of steel and iron welded together 1 Abstract of Thesis, B. F. Hart, Jr., and J. Calisch : Stevens Indicator, 9, 49-65. CHROME STEEL. 327 and designed for prisons, bank buildings, etc. The gratings or bars are first fitted and then hardened , the steel receiving a tem- per that will resist any saw, file, or drill ; while the iron remain- ing soft and ductile, will not fracture under heavy blows. This combination of iron and steel is also made in special shapes, and is largely used in safe building. Chrome steel is also exten- sively employed in the construction of large bridges. Chrome steel possesses great strength, as the following table of tests indicates (page 328). Tests are made by Capt. Eads upon sam- ples of chrome steel furnished in the construction of the Illinois and St. lyOuis Bridge. Analysis. Chromium Determination. Dissolve two grams of the sample in seventy-five cc. of hydrochloric acid (sp. gr. 1.12) in a 500 cc. flask fitted with a rubber cork containing a glass tube and a Bunsen valve (see page 29); heat gently. During the solution carbon dioxide is passed into the flask slowly to prevent oxida- tion of the iron. When solution is complete, nearly neutralize excess of free acid with sodium carbonate and render slightly alkaline with powdered barium carbonate. Add distilled water nearly to the containing mark, cork the flask tightly and allow to stand for twenty-four hours, with occasional shaking. All the chromic oxide and a small amount of ferric oxide are pre- cipitated, whilst all the ferrous chloride, manganese chloride, etc., remain in solution. Filter off the precipitate together with the excess of barium carbonate, wash with hot water, transfer filter paper containing the precipitate to a flask and dissolve in hydro- chloric acid with heat. Filter, wash well, and to the clear filtrate add ammonium hydroxide in slight excess and boil. The chromic oxide and the ferric hydroxide are thereby pre- cipitated while all the barium remains in solution. Filter, wash well with hot water, dry, ignite, and fuse in a platinum crucible with sodium carbonate and sodium nitrate. Extract the fused mass with hot water, boil and filter off the residual iron oxide. The filtrate contains all the chromium as the yellow sodium 328 QUANTITATIVE ANALYSIS. +5 en H^^ .^^-i;-,^^^-.-^' 5 H H spnnod UT 'g^^glCc^^vo'SSo'S^S^S'o'?^ vo Tt* T^~ O 10 *O 1 O VO T^- O **O <*O ^-O w ^J" vO 2 c 5 : !?a o ^ nT o a. x H/^ 3*7"^a33aia.9: i 3 344 QUANTITATIVE ANALYSIS. ASH IN FIBERS. Cotton 0.12 per cent- Italian hemp 0.82 ' " Rhea 5.63 " Best Manilla hemp 1.02 " " Sulphite fiber 0.46 ' ' ' ' Fine Flemish flax 0.70 " " China grass 2.87 " ' ' Jute 1.32 " " Esparto 3.50-5.04 " Soda fiber 1.00-2.50 " " Sixth. Determination of the Weight per Square Meter. It is best to use, when possible, five different pieces of the paper (from different packages or rolls), each piece about one square decimeter. These are placed in a drying oven and exposed to a tempera- ture of 105 C. until the weight becomes constant. The weight of the five pieces, multiplied by 20, gives the weight of one square meter of paper. 1 Seventh. Determination of the Thickness. The thickness of paper can be accurately determined by the apparatus, a sketch of which is shown in Fig. 100. By means of a delicate spring, a lever, s a , is held against s^ touching s l only at one point, ^carries a toothed segment, which moves a pointer, 2, along an arc divided into 500 parts. One division represents 0.002 mm. of thickness of the paper tested. Eighth. Determination of Breaking Strength. By the strength of a paper is understood the measurement of the resistance it offers to breaking or tearing strains. This re- sistance is always greater in the direction of the length of the web of paper, as it is made on the paper-machine, than across the web. On the other hand, the amount of elongation, which is measured while determining the breaking strain is greater in the direction across the web than parallel to it. 2 The tensile strength of the sheet, both across and parallel to the web, is determined separately, and the average values recorded. To ascertain the il,eitfaden fur Papier-priifung, W. Herzberg, Berlin, 1888. 2 Verhandlung des Vereins zur. Beforderungdes Gewerbefleisses in Preussen, 1885. CHEMICAL AND PHYSICAL EXAMINATION OF PAPER. 345 direction cor- responding to the motion of the paper ma- chine, in any sample of ma- chine-made paper, a cir- cular piece is cut and placed on the surface of wa- ter, when it will be. ob- served to roll up. The di- ameter of the disk where it is not curved indicates the di- rection of the length of the web. The strips of paper used for ascertain- ing the tensile strength and elongation are cut to the following size : 1 80 mm. long by fifteen mm. broad. Five strips, at least, are taken from different sheets and rep- resenting the length and across the web, in order to obtain good average ^ values. These strips Fig. ioo. must be carefully cut ; the edges should be smooth and run parallel. Cutting tools are provided for this purpose, consisting of an iron ruler and plates of zinc or glass. 346 4. Apparatus for QUANTITATIVE ANALY$IS. Before determining the tensile strength and elongation, careful attention must be paid to the amount of moisture in the atmosphere. The breaking strain of pa- per decreases with increase of moisture in the air, while under the same influ- ence the percentage amount of elongation increases. The humidity of the atmos- phere is very important when testing animal-sized paper and should on no ac- count be overlooked. Indeed, the break- ing strain values can only be compared when they are obtained in atmospheres of equal humidity. The percentage of atmospheric humidity chosen is 65, be- cause it is much easier to add moisture to the atmosphere than abstract moisture 2 from it. The former is done by boiling & water in the room. The instrument in use for measuring the humidity of the air is the Koppe-Saussure's air hygrom- eter. Before testing, the strips of paper are placed in the room for at least two hours. The principal machines in use for determining the breaking strength of paper are : The Hartig-Rensch, the Wendler and the Chopper Apparatus, a description of the Wendler being given herewith. This machine is used for ascertaining the strength and elasticity of paper. It consists in the main of four parts. (Fig. 101.) 1. The driver. 2. Apparatus for mounting. 3 . Apparatus for transmission of power, measuring force and stretch. CHEMICAL AND PHYSICAL EXAMINATION OF PAPER. 347 The driving is produced by a hand-wheel, a. The hub of this wheel turns in the bearing /, which is cast in one piece with the bed d. The screw, b, is led through this hub, which is hol- low, and is fastened to the slide c, and through its agency the slide is moved. The hand-wheel is equipped with a bolt-nut, consisting of the shell p, and two split nuts, which may be opened or closed by means of a worm, according as the motion of the slide is to be produced by the hand alone or through the agency of the wheel. The mounting apparatus consists of two clamps kk^ the first fastened to the carriage w t the second to the slide c. Between the jaws of these clamps the paper to be tested is stretched, The jaws of these clamps are normal to the axis of stress, wave- shaped, and are lined with leather, in order to prevent the slip- ping of the strip in the clamps. The jaws are pressed together by means of the screws ^ s a . The transmission of the force is done in this, as in most of this class of machines, by means of a spiral spring, those of Wendler's apparatus possessing respectively a maximum force of nine and twenty kilos. The spring is held at one end by means of the shell z, which is fastened to the bed d, at the other by the car- riage a/, and passes through the shell i. Fastened to the bed by means of screws are the catches , which work in the teeth of the rack, and which, as soon as the paper tears, prevent the spring from flying back. The measurement of the force is performed as follows : By means of the lever h the carriage pushes the pointer d be- fore it, which travels on the graduated bar, r. The pointer has a zero mark from which, after the breaking of the paper, the breaking strength is read in terms of kilograms. The measurement of the elasticity is done by reading the movement of the pointer in the opposite direction along the measuring rod o, graduated according to the percentages on a strip 1 80 mm. in length. After the breaking of the paper, the stretch can be read directly in per cent. In order to test paper with this apparatus, one adjusts the force measuring rod, by raising the catches, setting the spring in oscillation, allowing it to come to rest and then carefully 348 QUANTITATIVE ANALYSIS. sliding the pointer down until it touches the lever. Observe whether the zero of the pointer agrees with that of the measur- ing rod. If this is not the case, the latter is moved until both coincide. The spring is now fastened by means of a screw t and the sled is moved until the zero marks of both sled and stretch- measuring rod coincide. Take a piece of the paper to be tested, previously cut to standard size, clamp it in, loosen the screw /, drop the catches and begin the experiment, giving the wheel a slow and uniform motion. After breaking the paper, read off the loading as well as the stretch, relieve the spring by holding the carriage still with one hand, loosening the catches with the other and allowing the spring slowly to slide back into place. In order to insert a new spring, take the carriage and by means of it push the spring in the direction of the screw t, turn the spring through 90 and take out the carriage and the rack. In conducting the experiments, strips 180 mm. long and fifteen mm. broad should be used, and not less than five cut from each direction. In order to render the result independent of the cross section, use is made of the example of Profs. Reuleaux and Hartig. Using for the measure of strengh of paper the " tearing length," which is the length of a strip of paper of any breadth and thick- ness, which, if hung up by one end, would break in consequence of its own weight. x = unknown tearing length. = wt. of the torn strip (in 0.18 mm. length), in grams. 1= no. of kilos necessary to tear strip. 0.18 x 0.187.. -^^=^r^ or x=-K. Or K , Lr For testing materials which require more power to break than paper, as for instance cardboard, Schopper has constructed a more powerful apparatus, which has a maximum force of 150 kilos. As the apparatus is built on the same fundamental principles as the " Wendler," a description here is needless. References: " Handbuch der Papierfabrikation." By S. Mierzinski, 1886. "A Text-Book on Paper-Making." Cross & Bevan, 1888. "The Art of Paper-Making." Alex Watt, 1890. 1 Papier-Zeitung, 1891. SOAP ANALYSIS. 349 "The Chemistry of Paper-Making." By R. B. Griffin & A. D. Little, 1894- " Mittheilungen aus den Koniglichen technischen Versuchsanstalten zu Berlin," 1891, 1892, 1893. XLII. Soap Analysis. Soaps may be conveniently classified into Toilet soaps, the finest grades of which contain no impurities or free alkali ; Laundry soaps, in which rosin and generally an excess of alkali is present either as sodium silicate, sodium carbonate, sodium borate or free alkali ; Commercial soaps, which may be subdivided into (a) soft soaps, potash being the base, and (b) " hydrated" soaps, soda being the base, (" marine soap" being an example) formed by caustic soda and palmnut oil or cocoanut oil ; and Medicated soaps, containing medicinal agents such as carbolic acid, tar, sulphur, etc., etc. The complete analysis of a soap often presents considerable difficulty since many adulterants may be used in the cheaper grades, and many substances not adulterants, the use of which is permitted as colorants and for perfume. Allen states that be- sides the alkali and fatty acids and water requisite for the forma- tion of a soap, the following substances have been found in the different varieties ochre, ultramarine, sodium aluminate, borax, resin, vermilion, arsenite of copper, alcohol, sugar, vaseline, camphor, gelatin, petroleum, naphthalene and creosote oils, carbolic acid, tar, glycerine in excess, oatmeal, bran, starch, barium sulphate, sulphur, steatite, clay, Fuller's earth, pumice- stone, kieselguhr, chalk, whiting, etc. The common " yellow soap is formed by the saponification of tallow or palm tree oil with soda, " recovered grease" is also used in the cheaper grades; cotton-seed oil, olive oil, hemp-seed oil, palm oil, cocoanut oil, castor oil, lard, and lard oil, are all used in the manufacture of soap. The following scheme for soap analysis is by C. R. Alder Wright and C. Thompson. 1 1 Analyst, ix, 47. 350 QUANTITATIVE ANALYSIS. a a o CO Is 0*0 *- w-5 'P *-".* 'O S .lol *!1 SS ! &s- *S! m oil 'o* 8bo H* ! Q 5 ^'^ jj ^ ^X 1 if I o j'S S 'S w 4J '-C . -T. $ 2. i - ^5 ft w fl .o. - ^oo ft e^^ '. 03 a tn 3 J ^ ' * 1* S l (U 3 w J3 cfl *J TJ- 13 ? * rt fe d G rt ^ fc V4-I O CO c o '+J rt bfl .iH 4-1 CO G for the Physical and Chem Tab Is fica lue. Sap tion sl Polariza tion at 50-6o C ctive t 60 C Specific gravity 100 C., determin with Reimann's a paratus in conjun tion with the We phal balance 'SpIOB spioB SpIDB SpIOB - o oot>- \O ^OO OOOOOOOOOOVO TN OOONONOO>ONOiDOON t^ONON o : 00010^5 : q!J o q up q OOOOOO OOMO oooooo oooooooovdo OOMO ^" "^"vO OOO^vOO r^O> WM wOC^-w CO rO *O CO^O >-> TiOiOiO -^-^O 10 CS iO LO\O CO "^ Tj- Tj- Tj- ^ Tj- ^ Tf Tj- T^- siOo c^ \o oc oq oq oo_ oq oo oq oo \o oq oo oq oo_ qsoq oo oq oq oq oT d d d d 6 d d d oq" d d d d d d d d d d d d cc o o ^o \o 10 o m9 ID r~-vo 10 >o >o o m co o N ONOO O^OO 00 ON O> OM^ ONOO 00 O\ ONOO 00 00 ON ON d d d d d d d d 05 d d d d d d d d d d -o - i r^ ID t^vo LO ^^ * vO 10 t^vo vOvO "v uooo oooooooo . Joooooooooooo ;o d d o' o' o' o . d d o" 6 d d d d d d SOAP ANALYSIS. 359 Occasionally, fats, before being used in soap-making, are bleached by various chemical agents, the most common of which are, perhaps, potassium dichromate and hydrochloric acid, or sulphuric acid. If now such a mixture is heated in bleaching, as is frequently the case, the potassium dichromate acting on the hydrochloric acid liberates chlorine, and under favorable conditions, the chlorine combines with the unsaturated acids present in the fats as glycerides, thus utterly destroying the value of the iodine number, the most definite index as to the origin of the fats. Again, it frequently occurs that a mixture of two or more fats may be used, the combining weights, iodine number, and other properties of which closely approximate those of an individual fat, and so an erroneous conclusion maybe drawn from an examination of such mixed fatty acids. If, however, a mixture of two fats, in their natural state, without having under- gone any bleaching or refining process, is used, it is generally possible to ascertain, with considerable accuracy, the nature of the fatty acids by means of the iodine number, it having been found by actual experiment that the iodine number of a mixture of two fats corresponds within limits of analytical error with the theoretical numbers calculated for the pure fats. Glycerine in fats and soaps can be determined as follows : l three grams are saponified with an alcoholic potash solution, the soap solution diluted to 200 cc., decomposed with dilute acid, filtered from insoluble fatty acids, and the filtrate and washings, which should amount to above 500 cc., evaporated rapidly down to 250 cc., sulphuric acid added and titrated with standard potassium bichromate. For the titration by bichromate the following solutions are re- quired : 1. Bichromate solution containing about 74.86 grams of potas- sium bichromate and 150 cc. strong sulphuric acid per liter. The oxidizing value of the solution must be ascertained by titra- tion with solutions containing known amounts of iron wire. 2. Ferrous ammonium sulphate solution containing about 240 grams per liter. 3. A bichromate solution one-tenth as strong as the first. 1 O. Hehner : /. Soc. Chem. Ind., 8, 4. 360 QUANTITATIVE ANALYSIS. The ferrous solution is standardized upon the chromate solution, and the glycerol value of the chromate (contents of bichromate divided by 7.486) is calculated. One and five-tenths of the glyc- erol or soap lye is weighed into a 100 cc. flask, and a little silver oxide added to remove any chlorine or aldehydic compounds. After slight dilution, the sample is allowed to stand with the sil- ver oxide for about ten minutes. Basic lead acetate is then added in slight excess, the bulk of the fluid made up to TOO cc. and a portion is filtered through a dry filter. Twenty-five cc. of the filtrate are placed in a clean beaker, then forty to fifty cc. of the standard bichromate solution ac- curately measured, are added, and fifteen cc. strong sulphuric acid. The beaker is covered with a watch glass and heated for two hours in boiling water. The excess of bichromate solution is then titrated back with the ferrous ammonium sulphate solu- tion. The table of analyses of soaps on the following page comprises in each instance a complete analysis. In most analyses of soaps the following determinations only are made : Water, alkali combined as soap (Na 2 O), alkali free as sodium hydroxide, sodium carbonate, and total fatty acids as anhydrides. Thus, an ordinary yellow laundry soap, analyzed by Schnaible, gave : Water 19.12 per cent. f Alkali, combined \ as soap, Na 2 O / 8 ' 57 Alkali free, as NaOH 0.20 " Na. 2 C0 3 0.20 Insoluble in H 2 O 0.20 Fatty anhydrides 5 2 -3 2 Resin 19-45 Total 100.00 " " Washing Powders. The washing or soap powders contain besides powdered soap, a large percentage of sodium carbonate, usually in the form of dried soda crystals. These powders are generally prepared as follows : Anhydrous sodium carbonate or anhydrous soda ash is added to a "clear boiled" soap paste, and after thoroughly SOAP ANALYSIS. 361 ^^ s ? 2? o ^s ^ s:s sr 8*_ 5". c n n 3 5 00 ^ n> o 1 e 5' 5* r^ ^ . g- o o 2. ^ 2; ^ ? N M o o * . M O> M X p 3* 3^!? ^ >- o Q ^d o "t __A_ ~\ : 2.8 S B O-O B CL S is s F? SI|'f >.8 %% Origin. 2. ^~ v-^ ^ r- .^ . - O OO O f ! Fatty and resin anhydrides. vp OJ 5 Jo Cn ON vb ooui oo bo to 00 ^ Soda (Na.,O) exist- ing as soap. vO : 8 p OO M o a b M Silica. OJ 2 o o o B B OO to Cn O 00 *. OJ M 00 O B n> O B n Soda as silicate. oo* 8 8 O p p p WO Cn O a o Jo Sodium carbonate and hydrate. Ovvi _ o 00 O> 1-1 _^ ON-f^ OJ Sodium chloride. 00 ON M vO o o O o o o p o Sodium sulphate. On 00 to ^JW N ON 00 Lime and iron O M vO ON B SON ON 3 oxide. M tn Oi OJ Jo o> vy\ K> tn to t Jo M vO to *>J O Cn 4^> 1 to M Water. S $ 8 vgvg vg 8 8 Total. 5 "S 8> to ON -t- cS OO c^ ON *3 ON ->a ON q : o : 8 M to u O 00 O 4 8 Fatty and resin acids. 362 QUANTITATIVE ANALYSIS. mixing, the somewhat stiff material is drawn off into cooling- frames. 1 The cold and hard soap thus formed is then finely ground. 2 The composition varies greatly. Only a small proportion of resin soap can be used, as such a soap is sticky and cannot be powdered. Olein soap is generally used and is saponified with sodium carbonate. References. "Die Darstellung d er Seifen, Parfutnerien und Cosmetica. ' ' By C. Deite, 1867. " The Art of Soap-Making." By A. Watt, 1887. " The Manufacture of Soap and Candles. " By W. T. Brandt, 1888. " Lard and Lard Adulteration." By H. W. Wiley, 1889. " Die Untersuchungen der Fette, Oele and Wachsarten." By C. Schaed- ler, 1890. " Analysis of Washing Powders." Am. Chem.J., 14, 623. " Soap Powders." Seifen, Oel und Fett Industrie, 3, 973. "Oils, Fats, Waxes and their Manufactured Products." By Alder Wright, F.R.S., 1894. " Oils, Fats, and Waxes." By Dr. R. Benediktand Dr. J. Lewkowitsch, F.C.S.,i8 95 . XLIII. Technical Examination of Petroleum. Tnis is usually performed by fractional distillation of the petro- leum into three classes of distillates. 1. Light oils, distilling over up to 150 C. 2. Illuminating oils distilling over from 150 C. to 300 C. 3. Residuum. The method of Engler, which is largely used for this purpose, requires a glass flask of the form shown in Fig. 103. The measurements given in the figure are stated in centimeters. The flask is connected with a condenser in the usual manner. 100 cc. of the oil are taken and the temperature in the flask so regulated that two and one-half cc. of the distillate pass over every minute. Chemists vary the method of distillation, some using 300 cc. of the oil and a larger flask of same form, 1 Chem. Ztg., 1893, P- 412. 2 Scientific American Suppl., 1893, p. 14733. TECHNICAL EXAMINATION OF PETROLEUM. 363 though without standard rules respecting the number of dis'- tillates to be obtained : thus A. Bourgougnon and J. Mon- del 1 report the analysis of a sample of Ohio petroleum in which the distillation was in fifty parts, each part repre- senting two per cent, by vol- ume, the distillation commen-' cing at 23 C. The composi- tion of the oil being given as sixteen per cent, of naphtha, 70 B., sixty-eight per cent. of kerosene, six per cent, of.^ 4 paraffin oil and ten per cent. 1 of residuum . Durand Wood- man 2 gives an analysis of a crude petroleum from Ohio. 300 cc. of the oil were |taken and eighteen distillates each of fifteen cc. (five per cent, of total) were obtained, detail were as follows : k G,5 -->! Fig. 103. The results in Number of distillate. F. I ... 160 2 200 3 ... 210 4 ... 250 5 ... 263 6 ... 2 77 8 354 9 .... 370 10 400 ii ... 427 ... 476 14 "" 4^ i/ .... 466 .... 450 Residuum 70.5 65.0 61.0 57-5 54-0 52.0 48.0 45-o 43- 41.0 40.0 40.0 40.0 39-o 40.0 41.0 41.0 Per cent. 5 10 15 20 25 30 35 40 45 50 65 70 75 80 85 90 100 iy. Am. Chem. Soc., 13, 168. 2 Ibid, 13, 180. 364 QUANTITATIVE ANALYSIS. The result being Naphtha 10 per cent. Illuminating oil 50 " " Lubricating oil 30 " " Residuum 10 ' ' ' ' Total 100 " " A distillation of a Mexican petroleum, by the writer, made by the Engler method, gave Naphtha 10.0 per cent. Illuminating oil 60.0 " " Lubricating oil 15.5 " " Tar and Residuum 14.5 " " Total 100.0 " " ' Another sample of the same oil, submitted to a somewhat higher temperature during the distillation, using a similar flask excepting that the delivery tube was one and one-half inches higher in the neck of the flask (requiring higher heat upon the petroleum for tne same distillates as in the former case), gave a lower percentage of heavy oils, and a higher percentage in illuminating oils, the result being Naphtha 1 1 .o per cent. Illuminating oil 64.0 ' ' " Lubricating oil 10.3 " " Residuum-... 14.7 " " Total loo.oo " " By a careful regulation of the heat, the amount of illuminating oil can be increased or decreased to a certain percentage as desired. The three general divisions of the distillation of petroleum are still further technically divided as follows : i. Naphtha group, comprises : Cymogene, a gas, boiling point o c C., specific gravity 110 B. Rhigolene, liquid, boiling point 18.3 C., specific gravity 100 B. Petroleum ether, boiling point 40 to 70 C., specific gravity 85 to 80 B. Gasolene, boiling point 70 to 90 C., specific gravity, 80 to 75 B. Naphtha (Danforth oil) boiling point 80 to 110 C., specific gravity 76 to 70 B. Ligroine, boiling point 80 to 120 C., specific gravity 67 to 62 B. Benzene, boiling point 120 to 150 C., specific gravity 62 to 57 B. TECHNICAL EXAMINATION OF PETROLEUM. 365 2. Illuminating oils. The various varieties of kerosene, boil- ing points 150 to 300 C. 3. Residuum, (tar, etc.) boiling point 300 C., and above, from which is obtained : Lubricating oils, paraffin oils, and coke remaining as a solid body in the retort. The average percentage of the products obtained from Pennsylvania petroleum can be stated as : First group : Naphthas, 16.5 per cent. Second group : Illuminating oils, fifty-four per cent. Third group: Lubricating oils, seventeen per cent., paraffin, two per cent., coke, ten per cent. 1 The-manufacture of vaseline, petrolatum, cosmoline, etc., from the tarry residuum (vacuum process,) has increased largely in the last few years. 2 In the oil trade the principal mineral oils obtained from petro- leum are as follows : Benzenes and naphthas, 62, 65, 75, 88, 90 Baume. Paraffin gas oil. Paraffin oils, 22, 24, 25, 28, 30, 32 B. Red oil, 23 and 24 B. Neutral filtered, 32, 34, 37 B. "Extra cold test" 32 B. "Wool stock" 32. Black reduced (25 to 30 F. cold test) (15 F. cold test), 28 B. zero test. Black reduced, "Summer." Cylinder, light filtered, 600 F. fire test. Smith's ferry 32 to 34 B. Dark steam refined. West Virginia, natural 29 ; Franklin natural 29 B. Kerosene, the different grades and colors. The various valve oils, car oils, engine oils, spindle oils, loom oils, dynamo oils, etc., etc., are usually compounded oils, min- eral oil of some variety being the principal constituent v i ch varying amounts of lard oil, tallow oil, tallow, rape oil, etc., have been added. The best engine oil is a mixture of lard oil and paraffin oil in equal parts. This compound has been in use by the Pennsyl- vania Railroad for the past ten years, and after many experi- ments and trials of different substitutes, still remains the stand- ard. Passenger car oil is usually a mixture of well oil and lard 1 S. F. Peckham : Report on Petroleum, p. 165. 2 Consult Brandt : Petroleum and its Products, p. 650. 366 QUANTITATIVE ANALYSIS. oil in the proportion of two-thirds well oil and one-third lard oil. Lard oil in the proportion of one part to three of 500 well oil has been found to give the best results as a cylinder lubri- cator. 1 XLIV. The Examination of Lubricating Oils. The generally accepted conditions of a good lubricant are as follows : i st. Body enough to prevent the surfaces, to which it is ap- plied, from coming in contact with each other. 2d. Freedom from corrosive acids, either of mineral, animal or vegetable origin. 3d. As fluid as possible, consistent with "body." 4th. A minimum coefficient of friction. 5th. High "flash" and " burning " points. 6th. Freedom from all materials liable to produce oxidation or "gumming." The examinations to be made to verify the above are both chemical and mechanical, and are usually arranged in the fol- lowing order : ist, Identification of the oil, whether a simple mineral oil, animal oil, vegetable oil, or a mixture. 2d, Specific gravity. 3d. Cold test. 4th. Viscosity. 5th. Iodine absorption. 6th. Flash and fire tests. yth. Acidity. 8th. Maumene's test. 9th. Coefficient of friction. If the oil is a pure mineral oil, the tests numbered i, 5 and 8 are omitted. The first test, the nature of the oil, etc., is performed as fol- lows : 1 The Railroad and Engineering Journal, 64, 73-126. For formulas of locomotive and car lubricants as used on the railroads in Germany consult: " Die Schmiermittel." Von Josef Grossmann, 1894. THE EXAMINATION OF LUBRICATING OILS. 367 Ten grams of the oil are weighed out in a dry tared beaker (250 cc.), and to it is added seventy-five cc. of an alcoholic solu- tion of potash (sixty grams of potassium hydroxide to 1,000 cc. of ninety-five per cent, alcohol), and the contents evaporated until all the alcohol is driven off. In this process, if any animal or vegetable oil is present, it is formed into a soap by the potash, while the mineral oil is unacted upon. Water (seventy-fivecc.) is now added and the material well stirred to insure complete solution of the soap, and then it is transferred to a separatory funnel (Fig. 104), seventy-five cc. of sulphuric ether added, corked, the liquid violently agitated and allowed to stand for twelve hours. Two dis- tinct liquids are now seen, the lower, the solution of the soap, the upper, the ether solution (colored, if mineral oil is present, colorless, if not). The aqueous solution is drawn off in a No. 3 beaker, the ethereal solution remaining in the separatory fun- nel. The former is placed on a water-bath, heated for half an hour, and until all traces of ether (which is absorbed by the water in a very small amount) is gone. The solution is allowed to cool, diluted somewhat with water, and made acid with dilute sulphuric acid. Any animal or vegetable oil present will be indicated by a rise to the surface of the liquid of the fatty acids. (In this reaction the sulphuric acid decomposes the soap, uniting with the potash to form sulphate of potash and liberating the fatty acids of the oil.) If it be desired to weigh the fatty acids, proceed as follows : Weigh carefully about five grams of pure white beeswax, place it in the beaker upon the surface of the oil and water, Fig. 104. 368 QUANTITATIVE ANALYSIS. and bring the contents nearly to boiling ; the melted wax and fatty acids unite ; allow to cool, remove the wax, wash with water, dry between folds of filter paper and weigh. The increase in weight of the wax over its original weight gives the weight of the fatty acids of the animal or vegetable oil in the lubricating oil. Another method of determining the weight of the fatty acids after saponification is given on page 354. The weight obtained must be multiplied by the factor 0.97, since the fatty acids exist in the oil as anhydrides and not as hydrates, the latter being the form in which they are weighed, Instead of weighing the animal or vegetable oil, some chemists prefer to make use of the ether solution, determining the hydro- carbon oil directly. In which case proceed as follows : After drawing off the soap solution from the separatory funnel the ether solution is run into a weighed flask (about 250 cc.), and the ether distilled off. The residue in the flask now consists of the mineral oil and some water. It is quite difficult to get rid of all this water. Direct heat- ing is inadmissible, since the water spurts up through the oil out of the flask and is lost. This can be overcome by placing a glass tube through the stopper, in shape of the letter S. Any oil ejected against the tube or cork cannot escape, but returns to base of flask, while the heat is gradually increased in the flask and the water vaporized and passed out through the tube ; three or four weighings are generally required before a constant weight is obtained. The former process is preferable, since it is performed much more rapidly than the latter, and also the ani- mal or vegetable oil is positively shown, and generally can be identified ; also many lubricating oils contain as high as twenty percent, of hydrocarbon oil, volatile at or below 212 Fahren- heit. It is, of course, in the ether solution, and when the water is expelled from the oil, after the ether has been driven off, a large proportion of the volatile hydrocarbon is also vapor- ized. If now the animal or vegetable oil is not also determined, a serious mistake would be made; viz., reporting twenty per cent, of animal oil when it was volatile mineral oil. The fatty acids in another sample of the oil are separated and THE EXAMINATION OF LUBRICATING OILS. 369 subjected to qualitative tests for identification of the oil from which they are derived. These tests comprise determination of melting point, and congealing point, page 337, color reaction with nitric and sulphuric acid, iodine ab- sorption, and Maumene's test, rise of temperature upon addition of sulphuric acid. There are several methods of determining the melt- ing point ot the fatty acids. Where a considerable amount of the fatty acids is available for experiment, the apparatus in Fig. 105 can be used. The glass cylinder is filled one-half with fatty acids, the cylinder closed with a rubber stopper, through which a ther- mometer is inserted, the bulb of which is covered by the fatty acids. The apparatus is sup- ported in a beaker con- taining water. (Fig. 106). If the fatty acids are liquid at ordinary temper- atures, the water in the beaker must be cooled with ice until the fatty acids are congealed. The ice is re- moved, and the water grad- ually warmed until the fatty acids become melted. At this point the temperature | is taken and recorded. Greater delicacy in the de- termination of the melting point is obtained by using a small glass tube, sealed at one end. The liquid fatty acids are placed in this tube, then congealed, the tube then tied to a thermometer ( Fig. 107) and both inserted in a beaker of water, as shown in Fig. 108. Another method is to cover the ther- mometer bulb with a layer of the solid fatty acids, about three mm. thick and immersing it in water; gradually heat the water Fig. 105. Fig. 106. 