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ENGINEERING CHEMISTRY: 



A MANUAL OF 



QUANTITATIVE CHEMICAL ANALYSIS. 



FOR THE USE OF 



STUDENTS, CHEMISTS «» ENGINEERS. 



-BY- 



THOMAS B. STILLMAN, M.Sc, Ph.D., 

'I 

PROFESSOR OF ANALYTICAL CHEMISTRY IN THE STEVENS INSTITUTE 
OF TECHNOLOGY. 



WITH ONE HUNDRED AND FIFTY-FOUR ILLUSTRATIONS. 




BASTOH, PA.: 

CHBMICAL PUBUSHIlfO CO. 

1897. 



.■^/'3/ 
S^ 



CoPTUOBT, 1897, VI Edward Hart. 



PREFACE. 



The preparation of tiis 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 anal3rtical 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 ''Pjrrometry,*' by 
Wm. Kent, M.E. 



L>H^'i- 



IV PREFACE. 

"Carbon Comp6unds of Iron/' by G. C. Henning, M.E. 

'•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,i.man. 

Stevens Institute of Technowxjy, 
HoBOKEN, N. J., Dec. 31, 1896. 




CONTKNTS. 



Pasre. 

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 ; 
Volnmetrically with potassium cyanide solution, 4 ; As metal- 
lic copper by electrolysis, 5 ; Giilcher'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, d. 
Where the iron solution is in the ferric condition, 11 ; 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 CaS04, 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 ; Analvsis 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- 



VI CONTENTS. 



termination of ferrous oxide in FeO.Fe,Oa, 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 ; Analvsis 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 sla^s, 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- Perming 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- 
l^redients, 60; Determination of silica, alumina, oxide of 
iron, calcium oxide, ma^esinm 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 ; 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 ana 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 o-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 la^rer, 
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 Doilers, 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-incrustine, 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 
verv hard water, 97; Use of boiler compounds to prevent 
scale, 97 ; Formula for compound used by Chicago, Milwaukee 
& St. Paul Railwav 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 u]>on 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, loi; 
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, loi ; Example 
of composition of boiler water before treatment with the 



Vlll 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. l 

Use of Chemicals and Filtration for Purification of Boiler I 

Waters 105 

The Dervaux w^ter purifier, 105, 106; The Archbutt water j 

purifier, 107-109 ; Table showins; 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 iii 

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 preqipitates, 112 ; Description of a com- 
plete plant for water purincation, using superheater, chemi- 
cal precipitation with sodium carbonatd 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 hi a crucible with litharge, 11^; 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 use of calorimeters, (3 )The combustion of large ( 

amounts of coal in specially designed apparatus therefor, 115; 
Determination of carbon and hydrogen m coal, 11 5-1 17; De- 
termination of nitrogen, 117, 118 ; Data for calculation of the 
heating power from the analysis, i?o ; Definition of a calorie, 
120; Dennitionofa 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 amonnt 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. n. 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 ot 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 ; Refereuces 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 
ot Berzelius, 158 ; Method of Regnault, Deville, and Wohler, 
158 ; Ullgren*s method, Eggertz, Langley, Richter, Weyl and 
Sinks, Parry, McCreath, Boussineault, 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, FcjC ; 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 ; DifiFerences 
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, T79; 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 Mid vale 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 ; Reauirements 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 18S 

Drown'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 colori metrically, 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 
"Riehl^,'* 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 stren^h 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- 
X>erts, 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 testin? machine* 225, 226 ; Resum^ 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- 



Xll 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- 
tionsj 237. 

Analysis of Flue Gases with the Orsat-Miiencke Apparatus 237 
Advantages of this apparatus for rapid analyses, 238 ; De- 
8crii>tion 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- 
eert 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; MethcNi 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, 
359 ; 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^ 
P., 262 ; of carbon monoxide, 263 ; of marsh ^as, 363 ; Table 
of B. T. U. per cubic foot, products of combustion condensed, 
and products of combustion at 328° P., 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. xiil 

eacaping at 328° F., 264; Determination of calories per kilo, 
or B. T. U. per pound, from analysis of a gas stated in yolume, 
264. 

Manufacture of Water Gas and Calculation of Heating 

Power of Various Illuminating Gases 265 

Description of plant, 266, 267 ; Operation, 267 ; Composition 
of uncarburettea water ^as, 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 sam|>le of 
London coal ^as, 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 ^as, 289 ; Analysis of Wilkinson carburetted water 
eas, 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 gasi with B. 
T. U. per cubic foot, 270; Analysis of anthracite producer 
gas, with B. T. U. per cubic 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 tne 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 Pennsvlvania 
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 
g^, by W. A. Noyes, withB. T. U. per cubic foot, 273 ; Inves- 
tigations upon the composition of natural ^as by P. C. Phil- 
lips for the geological survey of Pennsylvaniai 274 ; Analysis 
of Predonia 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 ^as 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 instrumenti upon the municipal gas 
of New York City, by E. G. Love, 285 ; Determination of the 
heating power of the London coal gas, 286 ; Ayera&:e 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 I1.25 
per cubic foot. 

Junker's Gas Calorimeter 287 

Description of the instrument, 287 ; Method of operation, 288, 
289 ; Table of resum6 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 pqwer 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 CeH^O, 
CjHgO, CjoHg, C^Hjo, CgHio, C,H„, C,oH,4, 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 eflSciency due to carbon, hy- 
drogen, etc., of charcoal, co):e, 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 f 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 oif 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 

Bilica, 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 Riehl^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 Tagliabu^' 
freezing apparatus, 306; Freezing test as required in "Uni- 
form methods of Procedure in Testing Building iqid Struc- 
tural Materials** by J. Bauschinger, ( Mechanisch-iechnischen 
Laboratorium, Miinchen), 307; The testing of bricks, 308; De- 
termination of soluble salts in bricks, 309*; Examination of 
nnburnt clay for calcium carbonate,, iton, 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, ^10; 
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, a|ax metal, car-box metal, mag- 
nolia metal, pewter, *' Argentine,'* Ashbury metal, anti-fric- 
tion metal, pnosphor 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 allocs of the second class, 316 ; Alloys of 
the thira 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 leaa, copper, tin, and antimony in 
alloys, ^19 ; 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 326 

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, 3^7; 
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 papen 337; 
Color reactions of the different fibers with solutions 01 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 ana 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 ; Use of recovered grease, 349 ; List of oils used in the 
manufacture of soaps, 349 ; Scheme for the analysis of soap, 



CONTENTS. XVll 

350; Scheme for the analysis of unsaponifiable matters in 
80Ap> 351 f Determination of water, 352 ; Determination of 
waxes, 352 ; Determination of total alkali and fatt^ 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 ; HiibPs method for resin 
in soap, 356 ; Twitcheirs 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, cymoeene, 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, 36J ; 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 ; Baum^ hydrometers, 371 ; Taglia- 
bue*s hydrometer, 371 ; Table for converting Baum6 degrees, 
liquids liehter 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 '8 viscosimeter, 384, 385 ; Redwood's viscosimeter, ^85 ; 
The septometer of Mr. Lepenau, 386 ; Davidson's viscosime- 




ZVlll CONTENTS. 



ter, 387 ; Tagliabae't Tiscoeimeter, 589 ; Gibb's Tiscosimeter, 
3Spi 591 ! Table of yiscosities of valve oiU and stocks, 392 ; 
Viscosities of car and engine oils, 392 ; Perkin's viscosimeter, 
J93 ; Stillinan*s viscosimeter, ^94-396 ; Table of viscosities of 
fortv-lhree of the principle oils used in lubrication, at 66P P., 
122*^ P., 212° P., 302° P., 392° P., 397; Chart of above teste, 
398; Conclusions deduced from viscosity determinations, 390; 
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 ; Plash 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, 40S; Acidity of oils, 408, 40(); Method for de- 
termining the acidity of oils as performed in railroad labora- 
tories, 40^, 410; Maumene's teat for oils, 410, 411 ; Table giv- 
ing the nse 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 Lux, 414 ; Detection of rosm oil 
by the method of Holde or Valente, 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 amounte of animal and vegetable oils when 
mixed together, 415, 416; Wool grease, 410; Degras or sod 
oil, 416; Bone fat, 416 ; Coefficient of friction, 417; Descrip- 
tion of the Thurston, and the Henderson-Westhoven friction 
machines, 417-410 ; Description of the friction apparatus used 
by the officials of the Paris-Lyon Railway, 419-421; Descrip- 
tion of the Riehl^ lubricant tester, as used in many of the 
railroad laboratories in the United Stetes, 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, cvlinder, and freif^ht car oils, Balti- 
more and Ohio Railroad, 423, 424; Specifications for black 
en^ne oils and cylinder stock, Chicago, Burlington, and 
Qumcy Railroad, 425, 426 ; References to literature of lubri- 
cation, 426. 

Oils Used for Illumination 426 

Classification of illuminating oils into two ^oups : a, refined 
products of i>etroleum ; ^, 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, 42^; 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 pointe of illu- 
minating oils, 429, 430 ; Rules and regulations for making 
the teste, 430 ; Law regulating the standard of illuminating 
oils and fluids, stete of New York, 430-432 ; The trades 01 
colors in classifying kerosenes, 432 ; The Stemmer colorimeter 
for oils, 432 ; The Wilson colorimeter, 433 ; Colza and lard oil 
for illumination, 433 ; Different methods of car illumination, 
434 ; Pintech oil gas, method of manufacture and use for car 



CONTENTS. xix 

illamination, 434 ; The Poster system, 435 ; The Prost system, 
435 ; The electric system of car lighting, 436-438 ; Results of 
experiments made npon 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 I^ubricating Oils Containing Blown Rape- 
seed and Blown Cotton-seed Oils 441 

Rape-seed oil as the standard lubricant in Europe, 441 ; Pro- 

Sortion of rape-seed oil added to mineral oils, 441 ; Method of 
uplicating an oil from the analysis, 442, 443 ; Comparison of 
the chemical reactions of blown rape-seed and normal rape- 
seed oil, 444 ; Recognition in a mixture of the amounts of cot- 
ton-seed and rape-Med oil from the difiPerence 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 offatty 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 oi^ments, 454 ; Scheme for the 
analysis of white paint ground in oil, 455 ; Analysis of several 
rex>resentative 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; Pire-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 
I>resence 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 6cxP P., 469; Brown's metallic pyrometer, 469; 



XIS. 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 oif 
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 

JVork — 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 |>ound 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. 

Piffure t. Electrolytic apparatus for the determination of copper 6 

** 3. Gfilcher's thermo-electric pile 7 

** 3. Bunsen valve 12 

** 4. Apparatus for determination of CO9 in limestone 17 

** 5* I«ychenheim's apparatus for determination of phosphorus in coal and 

coke 22 

** 6. Th^hner 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 

" la Bettendorf's automatic water-bath 6z 

'* 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 loi 

** 23,23. The Derveaux water purifier 106 

" 24-26. The Archbntt and Deely apparatus for purification of boiler waters 108 

^ 37. Pilterpress iii 

** 26. 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 

'* 3o« 31* Apparatus for determination of carbon and hydrogen in coc^l 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 

** 3Mo- The Carpenter coal calorimeter i39» 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 
" 49t So> Agitation apparatus for determination of phosphoric acid, as used by 

chemists of the Pennsylvania Railroad ■ 181 

** 51. Picnometer 191 

** 52. Pairbank's cement testing machine 208 

** S3. RiehM's cement testing machine 209 



XXU WST OF ILLUSTRATIONS. 

Fig. 54. Briquette mold ato 

** 55. The MichAcUs cemeat testing machine an 

" 56. The Paij* testing machine an 

** 57>S8- The Reid and Bailey testing machine aia,ax3 

** 59. Cunre of breaking strengths of cements (Palja) ax5 

** 60. The Bfihme-Hammer apparatus ai6 

** 6x,6(a. Jameson's briquette making machine 917 

** 6^ French modification of the Michaelis cement testing machine 319 

" 64. The Buignet cement testing machine - «/ aao 

*' 65. The Bnchier compression machine aas 

" 66l The B6hme compression machine aa4 

" 67. The Porter automatic cement testing machine 3a6 

** 68. The BlUott apparatus for analysis of chimney gases* etc 933 

** 69. The OrsatrMllencke apparatus for analysis of flue gases 338 

** 70. The dasymeter of Siegert and Dnerr aia 

" 7it73* Charts showing heat losses in boiler practice 243 

" 75-83- The Hemi>el gas apparatus 346-450, asa-as4 

" 84. The Humphrey water gas plant 367 

" 815. The Bunsen photometer 376 

" 86. The Hartley calorimeter for combustible gases 384 

** 87,88. The Junker calorimeter 387-390 

" 89. Newbigging's experimental plant for the determination of the gas-pro- 
ducing qualities of coal a97 

*' 90. The Riehl6 United States standard automatic and autographic testing 

machine 505 

*' 91. The Tagliabue freezing apparatus 306 

" 93-99. Microphotographs of various fibers 335.336 

** 100. Apparatus for determination of the thickness of paper 345 

" xox. The Wendler paper testing machine 346 

** xoa. The Westphal balance with Reimann's plummet 357 

** X03. Fractional distillation flask for i>etroleum 3^ 

" X04. Separatory funnel for separation of oils 367 

** X05-X08. Apparatus for determination of melting-points of f^tty acids 369, 370 

" X09. Tagliabue's hydrometer for oils 37X 

'* xxo. Graphic method of determining percentages of oils in mixtures of oils. . 375 

*' XXX. The Westphal balance 375 

'* XX3. The Westphal balance modified for high temperatures 376 

** 113. Bichhom's araeo-picnometer 377 

** XX4,XX5. Cold test apparatus for oils 37&»379 

** 1x6. Sectional view, Tagliabue's freezing apparatus 383 

" XX7. Schubler's viscosimeter for oils 383 

** X18. Bngler's viscosimeter for oils 384 

** XX9. Redwood's viscosimeter for oils » 385 

** ISO, X3I. Lepenau's septometer for oils 386 

'* X33. Davidson's viscosimeter for oils 388 

" X33. Tagliabue's viscosimeter for oils 389 

" X34. Gibb's viscosimeter for oils 390 

** X35. Chart of curves showing viscosity of oils as determined by the Gibb's 

viscosimeter 393 

** X36. Stillman's viscosimeter for oils 395 

** 137. Chart of curves showing viscosity of oils as determined by the Stillman 

viscosimeter 398 

" 138. Doolittle's viscosimeter for oils 400 

" X39. Apparatus for determination of the *' flash " and ** fire " test of lubrica- 
ting oils 404 



IJST OP II,I,USTRATIONS. XXlll 

Flff. i30u Ta^liabue's open tester • 404 

** 131. The Saybolt tetter 405 

** X3S. 133. The Abel closed tetter 406 

** i34i 135- The Peiitky«Martent closed tester 407 

** 136,137. The Tretunann open tester 406 

** 138* i99> The Henderson-Westhoven f rictkm tester for lubricants 417 

** 140, X41. Apparatus used by the Paris-I«yon Railway for testing lubricants. 4x9, 4ao 

•• 142. The Riehl€ machine for friction tests of lubricants 4sx 

*' X43. The Wisconsin tester for illuminatinsr oils 4^ 

** 144. The Stammer colorimeter 43a 

** 145. The Soxhlet apparatus 448 

" 146. The air pjrrometer of Siegert and Duerr 467 

** 147. The Hobson hot-blast pyrometer 968 

•• 148. The Weinhold pyrometer 470 

** 149. The Saintiflrnon pyrometer 47a 

*' 159,151. Prof. Braun*s electric pyrometer 473*474 

** is>-i54- Uehling and Steinbart't pyrometer 475-477 



ERRATA. 