37 QUANTITATIVE ANALYSIS. and notice the temperature at which the fatty acids leave the thermometer bulb and ascend through the water. Fig. 108. TABLE OF MELTING POINTS AND CONGEALING POINTS OF FATTY ACIDS. Fatty acids. Melting point. Congealing point. Cotton-seed oil 33.0 C. Olive ' Rape-seed " Castor " Sesame " Cocoanut " Lard Tallow Wool-fat 42.0 Palm oil 48.0 26.0 20.0 13.0 26.0 24-5 44.0 45- 30.5 c. 21. 12.0 3O.O 32.0 24.0 39-o 42.0 40.0 43-o Specific Gravity. In the chemical laboratory the hydrometers used are generally marked with the specific gravity direct. In the oil trade, how- , ( J . = \ - I - \ I : E : E [ : : ~ -"~~ ever, and in general commercial practice the Baume hydrometer is used, and the following precaution is necessary. If the oil is not liquid enough to flow easily, it must be warmed until^so, and then tested with the hydrometer. The latter should move easily and freely in the liquid. As all specific gravities are comparable at 60 F., it will be necessary to make correction for temperature ; if the temperature of the oil is above 60 F.,the reading of the hydrometer is too large ; if below 6o c F.,the readings are too small. Suppose an oil reg- isters 28 Baume at 72 F., we make use of the table, on p. 372, and find the corrected reading to be 27.2 Baume. To convert this into specific gravity the following table is used : x cr. tr.tr. 'O -C 13 'C 11 ii II 11 "^' >> "*"" >> >> u >> H^S-w Dg 5 .C -<- l> j 5 .C <-i u H--- 1 - 1 WCB B;s ^ ccbe B;=; iJTbc B;S; tflbe B^^ t/Jbo 10 i.oooo 23 0.9150 36 0.8433 49 0.7821 ii 0.9929 24 0.9090 37 0.8383 50 0.7777 12 0.9859 25 0.9032 38 0.8333 51 0.7734 13 0.9790 26 0.8974 39 0.8284 52 0.7692 fj 1 1 i 14 0.9722 27 0.8917 40 0.8235 53 0.7650 I 5 0.9655 28 0.8860 41 0.8187 54 0.7608 1 Jll Pi 16 0.9589 29 0.8805 42 0.8139 55 0.7567 t FJC/K B 17 o-95 2 3 3 0-8750 43 0.8092 56 0.7526 18 0.9459 31 0.8695 44 0.8045 57 0.7486 19 0.9395 32 0.8641 45 0.8000 58 0.7446 i R m H 20 0.9333 33 0.8588 46 0.7954 59 0.7407 21 0.9271 34 0.8536 47 0.7909 60 0.7368 22 0.9210 35 0.8484 48 0.7865 70 0.7000 ^ and we find that 27.2 Baume are equal to 0.8928 Fig. 109. specific gravity. Figure 109 represents a Tagliabue hydrometer for oils ; it contains a thermometer, also a scale to make the readings at 60 F. Subtract i Baume for every 10 F. above 60 F., and add i Baume for every 10 F. below 60 F. 372 QUANTITATIVE ANALYSIS. j I -Tj--<^-<3-fotococococscscscsMMM MqqcocoflotSit>\qw> j ONMcovo^C'NMcovor'^o^MrovotxO^MiovDoocs^ood^'ocJ p M cs cs cs M cs cococococort-rj-'- vovovoiOinvorJ-'^t'TJ-rj-T^-cOco ON M co vo t^ ON M co vo tx ON M co ^vovovovovovovo 10 vo in *o vo io (D (H to 00 3 T*- ON *-> ro vo t^ L 4- ^>MCSCSCSNCSCOcOCOCOCOTt cd .t>.t>.t^.ts. g vo H co o vo r^ t^ t^ 00 CO 00 ON OV 4- %-O CS ^-VO'oO O N' rfiOOO O CS ^VOOO O CSVOCO O "^VO O CSVD O vo'oo d cs' ^fvdod d cs ^tvdoo* d cs'vdco d vo vo t^ r^. r^ oo U ivovovOvOvo t^-t^oOOOOOCO ONONONdO O ^ M M cs cs co ,t5 to'vO t^t^r^ooco ONONONO O O w M M cs cs coco^f' C/3 to ^ 00 00 ONOO O 1-1 MM cs CS CS cOtO'^J-^-vovO v O t^-00 ONONO -" **H o O* ( " O ^ H M M cs cs to co -^- TJ- -^- in vq vq oq co en q q N cs co jj^O M cs W CS cOTJ-rj-^vovovOvO IxCOOO O O 'J CS cOiOvovO 1^. CS CS CS CS Ci CO CO CO CO CO *^- ^- ^ ^ ^ VO VO VO VO VQ vQ \Q t^* t~^ t^ j/ M cs cs co to ^" vo vo vO VO vO t^ r^ CO Cft O O CS co CO vo vO t^* CO ON O o ft M covoi~>.d^M covor^.cnM covot^o>cN rj-co' d oivdod cs ^co* to- ^. CS CS CS CS CS CO CO CO CO CO ^ ^- T}- ^ ^- IO vo IO VO VO VO VO t^ t^ t^ 00 IJ. : I I I : I ::: I i :::;:::::::::: w^^fqwpqpqpQpqpqpqpQpQcQpqcqpqcQpqpqpqpQpQpqpqpqpqpqcQ. THE EXAMINATION OF LUBRICATING OILS. 373 t^* vO vO 10 ^" co O < r~ ON M co^vOCO O pi ^ vd 00 Pi < 3000 t^-vO IO 10 CO PI M O ONONOO t^ VO lOrfPI o *"" VO cOPI ON O 1^. ON M co >O t^. CT> M O ui VO* 00 O pi ^ VO* CO* pi -*t to O> M 10 t>- O W" HH M PI PI PI PI PI cOcOCOcOcO"3 -r 3''*' < 'J'Tf'O>Oi/-)iovovOvO^r> O ON OO r^ IO vO 10 ^f co PI M O ON O* 00 t^vO "^ co ** ON 00 vO ^ Pi O OO ON M co iO t^- ON M co O I**- ON O PI ^"VOOO P< ^ IO ON M 1C l^> M ^ .^ 14 M M ON ON 00 t** VO *O '^ CO PI PI *"* O O ON 00 VO *O ^" PI ^ CO t > * ^ PI ^ "rl-OO O M cOOt^.ONHH cOiOt^-ONM cOlOvdoO PI ^*O Q PI Ot^.i-3 10 > ~*' O*M PI PI PI W PI PI cOcOcOcOcO T ^'^'^^^'iO l oOVOvOVOvO t>-tx j fcp^OO>OOt^vOtOio T *'COc / 5'-'MOOOt^O^'cO l - l Ol > O rt O\I-H PI Pi PI PI PI Pi r f )r f )tr)r f )(*~i*3''*t^-*t'*frv~)ir)m < >O\&\&\O t~tx C f^ ^i, r^ rO N t^ O O O 1 ^ CO t^ 1 vO v ^ *O ^}" ^" CO *^ ^ O O^ 00 ^O i-O rO W O^ t 1 *** p o CO O d ^- O CO O^ ^^ ^i ift t^ o^ HN * **** \n t*** ^^ ^O ^* 10 O c-< vo 00 ^ 10 VH ^MdWc^W^WtOc^^r^cO^^t^-^t^iOiOin^^O^^O^^t^ H j^ to ^^ co pi PI HH o O ON oo ^** * x vo vo \n ^~ ^~ PI M o 00 r^ 10 ^* pi o jO g M PI PI cTpl PI cococOro r< ^f r|T ^" T: l"'5- T; l"'^" ir 5 loinv)vi:>vOv> t^tx o a.' ^o "P'l"'* ?^ ^ M . 9 . < ^. 00 . ^r^^ u ? T *" f ? c l 9 ^^^"pco ^ 3 nOO O PI ^vo'co O PI 'j-VO t^-oV 1 - 1 cOiot^O^cOotx>-' pivOOO Plvo" *^ ^ ( -(PIPI(NPlcocOPOCOcOcO'*'^^^-'!tOiOOvOvOvOvOr^tx O _..00' O pi rflOo6 O PI *^-VO*00 O P* cOiot>.CTNCOiOt>*-' cot^OO Plvo* ^j g M PI PI M pi P cocorocoro-3-Tfr'3-a-Tt-TfioiOiovovOvOvo t^t> jl ^'t^t^vOvO lO'O^'^l'cOCOPi PI IH 1-1 Q O ONt^t^VO ^TfPi PI Ooo *^ ruOO O PI ^vo'co' O PI ^-vo'cd O PI "^"vo'oO ONCOtot^ 1 - 1 cot^-ONcOvo" ^ cw 1 - 1 N N N W cOcOcococOT3-Tj-TJ-^--^-rl-ioiOiovOVOvOvO t^tx ON OO CO t^ f^ vO vO *O 10 ^ ^" co CO PI N M M ON ON 00 ^^ VO IO ^^ PI M rfTj--^-^-TtioiO*OOVOvOvOvO t^tx ^- m o ., O O^NONCOOOOO f^t^vO^O 1010*0 ^^cOfOM M Q PI TJ- vo' cO co CO O 00^ ^ ^" VD Q Q. c t T t'*o o Q.Q ^ rj-vooo Qrj-vpoo M I'M O O O OONONCOOOOO r^t>.vOvO tOiO-^-cOfOPI M M Q ONOC1O CO ^ M jj/PI M M HI O O O ONOONOOCOCO t^r^vO IO*OO'^'COPI PI O O O^ONM coiot>-ONMvo' -^-ID'OO d pi -^-vo'oo' d rt-vdoo' pi rj-oo d -^-t>. O O O O^ChONOOOO t>t^vOfi^rJ-coci ON - co TJ- vo' CO* O -4 v oo' PI 4 oo' O^ ^ oo" o >,i i-^r3WPQpQP5CQCGPQpQ> (i-^CHPGpQ^Wi-HKpQ >i HH PH PQ PQ PQ ^S^OOOOOOOOOOOOOOOOOOOUCOOOOO 374 QUANTITATIVE ANALYSIS. Thus, if the hydrometer, when placed in the oil, reads 26* Baume and the temperature of the oil 80 F., the correct reading will be 24 Baume at 60 F. The specific gravity test is an im- portant one ; by it an admixture of certain oils with mineral oil is indicated. For instance, a lubricating oil of specific grav- ity 0.915 was found by qualitative analysis to be composed of mineral oil and menhaden oil. Knowing the kinds of oil com- posing the mixture, an approximation of the per cents, would be obtained as follows : Mineral oil ........ Specific gravity = 0.890 ( B ) Menhaden oil ..... " " =0.927 (A) Specific gravity of mixture ........ = 0.915 (M) Let A M=C. (0.927 0.915 = 0.012) M B=D. (0.915 0.890 = 0.025) Then - = per cent, of A C+D \o. and C /o.oi2 per cent , /o. , of B\ Vo. , C + D Vo.037/ The result being Menhaden oil ............................... 67.5 per cent. Mineral " ............................... 32.5 " " A more rapid method is graphically thus': in Fig. 1 10 let the abscissas represent per cents, and the ordinates the specific gravities. From the point indicated (on the line A B) 0.915 the specific gravity of the mixture the per cents, are read on abscissa line 67.5 for A and 32.5 per cent for B. Another instrument used for the determination of the specific gravity of oils is the Westphal balance. This apparatus (Fig. in) is very accurate and should be used as a check determination of the gravity made by the hydrometer. If the oil is too thick, at ordinary temperatures, for the deter- mination of the gravity, it should be heated sufficiently and the modified Westphal balance (Fig. 112) used. THE EXAMINATION OF RUBRICATING OILS. 375 30 JJO .860 I 2 ZQ ' <- ^j** > ' ^^>^ ^ ^rf ^ ^ ^-^ f*^ r ^ ^^ ^ ^ ^ ^, <*" ' ^. ^ ; ;- ^ ^ ^ | - 4*> r^ :>- ^** f* f ^ f fc**"" y =. h I f^ HZ .. ^ ft s. fc t 5 . P, MP- 4- 6> JO 20 30 40 50 60 Fig. no. 70 80 90 100 Fig. in. 376 QUANTITATIVE ANALYSIS. Fig. 112. If only small amounts of the oil are obtainable a small pic- nometer, or an Araeo-picnometer of Eichhorn can be used. This invention is described by Dr. H. Hensoldt, of the Petrographical Laboratory of Columbia College, New York, in the "Scientific American Supplement" of March 21, 1891, with a drawing. The important feature of this instrument consists in a small glass bulb (attached to the spindle), which is filled with the liquid whose gravity is to be taken. Thus instead of floating the en- tire apparatus in the test fluid, only a very small quantity of the latter is required. (Fig. 113.) The glass bulb, when filled with the test .fluid, is closed by means of an accurately filling glass stopper, and the instrument is then placed in a glass cylinder filled with distilled water at 17-5 c. The gravity is then at once shown on the divided scale in upper portions of the spindle. The following table converts degrees of the various hydrome- ters into specific gravity. (Liquids lighter than water.) THE EXAMINATION OF LUBRICATING OILS. 377 Gay-Lussac, 4 C = - = specific gravity. 100 -\-n Beck, 12.5 C. = -- '. = specific gravity. 170 + n Carrier, i2.5C.= = specific gravity. Baume hydrometer, at 15 C. = - -. = sp.gr. I 34-7 y ~r n Brix hydrometer, Fischer 400 hydrometer at 15.6 C. ~~ 400 + w Sp ' gr< n = degrees indicated upon the spindle. TABLE OF SPECIFIC GRAVITY OF OILS USED WITH MINERAL OILS FOR LUBRICATING PURPOSES. Sperm oil ............................ 0.883 specific gravity. Olive oil ............................ 0.916 " Cotton-seed oil (white) .............. 0.925 " " Cotton-seed oil (brown) .............. 0.930 " Castor oil ............................ 0.960 ' * Dolphin oil .......................... 0.922 " " Neat's foot oil ........................ 0.915 ' ' Lard oil ............................. 0.915 " Tallow oil ........................... 0.903 " " Menhaden oil ........................ 0.928 " " Rape-seed oil ........................ 0.916 " Rosin oil ..................... 0.980 to 1.05 " Blown oils, made by oxidation of rape- seed oil, cotton-seed oil, etc., (consult Chapter 46) . . . 0.930 to 0.970 References on the specific gravity of oils : "On Fluid Specific Gravity Determinations for Practical Purposes." By C. R. Alder Wright, F.R.S., /. Soc. Chem. Ind., n, 297. "On the Chemistry and Analytical Examination of Fixed oils." By Alfred H. Allen, F.C.S., /. Soc. Chem. Ind., 2, 49- The Cold Test. The degree at which an oil becomes semi-solid and refuses to flow freely is considered the cold test, and is performed as fol- lows : Fifty cc. of the oil are transferred to a narrow bottle (capacity 373 QUANTITATIVE ANALYSIS. ft ioo cc.), stoppered with a rubber stopper, through which is in- serted a thermometer, the bulb of which reaches an inch or more into the oil. The bottle is placed in a mixture of ice and salt, or other freezing compound, and retained there until the oil becomes ^-^ solid. It is then removed and allowed to warm until the contents become somewhat thinner in consistence. The bottle is inclined from side to side until the oil begins to flow, when the temperature is taken. At this particular tempera- ture the oil is neither at its normal fluidity, nor is it solid, and while this method does not correctly indicate the ex- act temperature of the solidi- fying point, it does show the point at which the oil ceases to flow readily, the import- ant one to the oil inspector. In lubricating oils, to used in railroad practice, this cold test is a vital one, and receives in the laboratories of the different railroads of the United States considerable at- tention. A mineral lubricating oil, non-paraffin, of good quality, does not show any material difference in its consistency at 25 C. or 10 C., but a radical change would be indicated at 10 C. if some of the animal or vegetable oils were a component. While it is true that no proportion of one or the other can be indicated by the cold test, and that this test might not properly THE EXAMINATION OF LUBRICATING OILS. 379 be classed as a chemical, but rather as a physical one, yet so important is this property of congealing in lubrication, and as all laboratories connected with railroad work rely strongly upon it, it is included as one of the principal ones. In connection therewith is here included the drawings of the apparatus used for this purpose in the chemical laboratory of the 380 QUANTITATIVE ANALYSIS. Chicago, Burlington and Quincy Railroad Co., Aurora, 111. Fig. 114 represents the glass apparatus with the thermometer arranged for the cold test. Fig. 115 represents the cold box to contain the freezing mix- ture and in which the oil is tested. The following determinations of the cold test, made in my laboratory, will show the wide range in this regard between many of the oils, used in lubrication : Elain oil 6 C. Saponified red oil 5 Prime neat's foot oil 4 White neat's foot oil 4 Pure hoof oil 6 Prime lard oil 7 No. i lard oil 7 XXX lard oil 3 American sod oil i English sod oil 24 Tallow oil 26 Dog fish oil 7 Right whale oil ( Pacific) o Unbleached bowhead whale oil (Pacific) 7 Bleached whale oil ( Pacific) 13 Natural sperm oil (Pacific) o Bleached sperm oil " 4 Herring oil " o Natural winter sperm oil (Atlantic) i Bleached winter sperm oil " 4 Natural spring sperm oil " 10 Bleached spring sperm oil " 8 Natural winter whale oil " 2 Bleached winter whale oil " 5 Natural spring whale oil " 5 Bleached spring whale oil " 2 Prime crude menhaden oil 4 Brown strained menhaden oil 7 Light strained menhaden oil 7 Natural winter menhaden oil 9 Bleached winter menhaden oil 12 Extra bleached winter white menhaden oil 1 1 Bank oil 4 Straits oil 7 Sea elephant oil 5 THE EXAMINATION OF LUBRICATING OILS. 381 Black fish oil 8 C. Rosin oil , ist run 3 " ' ' 2d run 19 ' ' "3d run 20 Castor oil 18 Crude cotton-seed oil 7 Prime summer yellow cotton-seed oil 5 Off quality summer yellow cotton-seed oil 6 Prime quality winter cotton-seed oil 10 Off quality winter cotton-seed oil 8 Prime quality summer white cotton-seed oil 3 Off quality summer white cotton-seed oil 8 Prime quality winter white cotton-seed oil 9 Off quality winter white cotton-seed oil 5 No. i French Degras oil 25 No. 2 " " " 25 English Degras oil 18 Olive oil 3 Oleo oil 24 In the specifications, for the supply of oils to the various rail- roads, it is generally stated what degree is required for the cold test. Thus the Pennsylvania Railroad Co. requires as follows : Lard oil 8 C C. November i to April i. Tallow oil, 8 C. " Neat's foot oil,8 C. " Baltimore & Ohio Railroad Co : Engine oil from October i to May i, below 9 C. Passenger car oil " " " " " " " " Freight car oil " " " " " " " " Chicago, Burlington & Quincy Railroad Co. Black Engine oils : Summer oil must flow at 15 C. and above. 25 oil " " " i C. " 15 oil " " " 9 C. " Zero oil " " " 15 C. " Tagliabue's standard lubricating oil freezer is also largely used in this connection, and is thus described. It consists of a semi- cylindric metallic stand, neatly japanned, divided into three com- partments. (Apparatus is shown in Figs. 91 and 116). The first, y, is the oil cooling chamber, in which is the glass receiver, adjusted to a rocking shaft, g, to facilitate the introduc- 382 QUANTITATIVE ANALYSIS. tion of the regulation oil cup therein, and to show by its motion whether the oil is congealing or not. The second, c, is the ice chamber which is rilled with ice and rock salt for the cooling process ; a faucet, h, is connected with it, to allow the melted ice to flow out. The third, a, is a non- conductor jacket, lined with mineral wool filling, to maintain an even temperature in the cooling chamber, and to prevent a too rapid melting of the ice. Three thermometers, d, are inserted in the freezer, one on Fig. 116. each side of the cooling chamber, to denote its temperature and a third one in the center so adjusted that its bulb, penetrating the middle of the oil, enables one to see through the glass door, k, (without opening the same,) at what temperature the oil congeals. Two stop-cocks, 7, are attached to the bottom, with the cool- ing chamber, to force therein (by either opening or blowing through them with a rubber tube) atmospheric or warm air, whenever it is desired to raise its temperature. THE EXAMINATION OF LUBRICATING OILS. Viscosity. The first instrument for the deter- mination of the viscosity of oils was probably Schubler's. (Fig. 117). It consisted of a glass cylinder, open at the top and drawn to a one thirty- second inch tube at the bottom. Hav- ing filled the cylinder with the oil to be tested, the time required for 100 cc. of the oil to flow out through the aperture was noted, and this figure compared with that obtained from wa- ter under similar conditions. Thus, Schubler records, among many determinations, the following: Fig II7 Seconds at Seconds at Comparative Comparative 15 C. 7.5 C. thickness thickness with water at 15 C 18.0 21.6 9.6 203.0 o.o 222. 284.0 with water at 7.5 C. 22.4 31-5 3390.0 9 .0 377-0 o.o Colza oil 162.0 Olive oil 195-0 Hemp-seed oil 87.0 Castor oil 1830.0 Distilled water 9.0 The Pennsylvania Railroad Co. viscosity tests are made as fol- lows : A loo cc. pipette of the long bulb form is regraduated to hold just loo cc. to the bottom of the bulb. The size of the aperture at the bottom is then made such that 100 cc. of water at 100 F. will run out of the pipette down to the bottom of the bulb in thirty-four seconds. Pipettes with bulbs varying from one and three-fourths inches to one and one-half inches in diameter outside, and about four and one-half inches long, give almost exactly the same results, pro- vided the aperture at the bottom is the proper size. The pipette being obtained, the oil sample is heated to the required tempera- ture, care being taken to have it uniformly heated, and then is drawn up into the pipette to the proper mark. The time occu- pied by the oil in running out, down to the bottom of the bulb 384 QUANTITATIVE ANALYSIS. gives the test figures. A stop watch is convenient, but not essential, in making the test. The temperature of the room affects the test a little. The limiting figures were obtained in a room at from 70 to 80 F. It will not usually be possible to make duplicate tests without readjustment of the temperature of the oil. These pipettes are in use in many railroad laboratories in the United States, but are difficult to clean, and are not as convenient as the Kngler or Redwood viscosimeters. Kngler's viscosimeter (original form, Fig. 118) is con- structed of copper, and consists of A, a chamber holding the oil to be tested ; B^ the water bath, C, a flask graduated so as to receive 200 cc. of the oil ; # , $, ther- mometers ; e the open- ing through which the heated oil flows out upon the with- drawal of the plug d. In using this instru- ment the viscosity of an oil is stated in seconds required for 200 cc. of the oil to run into the flask C. Heat can be applied to the water-bath, the vis- cosity being deter- Fig. us. mined at any tempera- ture required up to 100 C. Any temperature up to 360 C. can be secured by filling B with paraffin instead of water. Kngler recommends that all viscosity be compared with water thus: THE EXAMINATION OF LUBRICATING OILS. 385 If water requires 52 seconds for delivery of 200 cc. into the re- ceiving flask, and an oil under examination requires 130 seconds, Fig. 119. the ratio is determined by -5 2.50, the oil thus having a viscosity of 2.5 times that of water. 386 QUANTITATIVE ANALYSIS. This instrument has been for many years the standard in Germany. Boverton Redwood 1 describes a viscosimeter (Fig. 119), the general principle of which is the same as Engler's. This is the standard viscosimeter for the English oil trade. The septometer (Figs. 120, 121), originated with Dr. Lepenau, is used for the direct comparison of the viscosity of two oils under similar conditions at the same moment. It consists of two cylindrical vessels, B, B, which hold the oils to be compared, Fig. 120. Fig. 121. and which stand in the same water bath. A, and have the same temperature. To use the apparatus the holder, A, is filled with water, which can be heated at any temperature desired below 100 C. ; if higher temperatures are desired, A must be filled with oil. The vessel, B, is rilled with the oil which is taken for the standard, such as rape oil or lard oil, and the second one is filled with the oil to be tested. Since the heated or cooled water is stirred regularly the oils have the same temperatures which are read from the thermometers, /, t. For comparison the oils are allowed to flow out, at the same time, for the same length of time. The relative value sought is found then by measuring or weighing the amounts which have flowed out. i/. Soc. Chem. fnd., 5, 158. THE EXAMINATION OF LUBRICATING OILS. 387 Davidson's viscosimeter (Fig. 122) is designed especially for determining the relative viscosity of oils and greases when heated to the temperature of locomotive cylinders (250 to 375 F.). The entire apparatus, except the glass portion, is made of copper and the joints brazed. The oil to be tested is put into the cylinder, A, and the cup, R, which are connected through the stop-cock C. The cylinder, A, is also connected with the glass gauge through the tubes, H, and H, so that the height of the oil in the cylinder can be seen. The bottom of cylinder A is covered by a brass plate, through which is bored a hole three and one-half inches in diameter, which can be closed by the slide valve, E, against the plate by a spring. The outside of the plate is beveled from the hole, so that the hole is in a very thin plate, and thus lateral friction is reduced to a minimum. A long thermometer is used, so that the bulb will be near the bottom of cylinder A. The cylinders, B and B\ contain the lard oil bath that is used for conveying heat to the oil in cylinder A . Heat is applied by lamp or gas burner at the base of cylinder B\ and the hot prod- ucts of combustion allowed to pass through the cylinder G. As the lard oil in ' becomes heated, it rises to the top of this cylinder, and passes over to cylinder B, down B, passing around the cylinder A, and back to B\ where it is reheated and recircu- lated, as shown by the arrows. The oil in cup R is heated by the products of combustion escaping from the top of cylinder G, and in case of a high temperature by an additional lamp placed under the cup R. When the oil under test in A and R has reached the desired temperature, the valve, , is opened and the stop-cock C is adjusted to keep the height of oil in A the height desired, as shown by the glass gauge. A 100 cc. flask, which is immersed in hot oil, is then placed under the stream of oil flowing from the hole, and a stop-watch is started the instant the oil com- mences to run into the flask. When 100 cc. have been delivered into the flask, the watch is stopped. The number of seconds required for this is the viscosity of the oil under examination. Fig. 122. THE EXAMINATION OF LUBRICATING OILS. 389 Tagliabue's vicosimeter (Fig. 123), consists of a copper basin, C, extending by means of the coiled tube to the outlet at the stop- cock on the outside of the vessel. This is surrounded by the water bath, B, which has an outer chamber a connected by two tubes, and in which the water is poured into the bath. D is a thermometer, and records the temperature of the water-bath. J AJ Fig. 123. To test an oil, the water-bath is filled two-thirds full and heated by means of a small Bunsen burner or alcohol lamp. The top basin, C, lined with wire gauze is filled with the oil to be tested, and when the thermometer, D, indicates 100 C., the glass measuring flask, E, is placed under the faucet, which is opened with the starting of the watch. When fifty cc. of the oil have run out and reached the mark 390 QUANTITATIVE ANALYSIS. upon the neck of the receiving flask, E, the watch is stopped, and the number of seconds required noted. The viscosity of the oil is stated in seconds. This viscosimeter has a very extended use in the oil trade but it is a difficult piece of apparatus to clean when any particles of AM.BK.NOTECO.N.Y. c. M. & ST. PAUL nr. co. (Motive Power Dept.) GIBBS 1 VISCOSIMETER. Fig. 124. dirt have become lodged in the coil. This materially interferes with the flow of oil through the tube and gives false results. The basin, C, as well as the coil, cannot be removed, as they are brazed to the water-bath. For this reason, and also when used at higher temperatures, the faucet being metallic and not heated to the temperature of THE EXAMINATION OF LUBRICATING OILS. 391 the oil, the oil leaves the apparatus much cooler than the tem- perature recorded by the thermometer of the water-bath. Gibb's viscosimeter, Fig. 124 (George Gibbs, M. E., Chicago, Milwaukee and St. Paul Railroad) , was designed to overcome some objectionable points in existing forms of viscosimeters. The idea being : First. To have a large body of hot oil as a bath surrounding the oil to be tested in order to keep the latter at a perfectly uniform temperature. Second. To apply a forced circulation to the bath by means of a double action pump, to insure equality of heat in all parts. Third. To deliver the oil to be tested at the orifice under a constant head, which is accomplished by means of a pneumatic trough. Fourth. To supply convenient means for accurately measur- ing the temperature of the oil near its delivery point. The large reservoir a is of copper, with heavy brazed bottom. This contains the cylindrical inside chamber with conical bottom, B. At the lower end of this is the gauged aperture, T. Inside of this chamber fits the inverted reservoir, C, holding the oil to be tested. In the interior of this chamber is a tube, D, extending nearly to the bottom of the same. This tube admits air to deter- mine the head of the oil, and also to admit the thermometer, F. The outside bath, a, contains the deflector plates, O, /'and R to obtain proper mixing of the bath. The heating of the bath is done by a lamp, W, set underneath the separate heating chamber, G. The size of the orifice at T is one-sixteenth inch. The following table shows the result of viscosity tests upon various oils made with this instrument. 392 QUANTITATIVE ANALYSIS. VISCOSITIES OF VALVE OILS AND STOCKS. Gravity. Flash. F. Per cent, mineral oil. VISCOSITIES 250 F. 300 F. 350 F. 400 F. Nat. Ref'g Co., Loco. Cv1 26.8 25-8 26.0 25-7 25-9 25.2 26.4 525 550 510 undet 5'o 535 485 75-7 7.00 54-7 65.0 undet. 95-o 66.7 38 sec. 43 35 34 32 33 29 28 26 28 25 24 23 27 23 21 26 26 25 27 Nat. Ref'g Co., German Perfection valve oil "(another) 21 23 21 20 22 22 21 23 C., M.& St. P. valve oil Extra lard oil (average 25 46 47 39 46 23 32 32 30 33 St d Oil Co., No. i stock " " 2 " " 4 27.0 27-3 2 7 .8 26.2 520 5io 490 525 100 100 100 IOO Viscosities expressed in seconds for 50 cc. VISCOSITIES OF CAR AND ENGINE OIL. Gravity. Flash. F. Per cent, mineral oil. VISCOSITIES. 75 F. 110 F. 150 F. National Ref'g Co., car oil. Relief Oil Works, Galena car oil 30.8 30.4 28.5 28.2 28. 7 27.8 26.3 265 30.1 26.5 200^ 200 1 60 I6 5 155 170 285 260 210 385 IOO IOO 9 90 9 9 91.9 9I.O IOO IOO 22 3 163 102 83 102 88 234 257 130 740 68 61 54 50 54 52 99 98 64 H3 41 $ P 34 49 48 37 54 , ( , ( Relief Oil Works, engine oil. National Ref'g Co., " il . Viscosities expressed in seconds for 50 cc. OF THR UNIVERSITY THE EXAMINATION OF LUBRICATING OILS. 393 Sou The viscosities of a number of other oils, at the temperature of locomotive cylinders, as made by this instrument, are shown in the chart of curves. (Fig. 125.) .85 _ _30 35 40 45 50 55 60 65 TO 75 SO 85 90 95 100 C. M. & ST. PAUL RY. CO (Testing. Department.} 95 100 Fig 125. A viscosimeter on an entirely different principle than the others already described is the Perkins instrument (G. H. Perkins, Supt. Atlantic Oil Refinery, Phila., Pa.) It consists 394 QUANTITATIVE ANALYSIS. of a cylindrical vessel of glass, surrounded by a proper heating vessel, and fitted with a piston. This piston fits into the cylin- der to within y-^ of an inch. In practice, the cylinder is filled nearly full with the oil to be tested and the piston inserted. The time required for the piston to sink a certain distance into the oil is taken as the measure of viscosity. A full description of the apparatus will be found in Transactions of the American Society of Mechanical Engineers, 9, P. 375- J. I^ew 1 , introduces an instrument not only for the viscosity but also to include the internal friction of an oil. By these means it is claimed the lubricating value of the oil is absolutely determined. The author states that the internal frictional resistances are different, and vary in the different oils at various temperatures. Formulas and methods are given by which coefficients are determined and used in the examination of the lubricating value of oils. Figure 126 represents the viscosimeter designed and used in the chemical laboratory at the Stevens Institute of Technology. It consists of a copper bath, B, surrounding the vessel, A, also of copper, and which holds the oil whose viscosity is to be deter- mined. The tube/ is of copper, but at e it is joined to a glass tube, which is extended to d this latter is used for measuring the oil, and is carefully graduated. Sizes and dimensions of the apparatus are given in the figure. This apparatus was designed to overcome two difficulties usually occurring in the use of other viscosimeters ; viz. : First, loss of heat in the oil during its passage from the containing vessel to the receiving flask ; and second, to have the chamber, A, of size to work small quantities of oil. First. When the vis- cosity of an oil is taken at the ordinary temperature the measure- ment of the oil in the receiving flask will correctly indicate the amount of oil delivered through the aperture. The conditions are altered, however, when high temperatures are required, since the oil in running in a fine stream through the orifice is chilled in contact with the air, and if its temperature be taken l Ding. poly. /., 1891, 280. Fig. 126. 396 QUANTITATIVE ANALYSIS. at the moment its volume is read in the receiving flask, a notable difference is indicated, depending upon the temperature of the room and of the oil before delivery. In this instrument provision is made for reading the volume of the oil directly in the chamber A without any graduated re- ceiving flask, as follows : The tube fedis graduated so that when the oil in the vessel A is at the proper level, the oil also reaches the upper graduated mark upon the tube d e. The lower graduated mark upon the tube indicates when twenty-five cc. of the oil have been delivered from A through the orifice \ This graduation is absolutely correct for the purpose, and shows accurately the viscosity of the oil at any temperature, as indicated by the thermometer in A. None of the oil in tube from e to d passes into A during the delivery of the twenty-five cc. through^-, since the tube/. 104.0 104.4 Olive oil 81.0 83.0 Herring oil 122.1 123.8 Dog-fish oil 102.7 104.7 Porpoise head oil 28.9 29.1 Rosin oil, second run 92.1 93.4 " " third " 90.4 92.2 Flash and Fire Test. The flashpoint is the degree of temperature at which ignitable volatile vapors are given off by the oil, producing a flash when brought in contact with a small flame. The fire test is a contin- uation of the flash test until the oil permanently ignites. A sim- ple apparatus that gives approximate results is shown in Fig. 129. It consists of a porcelain crucible two and one-eighth inches wide at the top, five-eighths inch wide at the bottom and one and one-half inches deep. This is surrounded by an asbestos pad three and one-half by three and one-half inches and one-eighth inch thick. This prevents the direct contact of the gas flame upon any portion of the crucible except the base. The oil to be 1 Chem. News, 62, 215 : J. Anal. Appl. Chcm... 5, 215. 404 QUANTITATIVE ANALYSIS. tested is placed in the crucible, a thermometer inserted at such a depth that the bulb is just covered by the oil, and the heat applied. The rise of temperature in the oil should not exceed 2 F. per minute. The " test-flame" (the smallest possible) is passed over and across the surf ace of the oil once every minute beginning at 100 F. Oils that flash below 110 F. are considered unsafe for light- Fig. 129. Fig. 130. ing purposes, and for lubricating purposes; oils should not flash under 250 F. The Cleveland cup oil tester is very similar to this instru- ment in design and operation, with the exception that the porce- lain crucible is replaced by a copper one of the same size and heated in a sand-bath instead of being surrounded by an asbestos pad. Tagliabue's open tester, has a very extensive use in the oil trade. It consists (Fig. 130) of a copper cylinder, B, into THE EXAMINATION OF LUBRICATING OILS. 405 which fits the copper water-bath, A, and a glass cup, D, which contains the oil to be tested. This apparatus has been super- seded somewhat by another form of open tester. The "Say- bolt" which is used by the chemists of the Standard Oil Co., and officially adopted by the New York Produce Exchange. It consists of a water-bath, F, (Fig. 131) surround- ing an inner cup con- taining the oil. An in- duction coil, E, furnishes an induction spark that passes over the oil. Bat- teries for generating the current are situated un- der the frame, C. All open cup testers give higher readings for the flash test than closed testers and it is generally conceded that the closed testers admit of more ac- curate determinations. The Abel closed tester Figs. 132, 133, has been adopted by the English government, and in a modified form (Pensky- Martens) by the German government as the official instrument for this purpose. The specifications for this instrument require that the oil cup be a cylindrical vessel, two inches in diameter, two and two- tenths high (internal), with outward projecting rim five-tenths inch wide, three-eighths inch from the top, and one and seven- eighths inches from the bottom of the cup. It is made of gun- metal or brass (17 B. W. G.) tinned inside. A bracket, con- sisting of a short stout piece of wire, bent upward, and termi- nating in a point, is fixed to the inside of the cup to serve as a gauge. The distance of the point from the bottom of the cup is Fig. 131. 406 QUANTITATIVE ANALYSIS. one and a half inches. The cup is provided with a close-fitting, overlapping cover, made of brass (22 B. W. G.) which carries the thermometer and test-lamp. The latter is suspended from two supports from the side by means of trunnions, upon which it may be made to oscillate ; it is provided with a spout, the mouth of which is one-sixteenth of an inch in diameter. The socket which is to hold the ther- mometer is fixed at such an angle, and its length is so ad- justed, that the bulb of the ther- Fig. 132. Fig. 133. mometer, when inserted to full depth, shall be one and a half inches below the center of the lid. The cover is provided with three square holes, one in the center, five-tenths inch by four- tenths inch, and two smaller ones, three-tenths inch by two-tenths inch, close to the sides and opposite to each other. These three holes may be closed and uncovered by means of a slide moving in groves and having perforations corresponding to those on the lid. In moving the slide so as to uncover the holes, the oscilla- ting lamp is caught by a pin fixed in the slide and tilted in such a way as to bring the end of the spout just below the surface of THE EXAMINATION OF LUBRICATING OILS. 407 the lid. Upon the slide being pushed back so as to cover the holes, the lamp returns to its original position. The flash test of this apparatus is about 27 F. lower than the open cup apparatus, so that 73 F. Abel test is equivalent to 100 F. test, open-cup test. The Pensky-Martens closed tester, Figs. 134, 135, in action Fig- 134- Fig 135- is very similar to the Abel closed tester. The apparatus of Treumann, Figs. 136, 137 is used by the chemists of the Prus- sian railways for the determination of the flash and fire test of both illuminating and lubricating oils. It is very similar in construction and operation to the Cleve- land cup, in use in this country for the same purpose, with the ex- ception that the oil is placed in a porcelain crucible, a, Fig. 137, instead of a copper one as in the Cleveland cup. 408 QUANTITATIVE ANALYSIS. The larger containing vessel is of iron and contains sufficient sand to raise the bottom of the crucible containing the oil, one- half inch from the point of contact of the flame. The flash and fire tests are required of all lubricating oils as a test of their power to resist combustion by overheating in work. Valve oils with mineral stock are especially liable to have low flash points caused by imperfect distillation in their manufacture. Thev should be Fig. 136. Fig. 137. free from any of the lighter oils (naphtha, keroserie, etc.,) and should not flash under 300 F. For cylinder oils the require- ment is much higher. Animal and vegetable oils used in lubri- cation rarely flash under 400 F. Acidify. Acidity in oils is generally due to a partial decomposition of the oil with liberation of fatty acids. These latter act as cor- rosive agents, attacking the metal bearings of machinery, form- ing "metallic soaps" and producing gumming and thickening of the lubricant. Properly refined mineral oils are free from acidity, but nearly all animal and vegetables oils possess it more or less. THE EXAMINATION OF LUBRICATING OILS. 409 In palm oil, for instance, the free fatty acids vary from twelve to eighty per cent. In eighty-nine samples of olive oil intended for lubricating purposes, D. Archbutt 1 found from 2.2 to 25.1 percent, of free acid (oleic) the mean being 8.05 percent. Oleic acid cannot be present as a constituent of a pure mineral oil ; still the acid test should be made, since poorly refined mineral oils are liable to contain small amounts of sulphuric acid left in the process of refining. The sulphuric acid is easily indicated by warming some of the oil with distilled water, adding a few drops of hydrochloric acid (dilute) and solution of barium chloride. A white cloud or precipitate shows the presence of sulphuric acid. The action of free acid on journals, bearing, etc., as a corro- sive element, has led many engineers to include a test of free acid direct upon copper and iron. This is done by suspending weighed pieces of sheet copper and iron in the different oils, for a number of days, heating if \ necessary, and determining the amount of metal dissolved by the oils. While this test may be indicative of the acidity of oils, no ratio exists between the action upon copper and iron or even between the oils themselves in this respect, owing to the varying quantity of acid in the same oils. The results of a few tests are shown in the following table : Copper dissolved after Iron dissolved after Name of oil. 10 days. 24 days. Linseed oil 0.3000 gram. 0.0050 gram. Olive oil 0.2200 " 0.0062 " Neat's foot oil o.iioo " 0.0875" Sperm oil 0.0030 " 0.0460 " Paraffin oil 0.0015 " 0.0045" Lard oil 0.0250 " The following is the method for determining the acidity of oils, as used in many of the railroad laboratories : Materials Required. One fifty cc. burette, graduated to tenths. Two ounces alcoholic solution phenolphthalein. 1 Analyst, 9, 171. 4IO QUANTITATIVE ANALYSIS. Three ten cc. pipettes. One druggist's graduate, four ounces. One gallon ninety-five per cent, alcohol. One dozen four ounce sample bottles. One thermometer graduated from 15 to 215 F., and bearing the certificate of the Yale Thermometer Bureau. Two hydrometers 15 to 25 and 25 to 35 B., each degree graduated to tenths (Tagliabue's.) One hydrometer jar. One quart caustic potash solution of such strength that 31.5 cc. exactly neutralize five cc. of a normal solution of sulphuric acid ( contains forty-nine mgms. per cubic centimeter of sulphuric acid.) 1 Take two ounces of alcohol and warm tq about iooF.; add ten drops of alcoholic solution of phenolphthalein. Fill the burette to the top of the graduation with the caustic potash solu- tion ; then add solution drop by drop to the alcohol until it as- sumes a pink tint. Add ten cc. of the oil to the alcohol, refill the burette with the potash solution and add the latter until the mixture of oil and alcohol maintains a pink color after thorough shaking. Read off the number of cc. of potash solution used, and this amount divided by two, gives the per cent, of free acid. For example, if 10.6 cc. caustic potash solution have been used, the oil contains five and three-tenths per cent, of free fatty acid. Lard and tallow are very liable to have considerable amounts of free acid. The specification of purchase therefore generally states the limits of free acid permitted. Maumene' 1 s Test. The rise of temperature produced when sulphuric acid is brought in contact with certain oils was first investigated by Maumene, and the results of his experiments published in Comptes Rendus, 35, 572. The subject has been investigated by Fehling, Faist, L. Arch- butt, C. J. Ellis, A. H. Allen and others, with the result that 1 Hydrometers and thermometers should be procured through Chas. A. Tagliabue, New York. THE EXAMINATION OF LUBRICATING OILS. 41 1 this test has been generally accepted as of importance in the distinction of oils in mixtures. When a mixture of oils has been analyzed and the components recognized the proportions oftentimes can be determined by this reaction ; that is to say, suppose the oil under examination to show a rise of temperature of 80 C., and the oils found by analysis to be lard oil and menhaden oil ; their relative propor- tions can be determined by the following formula : W^ = proportion by weight of menhaden oil. W,= " " " " lard W^ =. weight of mixture. t l = temperature of menhaden oil. / = " " lard / 3 = " " mixture. The method is as follows : Fifty grams of the oil are placed in a narrow tall beaker and ten cc. of C. P. sulphuric acid added drop by drop with stirring and the rise of temperature during the operation noted. Lard oil alone when treated with sulphuric acid gives a rise of temperature of 40 C.; menhaden oil, under similar conditions, a rise of 128 C. Using these values in the above formula we obtain 54.6 per cent, lard oil and 45.4 per cent, menhaden oil. In the mixture containing a mineral oil mixed with animal, marine or vegetable oil the distinction would be even more pro - nounced, since the mineral oil shows but a very slight increase of temperature (generally from 2C. to 5 C.). The increment of temperature would be dependent upon the other oil added to the mineral oil. Briefly stated, the rise of temperature of the following oils would be : 4 I2 QUANTITATIVE ANALYSIS. Name of Observer. Maumene. C. Schaedler. C. Archbutt. c. Allen. C. Stillman. c. 40 41-43 45 102-103 58 47 42 67 50 103 69.5 4 8 43 28 67 28 43 37^ 5i 92 123-128 70 46 41-45 47-60 41 38* 45-47 9 1 126 H3 67-69 65 41-43 18-22 3-4 22 39-5 39 40 37 38 48 92 128 80 no 74 60 45 42 10 3 10 65 Tallow oil Olco oil * Ela.in oil Whale oil Crude cotton-seed oil. Olive oil Mineral lubricating oil- "PartVi Trnt Attention is drawn to the differences in the determinations in rosin oil. Rosin oil of the first run is a white, opaque, thick liquid con- taining all of the water of the rosin from which it is distilled, and it is this water that causes the rise of temperature above 10 when the oil is mixed with the sulphuric acid. Rosin oils of the second and third runs are clear, limpid, dark red colored fluids, practically free from water, and when treated with sulphuric acid do not indicate more than 10 rise of tempera- ture. From these tests it is concluded that both Schaedler and Allen tested rosin oil that was a mixture of the first and second runs, or of an oil not properly separated into the different distillates. Color Reactions of Oils with Nitric and Sulphuric Acid. Of the many color tests introduced for the identification of simple oils, preference is given to Heidenreich's sulphuric acid test and Massie's nitric acid test. The color reactions of Chateau 1 in which barium poly-sulphide 1 Spon's Encyclopedia, 4, 1472-1475. THE EXAMINATION OF LUBRICATING OILS. 413 zinc chloride, stannic chloride, phosphoric acid and mercuric nitrate, in solutions, are used, while very interesting, seldom are of any advantage over the two tests noted above. Glassner's 1 nitric acid reactions are practically the same in results as Massie's so that no advantage would be obtained in including the former. Heidenreich's test is as follows : A clear glass plate is placed over a piece of white paper, ten drops of the oil under examination are placed thereon, and one drop of concentrated sulphuric acid is added. The color produced when the acid comes in contact with the oil is noticed as well as the color produced when the two are stirred with a glass rod. Many oils give off characteristic odors during the reaction, especially neat's foot oil, whale oil and menhaden oil. Massie's test is thus performed : Nitric acid of specific gravity 1.40, free from nitrous acid, is mixed in a test tube with one- third its volume of the oil, and the w r hole agitated for two minutes. The color of the oil after separation from the acid is the indica- tion. In mixtures of oils, the characteristic colors produced, by either Heidenreich's or Massie's test, are often clouded, and in many instances no inferences can be drawn, yet with single oils the reactions are often distinctive and sufficiently strong to give confirmatory results. In cod liver oil, or whale oil, when mixed with a mineral or even vegetable oil, the characteristic brilliant violent color pro- duced with sulphuric acid cannot be mistaken. This color, due to the presence of cholic acid, is found in most of the fish oils, but is much more pronounced in cod liver oil. The following table will indicate the colors produced by Hei- denreich's and Massie's test. 1 Chem. Centrbl., 1873, 57. 4 i4 QUANTITATIVE ANALYSIS. Heidenreich's test. Before stirring. After stirring. Massie's test. Yellow. Yellow. Yellowish. Colorless. Light green (turn- ing to brown). Brown with pur- ple streaks. Red violet. Red. Violet. Red violet. Brilliant red. Reddish brown. Yellow brown. Lgt. yel. to brown. Light green. Brown. Yellow to orange. Brown. Orange. Red brown. Orange. Brown. Reddish brown. Violet brown. Brown. Dark brown. Dark brown. Brown. Red. Brown. Pale brown. Greenish to light brown. Brown. Greenish. Yellow. Colorless. Red. Pink. Orange red. Red. Red. Dark red. Orange. Orange red. Brown. Orange red. Orange. Orange. Yellow to greenish. Orange. Reddish. Neat's foot oil O1po nil \VTia1f* 01 1 Menhaden oil Crude cotton-seed Ref 'd cotton-seed Earth nut oil The oils made use of in lubrication can be separated into two groups: saponifiable and unsaponifiable. To the former belong all the fatty oils ; to the latter the mineral and rosin oils. The method of Lux 1 is made use of to determine if any fatty oils are present in a mineral oil. If rosin oil is suspected to have been added to the mineral, it can be identified by the method of Holde 2 or the process of E. Valenta s can be used. These three tests will indicate, qualitatively, the presence of any fatty or rosin oil in a mineral oil. It is rarely, in the bet- ter class of lubricating oils, that more than one oil is added to a mineral oil, such, for instance, as lard oil, or tallow, in which case saponification easily separates the two oils, and identifica- tion of each by special tests can then be made. When, however, the oil added to the mineral oil itself contains an adulterant, such as lard oil to which cotton-seed oil has been added, then the fatty acids separated by saponification will re- quire a more extended examination to prove the presence of both lard oil and cotton-seed oil. 1 Ztschr. Anal. Chem., 24, 347. 2 Mittheil der Konig. tech. Versuchsanstalten, 1890, 19. * Ztschr. anal. Chem., 25, 441. THE EXAMINATION OF LUBRICATING OILS. 415 The following skeleton scheme is given to show the applica- tion of the above upon a lubricating oil that qualitative analysis has shown to contain mineral oil, lard oil, and cotton-seed oil. Twenty grams of the oil are weighed out in a No. 3 beaker, loocc. of an alcoholic solution of potash (eighty grams potassium hydroxide to one liter alcohol of ninety-eight per cent. ) are added, and heat applied with stirring until the alcohol is all driven off ; add 100 cc. water, heat with agitation, cool, add fifty cc. ether, transfer to separatory funnel, stopper, shake well and allow to stand two hours. Draw off the soap solution. i. Soap solution (containing the fatty acids of the lard and cotton- seed oils). Heat ten minutes nearly to boiling, cool, acidify with dilute sulphuric acid, allow to stand a few hours ; collect the separated fatty acids; deter- mine their weight, then test as follows : First portion : Determine the "melt- ing-point." Second portion : Determine the "iodine absorption" and their rates by formula : 2. Ether solution remaining in the separatory funnel is transferred to a flask, the ether distilled and the mineral oils weighed. There are several methods for the quantitative determination of the amounts of vegetable and animal oils when mixed with each other, or when the mixture is incorporated with a mineral oil. The determination of the iodine absorption is the most delicate and correct provided no fish blubber or olive oils are present. If the fatty acids have been separated, by saponification, from a mineral oil, this iodine value can also be determined. Consult soap analysis, for table of constants. The method of Salkowski 1 depends upon the fact that vegetable oils (except olive) contain phytosterol and that animal fats (butter excepted) are free from it, containing cholesterol, the latter not being present in vegetable oils. i Benedikt : Oils, Fats and Waxes, 255. 416 QUANTITATIVE ANALYSIS. Fifty grams of the sample free from mineral oil are saponified with alcoholic potash ; the soap solution is diluted with a liter of water and exhausted with ether. When the two layers have separated, the aqueous layer is run off and the ethereal liquid filtered and evaporated to a small bulk. To insure complete absence of unsaponified fat, it is best to saponify again with alcoholic potash and to repeat the exhaustion with ether. The ethereal layer is then washed with water and the ether evapo- rated in a deep basin. The residue is next dissolved in hot alcohol, the solution boiled down to one or two cc. and the residue allowed to cool. If phytosterol or cholesterol be present, crystals will separate out. They are dried on unglazed porce- lain and their melting points determined. The saponification value of oils is often made use of for identification : but as this value varies with the age of the oil, it is extremely difficult to obtain concordant results, and as the majority of oils have a saponification value of 193, excepting rape-seed oil and castor oil which are lower, it can not be relied upon. It however is of value in determining the amount of liquid waxes in the presence of oils. Wool-grease is used to some extent in the cheaper grades of lubricants, the consumption for this purpose increasing yearly. It is unsaponifiable and, if present, will be found in the ether ex- tract with the mineral oil, in the analysis as usually conducted of a mixed lubricating oil. Degras or sod oil is a waste product obtained in the chamois- ing process. It is largely derived from whale oil or poor quality of cod liver oil used in chamoising. The English-German method of treating skins produces sod oil as a waste product. The French method produces De- gras. These fats are largely used in the production of cheaper lubricants. Consult Benedikt: Oils, Fats and Waxes, 589; J. Am. Chem. Soc., (Bush), 16, 535. Bone Fat is made use of in lubrication mixed with mineral oils. It is recovered from bones, either by boiling with water or extracting with solvents. It does not readily become rancid. Its examination is made similarly to that of tallow. THE EXAMINATION OF LUBRICATING OILS. 417 Coefficient of Friction . The ratio of the force required to slide a body along a hori- zontal plane surface to the weight of the body is called the coeffi- cient of friction. It is equivalent to the tangent of the angle of repose, which is the angle of inclination to the horizontal of an inclined plane on which the body will just overcome its tendency to slide. The angle is usually denoted by q>, and the coefficient by/. /=tan q>. (Kent.) Of the various machines used for this purpose nearly all are deficient in conducting tests under extreme pressure. However as all the tests are relative, an idea of the value of a lubricant can be formed by a series of comparative tests upon the same instrument. G. B. Heckel thus describes the Thurston and Henderson- Westhoven machines : The primary idea of determining dura- Fig. 138. Fig. 139. bility is to determine how much rubbing a lubricant will with- stand before exhaustion of its power to maintain the friction at some agreed minimum. For this there is no device superior to the Thurston oil-tester, in which a pair of brasses are forced against a journal in opposite directions by a spring being lodged in a pendulum which is free to swing about the journal, the friction being measured by the inclination to the vertical of a line join- 41 8 QUANTITATIVE ANALYSIS. ing the center of the journal and the center of gravity of the pendulum. The defects of this machine lie in the infinitely variable rate of metallic wear between rubbing surfaces, which contaminates the oil before it has been exhausted, as well as in the escape of the lubricant between the surfaces. These imperfections have been overcome in the Henderson machine or the so-called Henderson- Westhoven machine, a modified Thurston tester. (Figs. 138, 139.) With this machine lubricants can be tested at the same moment for the degree of heat developed in the bearing surfaces as well as their friction reducing qualities. The journal, A, rests upon the supporting beds, BB, and is revolved by the pully, C. This journal, A, extends on both sides beyond the supports, BB, and the projecting ends are em- braced by brass boxes DD, to which are fastened the pendulum parts EE. Strong spiral springs mm, in the interior of the pendulum arms, force the lower pair of brasses, DD, against the journal, A, and the pressure of these springs may be regulated by means of the screw, N. A pointer attached to the movable block, o, indicates on the scale, /*, as in a spring balance, the thrust of the spring against its bed, in kilograms per cubic centi- meter. By the revolution of the journal, A, the swinging arms, EE, are actuated by friction in the direction of the motion, and the degree of their deviation from the vertical is read by means of the pointers, FE, on the quadrants GG. On many machines the scales give, besides the deviation, also the coefficient of fric- tion which has been calculated from the former. In the upper brasses, DD, a thermometer, H, is fixed to show the degree of heat developed by the friction, and the revolution counter, /, actuated through the endless screw, q, records the revolutions of the journal, A. The column, K, through its two arms, L, carrying the boxes, BB, serves to support the entire device. In operation the oil to be tested is introduced by means of a small glass tube or pipette, through an orifice in the upper brasses, DD, the journal having been thoroughly cleaned. The position of the thermometer and of the revolution counter are noted, and the journal is then put into motion with 200 or 300 THE EXAMINATION OF LUBRICATING OILS. 419 revolutions per minute. At each succeeding five-hundredth or thousandth revolution the temperature and the degree of devia- tion of the pendulum arms, as shown by the quadrant, are noted, and when the friction has raised the temperature in the boxes about 30 (usually in about half an hour) the machine is stopped. In figuring up results, the sample of oil which, with an equal rise in temperature at the point of friction, gives the slightest deviation of the swinging pendulum arm, and the greatest num- Fig. 140. ber of revolutions, is regarded as the best. The advantages noted in this device are its facilities for testing materials under any pressure, even up to the load limit on a freight car axle ; the number of data obtainable at one time ; and the ease with which two simultaneous tests of competing oils can be made on the one machine. The apparatus used for testing lubricants by the officials of the Paris-Lyon Railway is shown in Figs. 140, 141. Here the conditions are maintained as nearly as possible as would occur 420 QUANTITATIVE ANALYSIS. in railroad practice, the friction being determined by means of two freight-car wheels. The heavy cast-iron frame, A, stands upon a firm stone founda- tion and carries the shaft, B, on which are fastened the two fric- tion wheels, CC. These are placed at the same gauge as the railroad track. Two ordinary car wheels, DD, with axle, E, are placed above and in contact as shown in the figure. The car axle, E, is fitted at each end into the axle boxes, mm. The boxes have the same arrangement as those in the railroad cars Fig. 141. and serve for the reception of the lubricant. Resting on each side of the axle boxes are the strong springs, nn, Fig. 140, on the end of which the weights, FF, work by means of the levers, oo. By taking off or putting on of weights, FF, E can carry any load desirable. On the lower shaft is the driving wheel, G, also a screw by which the movement of the shaft is carried to a figured dial. This dial sets not only the index showing the number of revolu- THE EXAMINATION OF LUBRICATING OILS. 421 tions but also the index needle, t, in motion which indicates on the scale, u, the approximate rapidly of the wheel-rims in kilo- Fig. 142. Extreme length 7j feet. Extreme height 6 feet. Extreme width 6 feet. Weight 6250 pounds. Shipping weight 6500 pounds. meters per hour. The two friction wheels, cc, are turned eccen- trically about two and five-tenths mm. that by the motion a weak vertical oscillation arises which is communicated to the upper 422 QUANTITATIVE ANALYSIS. wheels whereby the rattling of the wheels upon the car track is imitated. In making a trial, the lubricant to be tested is placed in the thoroughly cleaned axle boxes, mm, the springs are lifted to the utmost release of the upper shaft and the lower shaft is placed in rotation. Not until the whole is in motion are the springs brought down, and later loaded with the intended weight. The oil which by this test carries the burden with the greatest rapidity without heating of the axle-boxes is to be considered the best. By this apparatus it is possible to judge of the practical working of an oil or compounded oil, and especially if the car axles would become heated, a point of vital importance as regards the use of the lubricant. Another instrument of a similar design is the Riehle, (Fig. 142,) in use in many railroad laboratories in the United States, for testing lubricants. The capacity is 20,000 pounds ; it deter- mines the coefficient of friction, the pressure per square inch of journal and records the temperature. It consists.of a Master Car Builder's Axle journal, w T hich is re- movable from the main spindle. This journal is made to revolve by cone pully at different speeds, and in either direction, and can be loaded to different pressures per inch by means of the lever system. The oil can be supplied through a hole in the top, which is tapped to receive a sight-feed oiler, or funnel, or other arrangement. The friction is weighed on the beams, which are arranged in double system to balance each other, allowing the machine to be run in either direction. The opening in the frame over the journal is made large enough to take a regular car box if desired. The frame and beams can be raised by rope sling and hoist for change of journal, cleaning up, etc. There is an end motion of about one-fourth to three-eighths inch given to the axle by the gearing shown at the end, giving a natural movement like cars. The weighed end of spindle runs loose on large rollers, to avoid friction and heating. An oil tested upon the tester may show a fine lubricant, while put under practical working upon a freight car (for instance) would prove vastly inferior. This very often happens, and it THE EXAMINATION OP LUBRICATING OILS. 423 has led many engineers to test each oil by a long run, with the particular kind of machinery upon which it is to be used. A record-blank used by the engineers of the Baltimore and Ohio Railroad, for testing oils upon their locomotives is given herewith. It is a point in instance. After experimenting months upon an oil its work is established so that a practical compari- son can be made with other brands of similar composition for the same purpose. BALTIMORE AND OHIO RAILROAD. Subject 189 Engineer of Tests, DEAR SIR : Below please find report from locomotives inspected this day. i I JI Engineer. Fireman. ! o = || | Arrived. 1 :- I I i Average speed, 1 miles per hour. Condition of bearings. Kind of oil used. Miles run per pint of oil allowed- Miles run per pint of oil used. Number of drops per minute. tj ij )j Cylinder. Journal. a *> o 3 3 O i , fl ">, s 1 a ", \ o Inspector. BALTIMORE AND OHIO RAILROAD. OFFICE OF SUPERINTEND- ENT OF MOTIVE POWER. (Specifications for Compound Oils.) DETAIL SPECIFICATIONS. Engine and Passenger Car Oil. This oil must conform to the following requirements . 1. It must have a flashing point from October i to May i, above 200 F. ; from May i to October i the flashing point must be above 250 F. 2. From October i to May i it must have a cold test below 15 F. 3. It must show no sediment in fifteen minutes when five cc. are mixed with 100 cc. of gasoline of 85 B. 4. It must contain not less than thirty per cent, saponifiable animal oil. 5. Its gravity must be between 26 and 30 B. 424 QUANTITATIVE ANALYSIS. Cylinder Oil. This oil must conform to the following requirements : 1. It must have a flashing point above 440 F. 2. It must contain not less than thirty-five per cent, of saponifiable ani- mal oil. 3. It must show not more than six per cent, of fat acid or its equivalent. 4. It must riot show any precipitation when five cc. are mixed with 100 cc. of gasoline of 85 B. Freight Car Oil. This oil must conform to the following requirements : 1. It must have a flashing point from October i to May i above 200 F. ; from May i to October i the flashing point must be above 250 F. 2. From October i to May i it must have a cold test below 15 F. 3. It must show no sediment in fifteen minutes when five cc. are mixed with 100 cc. of gasoline of 85 B. 4. It must not contain less than ten per cent, of saponifiable animal oil. Special Mixture. All special mixtures of oil not coming under the above specifications will be purchased on sample, which must be of one gallon. Shipments will be required to conform to sample in every particular. Samples must be sent as the purchasing agent may direct. CHICAGO, BURLINGTON AND QUINCY RAILROAD Co. CHEM- ICAL LABORATORY. AURORA, ILL., i8- To Supt. M. P. : DEAR SIR : I have made an examination of sample of above oil, and have obtained the following results : Flashing point C F. Ash %. Tar %. Burning " F. Cold test at F. Specific gravity C B. Viscosity at F. 100 cc. oil Loss at F. for 3 hours %. flows from instrument in . -seconds. FRICTION TEST ON THE THURSTON OIL TESTER. Date. ist trial. 2d trial. 3d trial. Average. Amount used., oz. Temp. Highest reading. Lowest " Range of " Average Arc. Temp. Arc. Temp. Time run in minutes Total revolutions Revolutions per minute Speed, miles per hour Pressure, total Ibs Ibs. per sq. inch Coefficient of friction Lubricating value, with Extra Lard Oil as 100 , THE EXAMINATION OF LUBRICATING OILS. 425 Received 18 . . Car No. and Initials Tested 18 . . Tank or No. Bbls Sample No. or Letter Name of firm supplying Blank No Price .... cents per gallon. Letter Book No Page Yours truly, Chemist. For the R. R. Co. CHICAGO, BURLINGTON AND QUINCY RAILROAD COMPANY. Specifications for Black Engine Oils. ("Petroleum lubricating oils;" "well oils;" "petroleum stock oils;" or " passenger and freight car lubricating oils.") Uses. For lubricating the journals of passenger and freight cars and locomotives, and for miscellaneous lubrication. Grades. : " Summer," " 25 degree," " 15 degree" and " zero." Requirements. For all grades : Specific gravity, between 26 and 29 B. Loss at ioo c F. for three hours, not over one-fourth per cent. Flashing point, for all but "zero" oil, not under 300 F. Flashing point, for "zero" oil, not under 250 F. Burning point, for all but "zero" oil, not under 375 F. Burning point, for "zero" oil, not under 300 F. Cold Test Summer oil must flow at 60 F. or above. 