Page 80, line 14, for " NO, " read " NOj.** 

Page 81, line 19, add ** with dilute acetic acid.*' 

Page 82, line 22, for " 1000 parts of salt *' read '* 1000 parts of water.*' 

Page 119, line 16, for "hydroscopic" read " hygroscopic.'* 

Page 125, line 10, for "hydroscopic" read "hygroscopic." 

Page 170, line 22, for " Leduber " 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^H^ = 11900 calories" read "C,H4=ii9ii 
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° Baum^ at 60° F.'* read *'2/^.'f Baum^ at 
60° F." 

Page 433i line 19, for " Wilson's calorimeter** read " Wil8on*s colorim- 
eter.** 



UNIVERSITY 



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,' and wash precipi- 
tate with hot water until the washings no longer react alkaline. 
Dr>' 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^Oj 9-432 grams. 

Crucible 8.721 " 

FejOj 0.71 1 gram. 

Then 

Fe^Oa : Fe^ : : 0.711 : ^r. 
X = 0.4977 weight of Fe. 

04977 X ^00 -_ go c^ per cent. Fe in the wire. 
0.500 

References, — Frescuius* *' Quantitative Chemical Analysis'* (London 
Edition), § 703. i, a. ; ** Hints to Beginners in Iron Analysis,*' by 
David H. Browne,/. AnaL Chein., 5, 325. 
1 13 cm. dtameler. 

(I) 



2 QUANTITATIVE ANALYSIS. 

II. 

Alumina in Potash Alum. 
(K.SO, + Al,(SO,). + 24H.O). 
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 150CC. 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 grams. 

Crucible -I- A1,0, i7-5i3granis. 

Crucible 17258 " 

AljOj 0.255 gram. 

0.255 X ia> r * Ai iA 

— -- o =10.69 per cent. AI-O3. 

2.384 ^ ^ 

Theoretical Percentage : 

K^SO, -I- A1,(S04), -I- 24H,0 : A1,0, : : 100 : ;r. 
.r= 10.85 per cent. Al^O,. 

III. 

Copper in Copper Sulphate. 

(CuSO, + 5H.O). 

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 SUI.PHATE. 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 : 

CuSO, + 2(NaOH) = CuO + Na,SO, + H.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 CUSO4+ SHjO . 7.0250 grams. 
Second weight of weighing tube and CuSO^ -f- 

5H,0 5^9605 " 

Copper sulphate taken 1.0645 '* 

Crucible + CuO 153744 ** 

Crucible 15.0360 *' 

0-3384 gram. 
CuO : Cu : : wt. of CuO : x (=wt. Cu) 

79.5 : 63.5 : : 0.3384 : x 
;ir= 0.2702. 



4 QUANTITATIVE ANALY3IS. 

Then, 

0.2702X100 _ 8 per cent, of Cu. 
1.0645 
Theoretical Calculation : 

CuS04 + 5HjO : Cu : : 100 : ;ir 
2495 ' 63.5 : : 100 : ;r 
jr:= 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 grams 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 well. 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 =0.40 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 OP 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 
electrolj'^tic 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, take out 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 loo'' C, and weigh. 



QUANTITATIVE ANALYSIS. 




Fig. X. 



DETERMINATION OF COPPER BY EI.ECTROI.YSIS. 7 

Example : 

Amount of copper sulphate taken = 5.000 grams. 
Solution 500 cc. 
Fifty cc. taken for electrolysis. 

Platinum cone + metallic copper 36.656 grams. 

Platinum cone 36.529 ** 

Copper deposited 0.127 gram. 

Then, 

0.127X10X100 _ ,5^ ^^ ^^^, 

Where many determinations of copper, by this method, are to 
be made, the apparatus described by W. Hale Herrick, /. AnaL 
Chem., a, 67, can be used. 

A very convenient instrument for generating the current of 
electricity is Giilcher's thermo-electric pile, Figure 2. 




Fig. 2. 

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 amp&res. 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. 



i 



8 QUANTITATIVE ANALYSIS. 

References: *' Bibliography of the Electrolytic Assay of Copper," by 
Stuart Croasdale,/. Anal, Chem,^ 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 I^ight Current for Quantitative 

Chemical Analysis," by P. T. Austen and J. S. Stillwell,/. AnaL 

Chem.y 6, 127. 
" On the Analysis of American Refined Copper," by H. F. Keller, 

y. 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* ashless filters, testing the filtrate with a 
few drops of barium chloride solution, to make certain that all 
the sulphur trioxide is precipitated. 

MgSO, + BaCl. = BaSO, + MgCl,. 

Wash the precipitate thoroughly with hot water until a drop 
of the filtrate 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 -|- MgS04 -f- yHjO 7-9040 grams. 

2nd " " " " " 6.5435 •* 

MgSO* + 7H,0 taken 1.3605 't 

Crucible -f- BaSO^ 23.502 grams. 

Crucible 22.214 " 

BaSO^ 1.288 •• 

BaSO^ : SOj : : 1.288 : x 

X =s 0.442 gram SOj. 

0.44^)000 ^ ^ ^3 ^^^^ sQ^ 

1.3605 
1 9 cm. in diameter. 



DETERMINATION OF LEAD IN GALENA. 9 

Theoretical : , 

MgSOi + 7H,0 : SO3 : : 100 : at 
X = 32.52 per cent. SOj. 
References: Fresenius, ** Quant. Chem. Analysis," §132, i. 

** The Volumetric Estimation of Sulphates," by D. Sidersky 
J. Anal. CAefn,y.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 
Xo. 3 beaker, using not over seventy-five cc. water ; add 100 
cc. of a solution of sodium carbonate in water, (i to 10) and boil 
the contents of the beaker for fifteen or twenty minutes. Solu- 
tion must be strongly alkaline. 

B}'' 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 



lO QUANTITATIVE ANAI.YSIS. 

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 : 

I8t weighing of tube and Galena 16.670 grams. 

2d " •• •* '* 14.503 '* 

Galena taken 2.167 " 

Crucible -f- PbSO* 17-576 grams. 

Crucible....; 16.564 *' 

1.012 " 
PbSO^ : Pb : : 1.012 : x 
X ^ 0.6914. 

0.6914 X 100 _. ^j^ p^j. 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 i .503 gram. 

12.27 cc. bichromate solution required to oxidize. 
I cc. ^ 0.0168 gram iron. 
Then, 12.78 cc. = 0.2147 gram iron. 

^'^'47 X 100 ^ ^ ^ ^^^^ j^^„ 
1.503 
Theoretical percentage : 

(NH4),S04.FeS04 -f- 6H,0 : Fe : : 100 : ;ir 
^= 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,' 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 QXJANTITATIVE 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 
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 
Fio. 3. where a number of reductions are to be made.— y. 
AnaL Chem., 3, 124. 
Example : 

Ferric sulphate taken 1.520 gram. 

18.01 cc. bichromate solution required to oxidize. 
Then, £g-oi X 0.0168 X 100 ^ ^^^^ .^^^^ .^ ^^^^..^ sulphate. 

1.520 
Theoretical Percentage : 

Fe,( 804)3 4- 9HsO : Fe, : : 100 : x 
X ^ 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 to dryness. 
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 3'ellow 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 sufiicient 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 -|- Mg,PgO, 15-6037 grams. 

Crucible 15-5210 ** 

MgjPjO; 0.0827 " 

Then, MgjP.O, : PjOj : : 0.0827 : x 

X = 0.0529 gram. 
If the P2O5 in 25 cc. = 0.0529 gram, in 250 cc. or entire solu- 
tion = 0.529 gram. 

. 0.529 X ioQ ^45.y per cent. P^ in CajCPO^),. 
1-157 



{ 



14 QUANTITATIVE ANALYSIS. 

References : A very complete article on '* Mineral Phosphates and 
Superphosphates of Lime '* will be found in the American Chemist^ 7i 
103-108; also 

Bu/MtHt No, S^ {Oct. 9, 1892 )y "New Jersey Agricultural Experi- 
ment Station, Analysis and Valuations of Complete Fertilizers, Ground 
Bone, and Miscellaneous Samples." 

/. 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, a, 
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 : 

1st weight tube and salt 10.942 grams. 

2d ** " ** *• 8.902 ** 

KjCrjOy taken 2.040 ** 

Crucible and CraOg 43.270 '* 

Crucible 42.230 ** 

1.040 



\ 



CHROMIUM TRIOXIDE. 

This weight of Cr^Os must now be converted into CrOg. 
Cr,Os:(CrO,),:: 1.044:^ 
;r= 1.3705 grams. 

^•3715 X 100 ^67.23 per cent. CrO,. 
2.040 
Theoretical : 

KjCrjOy : (CrOs)2 : : 100 : ^ 
295 : 201 : : 100 : x 
;r = 68.13 P^r cent. 
References : 

Fresenius, Quant. Anal., § 106, i a. 

Volumetric Determination of Chromic Acid,/. AnaL Chem.y 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 Z Ih 

Ji - 



c 
o 

4-» 
80 



80 
80 
>^ 

73 



^-g 



« * a 






«:§ «u 

.2*5 

a; u +J 
o o p, 

a >^s 

•»:• _fl ^^ 

i^2 

CO c^ a; 

•"sis 

*S a a; 

«'d 08 
*^ • J 

!i a! a> 
« ^ ti 



&• 



J a 3 

4; « v! 

s CO a> 

^^« 

*"d o 
©2.2 

S S ^ 



4^ ^ 



ti'd' 



CO 

o s r 

4» 



&£ 



8ll 



O 






Q 3 2 « o «n •'2 — ^ " 






^»j ft 4J ft 



o 







O 
CO 

n 



d-« 
555. 

g . 

S S' 

>. 3 

it « H 

« a « 
9.95 

1 P «^ 

B « « 



a 



S' 



5 « 

o it 

SX 
A 5 

as 

V 2 

•IS 

^ 2 

cd e> 

>» *; 

c« ^ 
a (o 

(C - 

•o § 
« .5 



^ 73 



-^ 



« s » 

^ •« s 
§ S 55 

a fc o 

ss e 

g £ o 
o55 

o k. S 
■■5 5 i 

li§ 

•o «« .5 

5 v-S 

'• g 
g « 8 



~2 tit; n^ -yo *» 4» 

"S * g^ «.2 Ji.9 
s—^ £ o « « i^M 

^^5H*gf s&"S 






o 

Ct 

.'o be 
33 2 



O 

pT 

1 

s 

d 
pT 



o 

be 



? 2 



S 

X 



1 §1 






'S'S 



o 
E2 



5; i 

6 II 

§; 



iif^Sgfii.^ II 
a^ SgSs-§5 




•;uaD jad t-i = 



001 X S X tioo 



••o*ad **0*lV 78 njo ^ 



"|aa 

.*- 3:3 
D a 41 



.5 o 4; s 
V 4;bA.j, 

S5|-- 



S 
8 
bo 



to 

a 
o 



1 



?i 






Is 




2 


w 


^« 


u 


to 


S 


hg 


s 


■g 





1"^ 


s 

u 

a 




8 


58 


S) 


CO 


N 


5.S 


s 


II 


II 


S 




8- 


8 


bA 


, 


^!^ 


X .c 



o 



;^;t 



-I 



a 
? 
«> 
O 



I.IMESTONE ANALYSIS. 



17 



Determination of Carbon Dioxide, 

The ytube B (Fig. 4) contains water acidified with sulphuric 
acid. No more of the mixture should be placed in the tube 
than just suflBcieot to cover the neck at a'. 

The U tubes C and D contain granulated calcium chloride. 
As this chemical often contains free lime, it is always advisable 
before connecting these tubes with the apparatus to first pass 
carbon dioxide gas through them to saturate any free lime and 
then aspirate with air, to exhaust all free carbon dioxide. 

The U tubes E and F contain soda lime granulated, medium 
size, and are weighed carefully before using the apparatus. 

The U tube G contains calcium chloride to absorb any mois- 
ture that might enter F from the water in the aspirator H. 

Three grams of the limestone are transferred to the flask A, 
and the flask connected with the apparatus shown in figure 4. 




Pio. 4. 

Dilute hydrochloric acid (fifty cc.) is allowed to run into the 
flask A from the funnel tube, and heat is gradually applied 
until the liquid in the flask begins to boil. 

Connect the Bennert drying apparatus with the funnel tube of 
flask A and slowly aspirate air through the entire apparatus by 
means of the aspirator. The carbon dioxide is all absorbed by 
the soda-lime tubes. 

After aspirating about four liters of air, weigh the soda-lime 
tubes to constant weight. 



l8 QUANTITATIVE ANAI^YSIS. 

Soda-lime tubes and CO, 48.3265 grams. 

Soda-lime tubes 47.03» " 

CO, 1.194s 

1.1945 X 100 ^ ^^ gj ^^ ^^^^ cQ^ 

Resum^ : 

Organic matter 2.02 per cent. 

Silica • 4.80 ** 

Iron and aluminum oxides 1.40 ** 

Lime 42.16 " 

Magnesia 7-3i '* 

Sulphur triozide 2.50 '* 

Carbon dioxide 39.81 ** 

100.00 ** 
The SO, is united With CaO to form CaSO*. 
SO, : CaSO* : : 2.50 : x 

Subtracting the 1.75 CaO used to unite with the SO, there remains 
40.41 CaO to unite with CO,. 

CaO : CaCO, : : 40.41 : x 

X = 72.71 

MgO : MgCO, : : 7.36 : x 

X = 15.36 

. Organic matter 2.02 per cent. 

Silica, etc 4.80 ** 

Iron and aluminum oxides 1.40 " 

Calcium sulphate 4.25 ** 

Calcium carbonate 73.17 *' 

Magnesium carbonate 15*36 " 

100.00 " 
The analysis shows the limestone to be a dolomite or magne- 
sium limestone. The following is an analysis' 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. 



COAI. AND COKE ANAI^YSIS. 



19 



XII. 

Coal and Coke Analysis. 

Determination of Moisture^ Volatile and Combustible Matter, 

Fixed Carbon, Ash, and Stdphur, 
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. I^oss is moisture. 