11 25 " " " 30 " I5 C " " " 20 " Zero ." " " 5 " All these oils must be pure petroleum oils, free from other compounds, and from dirt, grit, lumps and specks ; transparent and greenish or red- dish (not black) in tint, when spread as a thin film on glass and looked through toward the light ; translucent and greenish when held in a hori- zontal position. Preference will be given to those oils which are low in tarry matters and in ash, and which do not " froth" when tested for flash and fire. Oils differing notably from above requirements will be rejected. CHICAGO, BURLINGTON AND QUINCY RAILROAD COMPANY. Specifications for Cylinder Stock. Use. For making cylinder lubricant. One grade. Requirements. Must have a flashing point not lower than 475 F., a burning point not lower than 575 F., and a specific gravity between 25 and 28 B. Must not undergo a loss greater than one-half Q) per cent., when exposed for three (3) hours to a temperature of 350 F. Must be 426 QUANTITATIVE ANALYSIS. free from dirt, grit, lumps and specks ; transparent and greenish or red- dish (not black) in tint, when spread as a thin film on glass and looked toward the light. References: " Measurements of Friction of Lubricating Oils." By C. J. H. Woodbury, Trans. Am. Soc. Mech. Eng., 6, 136. " On the Theory of the Finance of Lubrication and on the Valuation of Lubricants by Consumers." By R. H. Thurston, Trans. Am. Soc. Mech. Eng., 7, 437- " Cost of Lubricating Car Journals." By L, A. Randolph, Trans. Am. Soc. Mech. Eng., 10, 126-35. "Special Experiments with Lubricants." By J. B. Denton, Trans. Am. Soc. Mech. Eng., 12, 405-50. " Report of Committee on Lubrication of Cars to the Master Car Build- er's Association of the United States for 1893." The Railway Car Journal, 4, 156. (July, 1894.) " History of Attempts to Determine the Relative Value of Lubricants by Mechanical Tests." Proceedings of the American Association for the Advancement of Science, 34- " Car Lubrication." By W. E. Hall. Oils Used for Illumination. Oils used for illumination may be classified into two groups : 1. Refined products from petroleum, such as naphtha, gaso- line, kerosene, signal oil, etc. 2. Certain refined oils of vegetable and animal origin, as colza oil, rape oil, lard oil, sperm oil, etc. i. Refined Products from Petroleum. Kerosene is the refined product from petroleum that distills over (in the refining process) after the lighter oils, naphthas, etc., have been separated, and is the principle oil in use for illumina- tion. In color it varies from standard white to water white (colorless) , and its commercial value is dependent upon its flash and burning point. In the oil trade, the burning or fire tests are classified as 110 F., 120 F. and 150 F., and 300 F. The 150 F. is known as headlight oil and the 300 F. as min- eral sperm and mineral colza. The requirements for mineral oils to be used in railroad illumination are as follows : OILS USED FOR ILLUMINATION. 427 Specifications for Petroleum Burning Oils. (Conditions of shipment and General Specifications.) This material will be purchased by weight. Barrels must be in a good condition and must have the name of the contents and the consignee's name and address on each barrel, and plainly marked with the gross and net weight which will be subject to the Company's weight. When received all shipments will be promptly weighed. If not practi- cable to empty all barrels, ten per cent. (10%) will be emptied, and the losses of the whole shipment will be adjusted in accordance with the ten per cent, taken. Should the net weight thus obtained be less by one per cent, (i %) than the amount charged in the bill, a reduction will be made for all over one per cent. Prices should be given in cents or hundredths of a cent per pound. Shipments, one or more barrels of which are filled with oil cloudy from the presence of glue, or which contain dirt, water or other impurities, will be rejected. Two kinds of petroleum burning oils will be used, known as 150 fire test for general use, and 300 fire test for use in passenger cars. Detail Specifications. 150 Fire Test Oil. This oil must conform to the following requirements : i It must have a flash test above 125 F. 2 It must have a fire test not below 150 F. 3 It must have a cloud test not above o F. 4 It must be a " water white" in color. 5 Its gravity must be between 44 and 48 B. at 60 F. 300 Fire Test Oil. This oil must conform to the following requirements : i It must have a flash test above 250 F. 2 It must have a fire test not below 300 F. 3 It must have a cloud test not above 32 F. 4 It must be a " standard white" in color. 5 Its gravity must be between 38 and 42 B. at 60 F. Method of Making Tests. 150 Fire Test Oil. The " Open Tagliabue" cup is used for determining the flash- ing and burning points of this oil, heating the oil at the rate of 2 F. per minute and applying the test flame every degree from 120 for flash and every 4 after flash for the burning point. 300 Fire, Test Oil. The " Cleveland" cup is used for determining the flashing and burning points of this oil, heating at the rate of 5 per minute and applying the test flame every 5 from 230 F. 428 QUANTITATIVE ANALYSIS. Cloud Test. The cloud test is made as follows : Two ounces of the oil are placed in a four ounce sample bottle, with a thermometer sus- pended in the oil. The bottle is exposed to a freezing mixture of ice and salt and the oil stirred with the thermometer while cooling. The temperature at which the cloud forms is taken as the cloud test. The requirements for the flash and fire test for illuminating oils used for domestic purposes are not so rigid as for railroad practice. In fact large quantities of oil, flashing below 110 F. are used, the cheaper price being the incentive. So dangerous are these oils with low flash points, that many states have passed stringent laws against their use. An oil with a fire test of 110 F. very often has a flash test of 90 F. and many oils with a fire test of 120 F., flash at or below 100 F. It is the flash point of an oil that makes it dangerous and while the refiners of oils mark their products by the fire test, the laws as passed by many of the states, specify the flash test as the requisite. There is no absolute ratio between the flash and fire test of an oil, since while many illuminating oils have a high fire and flash test, others may have a high fire and a low flash test. The instrument that gives the best satisfaction in testing illuminating oils, not lubricating oils (see page 403) , for the flash and fire test is called the Wisconsin Tester. (Fig. 143.) It is thus described : On the left side of the figure is shown the instrument entire. It con- sists of a sheet-copper stand eight and one-half inches high, exclusive of the base, and four and one-half inches in diameter. On one side is an aperture three and one-half inches high, for introducing a small spirit- lamp, A, about three inches in height, or better, a small gas burner in place of the lamp when a supply of gas is at hand. The water-bath, D, is also of copper, and is four and one-eighth inches in height and four inches inside diameter. The opening in the top is two and seven-eighths inches in diameter. It is also provided with a one-fourth inch flange which supports the bath in the cylindrical stand. The capacity of the bath is about twenty fluid ounces, this quantity being indicated by a mark on the inside. C represents the copper oil-holder. The lower section is three and three-eighths inches high, and two and three-fourths inches inside diameter. The upper part is one inch high and three and three-eighths inches in diameter, and serves as a vapor-chamber. The upper rim is pro- OILS USED FOR ILLUMINATION. 429 vided with a small flange which serves to hold the glass cover in place. The oil holder contains about ten fluid ounces, when filled to within one- eighth of an inch of the flange which joins the oil cup and the vapor- chambers. In order to prevent reflection from the otherwise bright sur- face of the metal, the oil-cup is blackened on the inside by forming a sul- phide of copper, by means of sulphide of ammonium. The cover, C, is of glass, and is three and five-eighths inches in diameter ; on one side is a circular opening, closed by a cork through which the thermometer, B, passes. In front of this is a second opening three-fourths of an inch deep and the same in width on the rim, through which the flashing jet is passed in testing. The substitution of a glass for a metal cover more readily enables the oper- ator to note the exact point at which the flash occurs. A small gas jet, one- fourth inch in length, furnishes the best means for igniting the vapor. Where gas cannot be had the flame from a small waxed twine answers very well. (2). The test shall be applied ac- cording to the following directions : Remove the oil cup and fill the water-bath with cold water up to the mark on the inside. Replace the oil cup and pour in enough oil to fill it 'to within one-eighth of an inch of the flange joining the cup and the vapor- chamber above. Care must be taken that the oil does not flow over the flange. Remove all air bubbles with Fig. 143. a piece of dry paper. Place the glass cover on the oil cup, and so adjust the thermometer that its bulb shall be just covered by the oil. If an alcohol lamp is employed for heating the water-bath, the wick should be carefully trimmed and adjusted to a small flame. A small Bunsen burner may be used in place of the lamp. The rate of heating should be about 2 per minute, and in no case exceed 3. As a flash torch, a small gas jet, one-fourth inch in length, should be employed. When gas is not at hand, employ a piece of waxed linen twine. The flame in this case, however, should be small. When the temperature of the oil has reached 85 F., the testings should commence. To this end insert the torch into the opening in the cover, 430 QUANTITATIVE ANALYSIS. passing it in at such an angle as to well clear the cover, and to a distance about half way between the oil and the cover. The motion should be steady and uniform, rapid and without any pause. This should be re- peated at every 2 rise of the thermometer until the temperature has reached 95, when the lamp should be removed and the testings should be made for each degree of temperature until 100 is reached. After this the lamp may be replaced, if necessary, and the testings continued for each 2 C . The appearance of a slight bluish flame shows that the flashing point has been" reached. In every case note the temperature of the oil before introducing the torch. The flame of the torch must not come in contact with the oil. The water-bath should be filled with cold water for each separate test, and the oil from a previous test carefully wiped from the oil cup. (3). The instrument to be used in testing oils which come under the provisions of section 2 of the law shall consist of the cylinder D, and the copper oil cup C, together with a copper collar for suspending the cup in the cylinder, and an adjustable support for holding the thermometer. (4). The test for ascertaining the igniting point shall be conducted as follows : Fill the cup with the oil to be tested to within three-eighths of an inch of the flange joining the cup and the vapor-chamber above. Care must be taken that the oil does not flow over the flange. Place the cup in the cylinder and adjust the thermometer so that its bulb shall be just covered by the oil. Place the lamp or gas burner under the oil cup. The rate of heating should not exceed 10 a minute below 250 F., nor ex- ceed 5 a minute above this point. The testing flame described in the directions for ascertaining the flashing point should be used. It should be applied to the surface of the oil at every 5 rise in the thermometer, till the oil ignites. The following is a copy of the law of the state of New York regulating the standard of illuminating oils, etc.: AN ACT to regulate the standard of illuminating oils and fluids for the better protection of life, health and property. Passed June 6, 1882, three-fifths being present. SECTION i. No person, company or corporation shall manufacture or have in this State, or deal in, keep, sell or give away, for illuminating or heating purposes in lamps or stoves within this state, oil or burning fluid, whether the same be composed wholly or in part of naphtha, coal oil, petroleum or products manufactured therefrom, or of other substances or materials, which shall emit an inflammable vapor which will flash at a temperature below one hundred degrees, by the Fahrenheit thermome- ter, according to the instrument and methods approved by the State Board of Health of New York. 2. No oil or burning fluid, whether composed wholly or in part of OILS USED FOR ILLUMINATION. 431 coal oil and petroleum or their products, or other substance or material, which will ignite at a temperature below three hundred degrees by the Fahrenheit thermometer, shall be burned in any lamp, vessel or other sta- tionary fixture of any kind, or carried as freight, in any passenger car, or passenger boat moved by steam power in this State, or in any stage or street car drawn by horses. Exceptions as regards the transportation of coal oil, petroleum and its products are hereby made when the same is securely packed in barrels or metallic packages, and permission is here- by granted for its carriage in passenger boats moved by steam power when there are no other public means of transportation. Any violation of this act shall be deemed a misdemeanor and subject the offending party or parties to a penalty not exceeding three hundred dollars, or im- prisonment not exceeding six months, at the direction of the court. 3. It shall be the duty of the State Board of Health of New York to recommend and direct the nature of the test and instruments by which the illuminating oils, as hereinbefore described, shall be tested in accord- ance with this act. It shall be the duty of the public analysts, who may now be employed by the State Board of Health, or who may be hereafter appointed, to test such samples of suspected illuminating oils or fluids as may be submitted to them under the rules to be adopted by the said board, for which service the said board shall provide reasonable compen- sation at the first quarterly meeting of the State Board of Health after the passage of this act ; it shall adopt such measures as may seem necessary to facilitate the enforcement of this act, and prepare rules and regulations with regard to the proper methods of collecting and examining suspected samples of illuminating oils, and the State Board of Health shall be author- ized to expend, in addition to all sums already appropriated for said board, an amount not exceeding five thousand dollars for the purpose of carrying out the provisions of this act. And the sum of five thousand dollars is hereby appropriated, out of any moneys in the treasury not otherwise appropriated, for the purposes of this section as provided. 4. Naphtha and other light products of petroleum which will not stand the flash test required by this act may be used for illuminating or heating purposes only. In street lamps and open air receptacles apart from any building, fac- tory or inhabitated house in which the vapor is burned. In dwellings, factories or other places of business when vaporized in secure tanks or metallic generators made for that purpose in which the vapor so generated is used for light or heating. For use in the manufacture of illuminating gas in gas manufactories, situated apart from dwellings and other buildings. 5. It shall be the duty of all district-attorneys of the counties in this State to represent and prosecute in behalf of the people, within their re- spective counties, all cases of offenses arising under the provisions of this act. 432 QUANTITATIVE ANALYSIS. 6. Nothing in this act shall be so construed as to interfere with the pro- visions of chapter seven hundred and forty-two of the laws of eighteen hun- dred and seventy-one, as regards the duties of the Bureau of Combustibles of the city of New York, or any other statutes not conflicting with this act, provided that nothing in this act shall be deemed to interfere with or supersede any regulation for the inspection and control of combustible ma- terials in any city of this State made and established in pursuance of special or local laws or the charter of said city. 7. All acts or parts of acts inconsistent with this act are hereby repealed. 8. This act shall take effect sixty days after its passage. A very complete report upon the methods and apparatus for testing inflammable oils by A. H. Elliott, Ph.D., was ren- dered to the New York State Board of Health and incorpor- ated in their annual report for 1882. The grades of color of an oil are noted as standard white, prime white, superfine white and water white, 1 and the instrument generally used for determination of the color in oils, is the Stammer Color- imeter (Fig. 144). Tube /is closed at the bottom by a transparent glass plate, is open at the top, and a projecting lip on the side whereby the oil Fig. 144- to be tested can be poured in or out. The tube is fastened to the stand by two screws. The measuring tube /// is closed at the bottom by a colorless glass plate and is movable inside of tube /. The color-glass cube // which is joined firmly to the measur- ing tube ///, is open at the bottom and at the top contains a colored glass plate, which plate can be substituted with other tinted glass plates. The movement of the joined tubes //and ///is produced by inclosed racket work, the movement of the 1 In Bremen, the varieties are rated as, water white, prime white, standard white, prime light straw, light straw and straw. OILS USED FOR ILLUMINATION. 433 tubes being read on a scale on the back of the stand, and stated in millimeters. Since the color of a liquid is inversely propor- tional to the height of the column, which is necessary to give the standard color, and since this color is here expressed by 100, the absolute number for expressing the tone of color of any oil is obtained by dividing this 100 by the number of millimeters read off from the scale. For example : Millimeter scale = i. Color = 100.00 " =2. " = 50.00 " =7. " = 14.29 " =19- " = 5.26 The color, tone and thickness of the standard glass is so chosen that the scale shows the following values for the ordinary brands of illuminating oils. Standard white = 50.0 mm. Prime " = 86.5 " Superfine " = 199.5 " Water " = 300.00 " Wilson's calorimeter, largely used in England, is very similar in construction to the Sterner. 2. Vegetable and Animal Oils. The two principal oils of this class in use for illumination are colza and lard oil. In this country the former has never been used to any great extent, its use being confined principally to Europe, but lard oil and sperm oil, in former years, before the introduction of the petroleum products for this purpose, were largely used as illuminants. Except in railroad practice and then in yearly de- creasing amounts their use now is very limited in this direction. In the matter of illumination, the methods made use of by the railroads are worthy of study and comparison, and it is in a great measure due to the investigations carried out in their interests that the great advances in this direction are due. George Gibbs, mechanical engineer of the Chicago Milwau- kee and St. Paul Railroad, in a paper recently read before the Western Railroad Club of Chicago, states : There are about eight different means of car illumination ; viz., the use of 434 QUANTITATIVE ANALYSIS. i. Vegetable oils. 2. Candles. 3. Mineral or petroleum oils. 4. Ordinary coal gas. 5. Carburetted water gas. 6. Rich or oil gas. 8. Electric light. There are but four worthy of consideration. These are : First. Heavy mineral oils in lamps, such as mineral seal which ranges from 35 B. to 40 B. in gravity, has a fire test of 300 F. and gives off no inflammable vapor below 230 F. Second. The Pintsch oil gas. This is by far the most promi- nent attempt to devise any economical and practical gas-lighting system for railroad service. Its primary object is to reduce the bulk of stored gas necessary to produce an adequate illumina- tion for a considerable length of time. The Pintsch system has largely confined its attention to more efficient gas, which, it is claimed, is supplied by the use of a rich permanent oil gas. Ordinary city or coal gas when burned at pressure of the street mains, one to one and one-half ounces may be taken to give an illumination of, at most, four candles per cubic foot. Oil gas at the same pressure will give from four to six times as much, say sixteen candles per cubic foot. But one property of gas, which vitally affects the problem, is the loss of light-giving power upon compression and storage. This is true of all illuminating gas, and is due to the deposition of the rich oily hydrocarbons, but is not true to the same extent for oil and coal gas, the difference being materially in favor of oil gas. Reliable tests for this loss of light by compression have given the result that coal gas loses fifty per cent, and oil gas twenty-one per cent, of light-giving power upon compression of 300 pounds per square inch, and at 225 pounds per square inch pressure, the quantities required for equal illumination would be about as five of coal to one of oil gas. The material used for the manufacture of Pintsch gas is crude petroleum. The generation of gas is affected by vaporizing the oil at a high heat in suitably arranged cast iron retorts, the pro- cess of manufacturing being, on a small scale, essentially that followed for city gas. From the storage tank pipe connections lead to convenient places for filling the car tanks. A plant capable of making sufficent gas for 500 cars is contained in a OILS USED FOR ILLUMINATION. 435 one story building 26 ft. X 36 ft. The outfit on the cars consists of one or two cylinders for holding the compressed gas, a pres- sure regulator and a system of piping to the lamps. These are of special design, each having from four to six flames ar- ranged beneath a procelain reflector, the whole encased in a glass bell- jar ; ventilation is suitably provided for and a very steady light is obtained. Mention might be made here that an American system, the Foster, appeared a few years ago embodying the same principles and general features as the Pintsch. Third. The Frost Systems. In the Frost and all other simi- lar systems the principle is the same, being the property possessed by air of holding a vapor in intimate mixture and suspension, usually the vapor of gasoline. The amount of vapor absorbed depends upon its temperature; thus, at 14 above zero (F.), about six per cent, and at 68 F., twenty-seven per cent, will be taken up. This is, however, a mechanical mixture only and not a permanent gas. The vapor thus formed is capable of being burned similarly with gas, when mixed with air in the proper proportions, giving a highly luminous flame. This principle has been utilized for many years for making gas for household purposes in places where city gas is inaccessible, a simple form of air pump run by a falling weight forcing air under a few ounces pressure through a tank (generally under ground) which con- tains a barrel of liquid gasoline. This tank is divided into many compartments in which absorbent wicking is suspended, dipping into the liquid and drawing up the same by capillary attraction. The enriched air produced in this carburetter forms the gas for burning. The difficulties to be overcome in using this agent for safe car lighting are as follows : First, the presence of liquid gasoline. The Frost system overcomes this objection by filling the carburet- ting vessel almost completely with wicking and by merely satura- ting this with gasoline and drawing off the superfluous liquid. Second, the effect of variation of temperature in the amount of vapor absorbed by the air current. As above stated, in cold weather only a small percentage is absorbed, too little to produce a good light and in warm weather too much, producing a rich 436 QUANTITATIVE ANALYSIS. but smoky light. This is really the serious stumbling block to this system. The Frost system claims to overcome it by placing a small generator or carburetter above the light on the roof of the car, in such a manner that a portion of the heat generated by the burner is transmitted to the carburetter, insuring a uni- form temperature at all times. The system in detail consists of an air storage tank underneath the car, containing sufficient compressed air to supply light for six hours. This compressed air is obtained directly from the train pipe of the air brake and is led through a suitable pressure reducer and a regulator to the carburetters in the roof, one of these being placed over each lamp, and thence, after passing through them, to the lamps underneath. These are now con- structed on the Siemans or regenerative principle and give a brilliant white light without shadow. The supply of gasoline in the carburetters is sufficient for forty-three hours burning, and then can be recharged by filling from the roof. Fourth. The Electric System. The latest phase of train light- ing may be said to be the electric. In this direction numerous isolated experiments have been made in this country during the past five years. The different plans suggested for obtaining electric lighting are divided as follows : 1 . Primary batteries ; 2. Secondary batteries or accumulators ; 3. Dynamo machine connected to car axle, with or without accumulators as auxiliaries ; 4. Dynamo operated by special steam engine, either in a car or on the locomotive, and supplied with steam from locomotive or special boiler on a car : accumulators used or not, as desired, as equalizers. i. The first method has been tried in England on several rail- ways, and in France between Paris and Brussels. In all, a special form of primary battery having very low resistance, great surface, and furnishing a constant current at high pressure, was employed. The result was flat failures, on account of the enor- mous expense of the electrical energy furnished by chemical means. It can be said that in primary batteries chemicals are expended and zinc consumed, instead of coal under a boiler to OILS USED FOR ILLUMINATION. 437 produce energy ; at the lowest estimate, the former is forty times as expensive as the latter. 2. In England the London and Brighton railway made an extensive trial on a Pullman train of lighting by accumulators alone, placing batteries under each car, and having a sufficient number of charging stations, with boilers, engines and dynamos, to charge duplicate sets of batteries for immediate replacement. This system, after five years trial, was abandoned. In this country the Pullman Company gave the method a thorough trial on the Pennsylvania Railroad "Limited" between New York and Chicago, finally abandoning it. It was also tried and abandoned on the Baltimore and Ohio and Chicago, Burlington and Quincy. Description of this system may be dismissed by briefly stating that each car carries its own store of batteries in boxes hung underneath, arranged so that they can be readily removed at terminals for recharging by dynamo, or for substitution of fresh cells. The weight of batteries required for a standard coach is, approximately, one ton. 3. Third method. A favorite method for obtaining electricity at a low cost seems to have been to connect the dynamo to a car axle ; but the difficulties of obtaining regular motion and current and providing light when the train stops, have necessitated the employment of accumulators as regulators and auxiliaries. In these, automatic appliances are provided to cut off the current from the dynamo when the speed of the train falls below a cer- tain rate, and to deliver the current to the batteries in the same direction. The main difficulty, with this method, and one which the International Railway Congress states has not been solved satisfactorily, is the transmission of power from the axle to the dynamo. 4. The fourth method is the only prominent electrical one in this country for car lighting. It consists essentially in the use of a dynamo driven by special steam engine, with secondary batteries for reserve. The use of the method without the bat- teries as auxilaries has been often attempted without success, but recently by improvements made by Mr. Gibbs, the batteries are dispensed with and a system perfected that gives general satisfaction for the purpose. The plant in fact is made an exact QUANTITATIVE ANALYSIS. duplicate of stationary electric-lighting plants. The engine is a 15 horse-power Westinghouse automatic, the dynamo a 150 light Edison compound- wound, connection from one to the other being made by belting. In the summer season, when steam heat is not required for the train, this outfit is placed in the forward end of the baggage car, occupying twelve feet in the length of the car, but not obstructing passageway through it. Steam is taken, at sixty pounds pressure, from the locomotive boiler. In winter the drain upon the locomotive for steam heat is often ex- cessive ; to overcome this a special car for heating and lighting is used. Consult Engineering (London), January 5, 1894, for a complete description of this system as now used successfully on the Chicago, Milwaukee and St. Paul Railroad. Relative Advantages and Disadvantages of the Various Systems. The Electric may be considered adapted, in the present state of the art, to special service only. It fills a number of the re- quirements for a perfect light in a manner that no other light approaches ; it is cleanly, cool, safe, allows excellent distribution and is, in fact, a luxury which is duly appreciated by the public. It, however, is costly, and requires great attention to details; still, in many instances it will pay, and each manager must consider whether under his conditions its use is warranted. The Frost System is still in the process of development. It has many advantages from an outside point of view ; it is cleanly, the light is good, each car is perfectly independent of others for its supply of light, and it requires no external gas works. On the other hand the first cost is excessive ; the light is not cheap for running, its quality is not uniform due to the effect of vary- ing temperature and quality of gasoline the apparatus is com- plicated, and while the system may be considered safe to the car itself, the use of gasoline at various points on a large system is questionable. The Pintsch System. This, in spite of some defects, is probably the most feasible and promising method in the direction of safety car lighting. It is safe as any flame method of lighting can be, is cleanly and simple, and is cheap in maintenance and running. OILS USED FOR ILLUMINATION. 