Crucible + cover + coal 26.ii7grams 

Crucible + cover 24.617 

Coal taken 1.500 

Crucible + cover + coal, before drying 26.117 

Crucible + cover + coal, after drying 26.109 



ii 



CS 

S 
o 
a 

6 
c9 



U 



Moisture 0.008 

0.008 X 100 ^ Q^^ p^j. ^^^^ 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 
and combustible matter plus one-half of the sulphur. 
Crucible + cover + coal, before heating seven 

minutes 26.109 

Crucible -f- cover + coal, after heating seven 

minutes 25.569 



0.540 X 100 
1.5 



0.540 



= 36. per cent. 



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-f-cover+coal, before complete combustion 25.569 
Crucible + cover -f- residue, after complete^ com- 
plete combustion 24.669 

Fixed carbon + J S 0.900 

o^9ooj<joo ^ ^^ ^^^^ p.^^ ^^^^^ ^ J S_ 
. I 1-5 



20 QUANTITATIVE ANAI^YSIS. 

' Crucible + cover + residue of coal after complete 

combustion (Ash) 34.669 grams. 

Crucible and cover 24.617 ** 



ft 

< 



Ash 0.052 

?:25?X '^ = 3.46 percent, ash. 



1.5 
Resum^. 

Moisture 0.53 per cent. 

Volatile and combustible matter + i S 36.00 ' * 

Fixed carbon + iS 60.00 

Ash 3.46 

Total 99,99 

It is necessary, now, to determine the percentage of the sul- 
phur present in the coal and [subtract it from the amounts of 
volatile and combustible matter and fixed carbon. 

The method is as follows : 

Take one gram of the finely powdered coal, mix it, upon a 
piece of black glazed paper, with about ten grams of sodium 
carbonate (dry) and five grams of Sodium nitrate. 

Place a small portion in a platinum crucible of fifty cc. capac- 
ity, and heat to redness. When combustion is complete add 
some more of the coal mixture, repeating the operation until all 
has been transferred to the crucible from the glazed paper. Heat 
at a red heat for fifteen minutes, making certain that no parti- 
cles of carbon remain unconsumed. 

Allow to cool, transfer crucible and contents to a No. 3 
beaker, add 100 cc. water, and warm carefully until the mass 
dissolves. 

Remove the crucible froni the beaker, washing it once with 
hot water, allowing the washings to run into the beaker. Fil- 
ter the solution, acidify the filtrate with hydrochloric acid, boil, 
and add solution of barium chloride in slight excess. Allow to 
stand twelve hours, filter, wash well, dry, ignite, weigh as 
barium sulphate, and calculate to sulphur. 

Thus: 

Amount of coal taken 1.016 grams. 

Crucible + BaS04 16.553 

Crucible 16.511 '* 



BaSO^ 0.042 



COAI, AND COKE ANAI^YSIS. 21 

S = 0.0057 gram- 
0.0057 Xioo_ _ 06 per cent. S. 
1. 016 
Taking this amount and subtracting one-half of it from the 
volatile and combustible matter of the coal, and one-half from the 
fixed carbon, the coal analysis will be : 

Moisture 0.53 per cent. 

Volatile and combustible matter 35*72 

Fixed carbon 59«72 

Sulphur 0.56 

Ash 3.46 

Total 99-99 

In most cases the sulphur in coal exists combined with iron 
to form ferrous sulphide ; it also occurs as calcium sul- 
phate, or both forms may be present in the same coal. 

To determine the sulphur trioxide combined with the lime, 
take ten grams of the finely powdered coal and digest at a gen- 
tle heat, two hours, in a solution of sodium carbonate. It is fil- 
tered, washed with hot water, the filtrate made acid with hydro- 
chloric acid, and the sulphur trioxide precipitated with barium 
chloride solution. 

From the weight of barium sulphate obtained, the amount of 
sulphur trioxide is calculated. 

Determination of Sulphur in Coal by the Eschka-Fresenius 

Method. 
One gram of the finely powdered coal is mixed, in a platinum 
crucible, with twice its volume of a mixture of one part sodium 
carbonate and two parts of calcined magnesia, then heated in an 
uncovered platinum crucible until the mass becomes heated to a 
low red heat and the grey color of the mixture changes to a yel- 
low or brownish-yellow hue. Allow to cool, treat with bromo- 
hydrochloric acid, filter, boil out the excess of bromine, and 
precipitate the sulphur trioxide with barium chloride solution, 
as barium sulphate and determine percentage of sulphur. 
References : 

Ann. Chem. (Liebig), 76, 90. 
Ding. Polytech.f., aia, 403. 
Am. Chemisty 6, 83. 
J. Anal. Chem., 6, 86. 
f. Anal. Chem., 6, 385. 
y. Anal. Chem., 6, 611. 

" On the manner in which Sulphur in Coal and Coke is Combined," 
by Dr. F. Muck,/. Soc. Chem. Industry, 6, 468. 



22 



QUANTITATIVE ANAI.YSIS. 



Determination of Phosphorus in Coal and Coke, 

Five grams of the powdered coal or coke are transferred to a 
platinum boat (Fig. 5). This boat is two inches square, one- 
half inch deep, and made from 0.002 platinum foil. 

Care should be taken in making the boat that the comer flaps 
fit tightly, so that none of the ash will be lost by getting into 
the interstices.* 

A tripod, Krdman chimney, and two pieces of platinum wire 
bent three-fourths of an inch below top of the chimney complete 
the apparatus. 

The heat applied for the first 
five minutes should be a low 
red, in order that none of the 
coal shall be lost in the escape of 
the volatile matter. After that 
the gas should be turned on full, 
and a bright red heat main- 
tained. It is not necessary that 
the sample be ground very finely. 
After complete combustion of 
the carbon, the ash is transferred 
to a platinum crucible and fused 
with five grams of sodium car- 
bonate and one gram of po- 
tassium nitrate. The fused 
mass is dissolved in forty cc. of 
dilute hydrochloric acid in a No. 4 beaker and evaporated 
therein nearly to dryness ; thirty cc. of strong nitric acid are 
added and evaporated also nearly to dryness. The solution is 
then diluted with water, filtered from the silica, and the phos- 
phoric acid precipitated with molybdate solution. 

The analyses of a few representative coals are here given : 
** Bog Hkad Cannel" Coal. 

Moisture 0.60 per cent. 

Volatile and combustible, matter 71 .30 ' * " 

Fixed carbon 11.20 ** ** 




Sulphur 
Ash .... 



0.30 
6.60 



Total 100.00 ** 

1 Transaciums Amer. InsHtute Mining Engineers, 19, 66 [J. Lychenhcim]. 



COAL AND COKE ANAI^YSIS. 



23 



' Pittsburg Bituminous '* Coai,. 



Moisture 

Volatile and combustible matter • 

Fixed carbon - 

Sulphur 

Ash 



1.28 per cent. 
37.36 '* *' 

57.33 " " 
0.72 ** " 
3.31 '* '* 



Total 100.00 ** " 

'Pknn Anthracite," Wii.kbs-Barrb, Dei*. & Hudson Canal Co.'s 

'•Vein No. 5." 

Moisture 4.182 per cent- 

Volatile and combustible matter 4-283 

Fixed carbon 85.320 

Sulphur 0.794 

Ash 5.521 



Total 100.000 

It is found in practice that coal from the same vein or seam 
varies in composition with the size of the coal ; the percentage 
of ash increasing as the size of the coal diminishes. Thus, sam- 
ples collected from the Hauto Screen building of Lehigh Coal 
and Nav. Co., Pa., gave the following :* 



size of coal. 

Hgg 

Stove 

Chestnut . . 

Pea 

Buckwheat 



Moisture. 
1.722 
1.426 
1.732 
1.760 
1.690 



Volatile 
matter. 



Fixed 
carbon. 



Sulphur. 
0.609 
0.572 
0.841 
0.637 
0.714 



Ash. 

5.662 
10.174 
12.666 
14.664 
16.620 



Total. 
100 
100 
100 
100 
100 



3.518 88.489 

.4.156 83.672 

4.046 80.715 

3.894 79-045 

4.058 76.918 

These coals are separated into different sizes according to the 
mesh of the screen over which they pass. The sizes noted in 
the above table passed over and through sieve meshes of the fol- 
lowing dimensions : 

Broken or grate size • 

Egg 



Stove 
Chestnut 
Pea 
Buckwheat 



rough 4.00 m. 


over 


2.50 in 


** 2.50 




1.75 


1-75 




1.25 


1.25 




0.75 


0.75 




0.50 


" 0.50 




0.25 



The composition of the ash of coal or coke is sometimes de- 
sired. The analysis can be made in a manner similar to scheme 
XIV. 

1 TVaHSttciums A mer, Inst. Minify Engineers^ 14, 730. 



24 



QUANTITATIVE ANAI.YSIS. 



Analysis of a sample of ash of a Welsh coal, by J. A. Phillips, 
gave : 

Silica 26.87 per cent. 

Alumina and iron oxide 5^*95 

Lime 5.30 

Magnesia 1.19 

Sulphuric acid 7.23 

Phosphoric acid 0.74 

Undetermined 1.72 

Total 100.00 

An analysis, by Gaultier, of the ash of a sample of English 
coke, gave the following : 

Silica 42.10 per cent. 

Alumina 34-40 

Calcium carbonate 4.80 

Magnesium carbonate 0.40 

Calcium sulphate 12.55 

Ferric oxide 5.28 



Total 99.53 

Coke is the best solid fuel for the blast furnace in the manu- 
facture of pig-iron. 

Charcoal, while having less ash, and producing combustion 
more readily, cannot be used in furnace^ carrying large burdens, 
since it easily crushes and pulverizes. 

Anthracite coal ignites and bums slowly in the furnace, and 
though it can withstand the burden, generally, without crush- 
ing, its slow work in the furnace has caused coke to supersede it. 

The value of a coke is determined : 

First y by chemical analysis ; a good coke showing a low per- 
centage of ash, sulphur, and phosphorus, and a high percentage 
of fixed carbon. 

Second, by mechanical tests, which comprise ** Crushing 
Strength,*' ** Porosity,'* specific gravity, etc. 

The crushing strength can be determined by taking several 
samples of the coke, each one cm. high, and placing them in 
proper position in a Thonier compression machine, Fig. 6. 

Good coke gives a compression strength of 160 to 175 kilos 
per cubic centimeter. 



COAI, AND COKE ANAI^YSIS. 



25 



Connellsville coke usually gives a compression strength of 
275. pounds per cubic inch. 




Figr. 6. 



Porosity and specific gravity can be determined by the method 
used by Sterry Hunt in the Report of the Geological Survey of 
Canada, 1863, pp. 281-83. 

This method is to select suitable specimens of any size or 
shape, generally between twenty and forty grams in weight, dry 
and weigh them, then fill their pores with water and weigh in 
water ; the pieces are then taken out of the water, the excess of 
water upon their surfaces carefully removed, and weighed again 
in air. These three weighings furnish all the data necessary 
for calculating : 

1. The apparent specific gravity, or the relationship between 
the whole mass of material and an equal volume of water. 

2. The true specific gravity, or specific gravity of the particles. 

3. The volume of pores in 100 volumes of material, or per- 
centage of pores by volume. 

4. The volume of pores in a given weight of material, as cc. 
in 100 grams. 

The loss in weight of the material saturated with water when 
weighed in water, being equal to the volume of water displaced 
by the mass, enables us to determine the specific gravity of the 
latter; while this loss in weight, less the weight of the water 




26 QUANTITATIVE ANALYSIS. 

absorbed by the mass, gives the true volume of water displaced 
by its particles, and hence the means of determining their speci- 
fic gravity. The division of the amount of water absorbed by 
the amount of water displaced, gives the amount by volume of 
the pores in a unit of material, and the division of the weight of 
the water absorbed by the weight of the dry mass, gives the 
volume of pores in a unit of weight of the material : 

Leta := the weight of the dry material. 

b = the weight of the water which the material can absorb. 

^= the loss in weight in water, of the saturated material. 

Then : 

c\ aw looo : a = the apparent specific gravity, or the specific 
gravity of the mass. 

c — b\a\\ looo : a = true specific gravity, or specific gravity 
of the particles, water being looo. 

c\h\\ loo : a = percentage by volume of the pores in the ma- 
terial. 

a : b: : loo : a = volume of pores in loo parts by weight of the 
material, say cc. in loo grams. 

In filling porous substances generally with water two methods 
are in use, one to soak the specimens in water for a time and 
then to place them in water under the receiver of an air-pump 
and exhaust until no more air is given off ; and the other to 
keep them suspended in boiling water until the poifes are filled 
with water, as is shown by their ceasing to gain weight on tak- 
ing them out, cooling, and weighing. 

A combination of both methods will be found advisable in ex- 
perimenting with coke.* 

A series of nine specimens from the Bradford Works of Frick 
& Co., yielded as follows : 

True Apparent Per cent of Cc. in loo 

Moisture, sp. gr. sp. gr. cells by vol. grams. 

Maximum 0.096 1.79 1.033 54-37 66.31 

Minimum 0.008 1.73 a8i9 42.20 40.83 

Average 0.034 1.76 0.802 49.37 55.73 

Coke. El Moro, Colorado. Twelve samples. 

Maximum 0.225 1.85 1.047 54.66 71.36 

Minimum 0.025 1.61 0.766 61.47 41-56 

Average 0.114 1.69 0.919 45.75 50.39 

L FUfIs, Mills and Rowan, pp. i49-i50« 



COAI, AND COKE ANAI^YSIS. 



27 



The following is a report upon a sample of Connelsville coke : 
Anai«ysis op thb.Coai^ prom which the Coke was Made. 

Per cent. 

Water 1.105 

Volatile and combustible matter 29.885 

Fixed carbon 57-754 

Sulphnr 1.113 

Ash. 9.895 



100.752 



en u 



Analysis of the Coke. 

Per cent 

Water 0.030 

Volatile and combustible matter 0.460 

Fixed carbon 89.576 

Sulphur 0.821 

Ash 9.113 

Total 100.000 



►.a 

CO 



Specipic Gravity, Porosity, Per Cent op Cei,i*s, Weight 
PER Cubic Foot, Etc. op the Coke. 



^1 
•is 

833 



Apparent specific gravity 

True specific gravity 

Per cent, of cells by volume 

Volume of cells ; cc. in 100 grams. 
Weight per cubic foot (lbs. ) 



style 

of 
oven. 



Bee-hive 



Coke. 



n«tho4 of rUuiotecture. 

Charge 

in 
pounds. 



Size. 
11X5' 6" 

12' X 6' 



Yield 
per 



7600 63 



Time 
of 
cent, coking. 

48 

and 

72 



0.892 
1.760 
49.37 
55.73 
55.68 



To be used for. 



Kind 

of 

furnace. 



Size of 
fur- 
nace. 



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. 



Fulton's Tablb Exhibiting the Physical and Chemical 
Properties of Coke. 

Revised Series. 



Locality. 


Grams in 

one 
cubic inch. 


Pounds in 

one 
cubic foot. 


Percentage 
by volume. 


III 
1 


ill 

Ui 


si 

02 
1^ 


• 

1 


i 




Dry. 1 Wet. 


Dry. 1 Wet. 