439 It is, however, very high iu first cost, and is not universally applicable on account of dependence upon gas works. But all main line traffic and many important branch lines can generally be provided for by this system at a moderate cost and under its rapid extension now taking place, it seems likely that gas works can be maintained by different roads at many points, to still further reduce the individual outlay. Oil Lighting by Lamps . Many of the requirements of a satisfac- tory car-lighting system appear to be embodied in the present oil system, or might be with some improvements which are readily attainable. In no system, with the exception of the electric, is it possible to obtain a better or more satisfactory distribution of light, the centers being of moderate intensity ; the fuel is safe to handle and may be obtained without delay ; each car is inde- pendent of the others ; it is cheapest in first cost and mainten- ance for a given amount of light ; it is simple and requires but little attention. On the other hand, it shares with flame systems the objections of giving out much heat ; the quantity of light is often irregular and the smell objectionable when proper care is not exercised. The possible improvements in this system should have more attention from railway officials. For instance, the button form of burners, of which the ' ' Acme' ' is a good example, appears to solve the problem of sufficient light as has been done in the other flame systems, and these burners should be substituted for the old uneconomical forms. 440 QUANTITATIVE ANALYSIS. aj tn a; t/j *~ o"o "CLOT'S jo }soo w w o 10 Smuanq sanon -jnoq aad as < g g" g g g < ^g Avod a^pnBD aad }so;> i d 6 o o o d o o o -dmba jo 8888888$ ! M M M 10 lOOO ro T3 VM c o rt a UBO JO Xpoq ui JBO jo Xpoq M N "?& o M \o v ni aauanq aaj M No. burn UBD IN N NVOVO TJ- 0^ Oi jo Apoq UI bne ers. ers u n rn hring plex bu me" bu Moc Du Ac il, ( il, ( il, s arbu rage a lectric, etted air nd direc , direct Colza oil Mineral oil, Mineral oil Mineral oil, Pintsch gas " Frost " ca Klect'c stor "Gibbs" el CN CO fl- UO^O t^CG XLVI. The Analysis of Lubricating Oils Containing Blown Rape- Seed and Blown Cotton-Seed Oils. Rape-seed oil has long been the standard oil in Europe for lubrication. Its constancy of viscosity at varying temperatures, its non-liability to acidity as compared with other seed oils, and its low cold test, unite in producing the results required of a good lubricant. It, however, is no exception to the rule that vegetable and auimal oils suffer partial decomposition when sub- jected to high temperature produced by friction, with the result that fatty acids are liberated and corrosion of bearings produced. The substitution of mineral oils in varying proportions with rape-seed oil has reduced this tendency, this reduction being determined by the percentages of mineral oil present, as the latter liberates no free acids. It is a peculiar fact, however, that a mineral oil alone does not give as satisfactory results in lubrication (especially cylinder lubrication 1 ) as does a mixture of mineral and vegetable or mineral and animal oils, one of the primary causes being that the viscosity of mineral oils rapidly diminishes at high tempera- tures, whereas the reduction of viscosity of vegetable and animal oils is very much less. If it were not for this peculiarity between these two classes of oils, mineral lubricating oils could easily supplant (on the score of cheapness) all other oils used in lubrication. The admixture of oils then being required for the better class of lubricants, it follows that in England where rape-seed oil has been the standard, its use should be continued in compounded oils. The proportion of rape-seed oil added to mineral oil varies from five to twenty per cent. Where the mineral oil is a clear paraffin oil twenty per cent, of the seed oil is used ; where the mineral oil is a dark, heavy oil, five per cent, is generally added. The separation and estimation of the rape-seed oil in these mixtures presents no difficulty to the analytical chemist when no other seed oil is present, since the saponification of the seed oil, 1 The Railroad and Engineering Journal, 64, 73-126. 442 QUANTITATIVE ANALYSIS. the separation of the fatty acids and recognition of the same are a part of the usual chemical work of this character. The recogni- tion of the constituents of a mixed lubricating oil by analysis is a very different problem from giving a formula by which the mixture can be made. This is evidenced as follows : Suppose the analysis shows Rape-seed oil, 20 per cent. Paraffin oil, 80 per cent. Paraffin oil varies in specific gravity from 0.875 to 0.921, and it is essential to include in the report of the analysis not only the amount of the paraffin oil but also the gravity, since paraffin oil of gravity 0.875 is a very different product from that of 0.921 gravity, the former selling at seven and one-half cents and the latter at twenty-three cents per gallon. This determination can be made by taking the gravity of the original mixed oil (0.912), then knowing by the analysis that twenty per cent, is rape-seed oil (gravity 0.918), the gravity of the eighty per cent, of paraf- fin oil is easily calculated. Thus : x = specific gravity of rape-seed oil (0.918) y = specific gravity of paraffin oil x = 20 per per cent, or \ y = So per cent, or f Then i x -\- f y = 0.912 0.183 ~\~ \y = 0.912 1^ = 0.729 y = 0.910 The mixture being composed, therefore, of Paraffin oil (sp. gr. 0.910), 80 per cent. Rape-seed oil (sp. gr. 0.918) 20 per cent. The direct determination by analysis from the ether solution of the mineral oil in the mixture does not give an oil of the same specific gravity as the mineral had before it was mixed with the seed oil. This can be accounted for by the volatilization of a portion of the lighter hydrocarbons of the mineral oil when the ether is expelled during the analysis. For this reason the determination of the percentage of seed oil and the calculation of the mineral oil offers less liability to failure than finding the mineral oil directly. The introduction of blown rape-seed oil instead of the normal ANALYSIS OP LUBRICATING OILS. 443 rape-seed oil complicates the investigation and renders the use of the formula above given, valueless. Rape-seed oil has a grav- ity of 0.915 to 0.920. Rape-seed oil blown has a gravity of from 0.930 to 0.960. Two difficulties are immediately presented : ( i ) The chemical analysis does not indicate whether the rape-seed oil is blown or not ; (2) The use of the formula given without the correct grav- ity of the blown oil would give false results regarding the par- affin oil. To overcome this difficulty some synthetical work is required. Suppose the specific gravity of the mixed oil is 0.922 and the analysis shows twenty per cent, of rape-seed oil. It will be nec- essary then to produce a mixture in these proportions that will duplicate the original sample. A check upon this will be the viscosity of the original sample as compared with the one to be made by formula. Thus : The original oil has a gravity of 0.922, contains (by analysis) twenty per cent, of rape-seed oil, and has a viscosity at 100 F. of 335 seconds (Pennsylvania Railroad pipette). First. Make a mixture of paraffin oil (sp. gr. 0.910) gen- erally used in this character of lubricant, eighty per cent., and rape-seed oil (unblown) twenty per cent. The viscosity is 165 seconds, showing that this mixture cannot be used in place of the original oil. Second. Make a mixture of paraffin oil (sp. gr. 0.910) and rape-seed oil partially blown, (sp. gr. 0.930) in the same propor- tions as above. The resulting viscosity is 267 seconds, showing that the compound is still lacking in viscosity. Third. Make a mixture of paraffin oil (sp. gr. 0.910) eighty parts, and rape-seed oil, blown (sp. gr. 0.960), twenty parts. The viscosity is 332 seconds. This now fulfills the conditions required and the synthetical sample agrees with the original in gravity, composition and viscosity. The use of blown rape-seed oil is being gradually re- placed by blown cotton-seed oil. The latter, which has had but a limited use in lubrication, owing to its liability to acidity, has been greatly improved by this process of " blowing," 444 QUANTITATIVE ANALYSIS. which is nearly complete oxidation of the oil under comparatively high temperature. This largely prevents the occurrence of the acidity in the oil, and thus the main objection to its use in lubrication disappears. It is much cheaper than rape-seed oil, since it costs thirty cents per gallon, to sixty cents per gallon for the latter. The chemical reactions of the two oils are very similar, and careful analytical work is required that the chemist be not misled. The following table of comparisons will indicate this : SPECIFIC GRAVITY. Cotton-seed oil 0.920 to 0.925 Rape-seed oil -9^5 to 0.920 Blown cotton-seed oil 0.930 to 0.960 Blown rape-seed oil 0.930 to 0.960 VISCOSITY (PENNSYLVANIA RAILROAD PIPETTE) AT 100 F. Seconds. Cotton-seed oil (sp. gr. 0.925) 162 Rape-seed oil (sp. gr. 0.918) 210 Blown cotton-seed oil (sp. gr. 0.960) 2143 Blown rape-seed oil (sp. gr. 0.960) 2160 HEIDENREICH'S TEST. Before stirring. After stirring. Cotton-seed oil Faint reddish brown Brown. Rape-seed oil Yellow brown Brown. MASSIE'S TEST. Cotton-seed oil Orange red. Rape-seed oil Orange. IODINE ABSORPTION. Cotton-seed oil 104 to 1 14 Blown cotton-seed oil 93 to 103 Rape-seed oil 102 to 108 Blown rape-seed oil 94 to 100 In the comparison of the two oils, when not mixed with a mineral oil, the above tests can be used. The conditions are altered, however, when either one or both are so mixed, since these tests apply only to the pure oils and not to those reduced with large percentages of mineral oil. After the separation of the seed oil from the mineral oil by saponification the identifica- tion of the seed oil depends upon the reactions of the fatty acids obtained, and a careful examination and comparison of these ANALYSIS OF CYLINDER DEPOSITS. 445 reactions shows that the melting points have the greatest differ- ence and thus become a means of recognition. Thus, the fatty acids from rape-seed oil melt at 20 C., and from cotton-seed oil at 30 C. Hence, if upon analysis of a lubricating oil under above conditions, the fatty acids obtained show a melting point of 20 C. the seed oil can be pronounced rape-seed oil. If the melting point is between these limits, say 23 C., the seed oils are present in a mixture, the proportions of which can be determined by the following formula : w l = proportion of rape-seed oil. Z/ a = proportion of cotton-seed oil. zt/ 3 = weight of mixture ( 20 per cent. ) ^ = temperature of melting point of fatty acids of rape-seed oil. /j = temperature of melting point of fatty acids of cotton-seed oil. t^ = temperature of melting point of mixed fatty acids. Then w l =w a * f ~~** /! t, Inserting the value : zu. = 20 2 3 3 _ j^ p er cen t. 2030 w., = 20 ^ = 6 per cent. 3020 Or, Paraffin oil .................................... 80 per cent. Rape-seed oil .................................. 14 per cent. Cotton-seed oil ................................ 6 per cent. Total ......................... loo per cent. By synthetical work upon these proportions, with comparison of viscosities of the sample submitted with the product, the re- sult will be not only a correct analysis, but a working formula can be given by which a manufacturer can duplicate the origi- nal oil. XL VII. The Analysis of Cylinder Deposits. The deposits in steam cylinders, formed by the decomposition of lubricating oils, may be classed as simple or compound, de- 446 QUANTITATIVE ANALYSIS. pending upon whether the deposit is due to the decomposition of the oil alone or if foreign matters, carried over in the steam from the boilers, are also present. In the. former case, carbon, hydrocarbons, oils and iron oxide are the principal constituents, whereas, inthelatter, oleate of lime, carbonate of lime, and silica are often present in addition to the former. The following analysis of a sample from a locomotive cylinder would indicate a simple deposit. Moisture 2.28 per cent. Animal I o54 ' ' einether I Mineral 11.23 Hydrocarbons insoluble in ether 47-97 Fixed carbon 23.73 FeO 2.83 Undetermined 1 .42 Total loo.oo " And the one given below, of a deposit from the steam cylinders of a large stationary engine, would show that scale-forming mate- rial from the boilers had become a component. Moisture 13.12 per cent. /Animal 8.15 Oils soluble in ether j Mineral 7>86 . , Soap. 2.10 " Hydrocarbons insoluble in ether 1.67 " Fixed carbon 2.71 " Oxides of Iron and aluminum 6.81 " Si0 2 3-65 CaCO 3 43.22 MgCO 3 10.17 Undetermined 0.44 ' ' Total loo.oo " In many samples I have found copper and zinc in the de- posits, formed by the corrosive action of the liberated oleic acid from the animal oil upon the brass or composition bearings. This corrosive action is very marked where a poor quality of lubricating oil, composed of animal or vegetable oil, is used, whereas, a pure neutral mineral oil has no acid action at steam ANALYSIS OF CYLINDER DEPOSITS. 447 temperature. Oftentimes the statement has been made to me, when the deposit was given for analysis, "All of our lubricating oil is pure mineral oil; we use no other." And yet, upon analysis, lard oil would be shown in comparatively large amounts. This is accounted for from the fact that while the consumer believes he is using pure mineral oil which was sold to him as such the manufacturer has introduced from three to thirty per cent, of lard or cotton-seed oil. A large majority of the so-called " pure mineral" lubricating oils for cylinder use contain at least five per cent, of animal oil ; and it is the exception and not the rule to find a ' ' pure mineral" oil for cylinder lubricating purposes. An analysis of a deposit from the steam cylinder of a large freight steamer gave as a result : Moisture 16. 16 per cent. (Castor oil 26.19 " Oils soluble in ether ( Mineral ^^ Fixed carbon 7.92 " CuO 0.50 FeO 25.10 " Undetermined 1.63 " Total 100.00 " Pure mineral lubricating oil was supposed by the officers of the vessel to be the only lubricant used, and special care had been taken to secure it, but it appears that the engineer added a small amount of castor oil to the mineral oil, as, in his opinion, it made a better lubricant. The decomposition of the castor oil and liberation of the fatty acids was the primary cause of the deposit. The action of the fatty acids upon the iron and metal bearings results in different products. That is to say, while the copper when present has generally been estimated as copper oxide the iron may exist only as oxide or as metallic iron, or both. No doubt the oleic acid acts to form salts of these metals, but it is certain, in many instances, that when formed, they are immediately decomposed or partially so, and a resulting mixture formed that is somewhat difficult of analysis. 448 QUANTITATIVE ANALYSIS. Fig. 145. ANALYSIS OF CYLINDER DEPOSITS. 449 In the analysis here given, it will be noticed that the iron was found both as metal and as oxide. Moisture 3.77 per cent. (Animal 21.27 " Oils soluble in ether { Mifleral ig ^ Soap traces Fixed carbon 10.90 " FeO 14.01 " Fe 27.85 PbO 0.82 CuO 1.07 " Undetermined 0.71 " Total loo.oo ' ' The evolution of hydrogen by hydrochloric acid, from the de- posit, after all the oils andfatty substances had been removed, indi- cated the presence of metallic iron, and the analysis jf the resi- due, after the combustion of the fixed carbon, gave figures by which the ratio of iron and iron oxide could be determined. A portion of the deposit, after extraction of oils by ether, 1 is dried, then weighed, the hydrocarbons driven off by heat, and the amount of fixed carbon present converted by combustion with sulphuric acid and chromium trioxide into carbon dioxide and weighed, this weight being calculated back to carbon. Another portion of the same residue is ignited in a platinum crucible until the carbon is all consumed, then weighed. If the amount of carbon found is small and iron large, this weight may be larger than the original weight of the residue taken, owing to oxidation of metallic iron to ferric oxide. Knowing the weight of carbon, and by making a determina- tion of iron in another sample before ignition, the amount of iron oxide is easily found. 1 The Soxhlet apparatus as shown in Fig. 145 is well adapted for this purpose. O O. u 'o c f g 11 8 i *t * o <" . I"- a c 41 fl "c in S bo a - ^S-ajj . - sil "If -- ' 'V3'v d QJ 5 rt a ff O U -t a* 2 |I B 3 o' OQ'^ 3 OQ'g. a ' o a j^: a> PJ H-^. o * = i? if. M e Q 9 2 a f B- 1 8 5- 5 . CTQ B* B* * g. > ro JIL. o . J? fH > QL, S 808 cr S. CO n n> r co *5* BT r o rt O O 3 rt 458 QUANTITATIVE ANALYSIS. Occasionally the following determinations are made : Water. Hygroscopic. Heat one-half gram at 105 C, in an air-bath to constant weight. Volatile Matter. Heat one gram in a porcelain crucible to low redness ; loss, less water, is volatile matter. Water Extract. (Acetates, sulphates, bichromates, or nitrates, indicating imperfect washing in manufacture.) Treat three grams with six successive portions of twenty-five cc. each, of cold distilled water, decanting and filtering each time, and evaporate the filtrate in a platinum dish to dryness on a water-bath. Analysis of Mixed Chromate, Sulphate and Carbonate of Lead . (Lemon, Chrome and White Lead.) Analysis made same as in scheme for Lemon Chrome ; excess of lead is to be calculated to white lead, 2PbCO 3 +PbH 2 O 2 . Analysis of Red Chr ornate of Lead? For the lead determination take one gram in a covered casser- ole, add twenty-five cc. concentrated nitric acid, heat to boil- ing, and while boiling add half a dozen drops, one at a time, of alcohol, by means of a pipette ; boil a while longer, add water, and all of the chromate, if it is pure, will be found in solution. Without this alcohol treatment great difficulty will be experi- enced in getting the chromate into solution ; with it, it becomes very easy. Add twenty-five cc. concentrated sulphuric acid, evaporate to white fumes and complete the analysis as described. For chromium and sulphur trioxide determinations, boil off alco- hol and proceed as previously directed. 1 Known by various names, as scarlet, dark or basic chromate of lead, chrome red, Chinese red, American vermilion and vermilion substitute. Formula : 2PbO.CrO 3 or PbCrO 4 + PbO. = jjjt cfq' . O *d re 5 "** * _:p*cr 5|8|| ^S re p^- ^ HfiKi r,.0 rc ETC 2. p n> n> co H-> P 'Q. Ocrrt> 2 ~- r B X T'rti P* 2. ght 3 ff Ji o C. fs cr.^ 53 S-g. o O If 2 3 O) & o B ^ 460 QUANTITATIVE ANALYSIS. Chrome green, in which the coloring matter is Cr 2 O 3 , is sel- dom found in the market pure. Usually it contains from twenty per cent, to seventy-five per cent, of barium sulphate. As an example of specifications for a compound chrome paint, the following is given : PENNSYLVANIA RAILROAD COMPANY. MOTIVE POWER DEPARTMENT. Specifications for Cabin Car Color. The standard cabin car color is the pigment known as scarlet lead chromate. It is always purchased dry. The material desired under this specification is the basic chromate of lead (PbCrO 4 PbO), rendered brilliant by treatment with sulphuric acid and as free as possible from all other substances. The theoretical composition of basic lead chromate is nearly 59.2 per cent, of the normal lead chromate, and 40.8 per cent, of lead oxide, but in the commercial article it is found that a portion of the sulphuric acid added to brighten the color remains in combination apparently with the normal lead chromate, slightly increasing the percentage of this constituent. Samples showing standard shade will be furnished on application, and shipments must not be less brilliant than sample. The comparison of sample from shipment with the standard shade, may be made either dry or by mixing both samples with oil. Shipments of cabin car color will not be accepted which 1. Contain barytes or any other adulterant. 2. Show on analysis less than fifty-seven per cent, or more than sixty per cent, of normal lead chromate, including the sulphuric acid combined as above stated. 3. Show on analysis less than thirty-eight per cent, or more than forty- two per cent, lead oxide, in addition to the lead oxide in the normal lead chromate. 4. Vary from standard shade. Office of Gen. Supt. of Motive Power, Altoona, Pa., Feb. /, 1891. The various red paints, Indian red, Tuscan red, and other iron oxides, etc., used in general practice are rarely pure, but contain added amounts of finely pulverized gypsum and calcium carbonate. These oxides, when properly ground and mixed with linseed oil, form paints that cannot be excelled for dur- ability, permanence of color and cheapness. Many of the mix- tures contain varying amounts of japans, but as the japans have been subject to great sophistications of late years, specifications now generally call for linseed oil, turpentine and pigment only. PAINT ANALYSIS. 461 Thus, two varieties of paints might be roughly classified as : (i) Paints for wood work, and (2) paints for iron work. The following specifications refer to class i : PENNSYLVANIA RAILROAD COMPANY. MOTIVE POWER DEPARTMENT. Specifications for Freight Car Color. Freight car color will be bought in the paste form, and the paste must contain nothing but oil, pigment and moisture. The proportions of oil and pigment must be so nearly as possible as fol- lows: Pigment seventy-five per cent, by weight. Oil twenty-five per cent, by weight. The oil must be pure raw linseed oil, well clarified by settling and age. New process oil is preferred. The pigment desired contains not over one-half per cent, of hygroscopic moisture, and has the following compo- sition : Sesquioxide of iron, fifty per cent, by weight. Fully hydrated calcium sulphate or gypsum, forty-five per cent, by weight. Calcium carbonate, five per cent, by weight. Samples of standard pigment showing shade will be furnished, and shipments will be required to conform with the standard. The shade of paint being affected by the grinding, the Pennsylvania Railroad standard shade is that given by the dry sample sent, mixed with the proper amount of oil and ground, or better rubbed up in a small mortar with pestle until the paste will pass Pennsylvania Railroad test for fine grinding. It is best to use fresh samples of the dry pigment for each day's testing. The comparison should always be made with the fresh material, and never with the paint after it has become dry. The com- parison is easiest made by putting a small hillock of the standard paste and of that to be compared near each other on glass, and then laying an- other piece of glass on the two hillocks, and pressing them together until the two samples unite. The line where the two samples unite is clearly marked if they are not the same shade. The paste must be so finely ground that when a sample of it is mixed with half its weight of pure raw linseed oil, and a small amount of the mixture placed on a piece of dry glass, there will be no separation of the oil from the pigment for at least half an hour. The temperature affects this test, and it should always be made at 70 F. The sample under test runs down the glass in a narrow stream when it is placed vertical, and it is sufficient if the oil and pigment do not separate for an inch down from the top of the test. Shipments will not be accepted which 1. Contain less than twenty -three per cent, or more than twenty-seven per cent, of oil. 2. Contain more than two per cent, of volatile matter, the oil being 462 QUANTITATIVE ANALYSIS. dried at 250 F., and the pigment dried in air not saturated with moisture at from 60 to 90 F. 3. Contain impure or boiled linseed oil. 4. Contain in the pigment calcium sulphate not fully hydrated, less than forty per cent, of sesquioxide of iron, less than two percent, or more than five per cent, calcium carbonate, or have present any barytes, ani- line colors, lakes, or any other organic coloring matter, or any caustic substances, or any makeweight or inert material which is less opaque than calcium sulphate. 5. Varying from shade. 6. Are not ground finely enough. 7. Are a " liver " or so stiff when received that they will not readily mix for spreading. Altoona, Pa., Office Supt. Motive Power. As an example of the composition of a paint for iron surfaces (Class 2) the following mixture as used for pain ting the structure of the elevated railroads in New York City is given : ! Boiled linseed oil 9 parts. Red oxide of iron finely ground y| ' ' Turpentine i part. In mixing paints for iron surfaces, it is of the first importance that only the best materials be used. Linseed oil is the best medium, when free from admixture with much turpentine. The large percentage of linolein formed in drying, makes the surface of the paint solid and of a resinous appearance, possess- ing toughness and elasticity. Linseed oil does not crack or blister, by reason of the expansion and contraction of the iron with variation of temperature. Another important characteris- tic is its expansion while drying, which adapts it to iron sur- faces. The Metropolitan Elevated Railway Company experi- mented very thoroughly with the various kinds and colors of paints ; their labors at last culminated in the selection of a metallic paint for the first coat (formula given above) and a white lead paint for the second and last coat, both paints to contain the best linseed oil and enough turpentine to make the paints cover well and facilitate their drying. The formula of the white lead paint as used is here given : 1 On the Construction of the Second Avenue Line of the Metropolitan Elevated Rail- way of New York. By G. Thomas Hall, C.E., Trans. Am. Soc. Civil Eng., 10, 130. PAINT ANALYSIS. 463 WHITE LEAD PAINT. OUVE COLOR. 147.42 kilograms white lead. 79.38 *' lime (CaSO 4 ). 34.02 " French ochre. 1.36 " Prussian blue. 0.45 " burnt umber. 79.50 liters boiled linseed oil. 5.67 " turpentine. 3.79 " liquid drier (boiled linseed oil and lead oxide). Some engineers prefer red lead instead of iron oxide as the pigment for paints to be used for iron structures. G. Bouscaren, C.E., states with regard to the painting of bridges, that having used both varieties of paint, he gives prefer- ence to the red lead. 1 The red lead paint adheres better to the iron and fails princi- pally by wear and a gradual transformation of the red lead into carbonate, whilst the iron paint fails by scaling. Asphalt Paint. Until within quite recent years little has been known in this country of the valuable properties of the asphalt. In the popu- lar mind it is often confused with certain coal-tar products, which, though similar in appearance, differ essentially from asphalt in character. Asphalt oils are of a nearly non-volatile nature, and are therefore permanent, while on the other hand, coal-tar is volatile. The so-called asphalt paints which have been used in the past are such only in name. They contain, at best, but a very small per cent, of asphalt, which is incorporated in the form of a pigment and which serves no valuable purpose. Asphalt, on the contrary, should be the main constituent, since the value of such a paint depends upon the presence of the permanent asphalt oils. 2 Fire Proof Paints, Silicate Paints, Asbestos Paints, etc. The principle of action of these paints is not to render wood work or similar material fire proof, but to retard combustion. Wood treated with a solution of zinc chloride, or with a solu- 1 Trans. Amer. Soc. Civil Engineers, 15, 429. 2 Am. Eng. and R. R. Journal. 65, 185. 464 QUANTITATIVE ANALYSIS. tion of sodium silicate, can be rendered nearly non-inflammable, and after such treatment and drying, paint can be applied. Instead of using the ordinary paints for this purpose, various compounds are incorporated in the paint itself to render the lat- ter non-inflammable. Thus the preparation of Prof. Abel J. Martin, of Paris, is as follows : Boracic acid, borax, soluble cream of tartar, ammonium sul- phate, potassium oxalate, and glycerine mixed with glue and incorporated with a paint. It is the result obtained after many experiments in response to a prize of 1000 francs, offered by the Society for the Advancement of National Industry of France. A committee consisting of Professors Dumas, Palaird and Troost, after testing the materials, consisting of painted woods and various fabrics, for seven months, reported in favor of this prepa- ration. The municipality of Paris made its use obligatory in all of the theatres there and it has stood the test of the last six years. Blue Pigments. Ultramarine beinga silicate, can be analyzed by Scheme XIV, page 37. COMPOSITION OF UI/TRAMARINE. SiO 2 49 ' 68 per cent. A1 2 8 23.00 S 9-23 SO 3 2.46 Na,0 12.50 H 2 3.13 Total 100-00 " COMPOSITION OF COMMERCIAL PRUSSIAN BI,UE. A1 2 O 3 2. 45 per cent. Fe 2 O 3 3.31 CaSO 4 -r-SiO 2 89-86 CN-fS 4.11 H 2 0-27 " Total 100.00 " COMPOSITION OF SMAI/TS. SiO 2 56.4 percent. A1 2 H 3-5 Fe 2 8 4.1 CoO 16.0 CaO 1.6 K 2 13.2 PbO 4.7 Total -.... 99.5 PAINT ANALYSIS. 465 Examination of the Oil after Extraction from the Paint. The only adulterants used in linseed oil, in this connection, are mineral oil and rosin oil. Their method of detection and estimation is given on page 414. Turpentine, when present, is not an adulterant, and a mixture, extracted from a paint, may contain linseed oil, mineral oil, rosin oil, turpentine, and rosin spirit. 1 The latter is quite dis- tinct from rosin oil and when properly prepared is a perfect sub- stitute for turpentine. If the liquid extracted from the paint is a mixture of linseed oil, turpentine, and rosin spirit the deter- mination of the amounts of each is somewhat difficult. Turpentine can be distinguished and determined in the pres- ence of rosin spirit by the action of the former on polarized light, rosin spirit being inert. Thus : the specific rotation of American turpentine varies between +8.8 to +21.5. The bro- mine absorption is also an indication : The bromine absorption of turpentine varies between 203 and 236 . The bromine absorption of rosin spirit varies between 1 84 and 200. The determination of the amounts of petroleum naphtha and turpentine in a mixture can be made by the method of H. H. Armstrong,/. Soc. Chem. Ind., i, 480; consult also Allen, Com. Org. Anal., 2, 48-50. References : " How to Design a Paint." By C. B. Dudley, Railway and Eng.J., 65, 174, 318. " On the Analysis of White Paint." By G. W. Thompson,/. Soc. Chem. Ind., 15, 432. " Detection of Rosin and Rosin Oil in Oils and Varnishes." By F. Ulzer, Ibid, 15, 382. "Technical Analysis of Asphaltum." By L. A. Linton, /. Am. Chem. Soc., 1 6, 809. " Rustless Coatings for Iron and Steel, Galvanizing, Electro-Chemical Treatment, Painting and Other Preservative Methods." By M. P. Wood, Trans. Am. Soc. Mec. Eng., 16, 1895, 350-450. " Preservative Coatings for Iron Work." By A. H. Sabin and A. O. Powell, Engineering News, Feb. 5, 1895, p. 86. " Chemische Operationen der Analyse von Farbstoffen." By F. Schmidt, Mitth. Malerei, 9, 121. " Chemistry of Paints and Painting." By A. H. Church. London, 1892. " Pigments, Paints and Painting." By G. Terry. London, 1893. 1 Coal tar naphtha has an extended use in the preparation of varnishes : the use of it in paints, however, is very limited. 466 QUANTITATIVE ANALYSIS. XLIX. Pyrometry. Pyrometry, or the art of measuring high temperatures, has received, in the past few years, considerable attention from en- gineers and metallurgists. This is especially so in the direction of metallurgical engi- neering, where, more uniform methods of heating and controlling heat have developed. In many processes of melting, refining, tempering, etc., certain temperatures are required, from which, should much variation occur, the products would be ruined. Many forms of pyrometers have been invented, but only a very few have accomplished their purpose. Many are admirable in design and construction, and prove accurate and trustworthy in the laboratory, but fail utterly when applied in practice at high temperatures. Pyrometers may be classified according to the principles upon which they operate : l 1. Expansion of mercury in a glass tube. When the space above the mercury is filled with compressed nitrogen and a specially hard glass is used for the tube, mercury thermometers can indicate correct temperatures to 1000 F. 2. Contraction of clay, as the Wedgew r ood pyrometers; very inaccurate as the contraction of the clay varies with the compo- sition of the clay. 3. Expansion of air, as in the air thermometer, Siegert's pyrometer, Wiborgh's pyrometer, Uehling & Steinbart's pyrom- eter, etc. 4. Pressure of vapors, as the Spannung's pyrometer, or the Bristol recording thermometer. 5. Relative expansion of two metals, as Brown's or Buckley's pyrometers. 6. Specific heat of solids, as iron-ball, copper-ball, or plati- num-ball pyrometer. 