CokelCells. 




1 


Standard Coke. 
















1 
j 






15.471 23.67 


.S«.98 


87.34 


49.96 


50.04 


301 


120 


I a-5 


1.89 


Conuellsville. 


! 























Chemical analysis. 






d 








• 






^ 


V 




%m 


2 

1 




Locality. 


5 

•a 
it 


1 


•s 

< 


s 

Ui 


IS 




b 








0. 




Standard Coke 
















87.46 


0.49 


11.32 


0.69 


0.039 


O.OII 


Connellsville. 















Remarks. 



References: "On the Density of Coke/'by Wm. A.Tilden, F. R.S.,/. 
Soc, Chem. Ind., 3» 610. 

"An Investigation Regarding the Differences Between Cokes,*' by Sir 
I. Lowthian Bell,/. Iron and Steel Institute y 1885. 

"The Physical and Chemical Properties of Coke,'* by John Fulton, 
Transactions Atnerican Institute 0/ Minin^^ Engineers^y 1885. 

Orundlagen 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 j: S '/; JO 









DO E — w r^ ■' s .^ ., J '^ 3C ' 



i2 ^ s* 






f? ? S* Jl I-I 

5 r a B 






rri jS^JS r^ a ft ►^ Q* — 



'3.1 




'; ? ȣ. 3 
- a 2 s 3 



iii.r5 







? o a '^ ^ 


^. » « » 2 


P § P g 2. 


S d ^ » 


Ssr°-S "^ 


2^''l > 


J "» 2. D 


2. Pi" 2. "^ fi} 


lysis 

red ore, 
d, and 
re grad 
1. 


3< ^ O 


» » 3* •-»> 


r ?a 


^ =• n 


matite 

as been d 
? to dryne 
Wash we 






"" Cft ft . ■ 


!«'3 


S ' ^. o 


?i » o D 




r o-S" •-»' 


» ^ rt 


ft o ^ 




ft *< o ft) 


o a»g OQ 


o ^ • 3 




rt 2 » r* 


B P B ^' 


rr -. » •^ 


(0 3* f«, jih 


and 

to six 

rochlo 

flask 


^ 3- 5* W 


Ir-^ 


o E'S ri 


2 - o Nj- 


IS3 ?;• 


Ir 

lain 
rm. 
iniu 


99 » rt O 


SS" 3 


Or 

sule 

one 

ark. 


r* ' n 


2f 3* 5 M 


ft - a . 


=: B o- 


fifty 
dred 
quid 



i 



30 QUANTITATIVB ANAI^YSIS. 

Example : 

Ten grams of iron ore taken. 

Insoluble residue and crucible 10.551 grams. 

Crucible 10.301 ** 

0.250 " 
o.25Xioo _.^^Q ^^j^^ insoluble matter. 
10 

Solution = 500 cc. 
Phosphorus pentoxldOt (100 cc.) 

a. Crucible + Mg^PsO, 8.923 grams. 

Crucible 8.919 " 

Mg,P,OT=o-«M " 

b. Crucible + MgjPjO^ 7.6140 grams. 

Crucible 7.6105 ** 

Mg,P,07= 0.0035 ** 
MgiPtO^ : PjOs : : 0.0038 : x 
:r^ 0.0024 
0.0024X5X100 ^^^^^ ^^„t, p o^^ 
10 

= 0.054 ** P. 
Iron determination. 

Fifty cc. reduced with zinc required 34.65 cc. standard 
K,Cr,0^ solution. One cc. K,Cr,0, corresponds to 0.0168 gram 
iron. 34.65X0.0168 = 0.58212 gram iron in fifty cc. of the 
iron solution. 

Then 0.58212 X 10x100 ^ 38.21 per cent. Fe in the ore. 
10 

= 83.16 *• Fe,0, in the ore. 

Sulphur Trioxlde (50 cc.) 

Crucible -|- BaSOf 11. 126 grams. 

Crucible ii.oii " 

BaS04= 0.015 " 
BaSO^ : SOj : : 0.015 : x 
:r ^0.0051 
0.0051 X IPX 100 ^ ^5, p^, ^^„t so, 

10 
Alumina (50 cc. from 250c. c. ^ 1-5 of 100 cc.) 

Crucible -|- Al,Os,Fe,Oa 12.6614 grams. 

Crucible 12.3160 " 

AlA,Fe,08= 0.3454 " 



IRON ORE ANAI^YSIS. 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,0,Al,0,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 ^ ^^^^ Ai o 

10 
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 ofif ferric oxide, wash, ignite and subtract weight from 
former weight of both oxides. Difference is weight of alumina. 
rUmSiuiese oxide ( 100 cc. ) 

Crucible + MtijO^ 12.166 grams. 

Crucible ' 12.131 ** 

Mnj04= 0.035 ** 
0.35X5X100 _ J ^^ ^^ ^^^^ ^^j^^ 
10 
Lime (100 cc.) 

Crucible + CaO 8.936 grams. 

Crucible 8.929 " 

0.007 " 
0.0027X5X100^^33 p^, ^^^t caO. 

10 

nagoesia ( 100 CC.) 

Crucible + MgjPjO, . . • 8.929 grams. 

Crucible 8.919 " 

MgjPj07= o.oio " 
Mg,P,07 : (MgO)j : : o.oio : x 
X = 0.0036 
0.0036X5X100^^,8 p^^ ^^^^ MgO. 
10 

Water off Hydration. 

Amount of ore taken 1.267 grams. 

CaCl,tube + H,0 29.065 *« 

CaCl, tube 28.963 ** 



H,0=o.io2 
5 per cent. H,0 ( 

Carbon dioxide absent. 



?:I^Ji^ = 8.05 per cent. H,0 (hydrated) 
1.267 



< 



32 



QUANTITATIVE ANALYSIS. 



J 












f1 


^ 


^^5i=:^"^ Hi^^j— 




r^ 


- l_ 




r 


9 



^mi^^M^^^^^.^^ 



'J<^^■>^v^^**>^ 



i*^m^ 



Fig. 8. 



Resum^. 



Insoluble mineral matter 2.50 per cent. 

A1,0, 

Fe,0, 

Mn,0, 

p,o, 



SO, 
CaO 
MgO. 



3.20 
83.16 

1.75 
0.12 

0.35 
0.18 



HjO (hyd rated) 8.05 " 

Total, 99.82 
If the ore is a magnetite, the iron exists as FeO.Fe^O,. There 
are several methods of determining theFeO in presence of Fe,0,. 
The one recommended by Whittlesay & Wilbur,' 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 

1 Chemical News, 19, 270. 



IRON ORE ANAI.YSIS. 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 gprams of the finely pulverized ore are fused with fifteen 
grams of fusion mixture (Na,CO, + K,CO,) in a large plati- 
num crucible for one hour. After cooling the fused mass i» 
treated with boiling water, the contents transferred to a four inch 
porcelain capsule, made acid with hydrochloric acid (carefully) , 
and evaporated to dryness, twenty-five cc. hydrochloric acid, fiv6 
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. 

Detennination of Chromium in Chrome Iron Ore.' 

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,0,. 

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 : 

iProcesB of DonaUi modified by I«. P. Kinnicutt and G. W. Patterson. /. Anal, 
Chem., 3, 132. 

s Chem. NewSy 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, 
f reat 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,0,. 

The following analyses indicate the varying amounts of chro- 
mium sesquioxide in chrome iron ores : 



Place. 



1. Chester Co., Pa 

2. Baltimore 

3. " massive 

4- " cryst 

5. Siberia 

6. Roraas, Nor 

7. Bolton, Ga 

9. X^ke Memphramag:og, U. S 

10. Beresof, Sib 

11. Baltimore 

la. Voltena, Tuscany 

13. Texas, Pa 



PeO MgO CraO, A1,0, SiO, 



35.14 
30.00 
18.97 
20.13 

34.00 
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 

11.00 
9.02 
3.20 
11.30 
10.83 

10.84 



2.09 = 99.32 

10.06 =z 99.11 

0.82 = 98.15 
= 99.45 

Mn. 

10.00, i.oo = 100 

4.83 = 78,95 

= 99.81 

= 100.46 

0.91 ^ lOI.OI 

Ca. 

2.21, 2.01 = 99.06 

4.75 = 100.65 

Ni. 

. . . 2.25 = 104.32 



Analyst. 



Seybert. 
Abich. 

Lang^er. 

Hunt. 

Moberg. 

Rivet. 
Bechi. 

Garret. 



IRON ORE ANAI.YSIS. 35 

Reference, — " New process for the oxidation of chromium ores and the 
manufacture of chromates,*' by J. Massignon, /. AnaiyAppL Chem., 
5. 465. 

Determination of Titanium in Iron Ores. 

The method of Bettel* 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 thjin 300 cc. are to be used, as it generally 
causes a precipitation of some titanic acid) ; filter off from the 
silica, dilute to 1200CC., 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 page 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,/. Anal. 
Appl. Ckem., 5> 325- 

"Determination of Iron by Stannous Chloride," by R. W. Mahon, 
Amer. Chem.fonrnaly 15, 360. 

" The Volumetric Determination of Titanic Acid and Iron in Ores," 
by H. L. Wells and W. L. Mitchell, /. Am. Ghent. Soc, 17, 878. 

"The Constitution of Magnetic Oxide of Iron," by W. G. Brown,/. 
Anal. Appl. Chetny 7, 26. 

1 Crookes' ** Select Methods," p. 194. 



36 



QUANTITATIVE ANALYSIS. 



-910 3;q)«ds r^ 






$ 






o 6 d ^ 



s 






«*5 



8. 

d 



g; 



GO 

o 

G 

S 



09 

•c 

> 



a 
.9 

CO 

o 
a 

B 

o 
O 






•wo ^ 



O 
m 

d 



noil aozcMqo n 



? 
5 



8^ 



?1 « « « OO . g 






o o 
d d 









d d 






4, /5 ^-§ ^2 o q o S-^ iroa 



« 3 



0.865 X 100 _ 



cog 
Crucible -f- SiO, = 17.585 grams. d p. 
- =16.720 •• f ^C3 



= 43'3S per cent. SiOg. 



= 16.720 
SiO,=: o.8$5 



Crucible + Ms:,P,0, = 11.00935 grams. 
" — =11.00879 '* 

m, «^ «^ . Mg,P,07= 0.00Q56 •' 

MgjPjOT ; PjOj : : .00056 : x 

jr=.ooQ3594 
.000359 X 5 X 100 . „ ^ 

— ^^^^—r^ = 0.09 per cent. P,0, 









50 cc. require aQ58 cc. KsCr^Of solution. 
I cc. K«c:r«OT solution ■=: 0.0168 gram Fe. 
50 cc. solution of slag = 0.000974 •• •• 
J 350 cc. '* •• " =0.004870" •* 
C Fe :FeO:: 0.00487 :jr 
X = 0.0062 
0.0063 X 100 . « ^ 
=: 0.31 per cent. FeO. 



P 

5 



Crucible + AlgO, + Fe,0. = 11.94415 grams 
J Subtract Fe,0, f_ „!!!,« - 
j found by Utratlon ( -- °'»'39 

Crucible + Al.O, = r 1.94276 ** 
Crucible =■ 11.8790 •' 

^ _, Al,Oj= 0.06376 
0.06376 X 5 / s 100 . . , « 
^ = 15.94 per cent. Al,Oj. 



12.53 5U^ 
5^S<& 2 

'* P S M *^tt 



SPSS' 



5? 



g^ 



Goj-P 



Crucible +Mns04 = 11.87936 grams. 
*' — = X1.87900 



0.00041 X 5 X 100 



Mn304 = 0.00036 *' 
= o.io per cent. Mns04. 



^ 2 2. ? 
-p2.gg-- 



Crucible + CaO = 13.02484 grams. 
" — =11.87900 

CaO = 0.14584 " 
°'*^V'"°° =36.46 per cent CO. 






Crucible + MgaPsOf = 11.00253 grams. 
— =11.879 



r Mg,p,07 =0.02353 

C Mg,P,OT : (MgO), : : 0.02353 : ^ 

jr = 0.00843 
o.oo8«X5Xioo ^ 2.13 per cent MgO. 



•• O Nl » 

OB-d » 



2.IBB0 5 
=3 gag 5 

l*^ 5.2.1 I 
«p ^ 

1. 3 » 2. 

S^ (D S 

(• 0.0 o. 



8 S " Z^ ® 

< pB a fff^i 
p a« Q.'T'p 

5.-^ 3 '40 
2-pppg 

'*/'*£'• o 

a** B.o-c* 

§yg2.g^ 

P w r? T'vj 



Crucible + BaSOf = 11.92356 grams. 
— = 11.879 " 

BaSOf = 0.04456 '* 
S = 1.53 per cent. 



S?Sg5 S 
B^ B" °-s 



un 






I, 



» "d " 
rr o /> 

• 3 Jl 

S 5*;: 
2. » ^ 

l^s 

P "2 2 
^ Sg 

p ;i p. 

HI 

tf n <* 

M ." » 

V s 

f £■ 
ss-l 

ill 

o - « 



??3 

Pi O 

ll 



X 



P o «< 

p p o. 

I. 

M 



= §.2 

?&< 
g(S • 

p 2: sr 

5 •» 

2 p »xl 

>:2. 3 

ig > 

J? - g. 

2. ft ^* 
S^o* CO 

2 ^ * 

i§ 

p g 



!f 



•Q 25. "^ 

g qp 2. 
? 8 SS 



o P 



38 



QUANTITATIVE ANALYSIS. 



Resum^ 

Lime (CaO ) 36.46 per cent. 

Magnesia (MgO) 2.12 

Silica(SiO,) 43-25 

Alumina ( Al^O,) 15.94 

Ferrous oxide (PeO) 0.31 

Sulphur(S) : 1.53 

Manganese Oxide ( MnO«) 0.09 

Phosphoric Acid (P,Os) 0.09 

Undetermined 0.21 



Total, 100.00 



Form op Blank usbd for Rbporting Blast Furnacb 
Slag Analyses. 



SLAG. 



Date 

Furnace • . 
Ores used 



No. of Iron 

Lime (CaO) 

Magnesia ( MgO) 

Silica (SiO,; 

Alumina ( Al^Oj) 

Oxide of Iron (FeO) 

Calcic Sulphide (CaS) 

Manganese Oxide (MnO^) 
Phosphoric Acid (PjOj) . . . - 



Chemist or Laboratory 



SLAG ANALYSIS. 39 

Examples of Blast Furnace Slags Analyses, 

No. i.> No. 2.« 

FeO 0.270 per cent. 0.436 per cent. 

SiO, 45-460 '* 35«x) 

AlfO, 16.590 " 14.362 

CaO 32.80s '• 45-370 

MgO 1.080 ** 1.398 

MnO, 0.083 " trace 

Sulphur ) Sulphide of) 1.571 '* 1.875 

Calcium./ Calcium > i>963 " 1.500 

Phosphoric Acid (PjOj) 0.008 ** 0.059 

Undetermined Loss 0.070 " 



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, mill- 
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.^ 

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 Slagr made during' the run of Alice furnace, on mixture containing Bnterprise ore. 
s 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). 
s Presenitts Quant, p. 409, { 134. 



40 QUANTITATIVE ANAI.YSIS. 

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.* To 
produce one ton of iron, would require, approximately, 160,000 
cubic feet of air, engine measurement, which would be at the 

rate of 33,333 cubic feet per minute ( ^ 0,000 300 __. 33,333. ) 

\ 24 X 00 / 

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* 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 
0-55) 0.56 + 0.03 X 0.55 + 1.6 X 0.01+ I X 0.01 = 0.57526 ton 
of slag per ton of pig iron, or 0.57526X300=172.5 tons per 
day. 

1 '• The Modem Blast Furnace," E. A. Uehling^, Sin/en's Indicator, 8> p. 17. 

3 Well equipped and well managred furnaces using^ " lake ores" are making a ton of 
iron (2,240 lbs.) with 1.800 lbs. of coke, and in some instances the fuel consumption has 
been as low as 1,600 lbs. of coke. 



BLAST FURNACE SLAG. 4 1 

Summing up : 

Material charged into the blast furnaces per day : 

Ore 480 tons. 

Coke 300 ** 

Flux 165 *' 

945 tons. 
Blast 1743 *' 

Toul a688 " 

Tapped from bottom of furnace in molten state : 

Pig Iron 300 tons. 

Slag 172.5 " 

Total molten product 472-5 ** 

Gaseous product passing out at top of furnace : 

Total blast i743-oo tons. 

Oxygen from ore r 144.00 " 

Gasified Carbon, as CO and CO,, 246.00 ' ' 

Carbon dioxide from flux 7042 ** 

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 of gas there must be added an 
equal weight of air, or nearly so, since considerable excess is 
required for combustion. 

Thus the chimney of a 300- 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 300-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 ANAI^YSIS. 

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 lbs ; its average 
temperature will not be less than 800 degrees ; the specific heat 
of fire-brick, at that temperature, is about 0.18 ; therefore the 
amount of heat stored away in the lining is 800,000 X 800 X 
0.18 = 115,000,000 heat units. 

The regenerative stoves contain something like 48,000 cubic 
feet of fire-brick, which, at 150 lbs. per cubic foot, would make 
48,000 X 150 = 7,200,000 lbs. 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 1743 " 

Totolcharged 2688 " 

Discharged from furnace : 

Molten material from hearth 472.5 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* 

f Stored in the incandescent material \ « *. ^ .^ 

i X • J • r f 908,000,000 heat units. 

^ contained m 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 ^»348>OQO,ooo ^ ^^g_ 

2,000. 
913,272,000 foot-tons of mechanical energy. 



UNIVERSITY 
CHARGING OF BLAST FURNACS»i====**^ 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 ^ 83 mile-tons per 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 andilux, 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 
irregularitj' 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 OP BI,AST FURNACES. 45 

which in its upward course reduces the ore, as already stated, 
forming carbon dioxide, the remainder passing off as carbon 
monoxide with the other gaseous product^. 

The principle object in view in operating a blast furnace is to 
secure the best possible conditions for reducing, carbbnizing and 
melting the iron contained in the ores to be smelted, and to do 
this with the greatest regularity and the least expenditure of 
fuel for the quality of iron desired. 

The chemical phenomena which take place in a blast furnace 
are manifold and complicated, and not altogether understood; 
but for our present purpose it is necessary only to consider the 
two principal reactions, viz. : ** Reduction** and ** Oxidation ;** 
the latter always generating, and the former absorbing heat. 

One pound of iron in being reduced from its ore (Fe,0,) 
absorbs 3,396 heat units.* Carbon in being oxidized to car- 
bon monoxide generates 4,466 heat units, and when another 
atom of oxygen is added, forming carbon dioxide, 10,078 heat 
units more are developed. 

The reduction of ore to the metallic state may and does take 
place in three different ways :* First, by oxidizing the carbon 
at the tuyeres to carbon monoxide by the oxygen of the entering 
blast. The carbon monoxide thus formed, taking anotheratom 
of oxygen from the ore, forming carbon dioxide, which passes 
off as such; second, the carbon, taking direct from the ore two 
atoms of oxygen, forming carbon dioxide as which it escapes ; 
third, the carbon, taking directly from the ore only one atom of 
oxygen, passing off as carbon monoxide. Although it is true 
that the conditions in a blast furnace do not permit the full reali- 
zation of the first two modes of reduction, it is none the less a 
fact that all three modes take place side by side in the process of 
smelting ; and it now remains to be seen which one is the 
most economical, and what can be done in the way of charging 
a furnace to realize that one to the fullest degree. 

One pound of iron (Fe) in the form of hematite ore (Fe,0,) 
holds in combination three-sevenths pound of oxygen. One 

1 3,596 rvpresents the mean of Dttlong^'s Andrews' and Pavre and Silberman's experi- 

SBCflU. A 

s Prof. Gmner Etude sur Us Hau^ Foumeaux, 



46 QUANTITATIVE ANALYSIS. 

pound of carbon to become oxidized to carbon monoxide requires 
one and one- third pounds of oxygen, forming two and one-third 
pounds of carbon monoxide, which is capable of combining with 
one and one-third pounds more of oxygen, resulting in three and 
two-thirds pounds of carbon dioxide. 

The heat absorbed in reducing one pound of iron from its ore 
is not affected by the mode of reduction, being in each case 3,396 
heat units. The heat generated by the oxidation of the carbon 
\^^ by the first mode is 

^ ^->^-J X 4466 = 1435 '5 heat units generated at the tuyeres, 

and f X } X 10078 = 3239.5 ** ** in process of redaction. 



Total, 4675 

3396 " absorbed ** ** 

leaving 1279 " surplus. 

By the second mode of reduction we have 

.f X f X 14544 = 2337 heat units generated, 
3396 *' absorbed, 

leaving 1059 ** deficiency. 

By the third mode of reduction we have 

4 X } X 4466 = 1436 heat units generated, 
and, as before, 3396 *' absorbed, 

leaving i960 " deficiency. 

Thus we see that in the first case we have a surplus of 1279 
heat units, in the second case a deficiency of 1059 heat units, 
and in the third case a deficiency reaching i960 heat units, mak- 
ing a difference between the first and third cases, for the same 
consumption of carbon, of 3239 heat units in reducing one pound 
of iron. 

Time and space will not permit at this time to point out and 
formulate, quantitatively, the heat requirements in addition to 
that absorbed in the process of reduction, nor is it necessary for 
our present purpose. 

The total carbon requirement varies with the nature and 
amount of impurities contained in the ore, the temperature and 
hygroscopic state of the blast, the size, shape and construction 



CHARGING OF BLAST FURNACES. 47 

of the blast furnaces, etc., etc.; for our purpose it will suflBce to 
denote the heat required for smelting, in addition to that 
absorbed in the process of reduction, by the symbol X. Sub- 
tracting from this, our + or — surplus, we get for the addi- 
tional heat required to complete the process of smelting : 

First case, X — 1279 heat units. 
Second " X + 1059 " 

Third " X + i960 

Now, since all the heat required to satisfy X (excepting what 
is carried in by the heated blast) must be generated by burning 
carbon at the tuyeres, where a higher oxidation than carbon 
monoxide cannot result,* we have only 4466 heat units available 
per pound of carbon consumed by the blast. 

The weight of carbon consumed in reducing one pound of 
iron, according to the first mode of reduction, is ^^i = A 
pounds of carbon, resulting, as already shown, in a surplus of 
1279 heat units, available to meet the requirement of X, which 

surplus, expressed in weight of carbon, is equal to • ^ = 0.284 

pounds burnt at the tuyeres. 

By the second mode of reduction we have f X f = ^^ pounds 
of carbon oxidized, resulting in a deficiency of 1059 heat units. 
We have, however, in this case consumed only one-half as much 
carbon as in case first; making this the same, weget^ X 4466=718 
heat units additional, which reduces the deficiency to 1059 — 
718 =: 341 heat units. Expressed as above, we have available 

for X, ^>r = — 0.077 pound of carbon. 

4400 

Similarly we get by the third mode of reduction : f X f = ^ 
pounds carbon oxidized, resulting in a deficiencj'^ of i960 heat 
units, which, expressed in pounds of carbon available for X, 

would be ^-Tz = — 0.443 pound of carbon. 

44^^ 

1 whenever oxygen meets carbon in excess, and at a sufficiently high temperature, 
carbon monoxide results at once. The supposition that carbon dioxide is always 
formed first, and then again reduced to carbon monoxide, has not yet been demon- 
strated. It is much more probable that, when oxygen comes in contact with incandes- 
cent carbon, that carbon monoxide is the first product ; if another atom of oxygen is 
tbeo at hand (1. e., if oxygen is in excess, and the temperature is not above that of dis- 
sociation}, carbon dioxide is immediately formed; but even admitting that carbon 
dioxide is first formed, it can only be of momentary existence in the hearth of a blast 
famace, and does not alter the effect. 



48 QUANTITATIVE ANAI^YSIS 

To simplify the comparison, let us suppose, for the moment, 
that X is completely satisfied by the first mode of reduction, in 

which case we would have — ^ — 0.284= 0.00 pound of carbon 

required to complete the process of smelting one pound of iron. 

By the second mode of reduction we would have — tt- — 

4466 

( — 0.077) = 0.363 pound of carbon required to complete the 

process of smelting, and, according to the third mode of reduc- 

tion we would have — — — ( — 0.443) =0.727 pound of carbon 

required to complete the process of smelting one pound of iron. 

From these few calculations it becomes evident that it is a 
matter of vital importance which mode of reduction prevails in 
the furnace, and that the first mode should be sought to be real- 
ized to the fullest extent, and the third mode should be avoided 
entirely if possible. 

The first mode of reduction implies that no direct reduction 
shall take place, i. ^., no oxygen shall be abstracted from the 
ferric oxide by carbon, which necessitates that all the carbon 
shall reach the zone of combustion and be there burned to car- 
bon monoxide, which, on its upward course, reduces the ore 
(Fe,0,) and becomes itself oxidized to carbon dioxide.' 

Since the direct combination of the carbon of the fuel with the 
oxygen of the ore can only take place by actual contact, it does 
not require much meditation to arrive at the conclusion that 
such contact should be avoided as far as possible. This can be 
done to a limited extent in charging the furnace. 

Calculation of Blast Furnace Slag. 

Assume that we have a mixture of ores, of which the average 
composition is :* 

1 This mode of reduction, the desirability of which was first scientifically established 
by Prof. Gruner in his Etude sur Us Hautf Foumeaux, cannot be fully realized in the 
present form of blast furnace, because contact between fuel and ore cannot be entirely 
avoided. 

s Rossi :/. Am. Chem. Soc., la, 321. 



CHARGING OF BLAST FURNACES. 49 

Iron Ore. 

SiO, 20.00 per cent. 

AljO, 3.20 " ** 

CaO 310 ** " 

MgO 2.60 '* *' 

FcjO, 70.00 " ** 

Mn,04 0.20 " " 

PA 105 " " 

SOj 0.10 ** *' 

100.25 " " 
Metallic Iron = 50. per cent. 

Limestone. 

SiO, 6.00 per cent. 

A1,0, 1.15 " /' 

CaO 30.00 **■ ** 

MgO 19.00 '* " 

CO, 44.20 " '* 

100.35 *' ** 

Coal. 

Anthracite coal containing 6.28 per cent ash. Of which ash, the com- 
position, in the coal, in per cent, is : 

SiO, 3.35 per cent. 

A1,0, 2.73 " •* 

CaO o.io " " ' 

MgO o.io " " 

6.28 " " 

We have decided to obtain a slag of such a character that the 
fusibility will be about that of a sesquibasic slag, that is, if pre- 
ferred, of one in which oxygen ratio is 4:3. Looking at the 
table* we see that, for such a type, one of lime saturates 0.7 14 of 
siUca, crone of silica takes up 1.400 of lime. Assuming any 
proper amount of coal per ton of ore smelted and, in most cases, 
0.75 ton is all that is required, we have all the data necessary 
for our calculations. Transform all the analyses into lime : 

1 Sesqui- Sesqui- Tri- Quad- 

Compositiou. Acid. acid. Neutral, basic. Bibasic. basic, nbasic 

SiO^percent 68.19 61.65 51.72 41-66 34.88 26.30 21.13 

CaO per cent 31.81 38.35 48.28 58.34 65.12 73.70 78,87 

O of SiOf : O of bases 4:1 3:1 2:1 4:3 1:1 2:3 1:2 

iCaO saturates 5fO. 2.143 1.6071 1.0713 0.714 0.538 0.357 0268 

iSiOf '• CaO 0.466 0.622 0.932 1.400 1.858 2.829 3.73a 

(4) 



50 QUANTITATIVE ANALYSIS. 

Orb. 

SiO,as 20.00 per cent. 

Al,0, = 3.20Xi.63i 5.22 ** ** 

CaO=:3.io 3.10 ** *' 

MgO 3s 2.60 X 1.40 3.64 ** *' 

Mn304=o.20 0.15 " ** 

CaOsi2.11 ** ** 

The ore is equivalent per ton to 

SiO, 20.00 per cent. 

CaO 12.11 " 

LXMBSTOITB. 

SiO, 6.00 per cent. 

Al,0,= i.i5X 1.631 1.87 ** " 

CaO=s3o 30.00 " " 

MgO = i9Xi.4o 26.60 " " 

CaO«58.47 " " 
The limestone is equivalent per ton to 

SiO, 6.00 per cent. 

CaO CaO=58.47 ** ' 

Coal. 

SiO, 3.35 per cent. 

A1,0, = 2.73X 1.631 4.45 " " 

CaO 0.10 ** *' 

MgO 0.14 ** " 

Ca03s4.69 " *• 

The coal is equivalent per ton to 

SiO, 3.35 per cent. 

CaO 4.69 *' " 

Hence, as we use only three-fourths of a ton of coal per ton of 
ore, the coal used is equivalent to three-fourths of the above 
analysis, or : 

SiO, 2.52 per cent. 

CaO 3.52 ** •* 

SiO, == 20 + 2.52 =SiO, 22.52 ** " 

per ton of ore ; the coal and ores are equivalent to CaO = 12. 1 1 
+ 3.52=15.63., Since, to make the proper silicate, one 
of lime takes up 0.714 of silica, the 15.63 of lime in coal and 
ores will take up: 0.714 X 15.63= 11. 16 per cent, of silica, 



CHARGING OP BI,AST FURNACES. 5 1 

leaving of free silica in the ore and coal 22.52 — 11.16 = 11.36 
silica to saturate with limestone. The six per cent, of silica of 
the stone will require, at the rate of 1.400 pounds lime per pound 
of silica, 6 X 1.40=8.40 lime, leaving oifree lime or the equiva- 
lent in the limestone, 58.47 — 8.40 or ^o,ot free lime. We have 
to saturate in coal and ores, 11.36 free silica. At the rate of 
saturation adopted, it will take: 11.36 X 1.40 lime =15.91 
lime ; as 50.07 free lime in one ton of limestone requires only 
15.91 of lime to saturate the silica in coal and ores, we need 
only per ton of ore and three-fourths ton coal, 

15.91 

= 0.317 tanoi limestone. 