7. Melting-point of metals, alloys, etc. 8. Time required to heat a weighed quantity of water a water pyrometer. 1 Engineering News, 34, 322 (Nov. 14, 1895). PYROMETRY. 467 9. Increase in temperature of a stream of water or other liquid flowing at a given rate through a tube inserted into the heated chamber, as the Saintignon pyrometer. 10. Changes in the electric resistance of platinum or other metal, as in the Siemen's pyrometer. 11. Measurement of an electric current produced by heating the junction of two metals, as in the L,e Chatelier pyrometer. 12. Dilution of a stream of hot air or gas flowing from a heated chamber by cold air, and determination of the temperature of the mixture by a mercury thermometer, as in Hob- son's hot-blast pyrome- ter. 13. Polarization and refraction, by prisms and plates, of light radiated from heated surfaces, as in Mesure and Noel's op- tical pyrometer. The standard of refer- ence for all temperatures above 212 F. is the air thermometer and all py- rometers are usually standardized by compar- ison with it. The various forms of air thermometers are de- scribed by Prof. R. C. Carpenter in Engineer- ing News, Jan. 5, 1893. The air pyrometer of Messrs. A. Siegert and W. Duerr, Fig. 146, consists of a porce- lain cylinder connected by a thin copper tube with the meas- uring portion of the apparatus. This consists of a bell of sheet brass, the lower edge of which dips into a bath of petroleum. Fig. 146. 468 QUANTITATIVE ANALYSIS. The bell is attached to one arm of a balance beam, a counter- poise being carried by the other arm. The porcelain bulb being heated to the temperature to be measured, the air it contains expanding enters the brass bell, lifting this and moving the beam. The movement is shown on a scale and the temperature read direct from the divisions, into which the scale is divided. ( Consult Jour. Iron and Steel Inst., 1893, P. 340- Wiborgh's air pyrometer is fully described in Trans. Ant. Inst. Mining Eng., 21, p. 592. Hobson's hot-blast pyrometer is largely used for measuring Fig. 147. the temperature of the blast in hot-blast iron furnaces. It con- sists of a brass chamber having three arms and a handle, Fig. 147. An opening through a jet in one of the arms admits the hot blast, another arm admits atmospheric air, while the third arm is for the discharge of the mixture. To this third arm is at- tached a thermometer which indicates the temperature of the mixed current. A thermometer is also attached to the arm ad- mitting the atmospheric air. PYROMETRY. 469 This pyrometer can be used constantly to 2000 F., without danger of injury. Bristol's recording thermometer gives a continuous graphical record of temperatures up to 600 F. It consists of a copper coil which takes the place of a bulb and is inserted in the heated space. The bulb is partly filled with alcohol, which is partly vaporized by the heat. The pressure of the vapor is transmitted through a fine flexible copper tube, filled with alcohol, to any convenient distance not exceeding twenty- five feet, where it is measured by a recording pressure gauge. The interior of the gauge contains a flat Bourdon spring coiled into three complete coils. The movable end of the spring car- ries a pointer, which contains an inking pencil at its outer end. The clock-work revolves a paper chart once in twenty-four hours, and the marker thus makes a continuous record. The metallic pyrometer of Brown or Bulkley's form consists of the well-known copper and iron tube, and is based on the principle of the difference of expansion between copper and iron. An iron tube is encased loosely in a copper tube, the two being connected at one end. At the other end the exterior tube is connected to the casing of a graduated dial and the inner tube to a multiplying gear, which multiplies the relative motion of the free ends of the tubes and moves a rotating pointer on the dial. Temperature, higher than 1500 F., cannot be accurately measured with this instrument. The Copper- Ball or Platinum- Ball Pyrometer. If a weighed piece of metal, such as iron, copper, or platinum, be allowed to remain in a furnace or heated chamber till it acquires the tem- perature of the chamber and then be suddenly taken out and immersed in a vessel containing a quantity of water of known weight and temperature, the resulting increased temperature of the water may be used as a measure of the temperature of the ball when it was withdrawn from the furnace. A modification of the Weinhold pyrometer by Schneider is shown in Fig. 148. The calorimeter proper g, is surrounded by the containing vessel /, of sheet lead ; the space between and m is filled with 470 QUANTITATIVE ANALYSIS. air but conduction at p is reduced by a layer of paste-board. The cover d admits the thermometer t, the upright rod w, con- nected with the paddler r, is kept in motion by speed imparted to the wheel v. In practice the heated ball k is dropped through a, at the same instant c closes, and k falls into the wire net /. After thorough agitation of the water by r, the maximum rise of temperature of the water is taken. Let W= the weight of the water, w = weight of the ball, / = the original and T the final temperature of the water, and ,S the Fig. 148. specific heat of the metal, then the temperature of the heated chamber may be found from the following formula : Tt s T In practice many precautions are required. The metal ball should be enclosed in a small crucible, or other casing while in the furnace and until the instant the ball is dropped into the water, in order to avoid loss by radiation during the transfer from the furnace to the water; the water should be stirred PYROMETRY. 471 rapidly in order to cool the ball as quickly as possible ; the " water equivalent" of the heat-carrying capacity of the vessel containing the water should be carefully determined and added to the actual quantity of water used, to obtain the corrected value of W in the formula. Finally for scientific determinations, the actual specific heat of the metal ball should be carefully determined. The specific heat of metals generally increases with the temperature ; thus the specific heat of wrought iron, according to Petit and Dulong is 0.1098 from 32 to 42 F., and 0.1255 fr m 3 2 to 662 F. The specific heat of copper is 0.094 Fig. 149. from 32 to 212 F., and 0.1013 from 32 to 572 F. The mean specific heat of platinum between 32 and 446 F. is 0.0333, an( i it increases 0.0003 f r each increase of 100 F. For complete instructions regarding the use of the platinum ball for determin- ing high temperatures consult Trans. Am. Soc. Mech. Eng., 6, 702. The use of pyrometers dependent upon the melting point of alloys is extremely limited. The Seger Fire Clay Pyrometer which is included in this classification is fully described by H. M. Howe, in the Engineering and Mining Journal, June 7, 1890. A pyrometer dependent upon increase of the temperature of a 472 QUANTITATIVE ANALYSIS. stream of water flowing through a tube in the heated chamber is shown in the Saintignon pyrometer Fig. 149. Through the tube a enters a regulated stream of water, the temperature of which is measured by the thermometer /. The water passes through the heated oven o by means of the copper tube d and the increase of temperature is indicated by the ther- mometer T; from thence by the tube/^ to the manometer m and then through n it leaves the pyrometer. A water-current pyrometer invented by Carnelly and Burton is fully described in "Grove and Thorp's Chemical Technology," J > 342. Of the electrical pyrometers, four have had an extended use; viz; Siemen's pyrometer, the electric pyrometer of Prof. Braun, the thermo-electric pyrometer of Le Chatelier, and the Simond's thermo-electric pyrometer. A description of the Siemen's electric pyrometer will be found in Proceedings Royal Soc., 1886, p. 566. This pyrometer has been superseded by the Le Chatelier py- rometer. Prof. Braun' s Electric Pyrometer. The principle of its action is based upon the electrical resis- tance of platinum wire when exposed to high temperatures. The platinum wire is in a long fire-proof tube and is wound upon a fire-clay cylinder free from induction. It forms a part of a Wheatstone's Bridge which in connection with a sensitive galva- nometer permits the resistance to be measured rapidly and con- veniently and the corresponding temperature is directly obtained. The measuring apparatus proper is contained in a box (Fig. 150) so constructed that only the parts to be handled are visible, while the battery is placed in a separate compartment. The necessary manipulations are very simple. After the pyrometer has been placed in the heated chamber and the connection made with the measuring apparatus, the lever in the latter is turned forward to close up the circuit with the batteries and galvanometer. Then the graduated arc must be so placed that the pointer of the galvanometer (Fig. 151) is at zero, when the index on the arc (Fig. 150) will indicate at once the temperature of the pyrometer in degrees centigrade. PYROMETRY. 473 The distance between the pyrometer and the measuring apparatus may be quite considerable, twenty-five to thirty feet. Measurements are considered accurate up to 1500 C. Lt Chatelier's Thermo- Electric Pyrometer. When wires of two dissimilar metals or alloys are placed in contact with each other and highly heated at the point of con- Fig. 150. tact, an electric current is generated, the strength of which varies with the temperature, and may be indicated by a galvanometer. The pyrometer consists of a thermo-electric couple of two wires, one of pure platinum and the other of platinum alloyed with ten per cent, of rhodium and are connected with a D'Arsonaal gal- vanometer. The couple is inserted into the furnace or oven whose tempera- ture is to be measured, and the current is led by wires to the galvanometer placed at any convenient distance from the couple. 474 QUANTITATIVE ANALYSIS. The instrument is capable of measuring very high temperatures. A complete description of this pyrometer, by H. M. Howe, is given in Trans. Am. Inst. Min. Eng., 24, 746. The Mesure and Nouel pyrometric telescope is fully described in the Engineering and Mining Journal, June 7, 1890. The Uehling and Steinbart pneumatic pyrometer represents Fig- 151. the latest advances in pyrometry and is having an extended use in iron blast furnace work. This instrument Figs. 153, 154, 155, is designed especially for continuously indicating high temperatures, for making an auto- graphic record of the heat conditions, and is based on the laws governing the flow of air through small apertures. If two such apertures A and B, Fig. 152, respectively form the inlet and outlet openings of a chamber C, and a uniform suction is created in the chamber C by the aspirator D, the action will be as fol- lows : Air will be drawn through the aperture B into the cham- PYROMETRY. 475 her C', creating suction in chamber C t which in turn causes air from the atmosphere to flow in through the aperture A . The velocity with which the air enters through A depends on the suction in the chamber C, and the velocity at which it flows out through B depends upon the excess of suction in C over that existing in the chamber C, that is, the effective suction in C '. As the suction in C increases, the effective suction must decrease, and hence the velocity at which air flows in through the aper- ture A increases and the velocity at which air flows out through the aperture B decreases, until the same quantity of air enters at A as passes out at B. As soon as this occurs no further change of suction can take place in the chamber C. Air is very materially expanded by heat. Therefore the higher the temperature of the air the greater the volume, and the smaller will be the quantity of air drawn through a given aperture by the same suction. Now if the air, as it passes through the aper- ture A is heated, but again cooled to a lower fixed tem- perature before it passes through the aperture B, less air will enter through the aperture A than is drawn out through the aperture B. Hence the suction in C must increase and the effective suction in C, must decrease, and in consequence the velocity of the air through A will increase and the velocity of the air through B will decrease, until the same quantity of air again flows through both apertures. Thus every change of temperature in the air entering through the aperture A will cause a corresponding change of suction in the chamber C. If two manometer tubes p and q, Fig. 152, communicate 47 6 QUANTITATIVE ANALYSIS. PYROMETRY. 477 respectively with the chambers C and C 1 the column in tube q will indicate the constant suction in C' and the column in tube/> will indicate the suction in the chamber C, which suction is a true measure of the temperature of air entering through the aperture A. This principle was very fully demonstrated previously by Prof. Barus, in U. S. Geol. Survey, Bulletin No. 54., 1889, p. 239. Practical application of the above principles is made in the pneumatic pyrometer of Messrs. Uehling and Steinbart. Fig. 153 shows a side and front elevation of the instrument, and Fig. 154 shows the fire tube in connection with a hot- blast main of a blast furnace, and also a filter, K, for purifying the air to pre- vent the obstruction of the small aper- tures by particles of dust, etc. The fire tube M, Fig. 154, projects into the heated chamber. The air enters by h into the fire tube M, in which is to be heated to the temperature to be measured, and at this temperature it enters the small aperture at the end of the inner tube 27 into a coil , located in chamber B (Fig. 153), thence through the second aperture, located in the coupler R, into the air space above the water in the vessel A, from which it is continuously drawn by the aspirator D. A pipe, open at both ends, enters the vessel A from the top and dips into the water exactly forty-eight inches. The aspira- tor consists of a platinum tube, closed at one end, and having placed concentrically within it a smaller platinum tube, which has a small aperture at its end. The connection of the fire tube with the other pipes, which are of drawn copper, is protected against injury from the heat by the cooler G, held in position by the flange H, and is provided with water circulation by means of the pipes PP. The vessel A, four feet eight inches in height and eight inches internal diameter, and filled with water to within six inches of the top, serves as a suction regu- Fig. 154- 478 QUANTITATIVE ANALYSIS. lator, and the vessel B, into which the exhaust steam of the aspirator D is discharged, serves as the temperature regulator. Two manometer tubes, /and/, are fastened in front of the scale E, and dip into the liquid contained in the jar F. The tube /connects through the pipe d with the top of the regulator^, and shows the amount of suction, as at/ 7 . The tube /connects by the tube a at b with the space between the two small apertures, one of which is located in the end of the inner fire-tube, and the other in the coupling, R, just within the vessel B. A water connection is provided, by which the vessel A may be filled to the proper level. The instruments operate as follows : Steam being turned on the aspirator D, a partial vacuum is at once created in the apparatus. In consequence, atmospheric air enters the bottom of the tube K (Fig. 154), which tube being filled with cotton, cleanses the air from all dust, etc., and allows it to pass through the connecting tube apertures, the deficiency being drawn through the tube just described against the constant water col- umn of forty-eight inches. This insures a perfect and automatic regulation of the suction, which is always shown by the ma- nometer / at F . If the water column in A, in consequence of the gradual evap- oration, sinks, it will at once show at /', and can be replenished by simply opening the cock at M until /' comes to the exact mark. The aspirator D exhausts into the vessel B, and from there through C into the atmosphere ; the water of condensation drains off by the pipe K into the waste pipe W. By this ex- pedient the temperature in B is constantly kept at 212 P., and as the air passes through a coil located in B, it must assume this temperature before passing through the second aperture. Having thus secured, first, a constant difference of tension of the air before entering the first aperture and after leaving the second aperture, and also a constant temperature at which it passes through the second aperture, the tension between the two apertures must necessarily vary with the temperature of the air entering through the first aperture, which is located at the end of n. The manometer,/, communicating with the tube or chamber between the two apertures through the pipe a, indi- PYROMETRY. 479 cates the temperature surrounding the fire-tube, and can be read off on the scale EE at/', for example. The connecting pipe, z, may be several hundred feet longer, so that the main instrument, Fig. 153, can be placed in a con- venient place a considerable distance away from the hot-blast main furnace, etc., the temperature of which is to be measured. This pyrometer records correctly the temperature as high as 2,500 F. and in many instances at 2,700 F. Prof. W. C. Roberts- Austen gives, as the results of many de- terminations by various pyrometers, the following boiling and melting-points : Melting-point of lead 326 C. Boiling-point of mercury 358 " Melting-point of zinc 4 r 5 ' ' Boiling-point of sulphur 448 " Melting-point of aluminum 625 " Boiling-point of selenium 665 " Melting-point of silver 945 ' ' 11 " gold 1045 " " " " copper 1054 " " palladium 1500" " " platinum 1775 " References : " The Thermal Limit." By E. H. Griffiths. Phil. Mag., 40,431. (Capacity for heat of water at different temperatures. Consid- eration of certain thermal units other than those dependent on the capac- ity for heat of water.) " On the Determination of High Temperatures by Means of Platinum Resistance Pyrometers." By C. T. Heycock and F. H. Neville,/. Chem. Soc., 1895, p. 160. " Ueber die Messung hoher Temperaturaten. By L/. Holborn and W. Wein, Pogg. Annalen, N. F., 56, p. 360. (Die Oefen, Priifung der Constanz der Thermo-elemente, Schmelzpunkte von Nickel, Palladium, Platin, Widerstandsanderung von Platin- und Palladiumdrahten unter dem Einfluss von Wasserstoff und Kieselsaure, Widerstandsanderung von reinem Platin und Rhodium mit der Temperatur, Luftthermometer- gefasse aus schwerschmelzbarer Masse.) " Sur un Thermometre a Zero Invariable." M. L. Marchis,/. d. Phys., 4 p. 217. "The Thermophone." By C. Warren Whipple, Electric, 36, 285. " Pyrpmetry and the Heat Treatment of Steel." By Henry M. Howe, Trans. Am. Inst. Min. Eng., 24, p. 746. "Recent Advances in Pyrometry." By W. C. Roberts-Austen, F.R.S., Trans. Am. Inst. Min. Eng., 24, pp. 407-444. L. The Electrical Units. The electrical units may be derived from the three fundamental units of length, mass, and time, and so defined are known as the centimeter-gram-second units ; or, in short, the C. G. S. units. These units are as follows : Centimeter = unit of length. Gram = unit of mass. Second = unit of time. Dyne = unit of force, equal to that force which acting on one gram for one second, produces a veloc- ity of one centimeter per second. Erg. - unit of work, equal to the work done by one dyne acting through the distance of one cen- timeter. These are, in general, either too large or too small for prac- tical purposes, so that the practical units are taken as multiples or fractions of C. G. S. units. Two distinct systems may be derived , the electrostatic sys- tem, having for its basis the repulsion of two like charges of electricity, and the electromagnetic system, having for its basis the repulsion of two like magnetic poles. Only the latter sys- tem need be here considered. In this system the Unit Magnetic Pole is that which repels an equal and similar pole at one centi- meter distance with a force of one dyne. Unit pole produces unit magnetic field at a distance of one centimeter from it. Unit current is one which, in a wire of one centimeter length, bent into an arc of one centimeter radius, would act upon a unit pole placed at the center with a force of one dyne. Practical Units. These were adopted by the International Electrical Congress, Chicago, 1893, and are generally known as the international units. Current. The Ampere is one-tenth of the C. G. S. unit of current; practically represented by that current which, under standard conditions, deposits silver at the rate of 0.001118 gram per second. THE ELECTRICAL UNITS. 481 An ordinary 5o-volt incandescent lamp takes a current of about one ampere ; an arc lamp requires about ten amperes. Resistance, The Ohm is the resistance of an uniform column of pure mercury 106.3 centimeters long and 14.4521 grams in mass, at o C. The cross section of this column is one square mm. 100 feet of No. 20 B. and S. copper wire have an approximate resistance of one ohm, at the ordinary temperature. Electromotive Force. The Volt is the E. M. F., which steadily applied to a conductor whose resistance is one ohm, will pro- duce in it a current of one ampere. It is practically represented by |fff part of the E. M. F. of a Clark standard cell at 15 C. A Daniel cell has an E. M. F. slightly greater than one volt. Quantity. The Coulomb is the quantity of electricity con- veyed by one ampere in one second. Capacity. The Farad is that capacity which requires one coulomb of electricity to charge it to a potential of one volt. For ordinary use, the one-millionth part, or micro-farad, is em- ployed as the unit. Work. The Joule is the energy expended in one second by one ampere in one ohm. It is equal to 107 ergs. Expressed in heat units, one joule = 0.24 calories. (Calorie = gram-degree at 4 C.) Power. The Watt is the power expended by one ampere flowing under a pressure of one volt ; it is equal to work done at the rate of one joule per second. 746 watts are approximately equal to one horse power. Inductance. The Henry is such a disposition of the circuit that a change of current at the uniform rate of one ampere per second induces a counter-electromotive force of one volt. For convenience of expression, quantities respectively one million times greater or smaller than these are sometimes desig- nated by the prefixes megra- and micro-. Thus insolation re- sistances are usually expressed in megohms, one megohm being equal to one million ohms ; capacites, in terms of microfarads, a microfarad being equal to the one-millionth part of a farad. The prefixes kilo- and milli- denote quantities respectively one 482 QUANTITATIVE ANALYSIS. thousand times greater or smaller than the units to which they are prefixed. Thus dynamo machinery is ordinarily rated in kilo-watts, one kilo-watt being equal to one thousand watts, or very nearly equal to one and one-third horse power ; small currents, such as are used in medicine, are frequently expressed in milli-amperes. The relations between the international units of resistance and electromotive force, to those of the older units, are : i B. A. unit = 0.98660 International unit. r International unit = 1.01358 B. A. units. i Legal unit = 0.99718 International unit. i International unit = 1.00283 Legal unit. OHM'S LAW. The current flowing in any complete circuit is equal to the total electromotive force, divided by the total resis- tance of the circuit. For any part of a circuit, not containing a source of E. M. F., the current flowing is equal to the difference of potential between the ends of the part, divided by the resis- tance of that part. So, in general, Volts Amperes = . Ohms JOULE'S LAW. The heat developed in any conductor is proportional; ist, to its resistance, 2nd, to the square of the current strength, 3rd, to the time that the current lasts. The quantitative relation of these, known as Joule's Law, is 7=0.24 X CRt, or in units Calories = 0.24 (Amperes) 2 X Ohms X Seconds. Measurement of Electric Energy. The electrical energy given to any part of a circuit can be found by placing an ampere- meter in series with the circuit, and a volt-meter in shunt with the circuit. The product of amperes and volts gives the Watts and this divided by 746 gives the horse-power. That is Amperes X Volts Horse-power = - . 746 ENERGY EQUIVALENTS. 483 The ampere-meter and volt-meter may be combined into one instrument, called a watt-meter, which gives the power directly in watts. ELECTRO-CHEMICAL EQUIVALENTS. Grams per coulomb. Hydrogen 0.000010334 Gold 0.0006791 Silver o.ooi 1 180 Copper (Cupric) 0,000328 Mercury (Mercuric) 0.0010374 Zinc 0.0033698 Oxygen 0.00008286 Water 0.00009315 LI. Energy Equivalents. There frequently occur, in the course of engineering work, calculations of efficiency and consumption which are, more or less, long and tedious. The figures given in the following para- graphs will reduce any such calculation to a case of simple multiplication or division. This not only saves time, but greatly decreases the chance of errors, which can often pass unnoticed in many of the rarely understood and complicated expressions which such calculations involve. Only full theoretical values or equivalents are given, and when the delivery is not up to the figure the deficiency is the loss in the transformation, or if the consumption is greater than the equivalent, such excess is the waste of the process. Some of the equivalents are, at the present time, uncertain, and the figures given are subject to such changes as their definite determination will involve. Joule's equivalent has been used as 776, which is considered a conservative figure, as is also the light equivalent of i C. P. = 620 foot-pounds per hour. Logarithms of each number have been inserted, and the reciprocal of any equivalent will be found under its proper head- ing. WORK. One (i) Horse-Power = In Foot-Pounds. 33,000 (log. 4.518514) foot-pounds per minute. 550 (log. 2.740363) foot-pounds per second. 1,980,000 (log. 6.296665) foot-pounds per hour. 4 8 4 QUANTITATIVE ANALYSIS. In B. T. U. In Pounds Steam. In Combustion. In Electricity and Light. In H. P. In Electric Light. In B. T. U. In Steam. In H. P. In Electric Light. In B. T. U. In Steam. Rotary Delivery to Get H. P. .709 (log. 1.850646) B. T. U. per second. 42.53 (log. 1.628652) B. T. U. per minute. 2,552 (log. 3.406710) B. T. U. per hour. 2.219 (log. 0.346105) pounds of steam per hour at 80 pounds pressure (95 pounds absolute). 2.2104 (lg- 0.34/14/11) pounds steam at 100 pounds pressure (115 pounds absolute). .002933 (log. 3.467312) pounds carbon consumed per minute, or 0.176 (1.24551) pounds carbon per hour. .1823 (log. 1.260787) pounds ordinary coal per hour. .1169 (log. 7.067815) pounds = 0.0157 gals. (log. 2.19590) ordinary petroleum per hour. .1276 (log. 1. 105781) pounds good kerosene per hour 3.925 (log. 0.593890) cubic feet ordinary house gas per hour. 746 (log. 2.872739) watts or 2,750 (log. 3-43933) candle power. One (i) Foot-Pound per Second = .001818 (log. J.259594) horse power. J -3565 0g- 0.132343) watts, or 5 (log. 0.698970) candles. 4.64 (log. 0.666515) B. T. U. per hour. .004034 (log. 3.605699) pounds steam at 80 pounds pressure (95 pounds absolute) per hour. .004018 (log. 3.604035) pounds steam at 100 pounds pressure (115 pounds absolute; per hour. One Foot-Pound per Minute = .0000303 (log. 5.481443) H. P. .0226 (log. 7.354108) watts. .0833 (log. 2.920820) candles. 7733 (log. "2. 888348) B. T. U. per hour. .00006723 (log. 5.827548) pounds steam at 80 pounds pressure (95 pounds absolute) per hour. .00006696 (log. 5~.825874) pounds steam at 100 pounds pressure (115 pounds absolute) per hour. In Rotary Delivery. A force of 52.41 (log. 1.719333) pounds at an arm I foot long, making 100 revolutions per minute, gives one H. P. A force of 100 pounds acting on an arm I foot long, making 52.41 (log. 1.7*9333) revolutions per min- ute, gives i H. P. ENERGY EQUIVALENTS. 485 A force of 100 pounds, acting on an arm 0.5241 (log. 1.619333) foot =6^ inches long, making 100 revo- lutions per minute, gives T H. P. A force of 100 pounds, acting on an arm I foot long, and making 100 revolutions per minute, gives 1.904 (log. 0.279665) H. P. Roughly we have I H. P. for 100 pounds pull on a belt running over a i-foot pulley (i foot diame- ter), making 100 revolutions per minute. HEAT. One B. T. U. (i Pound Water Raised i F.) = 776 (log. 2.889862) foot pounds. One B. T. U. Consumed per Second = B. T. U. to Worki 1.411 (log. 0.149500 horse power, or Light and 1,052.6 (log. 3.022263) watts, or Electricity. 3,880 (log. 3.588832) candle power. One B. T. U. per Minute = .023515 (log. 2.371345) H. P., or 17-5433 (log- 1.244112"! watts, or 64.66 (log. 1.810569) candles. One B. T. U. per Hour = .000392 (log. 4.593200) H. P., or .2924 (log. 7.465977) watts, or 1.078 (log. 0.032619) candles. One Pound of Steam. Steam to Work, At 100 pounds pressure (115 absolute) takes Light and .7962 (log. 1.901000) pounds carbon, or 0.0824 Electricity. (log- ^9 I 59 2 7) pounds ordinary good coal to make it from water at 62 F., assuming no loss ; it contains 1.154.5 (log. 3.062368) B. T. U., or 895,892 (log. 5.9593!5) foot-pounds. If it were consumed in one hour it would represent with no loss 14,931 (log. 4.174089) foot-pounds per minute, or .45247 (log. ".655565; H. P., or 337.6 (log. 2.528304) watts, or 1,244.5 (log. 3-94893) candles. 486 QUANTITATIVE ANALYSIS. One Pound of Steam. Steam to Work, At 80 pjuiids pressure (95 absolute) takes Light and -0793 (log. 2.899328) pounds carbon, or Electricity. .0821 (log. 2.914343) pounds ordinary good coal to make it from water at 62 F., assuming no loss. It contains 1,150 (log. 3.060698) B. T. U., or 892,400 (log. 5.950551) foot-pounds. If it be consumed in I hour with no loss= 14,873 (log. 4.172400) foot-pounds per minute, or 4507 (log. 7.65388) H. P., or 336.2 (log. 2.526625) watts, or 1239 (log. 3.09322) candles. One Pound of Carbon Consumed in i Hour = Combustion. 14,500 (log. 4.161368) B. T. U. per hour. 11,252,000 (log. 7.051230) foot-pounds per hour. 5.683 (log. 0.754565) H. P. 4,240 (log. 3.627304) watts. 15,630 (log. 4.193895) candles. Fuels to B. T. U. 15 (log. 1.176091) pounds water evaporated from and at 212 F. 12.56 (log. 1.099000) pounds steam made from water at 62 F., to steam at 100 pounds pressure (115 pounds absolute). Steam work. 12.61 (log. 1.10067) pounds steam made from water at 62 F. to steam at 80 pounds pressure (95 pounds absolute). One Pound Ordinary Kerosene Consumed per Hour = Light and 20,000 (log. 4.301030; B. T. U. per hour. Electricity. 15,520,000 (log. 7.190892) foot-pounds per hour. 7.838 (log. 0.894227) H. P. 5,847 (log. 3.766966) watts. 21,560 (log. 4-333557) candles. 20.7 (log. 1.316053) pounds water evaporated from and at 212 F. 17.325 (log. 1.238673) pounds water from 62 F. to steam at 100 pounds pressure (115 pounds absolute). 17.40 (log. 1.240050 pounds water at 625 F. to 80 pounds pressure (95 pounds absolute). One Cubic Foot Ordinary Illuminating Gas per Hour = 6 5 (log. 2.812913) B. T. U. per hour. 504,400 (log. 5.702775) foot-pounds per hour. ENERGY EQUIVALENTS. 487 25475 (log. 7.4o6uo) H. P. 190 (log. 2.278849) watts. 700 (log. 2.845440) candle power. .6729 (log. "1.827936) pounds water evaporated from and at 212 F. .563 (log. 7.750585) pounds water at 62 F. to steam at 100 pounds pressure ( 1 15 pounds absolute). LIGHT. One Candle Power = Light to Work. .00036364 (log. 4.560672) H. P. .2713 (log. 7.433411) watts. 12 (log. 1.079181) foot-pounds per minute. 720 (log. 2.857332) foot-pounds per hour. B. T. U. .015464 (log. 2.189319) B. T. U. per minute. Electricity, -92783 (log. ".967470) B. T. U. per hour. Steam and .0008037 (log. 4.905102) pounds steam per hour at 100 Combustibles. pounds pressure (115 pounds absolute). .0008068 (log. 4.906772) pounds steam at 80 pounds pressure (95 pounds absolute). .000064 (log. 5.806102) pounds. .448 (log. 7.6512) grains carbon per hour. .0000661 (log. 5.820201) pounds ordinary coal per hour. .0000464 (log. 5.66644) pounds. .32475 Clog. 7.511538) grains. .001531 (log. 3.184975) cubic inches. 