50.07 
The charges are thus : one ton of ore, 0.75 ton of coal, 0.317 
ton of limestone and, as the ore contains fifty per cent, of iron, 
we require two tons of ore, one-and-a-half tons coal and 0.634 
ton limestone per ton of pig made. 
The composition of the slag is : 

Silica in ore and coal per ton of ore and per | ton of 

coal 22.526 per cent. 

In stone 6 X 0.317 ton 1.902 ** ** 

TotelSiO, 24.428 '* ** 

Lime in f ton coal and i ton ore (per ton ore) 15.63 '* ** 

In stone 0.318 ton X 58.47 per cent = 18.59 ** " 

Total lime 34.22 " ** 

equivalent to 

SiO, = 24.428 or reducing to SiO, = 41.66 per cent. 

CaO = 34.220 percentage: CaO = 58.34 ** " 

58.648 Total, 100.00 ** " 

exactly a sesquibasic silicate. 

Using the preceding charges of ores, stone and coal, we should 
have every reason to expect- a slag of the above composition or 
of one very close to it. 

We have adopted one and one- half tons coal per ton of pig. If 
greater accuracy were necessary the preceding calculations could 
be made over again with the new charges in coal ; but, practi- 
cally, it is absolutely useless, the ash of coal entering, as it may 



52 QUANTITATIVE ANALYSIS. 

be seen, as a small percentage into the general composition. 
With inferior cokes or anthracite it becomes an important factor 
not to be neglected but too often ignored. Cokes with fifteen 
per cent, of ash are not uncommon in certain localities. 

As an example of the close coincidence between slags actually 
run from known calculated charges and the slag determined, a 
priori, we quote the following slag run in a furnace sixty feet 
high, sixteen feet bosh, running on hot blast 850** to 900** F. 
Pressure of blast, seven and one-half pounds, American furnace,, 
anthracite coal. The analyses of materials were as follows : 

Ores. 
Per cent. 

SiOa 23.31 

AljOa 4.5^ 

CaO I.61 

MgO 3.41 

Alkalies 2.67 

M11JO4 traces 

PjOs 0.31 

S 0.08 

Making the calculations proportionally to the quantity of the 
different materials charged, we have : 

Charges : 
Iron ore, Dolomite, Coal, 
924 lbs. 378 lbs. 588 lbs. ToUl. 

Containing : 

Lbs. Lbs. Lbs. Lbs. 

Silica 215.38 37.42 17.64 270.44 

Alumina 41-67 14.66 13.52 69.85 

Lime 1490 105.84 0.59 121.33 

Magnesia 31 -50 60.48 0.47 92.45 

Alkalies 24.67 24.67 

Mang. oxide Traces .... .... .... 



stone. 


Coal. 


Per cent. 


Per cent. 


9.90 


300 


3.88 


2.30 


28.00 


0.10 


16.00 


0.08 



Amount of slag ingredients 578.74 

Nine hundred and twenty-four pounds of ore gave in iron 425 
pounds, the ores having 46.60 per cent. iron. With such slag, 
of which the character was sesquibasic, a light grade of iron 
was to be expected, such pig as contains in an average 1.50 per 
cent, silicon or 3.20 per cent, silica corresponding, in 425 pounds 
of pig iron, to 13.60 pounds of silica, which, subtracted from the 



CHARGING OF BLAST FURNACES. 53 

total silica which went to form slag and pig, leaves a balance of 
256.S4 pounds silica to be expected in. slag. The composition 
of the slag was then : 

Calculated. 

Lbs. Per cent. 

SiO, 256.84 45-44 

AljOj 69.85 12.36 

CaO 121.33 21.40 

MgO 92.45 16.36 

Alkalies 24.67 4.40 

565.14 99.96 

The analysis gave : 

Per cent. . 

SiO, 44.27 

A1,0, 12.91 

CaO 20.CX) 

MgO 16.50 

Alkalies 3.98 

FeO 2.47 

MnO Traces 

S 0.56 

100.69 

This quantity of iron oxide, 2.47 per cent., is not abnormal, but 
occurs in many slags. If we take it into consideration in calcu- 
lating the slag we have 99.96 + 2.40 = 102.36. Reducing to a 
percentage we find : 

Calculated Slag (iron added). Actual Analysis. 

Per cent. Per cent. 

SiO, 44-34 44.27. 

A1,0, 12.06 12.91. 

CaO 20.88..... 19.81. 

MgO 16.00 16.50. 

Alkalies 4-22 3.98. 

FeO 2.47 2.47. 

The iron was found to be No. 3 light gray, containing 1.53 
per cent, silicon. Transformed into lime, this slag corresponds 
to: 

Per cent. 

SiO, .* 40.66 

CaO 59.34 

100.00 



54 



QUANTITATIVK ANALYSIS. 





••0 Z 

?i X ^ 

a .. w 

V et II 

H 

o 
O 



St 
o2 



15 R 






i^ 



••si 



.a a 

a 



|3 






B-S 



•'-*-' bo 

at a 
3 es 

fc5 



a 






.•3 Xi 

a h 

flu - 



^.c go . 
o 2 2f « *l 

^ S.5 .0 H 5 



!i 






09 

cd 
CO 



09 



a 

s 
1 

8 



43 



K O 

o 






•^1 
(B '.4 



u 

a 






3 * 



<LI S ,, «* *" 




« ® M 

PS o r? 

a • • « 



;»€ 



S-Si 






i"2 

> 



9 P... 



9 el 



I 






o ^ 

P< o .. 

V « II 

o 
O 



o * 



P< o 



be u 

o 
O 






^ B 



00 n 



.Si 8 



§1-5 
2 ■ 



a ^ «« 
2«S 
2S 



.. -s 

O 



.-3 J3 

.•2 • 
a a 



a 
s a. U 
SBbo-2 

M 



8 P... . 

SSbo« 
-85 5 
o u ") % 

•S5S 2 



BLAST FUIINACK 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 (*) 
is fixed at right angles to a upon a block, ^:, which is capable of 
sliding motion in a groove parallel to a.* 




The point A, pven 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. JenUns, 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 tjrpical 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 atQmic weight of lime, and corres- 
ponds to calcium silicate : this line, therefore, is marked *Xime." 

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 A£ is at an angle of 41"^ 25^ and this having a 
tangent corresponding to the ratio of the atomic weight of 3 SiO„ 
to that of 2A1,0„ 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 matterto 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 
CaO 5 
Al A 3 
SiO, 3 
CO, 36 



2.25 
2.68 
2.65 



Then setting the movable scale b against 3 on the fixed scale 
A and looking along ^ 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 



BlvAST 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,, a,, a^ be the percentages of iron in the ores, 
and *,, ^,, b^ percentages of deficiency (or excess) of silica in the 
same, 2Lndx,y, z, the number of parts required of the component 
ores per hundred of the charge 

FcO SiOa 

y K + ^) 

then, 

(i) x-^-y •\- z^=^ \QO, 



(2) 



xa^ + ya^ + ^g, — 



100 

(3) xb,—yb,^zb, = 
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. 

Shimer./. Atn. Chem, 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. 



i 



58 QUANTITATIVK 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' 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 Ctaarlestown S. C, analysed by the author in 1887 
had the following composition ; 

Carbon i.oi per cent. 

SiOa 1.5a •* 

AlaO, 0.43 " 

• NaCl 72.12 *' 

CaClg ; 10.32 *' 

KCl i.or " 

MgCl, 1.71 ♦• 

CaSOf 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 Monongahela River 
water, {Transactions Amer, Inst, 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 : 







5&« 
ic ? s? 

"S 'C 1! 
S ^ ii 

•B «M ^ 

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< 

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ANALYSIS OF WATER. 



6l 




Fig. lo. 

To show, in detail, the method of using the scheme, the fol- 
lowing water analysis is given. (Preliminary tests having 
shown the water to contain but little residue, eight liters of it 
were evaporated.) 

Platinum capsule and residue (8 liters) 147.460 grams. 

'* " without residue 146.620 



Total residue 



0.840 



Before ignition, capsule and residue 147.460 

After ** '* " " 147.197 



Organic, volatile, CO,, etc • 



0.263 



Crucible -|- SiO, i5-97o 

Crucible 15904 



SiO, 



0.066 



Solution made to 100 cc. — seventy-five cc. for bases 
five cc. for SO,. 
Twenty-five cc. (SO,). 

Crucible and BaSO| 1B.023 grams. 

Crucible 15903 ** 



twenty- 



BaSO^ 



62 QUANTITATIVE ANALYSIS. 

Seventy-five cc. 

Crucible + Fe,Oj( A1,0,) 159338 grams. 

Crucible 15.903 ** 

Fe,0,{Al,0,) 0.0308 " 

Crucible+ CaO 16.0197 " 

Crucible 15*903 *' 

CaO 0.1167 ** 

Crucible + MgO 15.928 " 

Crucible ^ 15-903 ** 

MgO 0.025 " 

Platinum dish + alkaline sulphates+MgSO^ 53.370 " 
Platinum dish ••••. 53.197 " 

Sulphates 0.173 *' 

Dissolved in water, made solution up to fifty cc. : twenty-five 
cc, for magnesia determination, and twenty-five cc. for potash 
determination. 

Crucible -f- Mg,P,OT 15942 grams. 

Crucible 15*904 ** 

Mg,PA 0.038 *• 

0.038 X 2=0.076 MgjPjO^. 
MgjPA : (MgSO*), : : 0.076 : x 
MgSOfSs 0.082 gram. 

Potassium platinic-cbloride on tared filters =0.023 gram, cor- 
responds to 0.0046 potassium sulphate in the fifty cc. 

Having determined the amounts of magnesium and potassium 
sulphates, the residue remaining is sodium sulphate, as follows : 

Total sulphates 0.173 grams. 

Magnesium sulphate 0.082 *' 

Sodium and potassium sulphates 0.091 *' 

Potassium sulphate 0.0046 ** 

Sodium sulphate 0.0864 " 

and calculated to their oxides would be as follows : 

MgO =0.027 grams for 75 cc. = 0.036 gram for 100 cc. or the 8 liters. 
Na,0 =0.0377 '* " 75 *' =0.0502 *' '* " 
KjO =0.0025 " ** 75 ** =0.0034 '* " *• 

The chlorine found by titration amounted to 0.0055 gram per 
liter or 0.32 grain per gallon. 



ANALYSIS OF WATER. 



63 



The weights thus obtained are in terms of the total residue, 
eight liters, and are converted into values corresponding to one 
liter, the result being as follows : 

SiO, 0.0082 gram per liter. 

SOj 0.0206 

CI 0.0055 

K,0 0.0005 

Na,0 0.0062 

MgO 6.0077 

CaO 0.0194 

Fe,0,( A1,0,) 0.0051 

CO, 0.0137 

Organic, etc 0.0193 

0.1062 
Oxygen in excess of CI 0.0016 



Total residue 0.1046 

It is necessary now to convert these values, grams per liter, 

into grains per gallon, in doing which the following table is 

used: 

tabi^ showing thb number of grains per u. s. gai^lon (58,318 
grains) and imperial gallon (70,000 grains) corres- 
ponding TO MILLIGRAMS PER LITER. 

Bfillifirnims 
per Uter. 

1 0.0700 

2 0.1400 

3 0.2100 

4 0.2800 



Grains per Imperial 
grallon. 



Grains per 
lion. 



5- 
6. 

7- 
8. 

9- 
10. 

II. 



0.3500 

0.4200 

0.4900 

0.5600 

0.6300 

0.7000 

0.7700 

12 0.8400 

13 0.9100 

14 0.9800 

15 1.0500 

16 1. 1200 

17 1. 1900 

18 1.2600 

19 1.3300 

ao 1 .4000 



U. S. irallon. 
0.0583 
O.I 166 
0.1749 
0.2332 
0.2915 

0-3499 
0.4082 
0.4665 
0.5248 
0.5831 
0.6414 
0.6998 
0.7581 
0.8165 
0.8747 
0.9330 
0.9914 
1.0497 
1. 1080 
1.1663 



64 



QUANTITATIVE ANALYSIS. 



Mini- Grains 

grams per 

8er Imperial 

ter. gallon. 

21 1.4700 

22 I-5400 

23 I.61OO 

24 1.6800 

25 I-7500 

26 1.8200 

27 1.8900 

28 1.9600 

29 2.0300 

30 

31 



2.1000 

2.1700 

2.2400 

2.3100 

2.3800 

2.4500 

2.5200 

2.5900 

2.6600 

2.7300 

2.8000 

2.8700 

2.9400 

3.0100 

3.0800 

3.1500 

3.2200 

32900 

3-3600 

3.4300 

3-5000 

3-5700 

3-6400 

3-7IOO 

37800 

3-8500 

3.9200 

3.9900 

4.0600 

4.1300 

60 4.2000 



32- 
33- 
34- 
35- 
36. 

37- 
38- 
39- 
40 
41. 
42. 
43- 
44. 
45- 
46. 

47- 
48. 

49- 
50 

51- 
52- 
53- 
54- 
55- 
56- 

57- 
58.. 

59- 



Grains 

ri 

gallon. 
.2246 
.2829 
-3413 
.3996 
.4579 
.5162 

.5745 
.6329 
.6912 

•7495 
.8078 
.8661 

-9244 

.9828 

2.0411 

2.0994 

2.1577 
2.2160 

2.2745 
2.3327 
2.3910 

2.4493 
2.5076 

2.5659 
2.6243 
2.6826 
2.7409 
2.7992 
2.8575 
2.9159 
2.9742 

3-0325 
3.0908 

3.1491 
3.2074 
3.2658 
3.3241 
3.3824 
3.4407 
3.4990 



Milli. Grains 
grams per 

per Imperial 

liter. gallon. 

61 4.2700 

62 4.3400 

63 4.4100 

64 4.4800 

65 4-5500 

66 4.6200 

67 4.6900 

68 4.7600 

69 4.8300 



70 

71- 
72- 
73- 
74- 
75- 



4.9000 
4.9700 
5.0400 
5.1100 
5.1800 
5.2500 



76 5-3200 

77-- 5.3900 

78 5.4600 

79 5.5300 

80 5.6000 



81. 
82. 

83- 
84. 
85- 



5-6700 

5.7400 

5.8100 

5.8800 

5.9500 

86 6.0200 

87 6.0900 

88 6.1600 

89 6.2300 

90 

91 

92 

93 

94 

95--"; 

96 

97 



6.3000 

6.3700 

6.4400 

6.5100 

6.5800 

6.6500 

6.7200 

6.7900 

98 6.8600 

99- •• 6.9300 

100 7.0000 



Grains 

gallon. 
3.5573 
3.6157 
3.6740 
3.7323 
3.7906 
3.8489 
3.9073 
3.9656 
4.0239 
4.0822 
4-1405 
4.1988 
4.2572 
4.3155 
4.3738 
4.4321 
4.4904 
4-5488 
4.6071 
14.6654 

4-7237 
4.7820 

4-8403 
4-8987 
49570 
5.0153 
5.0736 
5.1319 
5.1903 
5.2486 
5.3069 
5.3652 
5.4235 
5-4818 
5-5402 

5.5985 
5.6568 

5.7151 
5.7734 
5.8318 



ANALYSIS OF WATER. 65 

The amounts obtained being : 

SiO, 0.4771 grains per gallon. 

SO, 1.2012 ** 

CI 0.3206 *• 

K,0 0.0291 ** 

Na,0 0.3615 ** 

MgO 0.4490 ** " " 

CaO 1.1313 ** '* ** 

CO, 0.7987 " 

Fe,0„Al,0, 0.2973 " " " 

Organic 1.1254 ** " **' 

6.1912 ** " ** 
Oxygen in excess of CI • 0.0932 ** ** ** 

Total 6.0980 " 

Having determined the component parts of the water residue 
in grains per gallon, it becomes necessary to unite these in chem- 
ical union, as near as possible, as they exist in the water. 

The general rule may be stated as follows : The chlorine is 
combined with the sodium, if still in excess, then with the po- 
tassium, magnesium, and finally calcium. The sulphuric acid 
to the alkalies, provided there is not enough chlorine to saturate 
them, then to the calcium, and finally to the magnesium. 

The carbon dioxide is united with the calcium and magne- 
sium after the other combinations are made. There are excep- 
tions to this rule, mineral waters and many artesian well waters 
forming notable examples. 

Carrying out the above, the following is obtained : 

Gram Graias 

p«r liter. per gallon. 

NaCl 0.0091 0.5306 

Na,S04 0.0033 0.1923 

K,S04 0.0009 0.0524 

CaSO* o 0311 1.8136 

CaCO, 0.0118 0.6880 

MgCO, 0.0162 0.9446 

Fe,0„ A1,0, 0.0051 0.2973 

SiO, ,.... 0.0082 0.4771 

Organic, etc 0.0193 1-1254 

Total 0.1050 6.1213 

This analysis shows that the principal scale-forming ingre- 
(5) 



i 



66 QUANTITATIVE ANALYSIS. 

dient is calcium sulphate, being more than equal to the calcium 
and magnesium carbonates. 

The following analysis is of a water containing sulphuric acid, 
but the alkalies being present in sufficient amount to combine 
with all of it, as well as the chlorine, no calcium sulphate is 
present : 

Grain Grains 

per liter. per srallon. 

SiO, 0.0038 0.2215 

SO, o.oiio 0.6414 

CI 0.0062 0.3615 

K,0 0.0033 0.1923 

Na,0 0.0185 1.0788 

MgO 0.0165 0.9624 

CaO 0.0466 2.7175 

Al,0„Pe,0, 0.0020 0.1166 

CO, 0.0530 3.0908 

Organic 0.0246 1.4345 

0.1855 10.8173 

Oxygen in excess of CI 0.0021 0.1224 

Total 0.1834 10.6949 

Combined as follows : 

Gram Grains 

per liter. per gallon. 

NaCl 0.0154 0.8980 

Na,S04 0.0141 0.8233 

K5S04 0.0061 0.3557 

CaCO, 0.0833 4.8577 

MgCOj 0.0338 1.9710 

Al,0„Fe,0, 0.0020 0.1166 

SiO, 0.0038 0.2215 

Organic 0.0246 1.4345 

Total 0.1831 10.6773 

Where all the chlorine is not in combination with the sodium 
and potassium, magnesium chloride is usually present. 

The latter compound, while not scale-forming, is considered 
as an active, corrosive agent — upon the supposition that at the 
tempefature of 100** C, and higher, it is decomposed, and hydro- 
chloric acid formed and liberated. Consult Journal Society of 



AXAI^YSIS OF WATER. 67 

<lhemical Industry^ Vol. IX, p. 472 ; also Treatise on Steam 
Boilers, by Wilson, p. 168. 

The report, given below, is of a water from a driven well in 
Florida. Complaint having been made that not only was the 
scale excessive in amount, but that corrosive action was also very 
marked, an analysis was made ; reference to which readily ex- 
plains the difficulty encountered in the boilers. 

Gram Grains 

per liter. per traHoii. 

NaCl 0.323 18.83 

KCl 0.067 3.90 

MgCl, 0.104 6.06 

CaSOf 0.197 "-48 

CaCO, 0.293 17.08 

MgCO, 0.144 8.40 

SiO, o.oii 0.64 

Al,0„Pe,Os 0.007 0'4o 

Organic 0.138 8.04 

Total 1.284 74-83 

In all of the above analyses the constituents have been stated 
in grains per gallon, rather than in parts per 100,000, the former 
being in general use by the mechanical profession as the proper 
method by which to express the weights of the component parts 
of the residue of a water. 

The following is an analysis of boiler water, in which no scale 
was present, but where corrosion was rapid. Sample was marked 
*• Stand Pipe in Boiler.'* 

NaCl 33.70 grains per gallon. 

KCl 2.26 

Na,S04 16.33 

MgSO* 19.26 

Pe,Os( suspended particles) 5.64 

Fe,(NO,), 6.12 

Cu(NO,), 3.18 

Ca(NO,), 12.11 

Mg(NO,), 14.08 

Silica 14.16 

HNO,(free) 12.27 

Organic matter 24.12 

Undetermined 2.15 

Total 164.38 



68 QUANTITATIVE ANAI^YSIS. 

The water supplied to this boiler, also acid, was composed as 
follows : 

NaCl 0.73 grains per gallon. 

MgCl,(KCl) 0.87 

MgSO*.... 1.71 

CaSO* 1.53 

Ca(NO,), 0.38 

SiO, 0.52 

Fe,(NO,), 0.44 

HNO,(Frec) 0.90 

Organic matter 0.64 

Total solids 7.72 

This incl-ease of total solids from 7.72 grains per gallon in the 
supply water to 164 grains total solids, per gallon of water in the 
boiler shows neglect in the management of the boilers. 

By neutralizing the free acid, in the supply water, with sodium 
carbonate, corrosive action in the boiler was prevented. 

In coal-bearing districts the boiler waters, while usually 
selected with care regarding the total solids, often contain free 
sulphuric acid, derived from the oxidation of the iron pyrites in 
the coal beds and which enter into the water supply. 

The free acid in water can be determined quantitatively as 
follows : 

250 cc. of the water are transferred to a six-inch porcelain 
evaporating dish, a few drops of litmus solution added, and the 
water boiled five minutes, then titrated with a very dilute stand- 
ard solution of caustic soda. 

Thus: 

250 cc. of water taken, which required one and two-tenths cc. 
of the caustic soda solution. 

The caustic soda solution is of such a strength that 31. i cc. of 
it neutralizes five cc. of normal sulphuric acid solution. 

One cc. of the normal sulphuric acid solution contains 0.049 
gram sulphuric acid. 

Then one cc. of the dilute caustic soda solution corresponds 
to 0.00787 gram sulphuric acid. 

If 250 cc. of the water required one and two-tenths cc. of the 
caustic soda solution, one liter will require four and eight-tenths 



ANAI^YSIS OF WATER. 69 

cc. caustic soda solution ^ 0.0377 gram sulphuric acid, corres- 
ponding to 2.20 grains of free sulphuric acid per gallon of water. 

Determination of the Hardness of Water. 

The hardness of water may be temporary, permanent, or both. 

The former is caused by calcium and magnesium carbonates 
and which are held in solution by ths excess of carbon dioxide in 
the water. 

Boiling the water drives out the excess of the carbon dioxide 
and the calcium and magnesium carbonates are thereby pre- 
cipitated. 

The permanent hardness is usually caused by calcium sul- 
phate, which is not precipitated by boiling, or by magnesium 
chloride. The former, however, can be separated out of boiler- 
feed water by heating to 240° F. since at 230"* F. it is insoluble. 

Temporary Hardness, 

The temporary hardness is determined as follows : Standard 
sulphuric acid solution and standard sodium carbonate solution 
are required and are prepared as follows : 

1.96 g^ams of pure ignited sodium carbonate are dissolved in 
one liter of distilled water. One cc.=o.ooio6gram corresponding 
too.ooi calcium carbonate. The standard sulphuric acid solution 
is made of such strength that one cc. of it exactly neutralizes 
one cc. of the standard sodium carbonate solution. 

100 cc. of the water, to which a few drops of lacmoid solution* 
have been added, are heated to boiling, and the sulphuric acid 
^adually added until the color changes. 

Each cc. used represents one part of calcium carbonate per 
1 00000 parts of water, or if it be desired to express it in grains 
per gallon, the result in parts per looooo is multiplied by 0.583. 

Permanent Hardness, 
One hundred cc. of the water are taken and an excess of the 
sodium carbonate is added thereto, generally speaking the same 
volume will be sufficient. This is evaporated to dryness in a 
platinum dish, and the soluble portions are extracted with dis- 
tilled water through a small filter and the filtrate is titrated with 

1 Made by dissolving 3 grams lacmoid in 1000 cc. of dilute alcohol (50 $). 



70 QUANTITATIVE ANAI.YSIS. 

the Standard acid for the excess of sodium carbonate ; the differ- 
ence represents the permanent hardness. 
Reference, — Consult Sutton's volumetric analysis, p. 67. 

Determination of Hardness by the Soap-Test. — (Phillips.) 

The degree of hardness of a water is determined by ascertain- 
ing the amount of standard soap solution necessary to form a 
permanent lather with a definite volume of the sample ; the 
** harder'* the water the more soap it will consume, owing to 
the formation of insoluble calcium, magnesium, etc., soaps 
(** curd'*), brought about by the decomposition of the soda or 
potash soap added, by the salts of the alkaline earths present in 
the water. 

The hardness of water is usually expressed in terms of calcium 
carbonate. 

Preparation of the standard solutions : 

First, Solution of '* Hard Water." Dissolve i.ii grams of 
pure fused calcium chloride in a little water, and dilute to one 
liter at i5°C., or dissolve one gram of pure calcium carbonate in 
fifty cc. of dilute hydrochloric acid, evaporate to dryness, dis- 
solve in fifty cc. of water, and dilute to one liter. In either case 
each cubic centimeter of the solution will correspond to o.ooi 
gram calcium carbonate. 

Second, Solution of Soap. Castile soap, which is supposed 
to be made with soda and olive oil, is much used for standard 
soap solutions, but it has been found liable to considerable de- 
terioration on keeping, especially in cold weather, owing to the 
deposition of sodium palmitate. 

Sodium oleate makes a standard soap solution which suffers 
very little change on keeping, and can be generally recom- 
mended for the purpose. 

Thirteen grams of it are dissolved in a mixture of 500 cc. of 
alcohol and 500 cc. of water, and filtered if necessary. It now 
becomes necessary to standardize it, so that one cc. will be 
equivalent to o.ooi gram of calcium carbonate. In order to 
effect this, twelve cc. of the standard hard water are run into a 
250 cc. stoppered bottle from a burette and diluted to 58.3 cc. 
A burette is now filled with the soap solution which is run into 



ANALYSIS OF WATER. 7 1 

the bottle one cc. at a time, and the bottle vigorously shaken 
after each addition, until a point is reached where a persistent 
lather, lasting for at least five minutes, is obtained. Note the 
volume required. Twelve cc. of hard water should require thir- 
teen cc. of soap solution (distilled water itself requiring one cc» 
to form a lather) , but it will be a figure less than this, and 
therefore the soap solution is too strong and will require diluting, 
so that twelve cc. of standard ** hard** water will require thir- 
teen cc. of the soap solution. An example of an actual prepara- 
tion of a standard soap solution will explain this. 

Thirteen grams of sodium oleate were dissolved in a mixture of 
500 cc. of alcohol and 500 cc. of water, and filtered. On testing 
in the manner described, twelve cc. of the standard **hard** 
water diluted to 58.3 cc. required 11.4CC. of the soap solution to 
form a persistent lather. 

Now, since thirteen cc. should have been required, every 11.4 
cc. of the soap solution left, requires diluting by 13 — 11.4 = 
1.6 cc. 

There were 960 cc. of the solution left, therefore-? — =84.2, 

11.4 

and 84.2 X 1.6= 134.7 cc. more of the mixture of alcohol and 
water to be added. On adding this quantity, thoroughly mix- 
ing, and testing as before, twelve cc. of the standard hard water 
required exactly thirteen cc. of the soap solution. 

Determination of Total Hardness, 

58.3 cc' of the clear sample, of the water to be examined, are 
run into a 250 cc. flask, and the standard soap solution added in 
the manner described above, until a lather capable of persisting 
for five minutes is produced. The number of cubic centimeters 
required, minus one cc. for the water itself, will give the degrees 
of hardness in terms of calcium carbonate in grains per gallon. 
If the water contains a fair proportion of magnesia salts, there 
will be some difficulty in obtaining the right point, owing to the 
slowness with which magnesia salts decompose soap ; an appar- 

1 If it be desired to determine the hardness in strains per English Imperial gallon, 
instead of the United States gallon, seventy cc. of the water must be taken. This is de- 
pendent upon the fact that the English Imperial gallon contains 70,000 grains, and the 
United States gallon 58,318 grains. 



72 QUANTITATIVE ANAI^YSIS. 

ent persistent lather is formed, which on being allowed to stand 
a little while and again shaken up, will disappear ; a little ex- 
perience with magnesian hard waters will familiarize the operator 
with this peculiarity. 

The Permanent Hardness. 

250 cc. of the water are poured into a 500 cc. flask, and boiled 
for one-half hour, the original volume being kept up by frequent 
additions of boiling distilled water, free from carbon dioxide. 
After cooling, it is quickly poured into a 250 cc. graduated stop- 
pered flask, diluted if necessary to exactly 250 cc. at 15** C. with 
distilled water, well mixed and filtered. 58.3 cc. of the solution 
are now poured into the bottle and the permanent hardness de- 
termined as described. 

The Temporary Hardness, 
The temporary hardness, or that hardness removed by boiling, 
is obtained by deducting the degree of permanent hardness from 
that of the total. 

Standards of Hardness, 

The French standard of hardness of water is stated in terms of 
milligrams of calcium carbonate in 100 grams of water, or, parts 
calcium carbonate per 100,000 parts of water. 

The German standard represents milligrams of lime in 100 
grams of water, or parts lime per 100,000 parts of water. 

The English standard represents grains of calcium carbonate 
per gallon of 70,000 grains. 

The American standard represents grains of calcium carbon- 
ate per gallon of 58,381 grains. The French standard is to be 
preferred. 

Table Showing the Relative Hardness of the Water Supplied to 
Cities. Determinations made by A. R. Leeds. 



Calcium 
carbonate. 