0.000006628 (log. 6.821342) gallons ordinary kerosene per hour. .001427 (log. 3.154557) cubic feet ordinary gas per hour. ELECTRICITY. One (i) Watt = Electricity .0013405 (log. 3.127241) H. P. to Work. .057 (log. 2.755913) B. T. U. per minute. B. T. U. 3.42 (log. 0.534064) B. T. U. per hour. Steam, 44-24 (log. 1.645775) foot-pounds per minute. Light and 2,654.4 (log. 3.423966) foot-pounds per hour. Combustibles. 3.6863 (log. .566591) candle power. .000236 (log. 4.372696) pounds. 1.65 (log. .217794) grains carbon per hour. .000171 (log. 4.233034) pounds. 1.197 (log. 0.078132) grains good kerosene per hour. .005262 (log. 3.721151) cubic feet ordinary illumina- ting gas per hour. 488 QUANTITATIVE ANALYSIS. LIST OF THE PRINCIPAL ELEMENTS, WITH THEIR ATOMIC WEIGHTS, SPE- CIFIC GRAVITIES AND SPECIFIC HEATS. Atomic Specific Specific weight. gravity. heat. Aluminum 27.50 2.67 0.2143 Antimony 120.0 6.70 0.0508 Arsenic 75.0 5.63 0.0814 Barium *37-o 4-oo 0.0470 Bismuth 208.0 7-67-9.93 0.0380 Boron n.o 2.68 0.3660 Bromine 80.0 3.15 0.0843 Cadmium 112.0 8.45 0.0567 Calcium 40.0 i .58 o. 1670 Carbon 12.0 2.33-3.52 0.4590 Chlorine 35.5 1.38 (liquid) 0.1800 Chromium 52.5 7.01 o.iooo Cobalt 59.0 8.957 o. 1070 Copper 63.5 8.952 0.0950 Fluorine 19.0 ... 0.2600 Gold 197-0 19-50 0.0324 Hydrogen i.o 0.0692 (air = i.o) 2.3000 Iodine 127.0 4.94 0.0541 Iridium I93-O 22.42 0.0326 Iron 56.0 7.79 0.1138 Lead 207.0 n-35 0.0306 Magnesium 24.0 1.70 0.2499 Manganese 55.0 8.03 0.1217 Mercury 200.0 13-60 0.0319 Molybdenum 96.0 8.56 0.0722 Nickel 58.8 9.50 0.1082 Nitrogen 14.0 0.971 (air = i.o) 0.3600 Oxygen 16.0 1.105 (air = i.o) 0.2500 Palladium 106.5 11.40 0.0593 Phosphorus 31.0 1.84 0.1895 Platinum I95-O 21.15 0.0324 Potassium 39.0 0.86 0.1655 Silicon 28.0 2.49 0.2030 Silver 108.0 10.53 0.0560 Sodium 23.0 0.98 0.2934 Strontium 87.5 2.542 o. 1740 Sulphur 32.0 2.07 0.1776 Tin 118.0 7.20 0.0562 Titanium 48.0 3-588 0.1300 Uranium 240.0 18.40 0.0279 Vanadium 51.2 5.50 Wolfram (tungsten). 184.0 18.3 0.0334 Zinc 65.0 7.37 0.0955 TABLES. 489 CONVERSION TABLES. Found. Sought. Factor. Found. Sought. Factor. A1 2 3 Al, 0-530I5 Mg 2 P 2 7 2Mg 0.21883 NH 4 C1 NH 3 0.31882 Mn 2 O 3 2Mn 0.69695 PtCl 6 (NH 4 ) 2 2NH 3 0.07692 Mn 3 O 4 3 Mn 0.72084 PtCl 6 (NH 4 ) 2 N 2 0.06329 MuS Mn 0.63211 Pt 2NH 3 0.17518 Hg HgO 1.07984 (NH 4 ) 2 S0 4 2NH 3 0.25815 HgS Hg 0.86208 Sb 2 3 Sb 2 0.83366 MoS Mo 0.49992 Sb 2 O 5 Sb 2 0.75046 NiO Ni 0.78524 Sb 2 S 3 Sb 3 0.71438 NiSO 4 Ni 0.37849 As.,03 As, 0-75757 (NH 4 ) 2 PtCl 6 2N 0.06329 As 2 5 As, 0.65217 PbSO 4 Pb 0.68292 As 2 S 3 As 2 0.60928 Pt 2N 0.14414 BaSO 4 BaO 0.65654 PdI 2 Pd 6.29448 BaSO 4 Ba 0.58790 Mg 2 P 2 7 2P 0.27852 Bi 2 3 2Bi 0.89654 Mg 2 P 2 7 P 2 5 0.63756 KBF1 4 B 0.08683 U f PtO u P 2 5 0.19817 AgBr Br 0.42556 (NH 4 ) 2 PtCl 6 Pt 0.43911 CdS Cd 0.77712 K 2 S0 4 K 2 0.44898 CdS0 4 Cd 0.53786 K 2 SO 4 K 2 0.54075 CaO Ca 0.71428 K 2 PtCl 6 K 2 0.19404 CaS0 4 CaO 0.41158 AgCl Ag 0.75275 C0 2 C 0.27278 SiO 2 Si 0.47020 CaC0 3 C0 2 0.44002 SiFl 4 vSi 0.57878 BaC0 3 C0 2 0.22332 NajSOi Na, 0.32435 AgCl Cl 0.24725 Na 2 SO 4 Na 2 O 0.43674 Cr 2 3 Cr 2 0.68483 NaCl Na 0.39408 Cr 2 3 2Cr0 3 1.31520 BaSO 4 vS 0.13755 CoO Co 0.78696 BaSO 4 S0 3 0.34346 CuO Cu 0.79858 SrS0 4 Sr 0.47674 Cu 2 S Cu 2 0.79827 Tl 2 PtCl 6 2T1 0.50046 CaFl 2 F1 2 0.48088 SnO 2 Sn 0.78681 BaSiFl 6 6F1 0.40783 Ti0 2 Ti 0.60065 Agl I 0.54031 U 3 8 3U 0.84873 FA Fe 2 0.70000 VdA 2Vd 0.56145 Fe 2 3 2FeO 0.89999 Wo0 3 Wo 0.79310 LiCO 3 Li 2 0.18944 ZnO Zn 0.80338 MgO Mg 0.60375 ZrCV Zr o-739 I 3 i Improvements in Methods of Chemical Calculations." Consult J. Anal. Chem. t i. 402. 490 QUANTITATIVE ANALYSIS. COMPARISON OF CENTIGRADE AND FAHRENHEIT DEGREES. Degrees Centi- Decrees Fahren- Degrees Centi- Degrees Fahren- grade. heit. grade. heit. 2500 4532 274 525-2 2OOO 3632 273 523-4 1500 2732 272 521.6 I2OO 1992 271 5I9-8 IOOO 1832 270 518 950 1742 26 9 5l6.2 900 1652 268 514.4 8 5 1562 267 512.6 825 1517 266 510.8 8OO 1472 265 509 775 1427 264 507.2 75 1382 263 505.4 725 1337 262 503-6 700 1292 261 501.8 675 1247 260 500 650 1202 259 498.2 625 U57 258 496.4 600 III2 257 494-6 575 1067 2 5 6 492.8 550 IO22 255 491 500 932 254 489.2 475 88 7 253 487-4 450 842 252 485.6 425 797 251 483.8 400 752 250 482 375 707 249 480.2 350 662 248 478.4 325 617 247 476.6 300 572 246 474-8 299 570.2 245 473 298 568.4 244 471.2 297 566.6 243 469.4 296 564.8 242 467.6 295 563 241 465-8 294 561.2 240 464 293 559-4 239 462.2 292 557-6 238 460.4 291 555-8 237 458.6 290 554 236 456.8 289 552.2 235 455 288 550.4 234 453-2 287 548.6 233 451.4 286 546.8 232 449-6 285 545 231 447.8 284 543 230 446 283 541-4 229 444-2 282 539-6 228 442.4 281 537-8 227 440.6 280 536 220 438.8 279 534-2 225 437 278 532.4 224 435-2 277 530-6 223 433-4 276 528.8 222 431.6 275 527 221 429.8 Degrees Centi- Degrees Fahren- grade. heit. 220 428 219 426.2 218 424.4 2T7 422.6 216 42O.8 215 419 214 417.2 213 415.4 212 413.6 211 4II.8 210 410 209 408.2 208 406.4 207 404.6 206 402.8 205 401 204 399-2 203 397-4 202 395-6 2OI 393-8 200 392 199 390-2 I 9 8 388.4 I 9 7 386.6 I 9 6 384.8 195 383 I 9 4 381.2 193 379-4 192 377-6 191 375-8 I 9 374 189 372.2 188 370-4 187 368.6 186 366.8 185 365 184 363-2 183 361.4 182 359-6 181 3S7-8 1 80 356 179 354-2 178 352.4 177 350-6 176 348.8 175 347 174 345-2 173 343-4 172 341.6 171 339-8 170 338 169 336.2 r 68 334-4 167 332-6 TABLES. 491 COMPARISON OF Degrees Degrees Centi- Fahren- grade. heit. 166 330.8 165 329 164 327 163 325-4 162 161 321*8 1 60 320 159 318.2 158 316.4 '57 314.6 156 312.8 155 3" 154 309.2 153 3074 152 305-6 151 303-8 150 302 149 300.2 148 298.4 III 296.6 294.8 145 293 144 291.2 H3 289.4 142 287.6 141 285.8 140 284 J 39 282.2 138 280.4 HI 278.6 276.8 135 275 134 273.2 133 271.4 132 269.6 267.8 130 266 129 264 128 262.4 III 260.6 258.8 125 257 124 255.2 123 253.4 122 251.6 121 249.8 120 248 II 9 246.2 118 244-4 117 242.6 116 240.8 "5 239 114 237.2 IJ 3 23-54 CENTIGRADE AND FAHRENHEIT DEGREES Continued. Degrees Centi- Degrees Fahren- Degrees Centi- Degrees Fahren- grade. heit. grade. heit. 112 233-6 58 136.4 III 231.8 57 134.6 1 10 230 56 132.8 109 228.2 55 I 3 I 1 08 226.4 54 129.2 107 224.6 53 127.5 106 222.8 52 125.6 105 221 51 123-8 104 219.2 50 122 103 217.4 49 120.2 102 215.6 48 II8.4 101 213.8 47 II6.6 100 212 46 II4-8 99 2IO.2 45 "3 98 208.4 44 III. 2 97 206.6 43 109.4 96 204.8 42 107.6 95 20 3 105.8 94 201.2 40 104 93 199.4 39 102.2 9 2 1974 38 100.4 195-8 37 98.6 90 194 36 96.8 89 192.2 35 95 88 190.4 34 93-2 87 188.6 33 91.4 86 186.8 32 89.6 85 I8 5 3 1 87.8 84 183.2 30 86 84 l8l.4 2 9 84.2 82 179.6 28 82.4 8! 177.8 27 80.6 80 I 7 6 26 78.8 79 174.2 25 77 78 172.4 24 75-2 77 I7O.6 23 73-4 76 168.8 22 71.6 75 I6 7 21 69.8 74 165.2 20 68 73 163.4 19 66.2 72 161.6 18 644 19.58 17 62.6 70 158 16 60.8 69 156.2 15 59 68 154-4 57-2 67 152.6 13 55-4 66 150.8 12 53-6 65 149 II 51.8 64 147.2 IO 50 63 145-4 9 48.2 62 143.6 8 46.4 6! 141.8 7 44-6 60 140 6 42.8 59 138.2 5 4i 492 QUANTITATIVE ANALYSIS. COMPARISON OF CENTIGRADE AND FAHRENHEIT DEGREES Continued, Degrees Centi- Degrees Fahren- Degrees Centi- Degrees Fahren- Degrees Degrees Centi- Fahren- grade. heit. grade. heit. grade. heit. 4 39-2 8 I 7 .6 2O 4 3 37-4 9 15-8 21 ~ 5-8 2 3.56 10 14 22 - 7-6 4- i 33-8 II 12.2 23 9.4 o 32 12 IO.4 24 II. 2 I 30.2 13 8.6 25 13 2 28.4 14 6.8 30 22 3 26.6 15 5 35 3 1 4 24.8 16 3-2 -38 3 6 -4 5 23 17 i i'4 40 40 6 21.2 18 0.4 7 194 19 2.2 STEAM PRESSURES EXPRESSED IN POUNDS PER SQUARE INCH AND ATMOSPHERES FOR DIFFERENT TEMPERATURES. Pounds Pounds per per square inch. Atmos- pheres. Temperature of steam. square inch. Atmos- Temperature pheres. of steam. I 0.07 33 2.24 2 0.14 34 2.31 3 0.21 60 C. 35 2. 3 8 4 0.28 [i 4 oF.] 36 2-45 5 0-35 37 2. 5 2 128.8 C. 6 0.41 38 2. 5 8 [ 263. F.] 7 0.48 39 2.65 8 0-54 4o 2.72 9 0.61 86 C. 2-79 10 0.68 [i86.8F. 42 2.86 ii 0-75 43 2.92 12 0.81 44 2.99 135-1 c. 13 0.88 3.06 [275 F.] 14 0-95 46 3-13 15 1.02 100 C. 47 3.20 16 1.09 [212 F.] 48 3-26 17 1.16 49 3-33 18 2 3 50 3-40 19 30 3-47 140.6 C. 20 36 52 3-54 [284 F.] 21 43 53 3.60 22 50 112. 2 J C. 54 3-67 * 23 56 [234 F.] 55 3-74 24 63 56 3.81 25 .70 57 3-88 26 58 3-94 1454 C. 27 .84 59 4.01 [2 9 4 C F.] 28 .90 60 4.08 29 97 61 4-15 30 2.04 121.4 C. 62 4.22 31 2. II [250. F.] 63 4.28 32 2.18 64 4-35 TABLES. 493 STEAM PRESSURES EXPRESSED IN POUNDS PER SQUARE INCH AND ATMOSPHERES FOR DIFFERENT TEMPERATURES Continued. Pounds Pounds per per square inch. Atmos- pheres. Temperature of steam. square inch. Atmos- pheres. Temperature of steam. 65 442 95 6.46 67 68 4.49 4.56 4.62 I49-I C C. [300.4 P.] 96 P 6-53 6.60 6.66 163-5 C. [325.3 p.] 69 4.69 99 6.73 70 71 4.76 4.83 100 101 6^87 72 4-95 IO2 6.94 73 4.96 103 7.00 166.5 C. 74 5-03 153-1 c. 104 7.07 [331.7 p.] 5-15 [307-6 P.] 105 7.14 76 5-17 106 7.21 77 5-24 107 7.28 78 5-35 108 7-35 79 5-37 109 7.42 80 5-44 no 7-49 169 C. 81 5-51 156.8 C. 120 8.17 [336.2 p.] 82 5-57 [314.2 p.] 130 8.85 83 5-64 140 9-53 180 C. 84 5.78 10.21 10.89 [356 C F-] 86 5-85 170 H-57 190 C. 87 5-92 180 12.25 [374 p.] 88 5-98 160.2 C. 190 12.93 89 6.05 [320 P.] 200 13.61 90 6.12 210 14.29 6.19 220 14.97 200 C. 92 6.25 230 15-65 [392 p.] 93 6.32 240 16.33 94 6-39 250 17.01 257 C. [494-6 P.] 494 QUANTITATIVE ANALYSIS. United States System cf Measures and Weights Compared With the Metric System. i. Linear Measure. i mile=8 furlongs=8o chains=32O perches=528o {661=1609.344 meters, i furlong =10 chains= 40 perch es= 660 feet= 201.168 " i chain = 4 perches= 66 feet= 20.1168 " i perch = i6\ feet= 5.0292 " i chain = 100 links. i link=7.92 inches=o. 201168 meters, i yard=3 feet=36 inches=o.9i44 " i foot=i2 inches=o.3048 " i inch =0.0254 " 2. Surface Measures. i square mile=64o acres. i acre=io square chains=i6o square perches=4356osq. feet=4o. 4694 ares. 3. Measures of Capacity. A. DRY MEASURE. i bushel=2i5o.42 cubic inches. i bushel=the volume of 77.627 pounds of distilled water at 4 C. Legal : i Iiter=o.9o8 quart. i bushel=4 pecks=8 gallons=32 quarts=35. 24229 liters. i peck =2 gallons= 8 quarts= 8.81057 liters. i gallon = 4 quarts^ 4.40528 liters. i quart = 1.10132 liters. i cubic foot=748 gallons=28.3i5 liters=62.42 pounds of water at 60 F. B LIQUID MEASURE. i gallon=23i cubic inches. i gallon=the volume of 8.3388822 pounds=58378 troy grains of distilled water at 4 C. Legal : i liter=i.O567 quart=o.264i7 gallon. i gallon=4 quarts=8 pints=32 gills=3. 78544 liters, i quart =2 pints= 8 gills=o.94636 liter, i pint = 4gills=i.473i8 liter, i gill =0.118295 liter. 4. Weights. i grain troy =0.0648004 gram. i pound troy= 0.822857 pound avoirdupois. i pound avoirdupois^ 7000 grains troy= i. 215279 pounds troy. TABLES. ^AVOIRDUPOIS WEIGHTS. 495 i ton=2o hundred weight=224o pounds= 1016.070 kilograms. I hundred weight= 112 pounds= 50.8035 kilograms. i pound= 16 ounces= 256 drams= 768 scruples= 7680 grains=453.6o3 grams i ounce = i6drams= 48scruples= 48ograins= 28. 350 grams I dram = 3 scruples= 30 grains= 1.772 grams i scruple = iograins= 0.5906 gram B TROY WEIGHT FOR DRUGS. i pound = 12 oz. =96 drachms^ 288 scruples=576o grains= 373. 2503 gms. i oz. = 8 drachms = 24 scruples= 480 grain s= 31.1042 gms. i drachm = 3 scruples= 60 grains= 3. 888025 gms. i scruple 20 grains= i. 296008 gms. i grain =0.064804 gm. C TROY WEIGHT FOR JEWELS AND PRECIOUS METALS. pound= 12 ounces=24 carats=24o pwts=576o grains= 373. 2503 gms. i ounce = 2 carats= 20 pwts= 480 grains= 31.1042 gms. i carat = 10 pwts= 240 grains= 15.5521 gms. i pennyweight = 24 grains^ 1.55521 gnis. i grain = 0.0648004 gm. Percentages and Gravity of Ammonia. TABLE SHOWING THE PERCENTAGES OF AMMONIA (NH 3 ) IN AQUEOUS SOLUTIONS OF THE GAS OF VARIOUS SPECIFIC GRAVITIES. Carius. Temperature 15 C. Specific gravity. NH S per cent. Specific gravity. NH 3 per cent. Specific gravity. NH 3 per cent. 0.8844 36 0.9133 24 0.9520 12 0.8864 35 0.9162 23 0.9556 II 0.8885 34 0.9191 22 u-9593 IO 0.8907 33 0.9221 21 0.9631 9 0.8^29 32 0.9251 20 0.9670 8 0.8953 3i 0.9283 19 0.9709 7 0.8976 30 0.93H 18 0.9749 6 0.9001 29 0-9347 i? 0.9790 5 0.9026 28 0.9380 16 0.9831 4 0.9052 27 0.9414 15 0.9873 3 0.9078 26 0.9449 H 0.9915 2 0.9106 25 0.9484 13 0.9959 I 496 QUANTITATIVE ANALYSIS. TABLE SHOWING THE AMOUNT OF K 2 O IN POTASH LYE OF DIFFERENT SPECIFIC GRAVITIES. TEMPERATURE 17.5. (Hoffman-Schaedler, "Tabellen fur Chemiker," p. 119.) K 2 O K 2 O K 2 O K 2 O per cent. Specific gravity. per Specific cent. gravity. per Specific per cent. gravity. cent. Specific gravity. 45-o I-576 34-0 .414 23.0 1.269 I2 .o I-I35 44-5 1.568 33-5 407 22.5 -263 11.5 1.129 44.0 1.560 33-o .400 22.0 -257 n.o 1.123 43-5 1-553 32-5 393 21.5 .250 10.5 1. 117 43 .0 1-545 32.0 .386 21.0 .244 10.0 1*111 42-5 1-537 31-5 379 20.5 238 9-5 1.105 42.0 1-530 31.0 -372 2O.O .231 9.0 1.099 41-5 1.522 30.5 -365 19-5 -225 8.5 1.094 41.0 I.5H 30.0 -358 19.0 .219 8.0 1.088 40-5 1.507 29-5 352 I8. 5 213 7-5 1.082 40.0 1.500 29.0 345 18.0 .207 7.0 1.076 39-5 1.492 28.5 339 17-5 .201 6.5 1.070 39-0 1.484 28.0 332 17.0 .195 6.0 1.065 38.5 1-477 27.5 -326 16.5 189 5-5 1.059 38.0 1.470 27.0 .320 16.0 .183 5.0 1.054 37-5 1.463 26.5 .313 15-5 177 4-5 1.048 37-o 1.456 26.0 307 15.0 .171 4.0 1.042 36.5 1.449 25.5 .301 14-5 -165 3.5 1.037 36.0 1.442 25.0 .294 14.0 -159 3-o 1.031 35-5 '435 24-5 .288 13-5 .153 2.5 1.026 35-o 1.428 24.0 .282 13.0 .147 2.0 I.O2I 34-5 1.421 23-5 275 12.5 .141 1.5 I.OI5 TABLE SHOWING THE AMOUNT OF SODIUM OXIDE (Na 2 O) IN SODA L,YES OF DIFFERENT SPECIFIC GRAVITIES. TEMPERATURE 17.5. (Hoffman-Schaedler, "Tabellen fur Chemiker.") Na a O Na 2 0. Na 2 O Na,O per Specific per Specific per Specific per Specific cent. gravity. cent. gravity. cent. gravity. cent. gravity. 35-0 1.500 27-5 1.389 20.0 I.28l 12.5 I.I74 34-5 1.492 27.0 1.382 19.5 1.274 12.0 .I6 7 34-0 t-485 26.5 -375 19.0 1.266 11.5 .160 33-5 M77 26.0 .367 18.5 1.259 I]C -o 153 33-0 1.470 25-5 -360 18.0 1.252 10.5 .146 32.5 1.463 25-0 .353 17.5 1.245 I0 -o -139 32.0 1-455 245 -345 17.0 1.238 9.5 .132 31-5 1.448 24.0 .338 16.5 I.23I 9.0 .125 31.0 1.440 23-5 -331 16.0 1.224 8.5 .118 30-5 1.433 23.0 .324 15.5 1.217 8.0 .III 30.0 1.426 22.5 .317 15.0 I. 210 7.5 .104 29-5 1.418 22.0 .309 14.5 1.203 7-o .097 29.0 1.411 21.5 .302 14.0 1.195 6.5 .090 28.5 1.404 21.0 .295 13.5 1.188 6.0 1.083 28.0 1.396 20.5 .288 13.0 1.181 5.5 1.076 TABLES. 497 SPECIFIC Specific GRAVITY Per cent OF SOLUTIONS OF CALCIUM CHLORIDE AT 18.3 CSCHIFF.) Per cent. Specific Per cent. Per cent. gravity. CaCl 2 -|-6H.,O. CaCl a . gravity. CaCla+eHjO. CaCl 2 . 1.0039 I 0.507 1.1575 36 18.245 1.0079 1 1,014 I.I662 37 18.752 I.OH9 3 1.521 1.1671 38 19.259 I.OI59 4 2.028 LI7I9 39 19.766 1.0200 5 2-534 .1768 40 20.272 I .O24I 6 3.041 .1816 4i 20.779 1.0282 7 3.548 .1865 42 21.286 1.0323 8 4.055 .1914 43 21-793 1-0365 9 4.562 .i9 6 3 44 22.300 1.0407 10 5.068 .2012 45 22.806 1.0449 ii 5-575 .2O62 46 23.313 I.049I 12 6.082 .2112 47 23.820 1.0534 13 6.587 .2162 48 24-327 1-0577 H 7.096 1 .2212 49 24.834 1.0619 15 7.601 .2262 50 25-340 1.0663 16 8.107 .2312 5i 25.847 1.0706 17 8.6II 2363 52 26.354 1.0750 18 9.I2I .2414 53 26.861 1.0794 19 9.625 2465 54 27.368 10838 20 10.136 .2516 55 27.874 1.0882 21 10.643 .2567 56 28.381 1.0927 22 II.I5O ] .26l8 57 28.888 1.0972 23 11.657 .2669 58 29-395 I.I017 24 12.164 1 .2721 59 29.902 I.IO62 25 12.670 2773 60 30.408 I.II07 26 I3-I77 .2825 61 30-915 I.H53 27 13.684 .2877 62 31.422 I.II99 28 14.191 .2929 63 31.929 I.I246 2 9 14.698 .2981 64 32.43 6 I.I292 30 15.204 3034 65 32.942 I-I339 31 I5.7H .3087 66 33-449 I.I386 32 16.218 .3140 67 33.956 I-H33 33 16.725 3 T 93 68 34.463 1.1480 34 17-232 .3246 69 34.970 1.1527 35 17.738 .3300 70 35476 SPECIFIC GRAVITY OF SOLUTIONS OF SODIUM CHLORIDE AT 15 C. Specific Per cent. Specific Per cent. Specific Per cent. gravity. NaCl. gravity. NaCl. gravity. NaCl. 1.00725 I.I 1.07335 10.0 I.I43I5 19.0 1.01450 .2 1.08097 n.o .15107 20.0 1.02174 3 .08859 I2 -o .15931 21.0 1.02899 4 .09622 13.0 16755 22.0 1.03624 5 .10384 14.0 .17580 23.0 1.04366 .6 .11146 15.0 .18404 24.0 1.05108 7 .11938 16.0 .19228 25-0 1.05851 .8 .12730 17.0 .20098 26.O 1 -06593 9 .13523 18.0 .20433 26.395 498 QUANTITATIVE ANALYSIS. SPECIFIC GRAVITY OF GASES AND VAPORS. Weight of one liter in Specific grams at Molecular gravity. atoC.and Gas or vapor. Formula. weight. (air=i). 760 mm. Acetone C 8 H.O 58.0 2.0025 2.5896 Acetylene C 2 H 2 26.0 0.9200 1.1650 Air I.OOOO 1.29387 Aldehyde C 2 H 4 44.0 1.5320 1.9811 Ammonia NH 3 iy.O 0.5960 0.7707 Amylic alcohol C 5 H 12 88.0 3.1470 4.0696 As 4 300.0 10.3900 13.4362 Arsenious anhydride As 2 3 198.0 3.8500 7.9105 Arsine AsH 3 78.0 2.6950 3-4851 Benzene C 6 H 6 78.0 2.7700 3.5821 Bromine Br 2 160.0 5-3933 6.8697 Butane C4H 10 58.0 2.0041 2.5914 Carbon bisulphide CS 2 76.0 2.6450 3.4204 Carbon dioxide C0 2 44.0 1.5290 1.9662 Carbon monoxide CO 28.0 0.9674 1.2510 Carbon oxychloride COC1 2 99.0 34163 44174 Carbon oxysulphide COS 60.0 2.0748 2.6828 Chlorine C1 2 71.0 2.448 3.1801 Chlorine cyanide CNC1 61.5 2.1244 2-7473 Chloroform CHC1 3 II9-5 4.2150 44507 (CN) 2 52.0 1.8064 2.3360 Ethane C 2 H 6 30.0 i .0366 1.3404 Ether C 4 H ]0 74-0 2.5650 3-3I70 Ether acetic C 4 H 8 0, 88,0 3.0670 3.9662 Ethylic alcohol C 2 H 6 46.0 1.6133 2.0862 Ethylene C 2 H 4 28.0 0.9674 1.2510 Hydrobromic acid HBr 81.0 2.7310 3.5316 Hydrochloric acid HC1 36.5 1.2474 1.6131 Hydrocyanic acid HCN 27.0 0.9456 1.2228 Hydrofluoric acid HF 2O.O 0.6930 0.8960 Hydrogen H 2 2.0 0.06926 0.08958 Hydrogen sulphide (sulphuret- ted hydrogen) H 2 S 34-0 1.1921 I.54I6 Hydroiodic acid HI 128.0 4-433 5.7456 Iodine la 254.0 8.7160 11.2710 Mercury Hg 2OO.O 6.9760 9.0210 Methane CH 4 16.0 0.5560 0.7155 Methylic alcohol CH 4 32.0 1. 1200 4483 Nitric oxide NO 30.0 1.0390 .3436 Nitrogen N 2 28.0 0.97137 .25617 Nitrous oxide N 2 O 44.0 1.5269 9745 Oxygen 2 32.0 I.I056 .4298 Phosphine (phosphuretted hy- PH 3 34-0 1.1850 J-SSS Phosphorus P 4 124.0 4.3550 5-6318 Phosphorus pentachloride PC1 5 208.5 3.6500 4.7201 Phosphorus trichloride PC1 3 137-5 4.7420 6.1299 Propane C 3 H 8 44.0 1.5204 1.9660 Selenium Se 2 158.0 5.7000 7.0229 Selenium hydride SeH 2 81.0 2.7846 3.6011 TABLES. SPECIFIC GRAVITY OF GASES AND VAPORS Continued. 499 Gas or vapor. Weight of one liter in Specific grains at Molecular gravity: atoC. and Formula. weight. (air=i). 760 mm. SiCL 169.5 c n<~& SiF 4 104.0 O'7J7~ 3.6000 46^,1 H 2 O 18.0 o 62^"; V3O*t 0.8063 Si 64.0 ***^*OQ 2.2OOO 2 8<1^O Sulphuric acid Sulphuric acid Sulphurous aci H-jSO* 98.0 S0 3 80.0 SO 2 64.0 2.1500 2.7630 2.234 ^"^ JL ro 2.7803 3-5730 2.8689 anhydrous . d, anhydrous .... Te 2 256.0 8.9160 II ^"*IO Tellurium hyd T"irl# TeH 2 130.0 4.5276 * oo i ^ J 5.8550 COMPARISON OF THE DEGREES OF BAUME'S HYDROMETER WITH THE REAL SPECIFIC GRAVITIES. i. For Liquids Heavier than Water. 1 Specific Specific Specific Degrees. gravity. Degrees. gravity. Degrees. gravity. 1. 000 26 1. 206 52 1.520 I 1.007 27 1.216 53 1-535 2 1.013 28 1.226 54 i-55i 3 1.020 29 1.236 55 1-567 4 1.027 30 1.246 56 1-583 5 1.034 31 1.256 57 i. 600 6 I.04I 32 1.267 58 1.617 7 1.048 33 1.277 59 1.634 8 1.056 34 1.288 60 1.652 9 1.063 35 1.299 61 1.670 10 I.O7O 36 I 310 62 1.689 ii .078 37 1.322 63 1.708 12 .085 38 1-333 64 1.727 13 .094 39 1-345 65 1-747 14 .101 40 1-357 66 1.767 15 .109 4i 1.369 67 1.788 16 .118 42 1.382 68 1.809 i? .126 43 1-395 69 1.831 18 .134 44 1.407 70 1.854 19 .143 45 1.420 7i 1.877 20 .152 46 1-434 72 1.900 21 .160 47 1.448 73 1-924 22 .169 48 1.462 74 1.949 23 .178 49 1.476 75 1.974 2 4 .188 50 1.490 76 2.000 25 .197 5i 1.504 1 The Table of Comparison of the Degrees of Baum's Hydrometer with the real Specific Gravities for liquids lighter than water will be found on page 371. QUANTITATIVE ANALYSIS. OF THE PROPORTION BY WEIGHT OF ABSOLUTE OR REAL ALCOHOL IN 100 PARTS OF SPIRITS OF DIFFERENT SPECIFIC GRAVITIES. (MENDELEJEFF. y Specific Per Specific Per Specific Per gravity atisC. cent, of real gravity, at 15 C. cent, of real gravity at 15 C. cent, of real alcohol. alcohol. alcohol. 0.9991 0-5 0.9501 34 0.8773 68 0.9981 I 0.9491 35 0.8750 69 0.9963 2 0-9473 36 0.8726 70 0-9945 3 0-9455 37 0.8702 71 0.9928 4 0.9436 38 0.8678 72 0.9912 5 0.9417 39 0.8655 73 0.9896 6 0-9397 40 0.8631 74 0.9881 7 0.9377 4i 0.8607 75 0.9867 8 0-9357 42 0.8582 76 0-9853 9 0.9336 43 0.8558 77 0.9839 10 0.9316 44 0.8534 78 0.9826 ii 0.9294 45 0.8510 79 0.9813 12 0.9273 46 0.8485 8, 0.9801 13 0.9251 47 0.8460 81 0-9789 14 0.9230 48 0.8435 82 0-9777 15 0.9208 49 0.8410 83 0.9765 16 0.9186 50 0.8386 84 0-9753 17 0.9164 51 0.8360 85 0.9741 18 0.9142 52 0-8335 86 0.9728 19 0.9119 53 0.8309 87 0.9716 20 0.9097 54 0.8283 88 0.9704 21 0.9074 55 0.8257 89 0.9691 22 0.9052 56 0.8230 90 0.9678 23 0.9029 57 0.8203 9 1 0.9665 24 0.9097 58 0.8176 92 0.9651 25 0.8983 59 0.8149 93 0.9637 26 0.8960 60 O.8l2O 94 0.9623 2 7 0.8937 61 0.8092 95 0.9608 28 0.8914 62 0.8063 96 0-9593 2 9 0.8890 63 0.8034 97 0-9577 30 0.8867 64 0.8004 98 0.9561 31 0.8844 65 0-7973 99 0.9544 32 0.8820 66 0.7942 100 0.9527 33 0.8797 67 iPogg. Annallen , 138, p. 103. TABLES. 501 OF THE PROPORTION BY VOLUME OF ABSOLUTE OR REAL ALCOHOL IN 100 VOLUMES OF SPIRITS OF DIFFERENT SPECIFIC GRAVITIES AT 15. 5 C. (MENDELEJEFF.) 1 100 volumes spirits. Contain volumes TOO volumes spirits. Contain volumes zoo volumes spirits. Contain volumes Specific gravity. of real alcohol. Specific of real gravity. alcohol. Specific gravity. of real alcohol. 1. 0000 0.9604 34 0.8950 68 0.9985 I 0-959 1 35 0.8925 69 0.9970 2 0.9577 36 0.8901 7 0.9956 3 0.9563 37 08876 7 1 0.9942 4 0.9548 38 0.8851 72 0.9928 5 0.9534 39 0.8826 73 0-99I5 6 0.9518 40 0.8800 74 0.9902 7 0.9503 4i 0.8774 75 0.9889 8 0.9486 42 0.8747 76 0.9877 9 0.9470 43 0.8721 77 0.9866 10 0.9454 44 0.8694 78 0.9854 ii 0.9436 45 0.8667 79 0.9844 12 0.9419 46 0.8640 80 0.9832 13 0.9400 47 0.86II 81 0.9822 H 0.9382 48 0.8583 82 0.9811 15 0.9364 49 0.8554 83 0.9801 16 0.9344 50 0.8525 84 0.9790 17 0.9325 51 0.8496 8 5 (5.9781 18 0.9305 52 0.8466 86 0.9771 19 0.9285 53 0.8435 87 0.9761 20 0.9265 54 0.8404 88 0-9751 21 0.9244 55 0.8372 89 0.9741 22 0.9222 56 0.8340 90 0.9731 23 0.9201 57 0.8306 9i 0.9720 24 0.9180 58 0.8272 92 0.9709 25 0.9158 59 0.8236 93 0.9699 26 0.9139 60 0.8199 94 0.9688 27 0.9113 61 0.8161 95 0.9677 28 0.9090 62 0.8121 96 0.9667 29 0.9067 63 0.8080 97 0.9654 30 0.9045 64 0.8035 98 0.9642 31 0.9022 6 5 0.7989 99 0.9630 32 0.8997 66 0.7939 100 o. 9 6 I7 33 0.8974 67 Pogg. Annallen, 138, 230. 5 02 QUANTITATIVE ANALYSIS. TABLE SHOWING PERCENTAGES OF REAL SULPHURIC ACID (H 2 SO 4 ) COR- RESPONDING TO VARIOUS SPECIFIC GRAVITIES OF AQUEOUS SULPHURIC ACID. Bineau ; Otto. Temperature 15 C. Specific gravity. Per cent. Specific gravity. Per cent. .Specific gravity. Per cent. Specific gravity. Per cent. 1.8426 100 I-675 75 1.398 50 I.I82 25 1.842 99 1.663 74 1.3886 49 I.I74 24 1.8406 98 1.651 73 1-379 48 1.167 23 1.840 97 1.639 72 1.370 47 i.!59 22 1.8384 96 1.627 7i 1.361 46 1.1516 21 1.8376 95 1.615 70 i'35i 45 1.144 20 1.8356 94 1.604 69 1.342 44 1.136 19 1.834 93 1-592 68 1-333 43 1.129 18 I.8 3 I 92 1.580 67 1.324 42 1. 121 17 1.827 9i 1.568 66 I.3I5 4i I.II36 16 1.822 90 1-557 65 1.306 40 1.106 15 1.816 89 1-545 64 1.2976 39 1.098 14 1.809 88 1-534 63 1.289 38 1.091 13 1.802 87 1-523 62 1.281 37 1.083 12 1.794 86 1.512 61 1.272 36 1.0756 II 1.786 85 1.501 60 1.264 35 i. 068 IO 1.777 84 1.490 59 1.256 34 1.061 9 1.767 83 1.480 58 1.2476 33 1-0536 8 I-756 82 1.469 57 1.239 32 1.0464 7 1-745 81 1-4586 56 1.231 3i 1.039 6 1-734 80 1.448 55 1.223 30 1.032 5 1.722 79 1.438 54 1.215 29 1.0256 4 1.710 78 1.428 53 1.2066 28 1.019 3 1.698 77 1.418 52 1.198 27 1.013 2 1.686 76 1.408 5i 1.190 26 1.0064 I TABLES. 503 TABLE GIVING THE PERCENTAGES OF HYDROCHLORIC ACID CONTAINED IN AQUEOUS SOLUTIONS OF THE GAS OF VARIOUS SPECIFIC GRAVITIES. Ure. Temperature 15 C. pacific Per cent. Specific Per cent. Specific Per cent. Specific Per cent avity. HC1. gravity. HC1. gravity. HC1. gravity. HC1. 1.200 40.777 I.I5I5 30.582 1. 1000 20.388 1.0497 10.194 .1982 40.369 I.I494 30.174 1.0980 19.980 1.0477 9.786 .1964 39.961 .1473 29.767 1.0960 19.572 1.0457 9-379 .1946 39-554 .1452 29-359 I-I939 19.165 1-0437 8.971 .1928 39-I46 -I43I 28.951 I.09I9 18-757 1.0417 8.563 .1910 38.738 .1410 28.544 1.0899 18.349 1-0397 8.155 .1893 38.330 .1389 28.136 1.0879 17.941 1.0377 7-747 1875 37.923 .1369 27.728 1.0859 17.534 1.0357 7-340 .1857 37.5I6 -1349 27.321 1.0838 17.126 1-0337 6.932 .1846 37-108 -1328 26.913 I. O8l8 16.718 1.0318 6.524 .1822 36.700 .1308 26.505 1.0798 16.310 1.0298 6.116 .1802 36.292 .1287 26.098 1.0778 15.902 1.0279 5.709 .1782 35.884 .1267 25.690 1.0758 15494 1-0259 5-301 .1762 35.476 .1247 25.282 1.0738 15.087 1.0239 4-893 .1741 35.068 .1226 24.874 I.07I8 14.679 1.0220 4.486 .1721 34.660 .1206 24.466 1.0697 14.271 1. 0200 4.078 .1701 34.252 .1185 24-058 1.0677 13.863 I.OlSo 3.670 .1681 33.845 .1164 23.650 1.0657 13456 I. Ol6o 3.262 .1661 33-437 1143 23.242 1.0637 13.049 I.OI40 2.854 .1641 33-029 .1123 22.834 I.o6l7 12.641 1. 0120 2-447 .1620 32.621 .1102 22.426 1.0597 12.233 I.OIOO 2.039 1599 32.213 .I082 22.019 1-0577 11.825 I.OOSO 1.631 .1578 31-805 .1061 2I.6II L0557 11.418 I. 0060 1.124 1557 31.398 1.1041 21.203 1.0537 I I. 010 I.OO4O 0.816 .1536 30.990 1. 1020 20.796 I.05I7 10.602 1.0020 0.408 504 QUANTITATIVE ANALYSIS. Percentages and Gravity of Nitric Acid. TABLE SHOWING THE PERCENTAGES OF NITRIC ACID (HNO 3 ) IN AQUEOUS SOLUTIONS OF VARIOUS SPECIFIC GRAVITIES. Kolb, Ann. Chem. Phys., 4, 136. Temperature 15 C. Per cent. HNO,. Specific gravity. Per cent. HN0 3 . Specific gravity. Per cent. HNO 3 . Specific gravity. Per cent. Specific HNO 3 . gravity. IOO.OO 1-530 80.96 1.463 59-59 1.372 39-00 244 99.84 1.530 80.00 1.460 58.88 1.368 37-95 237 99.72 1.530 79.00 1.456 58.00 L363 36.00 .225 99-52 1.529 77-66 1.451 57.00 1.358 35-oo .218 97.89 1.523 76.00 1-445 56.10 1-353 33-86 .211 97.00 1.520 75-00 1.442 55-oo 1.346 32.00 .198 96.00 1.516 74-01 1.438 54.00 I.34I 31.00 .192 95-27 I.5H 73.00 1-435 53-81 1-339 30.00 .185 94.00 1.509 72.39 1.432 53-00 1-335 29.00 .179 93.01 1.506 71.24 1.429 52.33 i-33i 28.00 .172 92.OO I.503 69.96 1-423 50.99 1-323 27.00 .166 9I.OO 1.499 69.20 1.419 49-97 !-3 J 7 25-71 157 90.00 1.495 68.00 1.414 49.00 1.312 23.00 .138 89.56 1.494 67.00 1.410 48.00 1.304 20.00 .120 88.00 1.488 66.00 1.405 47.18 1.298 17.47 .105 8745 1.486 65.07 1.400 46.64 1-295 15.00 .089 86.17 1.482 64.00 1-395 45-00 1.284 13.00 .077 85.00 1.478 63-59 1-393 43-53 1.274 11.41 .06 7 84.00 1.474 62.00 1.386 42.00 1.264 7.22 045 83.00 1.470 61.21 1.381 41.00 i- 2 57 4.00 .022 82.00 1.467 60.00 1-374 40.00 1.251 2.00 .010 NORMAL SOLUTIONS. Normal sulphuric acid contains 49.0 grams H 2 SO 4 per liter. One cc. contains 0.049 gram H Q SO 4 . Normal hydrochloric acid contains 36.37 grams HC1 per liter. One cc. contains 0.036 gram HC1. Normal nitric acid contains 63.0 grams HNO 3 per liter. One cc. con- tains 0.063 gram HNO 3 . Normal oxalic acid contains 63.0 grams C^H^H^O per liter. One cc. contains 0.045 gram C 2 O 4 H 2 . Normal potassium hydroxide contains 56.0 grams KOH per liter. One cc. contains 0.056 gram KOH. Normal sodium hydroxide contains 40.0 grams NaOH per liter. One cc. contains 0.040 gram NaOH. Normal sodium carbonate contains 53.0 grams Na 2 CO 3 per liter. One cc. contains 0.053 gram Na 2 CO 3 . One-half normal ammonium hydroxide contains 8.5 grams NH 3 per liter. One cc. contains 0.0085 gram NH 3 . NORMAL SOLUTIONS. 505 One-tenth normal potassium permanganate contains 3.156 grams K 2 Mn 2 O 8 per liter. One cc. contains 0.0008 gram oxygen. One-tenth normal potassium bichromate contains 4.913 grams K 2 Cr 2 O 7 per liter. One cc. contains 0.0049 gram K 2 Cr 2 O 7 . One-tenth normal iodine contains 12.65 grams I per liter. Onecc. equiv- , f 0.01265 gram iodine. \ 0.02480 gram Na^-A-sH^O. One-tenth normal sodium thiosulphate contains 24.8 grams Na.jS 2 O 3 . 5 H,0 per liter. One cc. equivalent to {$ Sis^O. One-tenth normal silver nitrate contains 16.966 grams AgNO 3 per liter. One-tenth normal sodium chloride contains 5.837 grams NaCl per liter. Onecc. equivalenttoj^S gram Nad. For ammonium molybdate solution consult page 177. For a magnesia mixture consult page 178. INDICATORS. Phenolphthaiein Alcoholic solution I : 30. Colorless by acids ; red violet by alkalies ; also by CO 2 . Methyl orange Water solution i : 1000. Yellow color by alkalies; pur- ple red by mineral acids ; not affected by CO 2 . Litmus Water solution. Blue by alkalies ; red by acids. Cochinelle Three parts cochinelle ; 400 parts H 2 O ; 100 parts alcohol. Violet by alkalies ; yellowish red by acids. INDEX. Page. ABEL'S closed tester for oils 45 Absorptive power of building stones 304 Acetylene, weight of one liter 237 heating value per cubic foot 259 Acids, free, detection of in paper 338 Acidity of oils 408 Adulterations in soap 349 Agalite, in paper 34 2 Air pyrometer 467 Air required for combustion of one kilo of hydrogen 122 carbon 122 specific heat of 261 thermometer 467 weight of liter 237 Ajax metal, composition of 316 Alcohol, table of specific gravity 5 Alkaline permanganate solution 74 Allen's method for determination of FeO in iron ores 32 scheme for analysis of unsaponifiable matters in soaps 351 Alloys, analysis of 311 Alum, determination of A1 2 O 3 in 2 in paper 339 Aluminum, " bourbounz," composition of 317 bronze, composition of 316 analysis of 317 determination of, in iron and steel 188 sulphate, in paper 339 Ammonia, free and albuminoid in water 74 free water, method of preparation 74 Table of gravities of solutions of 495 Ampere 480 Analysis of American waters 84 Animal size, detection of in paper 339 Anthracene, evaporative power in pounds of water at 100 C 292 Anthracite producer gas, analysis and heating value 270 Antifriction metal, composition of 316 Antimony and tin, separation of , in alloys 314 quantitative determination of, in alloys 323 vermilion 453 Anti-incru stating compound for locomotive boilers 97 Apparent specific gravity for cote 25 Approximate heating value of coals 145 Aqua regia method for determination of sulphur in iron and steel 155 Archbutt's apparatus for purifying water 107 Araeo-picnometer 376 Argentine, composition of 316 Arsenic bronze 317 trioxide solution 195 Asbestos, use of in mechanical filtration of water 113 paints 463 INDEX. ^- 507 Ash, determination of, in coal and coke .............................................. 20 paper ....................................................... 341 Ashless filters ......................................................................... I Ashbury metal... ..................................................... . ................ 316 Asphalt paint ........................................................................... 456 Asphaltum black ........................................................................ 454 Atomic weights, table of ................................................................ 488 Available heat of boilers ............................................................... 125 "B " ALLOY, P. R. R., composition of ................................................. I Babbit metal, composition of ........................................................... 316 method of analysis .............. ....................................... 314 Bacteriological examination of water, references upon ............................... 92 Barrus coal calorimeter ........ . ..................................................... 135 Barytes in paint ......................................................................... 423 Basic slag, analysis of .................................................................. 39 Baum hydrometer ..................................................................... 377 Beck hydrometer ....................................................................... 377 Beef tallow .............................................................................. 358 Bell metal, analysis of .................................................................. 313 Bettel's method for determination of Tiin iron ores ................................... 35 Bennert drying apparatus .............................................................. 17 Benzene, heating power per kilo ....................................................... 259 Berthelot's bomb ........................................................................ 126 Bibliography of electrolytic assay of copper, references .............................. 8 Bituminous coal, analysis of ............................................................ 23 Blanc Fixe ............................................................................... 453 Blank form for reporting slag analyses ................................................ 38 Blast furnace, mechanical energy of ................................................... 42 Blast furnace slag, analyses of ......................................................... 37 calculation of ...................................................... 48 table of types of ................................................... 54 Blast furnace, the charging of .......................................................... 43 graphical method ...................................... 55 Blown oils ............................................................................... 400 Bog head cannel coal, analysis of ...................................................... 22 Bohme-Hammer apparatus for cement ................................................ 210 Bohme, Dr., tests upon cement ......................................................... 214 Boiler compound, Chicago, Milwaukee & St. Paul Railway .......................... 97 Boiler scale, composition of ............................................................. 92 Boiler tests .......................................................................... 125, 144 Bone-black ............................................................................. 454 Bone-fat .................................................................................. 416 Brass, analysis of ............. . .......................................................... 313 Braun's electric pyrometer ............................................................. 172 Breaking strength of paper ................................................. . .......... 344 Bremen blue ............................................................................ 454 Brick, absorptive power of ............................................................. 304 crushing strength ................................................................ 304 the testing of .................................................................... 308 Brink and Hubner compressing machine for cements ................................ 222 Briquettes of Portland cement, preparation of ........................................ 210 and sand, preparation of .............................. 211 Bristol's recording thermometer ....................................................... 469 Britannia metal, composition of ........................................................ 316 British terne plate, analysis of ......................................................... 325 508 INDEX. Brix hydrometer 377 Bromine method for determination of sulphur in iron and steel 150 Bronze for bearings, analysis of 313 Brown's pyrometer 469 Bruce, E). M.,;Babbitt metal analysis 313 Brunswick blue 454 " B. T. U.," definition of 120 Buckley's pyrometer 469 Buignet apparatus for tensile strength of cements 220 Building stones, absorptive power of 304 analysis of 299 crushing strength of ... 304 frost test 306 Bunsen photometer 275 Bunsen valve * 12 Burham's Portland cement, analysis of 205 Butane, (C 4 H 10 ), heating power per cubic foot 259 " B. & O " R. R., specifications for compound oils 423 CADMIUM chloride solution for determination of sulphur in iron and steel 155 Cadmium yellow 453 Calcium carbonate, as an ingredient of Portland cement 201 Calcium chloride, table of specific gravity of solution 498 Calcium phosphate, determination of P 2 O 6 in 12 Calculation ol blast furnace slag 49 the heating power of coal 121 Calorie, the definition of 122 the pound, definition of 120 Calorific power of coal and coke 120 Calorimeter, the Barrus 135 the Carpenter 139 the Hartley 284 the Junker 287 the Mahler 125 Calorimetry 125 Camelia metal, composition of 316 Camp, J. M., iodine method for sulphur in steel 154 Campbell, K. D., method for determination of nickel 227 Caprylic anhydride 353 Carbon in coal, determination of 115 compounds of iron 170 determination in iron and steel 157 dioxide, determination of in chimney gases 234 limestone 17 specific heat of 261 weight of one liter 237 monoxide, determination of, in chimney gases 237 heating value of 259 specific heat of 261 solubility in distilled water 237 weight of liter 237 Carbonic acid as an ingredient of Portland cement 205 Car-box metal, composition of.. - 316 Carburetted water-gas, manufacture of 265 Carnelly's & Burton's pyrometer 472 Carnot's method for determination of aluminum in steel 190 INDEX. 509 Carpenter's coal calorimeter 1-59 Carder's hydrometer 377 Cast steel, determination of sulphur in 150 Castile soap, analysis 351 C. B. & Q. R. R.. specifications for black engine oil 425 Cement, Portland, examination of 200 Cementite 172 Centigrade degrees, table of 490 Charging of blastfurnaces 43 Chateau's color tests for oils 412 Chimney gases, analysis of 233 China clay 453 Chineseblue 454 yellow 453 Chlorine, determination of, in water 73 Chlorides, determination of, in paper 338 Cholesterol 416 Chrome green, analysis of 459 Chrome iron ore, analysis of 33 Chrome steel, designation of the various products of 326 determination of chromium in 327 mechanical tests of 328 method of analysis 326 Chrome yellow 457 analysis of 435 Chromium trioxide, determination of, in K 2 Cr 2 O 7 14 Chromous chloride for absorption of oxygen 251 Classification of iron and steel by Wm. Kent 187 Midvale Steel Co 183 Clay, analysis of 299 Cleveland cup for flash and fire tests of oils 427 Cloud test for oils 428 Coal, method of determining the quantity of tar in 299 Coal gas analysis 245 Coal and coke analysis 19 Coal and coke, determination of the heating power 114 Coal tar black 454 Cobalt blue 454 green 454 Coefficient of friction 417 Coal test for oils 377 Color method for determination of manganese 193 Colorimeter, Stammer's 432 Wilson's 433 Wolff's 77 Combustible gases, heating value of 258 Commercial soaps 349 Congealing points of fatty acids 370 Conversion tables 489 Converter slag, analysis of 39 Copper-ball pyrometer 469 Copper, determination of, in alloys 322 in copper sulphate 2 by electrolysis 5 volumetrically 4 510 INDEX. Copper green 454 Cotton fibers in paper, detection of 337 Cosmoline 365 Coulomb, the 481 Cracking of Portland cement 205 Cresol (C 7 H 8 O), evaporative power in pounds .of water at 100 C 292 Croasdale Stuart, bibliography of the electrolytic assay of copper 8 Crushing strength of coke 24 Crushing tests of cements 222 Cumol (C 9 H 12 ) 292 Cumberland semi-bituminous coal, analysis of 147 Cupric ferrocyanide as indicator 232 Cuprous chloride solution for absorption of CO 239 Current, electrical 480 Cylinder deposits, analysis of 450 Cylinder oil, specifications for 424 Cymogene 3 6 4 Cymol 292 DANFORTH oil 3 6 4 Dasymeter 242 Davidson's viscosimeter 3 8y Degras oil 4I 6 " Delta " metal for bearings 3 ! 3 Denton, J. E-, boiler test 225 Deoxidized "bronze," composition of 3I 6 Derveaux the, purifier for boiler water 105 Deville, determination of heating power of various petroleums 292 DeSmedt, E. J., tests upon Portland cement 214 " Dinas " fire clay, composition of 3 o 3 Directions for testing Portland cement by method of the American Society of Civil Engineers 205 Directions according to the official German rules 209 Donath's method for determination of Cr in chrome iron ore 33 Doolittle's torsion viscosimeter 400 Drown's method for the determination of aluminum in steel 163 Drown's method for the determination of carbon in iron and steel 163 Drying properties of paints 45 3 Dublin water works, description of the filter beds.' 86 Dudley & Pease, volumetric method for determination of phosphorus in iron and steel ... I79 Durability of paints 45 3 Dyckerhoff's Portland cement, analysis of 205 Dyne, the 480 EAST Liberty, Pa., natural gas, analysis of 273 Eggertz's method for determination of carbon in steel 168 Electrical units, definition of 480 Electrolysis, determination of copper by 5 Electrolytic method for determination of nickel 229 Electromotive force 48 1 Elementary analysis of coal 115 Elements, list of the principal 488 Elliott gas apparatus 233 Emerald green 454 Energy equivalents, table of 483 Engine oil, viscosity of 392 INDEX. 511 Engler's method for the examination of petroleum 362 viscosimeter 384 English specifications for Portland cement 213 Krd man chimney 22 Erg, the 480 Eschka-Fresenius method, determination of sulphur in coal 21 Esparto, detection of, in paper 337 Ethane (C a H 8 ), heating power per cubic foot 259 Ether petroleum 364 Ethylene (C 2 H 4 ), heating power per cubic foot 259 European river waters, composition of . 85 Evaporative power of coal 123 Evaporation, difference between theoretical and actual 125 Experimental plant for the gas-producing qualities of coal 297 PAI J A cement testing machine 211 Fairbank's cement testing machine 208 Farad, the 481 Fargo, D. T.. analysis of well-water from 99 Fatty acids in soap, determination of 353 Feed-water heaters - 99 Ferrite 171 Ferro-aluminum 316 analysis of 318 Ferro- tungsten 316 Fiber in paper, determination of 331 Filter presses '. in Filters, sand 86 Fineness, determination of, in Portland cement 206 Fire clays, composition of various 303 Fire-proof paints 463 Fire sand, analysis of 299 Fire test of oils 404, 428, 429 Fisher's coal calorimeter 139 Fixed carbon, determination of, in coal and coke.. 19 Flash test of oils 403, 428, 429 Flue gases, analysis of with Orsat-Muencke apparatus 237 Ford, S. A., analysis of natural gas by 273 France, specifications for cements required in 219 Fre nc ochre 463 Frankfort black 454 Fredonia natural gas, analysis of 274 Free acid in boiler water, determination of 68 Free acids in paper, determination of 338 Free alkali in soap 355 Free sulphur trioxide, determination of, in fuming H,S.,O 7 190 Freight car oil, specifications for 424 Friction, coeffici ent of 417 Fulton's table of physical and chemical properties of coke 28 GAIvENA, determination of lead in 9 Garrison, H. T v ynwood, microscopical examination of building stones 310 Gas, average production from one ton New Castle coal 299 coal, analysis and valuation 268 experimental plant for the determination of the gas-producing qualities of coal 297 natural , analysis and val uation 272 oil, analysis and valuation. 2- 1 512 INDEX. Gas, producers 270 production of, from coal 296 table to facilitate the correction of the volume of gas at different temperatures and under different atmospheric pressures 283 Tessie du Motay, analysis and valuation 270 water, analysis and valuation 267 Gases, chimney, analysis and valuation 267 Gasoline 364 Gaultier, analysis of ash of coke by 24 Gelatine, detection of, in sizing of paper 339 Gelatine oil 399 George's creek coal, determination of heating power 138 German Portland cements, analysis of 205 German silver, composition of 316 Gibb's viscosimeter 390 Glosway's method for determination of nitrites in water 81 Glycerine, in soaps and fats, determination of 359 Gold chloride solution for the detection of " mechanical wood fiber " in paper 333 Gottlieb's qualitative test for resin in soaps 355 Gottstein's method for determination of wood fiber in paper 334 Goubert feed water heater, the 100 Granite, absorptive power of 304 crushing strength of 304 Grant cement testing machine, the 213 Graphic method for calculating blast furnace slag 55 Graphite black 454 Green, chrome 454 copper 454 mineral 454 Paris 454 Griess' method for determination of nitrites in water 81 Gulcher's thermo-electric pile 7 Guthrie's " entectic " composition of 317 Gypsum in paint 453 HANNOVER coal gas, analysis of 269 Hardness of water, determination of 69 standards of. 72 Hart, B. F., Jr., chrome steel analyses by 327 Hartig-Rensch apparatus 346 Hartley's calorimeter for combustible gases 284 Hay, Dr. G., analysis of natural gas by 272 Heat effective, method of calculation for liquid fuels 293 Heat energy, in blast furnace 42 Heating power of coal and coke 114 Heating value of combustible gases 258 hydrogen 259 Heckel, G. B., description of friction machine 417 Heidelberg coal gas, analysis of 269 Heidenreich's color test for oils 412 Hematite, scheme for analysis of 29 Hemp fibers, detection of, in paper 337 Hempel gas apparatus 245 Henderson-Westhoven lubricant tester 418 Henry, the 481 Herrick, W. Hale, apparatus for electrolysis of copper 7 INDEX. 513 Hobson's hot blast pyrometer 468 Holde, method for detection of rosin oil 414 Hoppes feed-water heater, the 101 Hydration, water of, determination in iron ores 31 Hydrochloric acid, table of gravities 503 Hydrogen, determination of.incoal u 5 water gas II5 heating value of 263 specific heat of 261 weight of one liter 237 Hydrometry 371 Hygroscopic water, determination of, in coal 119 II/IyUMIXANTS, valuation of, in gases for heating purposes 259 Illuminating oils 363 Indian red . 453 Indicators used in titration 506 Inductance 481 Iodine absorption of oils 401 method for determination of tin in tin plate 325 sulphur in steel 154 Iron, determination of, in ammonio-ferric sulphate IT carbon in 157 in iron wire i manganese in 192 phosphorus in 176 silicon in 156 sulphur in rso in tin plate 325 Iron ores, scheme for analysis of 29 composition of various 36 JACKSONVILLE, Fla.. analysis of well water from 84 James River, Va., analysis of water from 84 Jameson apparatus for making Portland cement briquettes 217 Jenkin's method of calculating blast furnace charges 55 Jersey City, N. J., hardness of water supplied to 72 Joule, the 481 Joule's law 482 Jones' method for determination of manganese in manganese bronze 317 Junker calorimeter, description of 289 Jute, detection of , in paper 337 KANE natural gas, analysis of 274 Kaolin, analysis of 299 Keith oil gas 271 Kennicutt's method for determination of chromium in chrome iron ore 33 Kent, Wm., apparatus for determining the heating power of different fuels 142 table of approximate heating value of coals 145 calculations for determination of the various losses of heat in boiler practice 147 classification of iron and steel 187 Kerosene 365, 426 Kilo- Watts, definition of 482 King's yellow 453 Koppe-Saussure air hygrometer 346 Krem's white 456 514 INDEX. LAMPBLACK 454 Langley's method for determination of carbon in iron and steel 63 Lard '. 358 Laundry soaps 349 Law regulating the standard of illuminating oils 430 Lead, determination of, in galena 9 tin plate 324 alloys 321 peroxide, for determination of manganese in steels 194 sulphate paint 453 LeChatelier's thermo-electric pyrometer 473 LeChatelier, H., tests for hydraulic materials 221 Lemon chrome 458 Lennox creek, analysis of water of 98 Lepenau, Dr., septometer : 386 Ligroine '. 364 Limestone, scheme for analysis of 15 absorptive power of 304 crushing strength of 304 Limit of variation in composition of Portland cements 200 Limonite, scheme for analysis of 29 Linen fibers in paper, detection of 334 Liquid fuel 392 Litharge, use of, in determination of the heating power of coal and coke 114 Lithophone, composition of 455 Locomotives, water for 96 Love, E. G., calorimeter tests of illuminating gases 285 Lowe, the, water gas process 265 Lubricant, conditions required of a good 366 Lubricating oils, the examination of 366 Lux's qualitative test for fatty oils in mineral oils 414 MACADAM, W. Ivison, tests upon oil gas 271 Magnesia mixture, formula for preparation 178 limit of amount in Portland cement 201 Magnesium sulphate, determination of SO 3 in 8 Magnesium chloride, corrosive action in boilers 66 Magnesite 453 Magnet steel, composition of 330 Magnetic properties of nickel steel 185 Magnetite, scheme for analysis of 29 Magnolia metal, composition of 313 Mahler's calorimeter 126 Manganese, brown 453 green 454 colorimetric method for determination of 193 determination of, in iron and steel 192 Textor's method for rapid determination of 194 bronze, composition of , 317 determination of, in chrome steel 329 manganese bronze 317 tin plate 325 Marble, absorptive power of 304 crushing strength of 304 Margarine 358 Marine soap, analysis of 361 Martensite 172 INDEX. 515 Martin's formula for non-inflammable paint 464 Massie's nitric acid test for oils 413 Maumene's test for oils 410 Measurement of electrical energy 482 Mechanical energy developed by the blast furnace 43 Mechanical testing of Portland cement 205 Medicated soaps 349 Megohms 481 Melting-points of fatty acids 370 Mercury thermometers for high temperatures 466 Mesure and Noriel's pyrometer 474 Metalline, composition of 313 Methane, determination of, in gases 257 heating value of 259 specific heat of 261 weight of one liter 237 Metric system of weights and measures, tables of 494 Metropolitan R. R. formula for paints used 462 Mexican petroleum, analysis of 364 Mica grease 451 Micro-farad 481 Michaelis machine for testing Portland cements 211 Microscopical examination of building stones 310 paper <~ 334 Midvale Steel Co., classification of steel by 183 Mill cinder, analysis of 39 Mineral green ; 454 soap stock 352 Molybdate of ammonia, formula for preparation of standard solution of 177, 182 Monongahela river water, partial analysis of 59 Morgan's colorimetric method for determination of manganese in steel 194 Mortar, absorptive power of 304 Mt. Savage, Md., fire clay, composition of 303 Munz metal, composition of 313 Mutton tallow 358 NAPHTHA group in petroleum, divisions of 364 Naphthalene (C 10 H 8 ), heating value per kilo, per pound, per cubic foot 260 evaporative power in pounds of water at 100 C . . 292 Natural gas as the standard of heating value for combustible gases 263 Nessler reagent, for water analysis 74 Newbigging's experimental plant for the determination of the gas producing qual- ities of coal 297 New Castle coal, illuminating value of 299 New Lisbon, Ohio, natural gas, analysis of 273 New York City water gas, heating value per cubic foot 286 Nickel, determination of in nickel-steel 227 electrolytic method for determination of nickel in nickel-steel 229 volumetric method for determination of nickel in nickel-steel 230 steel, magnetic properties of 185 Nitrates, determination of, in water 81 Nitric acid, tables of specific gravities 504 Nitrites, in water, determination of 81 Nitrogen, determination of, in coal 117 in chimney gases 236 solubility of, in distilled water 237 specific heat of 261 516 INDEX. Nitrogen, weight of one liter 237 Nordhausen oil of vitriol, determination of SO 3 and H 2 SO 4 in 190 Normal solutions 504 Noyes, W. A., analysis of natural gas 273 OCEAN waters, composition of 85 Oleic acid 409 Ohm, The 481 Ohm's law 482 Oil, acidity of 408 Oil, American sod 380, 416 bank 380, 397 black engine 425 blackfish 381 blown 377 castor 380, 377, 398, 399, 412, 414 cocoanut 358, 370 codliver 358, 414, 412 color reactions with nitric acid and sulphuric acids 412 cotton-seed 370, 377, 381, 398, 403, 412 cylinder, specifications for 425 Danf orth 364 degras 380. 398, 416 dog fish 380, 412, 414 dolphin 377 earthnut 412, 414 elain 380, 414 engine 381 freight car 381, 424 gelatine 397.398 headlight '. 426 herring 381, 397, 403 hoof 381, 403 illuminating 426, 427 kerosene 362 lard 370, 377, 398, 399, 403, 409, 412, 414 linseed 358, 409, 453 marine 399 menhaden 377, 381, 412, 414 mineral sperm 426 neat's foot 377, 381, 398, 403, 409, 412, 414 oleo 403, 412, 414 olive 370,377. 381, 397,398,403, 409.4H palm 370,358,409 paraffin 365, 409 gas 362 passenger car 381 , 423 porpoise head 397, 398, 403 rape-seed 358, 370, 397, 398, 399, 412, 414 rosin 377,398,403,412,414 sea elephant 380, 397, 412 sesame 370 Smith's Ferry 365 sperm 377, 380,398,399,403,409,412,414 strait' s 380 sunflower 358 tallow 370,377,380,412,414 INDEX. 517 Oil , valve 392 whale 390,398.403,412,414 white seat blown 397, 398 150" fire test 427 300 fire test 427 Oils, flash and fire tests of 403 iodine absorption of 401 Maumene's test for 410 specific gravity of 371 viscosity of 383 Oil gas, analysis and heating value of 271 method of manufacture 271 Olefiant gas, heating power per kilo, per pound, per cubic foot 259 Olive oil soap, analysis of 361 Olsen cement testing machine 208 Organic and volatile matter in water, determination of 82 Orsat-Miiencke apparatus for analysis of flue gases 237 Oxygen, determination of , in chimney gases 235 required to oxidize organic matter in water 82 solubility of , in distilled water 237 specific heat of 261 weight of one liter 217 PAINT analysis 452 Palladium tube, for determination of hydrogen in illuminating gas 254 Palm oil soap, analysis of 361 Paper, the chemical examination of 331 determination of the ash of paper 341 breaking strength of 345 thickness 344 weight per square meter 344 clay, composition of 303 Paris-Lyon railway lubricant testing machine 419 Parson's white metal 316 Passenger car oil 365 Paul, Dr., formula for evaporative power of liquid hydrocarbons 292 Payne, H. I,., method for valuation of fuel gases 258 Peat, composition of, and evaporative power 294 Penna. anthracite coal, analysis of 23 Pensy-Martens The, closed tester for oils 407 Pentane (C 6 H 12 ) heating power per kilo, pound, and cubic foot 259 Per cent, of cells in coke 27 Percentage of fuel saved by heating feed water 104 Perkin's viscosimeter 393 Permanent hardness of water 69 Petrolatum 365 Petroleum burning oils 427 naphtha 416 technical examination of 362 Petroleums, heating power of various 292 Pewter, composition of 316 Phenol (CH 9 O), evaporative power of 292 Phillips, F. C., analysis of natural gas 274 Phillips, H. J., determination of hardness of water 70 Phosphor-bronze, composition of 316 Phosphor-tin, analysis of 319 Phosphoric acid, determination of, in calcium phosphate 12 518 INDEX. Phosphorus, determination of , in iron and steel 176 phosphor-tin 319 coal and coke 22 Physical tests of coke 24 Phytosterol 416 Pintsch oil gas, method of manufacture 271 " Pittsburg Bituminous" coal, analysis 23 Porosity of coke 26 Porter-Clark process for softening water 112 Porter, J. M., automatic cement testing machine 225 table of tests upon cements 218 Portland cement, determination of value 227 the chemical examination of 200 Potassium bichromate, determination of Cr 2 O 3 in 14 Potassium cyanide, sodium cyanide as a component of 197 Potassium hydrate solution for absorption of CO 2 239 Potter, B. C., comparative tests of heating power of coals and petroleums 296 Potassium permanganate method for determination of sulphur in iron and steel 153 Potash solutions, table of specific gravities 496 Potsdam sandstone 310 Practical photometry 275 " Pound of combustible," value of 144 Practical units (electrical) 480 Producer gas, method of analysis 245 Propane (C 3 H 8 ) , heating power per kilo, per pound, per cubic foot 259 Propylene (C 3 H 6 ,), heating power per kilo, per pound, per cubic foot 259 Prussian blue 454, 459, 464 Purification of sewage and of water by filtration 88 Pyrogallic alkaline solution of 239 Pyrometry '. 466 QUARTANE) (C4H 12 ) heating power per kilo, per pound, per cnbic foot 259 Quintane (C 6 H J2 ) heating power per kilo, per pound, per cubic foot 259 Quartz, as a constituent of Portland cement 205 Quartzites 310 RADIATION, loss of heat by 149 Railroad requirements for cold test of oils 381 Realgar 453 Recovered grease for soap making 349 Red lead 453 oil 365 Redwood's viscosimeter ... 385 Reid and Bailey's cement testing machine 212 Reimann's balance plummet 357 Refinery slag, analysis of 39 Relative heating values of coal, gas, and petroleum 295 Resin soap, analysis of 361 in soap , determination of 355 Hiibl's method for determination of 356 Twitchell's method for determination of 357 Results of tensile tests on the same sample of cement by different experts 218 Rhigolene 364 Richardson, T., method for valuation of coal for the production of gas 296 Richter's method for the determination of carbon in iron and steel 159 Riehl6 friction tester for lubricants 421 testing machine for Portland cements 209 U. S. standard automatic and autographic testing machine 305 INDEX. 519 Rock drill steel, composition of 331 Rose metal , composition of 316 Rosin, detection of, in sizing of paper 339 oil 377, 398. 403. 4", 414, 465 spirit 465 Rosine metal, composition of 316 Rossi, A. J., calculation of blast furnace slag 48 Rotary delivery 484 SAINTIGNON pyrometer 472 Salkowski's method for separation of animal and vegetable oils 415 Sand filters 86 Sandstone , absorptive power of 304 crushing strength of 304 Sanitary analysis of water 73 Saponification, method of 367 Saybolt's tester for oils 405 Saylor's Portland cement, analysis of 205 Scale forming ingredients in water, scheme for analysis of 60 Schumann's method for determination of rosin in paper 340 Secondary silica 310 Segar fire clay pyrometer 471 Sepia 453 Septometer 386 Sextane (C^H^), heating value per kilo, per pound, per cubic foot 260 Sheffield natural gas, analysis of 274 Sidersky. D., the volumetric estimation of sulphates 9 Siegert's formula 243 pyrometer 466 Siemen's producer gas, analysis and heating value 270 Siennas 453 Silicate paints 463 Silicon bronze, composition of 317 determination of, in chrome steel 329 iron and steel 156 Sizing, determination of, the nature and amount in paper 339 Slags, determination of manganese in 195 Smalts 454 Smith, E. F., electro-chemical analysis 8 Soap analysis 349 Soap-test for determination of hardness of water 70 Soda solutions, tables of gravity of 496 Sodium arsenite solution for determination of manganese in steel 195 chloride solution of, tables of gravity of 497 cyanide, as a component of potassium cyanide 197 nitrate solution 80 nitrite solution 81 Sod oil 416 Soft coal producer gas, analysis and heating value 270 Soft solder, composition of 313 Sorbite 172 South Chicago Steel Works, tests of fuels at 296 Spanning's pyrometer 466 Spathic iron ore, scheme for analysis of 29 Specific gravity of coke 24 the elements 488 oils, determination of 370 520 INDEX. Specific heats of the elements 488 Specifications for cabin car color 460 freight car color 461 Speculum metal, analysis of 313 Spiegelberg's agitation apparatus for determination of phosphorus in steels 179 Stammer's colorimeter for oils 432 Standard crushed quartz, for Portland cement briquettes 206 Standards of hardness of water 72 Starch, determination of, in paper 341 Stead's colorimetric method for carbon in steel 161 Steam pressures, tables of 492 Steel, determination of aluminium in 188 carbon in . 157 chromium in 327 manganese in 193, 194 nickel in 227 phosphorus in 176 silicon in 156 sulphur in 150 tungsten in 329 Steel plate for locomotive use 186 Steels, tensile strength of 183 " Sterro " metal, composition of 313 Stourbridge clay, composition of 303 Straw cellulose, detection of, in paper 337 Strontium white 453 Sub-carbide of i ron 171 Suchier machine 222 Sulphur dioxide, determination of, in Nordhausen oil of vitriol 192 determination of, in coal and coke 21 iron and steel 150 Sulphuric acid, determination of , in iron ores 29 limestone 16 magnesium sulphate 8 paper 338 tables of gravity 502 and free SO 3 , in H 2 S 2 O 7 190 TABI/EJ of heating value of solid combustibles 124 showing the yearly saving effected by the use of the feed water heaters for various horse-powers 103 Tagliabue's freezing apparatus 381 viscosimeter 389 Tallow soap, analysis of 361 Tannin, test for animal size in paper 339 Tap cinder, analysis of 39 Tar, quantity of, from distillation of coal 299 Temporary hardness of water 69 Ten-Brink furnaces 244 Tensile strength of Portland cement 206 steels 183 Tessie du Motay illuminating gas 270 Test of hydraulic materials, H. I,e Chatelier 221 Textor's method for the rapid determination of manganese 194 Thermo-electric pile 7 Theoretical evaporative efficiency of different combustibles 294 Thickness of paper, determination of 344 INDEX. 521 Thompson, C., scheme for soap analysis 350 Thompson, G. W., analysis of alloys 319 Thompson's calorimeter 132 Thorner compression machine 25 Thorner, W., table of constants of fats and fatty acids 358 Thurston lubricant tester 417 Tin and antimony, separation of. in alloys 314 quantitative determination of. in alloys 321 plate, method of analysis ... 323 Titanic oxide, determination of, in clays 302 iron ores 35 Tohin bronze, composition of , 316 Toilet soaps 349 Tollen's formula for Fehling's solution 341 Total alkali, determination of. in soap 353 solids, determination of, in water 82 Trap rock, crushing strength of 304 Treumann's apparatus for cils 407 Troilius, method for determination of phosphorus in iron and steel 176 Troostite 1 73 Tungsten, determination of, in chrome steel 329 Turpentine 452, 465 Tuscan red 453 Twitchell's method for determination of resin 356 UEHLING AND STEINBART'S automatic indicator for the composition of furnace gases 244 Uehling and Steinbart's pyrometer 474 Ullgren's method for the determination of carbon in iron and steel 160 Ultramarine, composition of 454, 464 Umber 453 Unsaponifiable matter in soaps 352 Unit current 480 Unit magnetic pole 48 Unwin, description of dasymeter 242 VALENTA'S method for determination of rosin cil in mineral oil 414 Valuation of coal 'for the production of gas 296 Value of coke, how determined 24 Valve, The Bunsen 12 Van Dyke brown 453 Variation in tensile strength of cements 215 volume of cements 223 Vaseline 365 Vegetable black 454 Verein deutsche Portland cement fabrikanten, rules for testing cement 214 Vermilion 453 Viscosity of oils 383 Viscosimeter, Davidson's 387 Doolittle's 400 Engler's 384 Gibb ' s 390 Lew's 394 Perkin's 393 Redwood's 385 Stillman's 394 Tagliabue 's 389 522 INDEX. Viscosity tests of various oils 398 Volatile and combustible matter in coal and coke 19 Volt, The 481 Volt meter 483 Volume of pores in coke , 25 Volumetric determination of copper 4 iron 10 manganese 193 nickel 230 phosphorus, in iron and steel 179 sulphur in iron and steel 154 tin in tin plate 324 Von. Shulz and Low, method for the determination of zinc in ores 195 WARREN water filter, description of 86 Water, ammonia free, method of preparation 74 Washing powders 360 Water analysis, conversion table 83 to determine the scale-forming ingredients 245 sanitary 73 determination of, in soaps 352 for locomotive use 96 tables of composition of various 84, 85 viscosity of 397 gas, carburetted, composition of 268 uncarburetted, composition of 267 Water gas, method of analysis 245 manufacture 265 Watt, the 481 Wausau water, composition of 98 Waxes in soaps 352 Wedgewood pyrometer 466 Weight per cubic foot of coke, determination of 27 square meter of paper, determination of 344 Welsh coal, analysis of ash of 24 Wendler apparatus for testing breaking strength of paper 346 Westphal balance 374 White lead 453 C0 2 in 455 White metal, scheme for analysis of 315 Whiting 453 Whittlesay and Wilbur's method for the determination of FeO in iron ores 32 Wiborgh's method for determination of carbon in iron and steel 165 pyrometer 466 Wilcox natural gas, analysis of 274 Wilkinson water gas, analysis of 270 Wiukler gas burette 247 Wisconsin oil tester 428 Wolff's colorimeter 77 Wood, composition of > 295 Woodman, Durand, analysis of petroleum 363 Wood cellulose, detection of, in paper 337 Wool grease 370, 416 Working qualities of paints 453 Wright's C. R. Alder, scheme for soap analysis 350 XYI^OI, (C,,H in ), evaporative power in pounds of water at 100 C 292 INDEX. 523 YELLOW cadmium 453 Chinese 453 chrome 453 Kiug's 453 ochre 453 soap 349 ZETTLITZ clay, composition of 303 Zinc, chrome 453 electro-chemical equivalent 483 technical determination of, in ores 195 AN IMPORTANT WORK ON CHEMISTRY JUST COMPLETED. WILEY'S PRINCIPLES AND PRACTICE OF AGRICUL- TURAL CHEMICAL ANALYSIS. In 3 volumes, octavo. Printed on fine paper, beautifully illustrated By HARVEY W. WILEY, Chemist of the United States Department of Ag- riculture. Vol.1. Soils. pp. x-f-6o7. 93 illustrations, including 10 full page plates in half tone. Price, cloth, 13.75. Vol.2. Fertilizers. pp. viii -j- 332. 17 illustrations. Price, cloth, $2.00. Vol.3. Agricultural Products. pp. xii+66o, 128 illustrations, includings full page plates. Price, cloth, $3.75. The Chemistry of Dairying. 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