Parts per 100,000. ..... 4.4 

Grains per U. S. gallon 2.56 



I 



> 

1 


1 

pq 


t 


1 


is 

1 


1 





3-3 


2.2 


3.2 


2.1 


4.8 


5.5 


6.4 


1.92 


1.28 


1.86 


1.22 


a.79 


3.20 


3.73 



ANAI.YSIS 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. 

/. Detefminatian of Chlorine, Standard Silver Solution. 

Dissolve five grams of pure crystallized silver nitrate in 1*000 
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. 
1000 cc. " " " *• 5.2 cc. •' *' ** 

Equivalent to 0.0052 grams of chlorine per liter. 

** " 0.52 parts chlorine in 100,000 parts of the water. 

.. J 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 ANAI^YSIS. 

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. iStandard 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 




76 



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 on^ of the comparison 
tubes)* 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. 11, at the 
base of which is an opening filled with cotton wool. 





#= 






^ 



Fig. 12. 



These comparitor tubes have a mark indicating fifty cc, and 



I See Fig. ii. 



ANALYSIS OP WATER, 77 

when the distillate reaches that mark, the handle of the stand 
containing the compaiitor 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, Pig. 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 DeterminaHans, 

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. 



78 QUANTITATIVE ANALYSIS. 

Free Ammonia, 
500 cc. of the water taken. 

First distillate (50 cc.) required 1.5 cc. ammonium chloride solution. 
Second *' (50 cc.) '* 0.3 cc. '* " *' 

Third '* (50 cc.) '* none 

ToUl for 500 cc. 1.8 cc. ** " 

" " 1000 cc. 3.6 cc. 
One cc. ammonium chloride solution is equivalent to o.ooooi gram nitro- 
gen, or 0.000012 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. 

Albuminoid Ammonia, 

750 cc. of the water taken. 

First distillate required 3.2 cc. ammonium chloride solution. 

Second ** ** 0.7 cc. 

Total *' 3.9 cc. '* ** " 

1000 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 
^ood 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 thano.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 




ir^^^*^ ^-'^Hfr^*^ 



•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. 10 per million begins to be a very suspicious 



8o 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,. 

A. 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 dryness 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 WATKR. 8l 

treatment and dilution to loo 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, per liter, corresponding to 0.52 grains per gallon, or 
0.9 part per 100,000, or 9.0 parts per 1,000,000. 

4. Nitrites, 
Glosway's modification of Griess's method is to be recom- 
mended for simplicity and accuracy. 
The solutions required are : 

1. Sulphanilic acid. Dissolve one gram in 300 cc. of acetic 
acid (sp. gr. 1.04). 

2. Sodium nitrite. Formed by dissolving 0.272 gram silver 
nitrite in 100 cc. water, adding a dilute solution of sodium 
chloride in slight excess, and diluting to 250 cc. 

Take 100 cc. of this solution, dilute to one liter for use. One 
cc. =0.00001 gram nitrogen. 

3. a-amido-naphthalene acetate. 

Two-tenths gram of naphthylamine is boiled with forty cc. of 
water, filtered and diluted to 400 cc. 

Process of Determination, 
Twenty-five cc. of water are taken and placed in one of the 
color comparitors, two cc. of the sulphanilic acid and two cc. of 
the amido-naphthalene acetate are added. If nitrites are pres- 
ent, a pink color is produced, which must be compared with the 
color produced by one cc. of the standard nitrite solution, to which 
two cc. of the sulphanilic acid, two cc. of the amido-naphthalene 
acetate and twenty-five cc. of pure distilled water (free from 
nitrites) are added. 

Suppose twenty-five cc. of the water required, six-tenths cc. 
of the standard nitrite solution, or 0.000006 gram nitrogen, or 
0.00002 gram NO,. 

Corresponding to 0.0008 gram NO, per liter. 
** ** 0.0466 grain per gallon. 

** ** 0.0800 part per 100.000. 

** ** 0.8000 part per 1,000,000. 

5. The total solids are determined by evaporating 500 cc. of 

(6) 



82 QUANTITATIVE ANALYSIS. 

the water in a platinum dish and drying the residue at 105'' C. 
to constant weight. The amount obtained multiplied by 2 
equals the weight per liter. 

6. The organic and volatile matter is approximately deter- 
mihed by igniting the weighed residue until all carbonaceous 
matter is consumed, and weighing ; the difference between the 
weight of the total solids and the weight after ignition is the 
volatile and combustible matter. 

7. Oxygen required to oxidize the organic matter in the water, 
.Solutions required : 

Standard potassium permanganate^ formed by dissolving 0.395 
gram potassium permanganate in 1000 cc. water. Each cc, con- 
tains 0.000 1 gram available oxygen. 

Potassium Iodide Solution, 100 grams of the pure salt dis- 
solved in 1000 cc. water. 

Dilute Sulphuric Acid Solution, One part by volume of pure 
sulphuric acid is mixed with three parts by volume of distilled 
water and solution of potassium permanganate dropped in until 
the whole retains a very faint pink tint, after warming to 80'' F. 
for four hours. 

Sodium Thiosulphate. One part of the pure crystallized salt in 
1000 parts of salt. 

Starch Indicator is made by mixing six grams of starch with 
100 cc. pure glycerine, heating for one hour to 100'' C, pouring 
it into 200 cc. of water, then adding sufficient strong alcohol to 
precipitate the soluble starch, which is filtered off and preserved 
in a moist pasty state. When required, a minute quantity is 
taken with a glass rod. 

Determination of the Oxygen Absorbed, 

Two separate determinations are required, viz,, the amount of 
oxygen absorbed during fifteen minutes and that absorbed dur- 
ing four hours. Both are to be made at a temperature of 27** C. 
It is most convenient to make these determinations in twelve 
ounce stoppered flasks, which have been rinsed with sulphuric 
acid and then with water. Put 250 cc. of the water to be tested 
into each flask, which must be immersed in a water bath or suit- 
able air bath until the temperature rises to 27** C. Now add to 




ANALYSIS OF WATERT****:^£4ii^Siss^*^ 83 



each flask ten cc. of the dilute sulphuric acid, and then ten cc. 
of the standard permanganate solution. Fifteen minutesT after 
the addition of the permanganate, one of the flasks must be 
removed from the bath and two or three drops of the solution of 
potassium iodide added to remove the pink color. After thor- 
ough admixture, run from a burette the standard solution of 
thiosulphate until the yellow color is nearly destroyed, add some 
of the starch solution and continue the addition of the thiosul- 
phate until the blue color is just discharged. If the titration 
has been properly conducted, the addition of one drop of per- 
manganate solution will restore the blue color. At the end of 
four hours remove the other flask, add potassium iodide and 
titrate with thiosulphate, as just described. Should the pink 
color of the water in the flask diminish rapidly during the four 
hours, further measured quantities of the standard solution of 
permanganate must be added from time to time so as to keep it 
markedly pink. The thiosulphate solution must be standard- 
ized, not only at first, but (since it is liable to change) , from 
time to time inthe following way : To 250 cc. of pure distilled water 
add two or three drops of the solution of potassium iodide, and 
ten cc. of standardized solution of permanganate. Titrate 
with thiosulphate solution as above described. The quantity 
used will be the amount of thiosulphate solution corresponding 
to ten cc. of the standardized permanganate, and the factor so 
found must be used in calculating the results of the thiosulphate 
titrations to show the amount of standard permanganate solu- 
tion used, and thence the amount of oxygen absorbed. The 
amount of thiosulphate solution thus found to be required to 
combine with the iodine liberated by the permanganate. 

Conversion Tabi^k. 

X 0.7 = Grains per Imperial Gallon. 

X 0.07 = 

X 0.553 = ** " U. S. 

X 0.058 = 

X 0.00833 = Avoir, pounds per 1000 U.S. Gal.. 

-«- 0.7 = Parts per 100,000 

" ** -«-o.o7 = ** *' 1,000,000 

U.S." ■*■ 0.583 = '• " 100,000 

*• " -«- 0.058 = ** ** 1,000,000 



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84 



QUANTITATIVE ANALYSIS. 






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ANALYSIS OF WATBR. 



85 



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86 



QUANTITA.TIVE 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 



ANAl,YSIS 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 




FiR. 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 befoundin the 
Transactions of the American Society of Civ^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, Z>, is provided. This con- 
sists of a heavy rake containing thirteen teeth twenty- 



ANALYSIS OF WATBR. 



89 




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. 



91 



pound to a square inch,) is the extreme pressure that can be 
brought to bear upon the filters, 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 therakebeginto plough up the surface 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 , QUANTITATIVB ANALYSIS. 

After waiting a few minutes the outlet valve, /% is slowly opened 
and filtration is resumed. A filter ten feet six inches 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. Prankland, 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 Bisenberg, Vienna, 1887. 

" Report of the Massachusetts State Board of Health for 1892. 

*' Bacteria and other organisms in water" by John W. Hill, Transac. 
Amer. Sac. Ctznl Engineers, Vol. xxxiii pp. 423-467. 

" Practical Bacteriology" by Dr. W. Migula, London, 1893. 

The Composition of Boiler Scale. ^ 

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 : 

i The scheme for analysis of Limestone, (XI), can be used in this analysis. Consult 
y. Anal. Chem. iv., Jan., 1890. 



COMPOSITION OF BOILER SCAI.E. , 93 

Silica and clay 11.70 per cent. 

PeiO„Al,0, 2.81 *• 

CaO 13.62 " 

MgO 41.32 " 

CO, 6.92 *' 

SO3 0.96 " 

H,0 (of hydration) 21.78 " 

H,0 (moisture at 212° P.) 0.69 ** 

Undetermined 0.20 '* 



Total, 100.00 ** 

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,Os, AljO, 2.81 •* 

CaSO^ 1.69 . ** 

CaCO, 5.45 " 

MgCO, 7.36 '* 

Ca(OH), 13.70 " 

Mg(OH), 56.37 " 

H,0 (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^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 hydration 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, 7.36 per cent. 

Al^Oj.FejO, 1.91 " •• 

CaCOs 62.71 «* " 

MgCO, 18.15 '* '* 

Mg(OH), •. 4.21 " *' 

H,0. atiio^C 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.* 

For instance, a 100 H.P. boiler evaporates 30,000 lbs. of water 
in ten hours or 390 tons per month : in the comparatively pure 
Croton water there would be 88 lbs. of solid matter in that quan- 
tity, and in many kinds of spring water as much as 2000 lbs. 

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 lb. of sodium hydroxide 
per horse power and steaming for some hours, just before clean- 

1 G. H. Babcock, "Steam," p. 63. 



96 QUANTITATIVE ANALYSIS. 

ing, will greatly facilitate that operation often rendering the 
scale soft and loose. 

Water for Lrocomotive Use. 

After many years of experiment upon waters for Locomotive 
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. 

*. Non-alkaline, bad and good. 

In the second class (2): 

a. Those causing foaming and corrosion, but non-incrusting. 

*. Hard, or incrusting. 

c. Soft non-alkaline and good. 

These two classes are related as follows : 

**«** of class 1, ** alkaline *' waters, will produce the trouble 
mentioned in ''a" of class 2 ; that is, foaming and in certain 
cases corrosion. 

***,** the bad '* non-alkaline," would be classed as hard or 
incrusting. 

**r,'* **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 East. 

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 meritioned, 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 lo grains of solids per gallon, soft water 

I o to 20 ' * ' * * * * * * * moderately hard water 

Above 25 * * * * * * " * ' ver)^ 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 he 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.* 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 compoond is a mixture of one pound of caustic soda and one-half ponnd of 
aodinm 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. 

r Oxide of iron 0.23 ** •* " 

Incrusting matter-^ CaCOg 2.26 ** ** •* 

ICaSO* 0.56 " 

Total 2.95 *' 

Non-incrusting / Organic and volatile 3.15 * * ' * * * 
matter \ Alkaline chlorides.. 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. 

Incrusting matterj^^^^.^-;;;;^ 4o.3i ;; ;; ;; 



Total 47.48 " 

Kr«« j«^-»..f f Organic and volatile 14.34 " '* *' . 

iSeSe;r^?S^^ ^^-^7 - - - 

^°S*°^"^^ I Alkaline chlorides.. 1.31 " 

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 f 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. 

J .. f Oxides '5.00 " ** " 

J^^-"**:?^1 Calcium carbonate.... 180.00 " 

matter. . ^ calcium sulphate 35.46 " 

Total 220.46 ♦' •* •* 

(Magnesium sulphate 20.90 '* *' *' 

Alkaline sulphates.. 150.92 " ** ** 

Alkaline chlorides.. 1.14 " •' ** 

Organic and volatile 23.42 *' " " 

Total 196.38 ** 

It is manifestly 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 every 300 or 400 miles 
run. As to the economy of using hot water ahvays, 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 



lOO 



QUA.NTITATIVE ANALYSIS. 



due to the fact that waters containing much calcium and mag- 
nesium carbonates when heated to the usual temperature in feed 
water heaters (200**-2io'*F) , 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 24.0** F, then the calcium sulphate precipitates. The 
additiontothe 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. 



lOI 



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 
thewatermovesinan 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. 




Pig. 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 



I02 QUANTITATIVE ANAI.YSIS. 

large steam pipe ^, and the exit pipe Z>. 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 •* " " 

Totalsolids 11.64 ** *' •* 






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USE OF CHEMICAM AND FII.TRATION. IO5 

' * Blowing-ofiF. ' ' The arrangement in a boiler for this purpose 
usually cotisists of one or two internal pipes extending along the 
bottom of boiler and connected with the blow-out tap. They 
are place<d 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.* 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 7/, 
passes'down through E, and is made to rise through a series of fun- 
nels or inclined funnel-shaped walls.* 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 /% 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 chemicall}'^ 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 5 ; 5 is 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 

iPmpiSr ZeituHg, 34, 984. 

« The Chemiatry of Paper Making, p. 345* 




io6 



QUANTITATIVE ANALYSIS. 




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 CHEMICAW ANB FILTRATION. IO7 

finite mark with water. This solution slowly passes through 
the tube provided with strainers : a float in the tube keeps the . 
water in ^ 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 Hto C is cut off, the float sinks, rais- 
ing iVand thus stopping the flow of the solution. At the same 
time the level in C sinks so low that the flow of water through 
Pzxkd 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 ly. Arch- 
butt, F. I. G., 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 16 feetX lo 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 s^dmitted 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^ and then the 



io8 



QUANTITATIVE ANALYSIS. 

PATtHT HABO WAT gW PURlRgR. 




Fig. 26. 



USE OF CHEMICAW AND FILTRATION. IO9 

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 water softened in this apparatus. 

The output can be calculated as follows : 

V = the number of gallons of softened water supplied continu- 
ously per hour. 

^ = the working capacity, in gallons, of each tank. 
jf= the number of minutes required to fill each tank. 
^ = the number of minutes required for settling. 

V = — f^-^. = the cost. 
25 +^ + ^ 



no 



QUANTITATIVE ANALYSIS. 



2 

o 

o 



o 






^ « (0 



5-8 OS ON ^ 1/5 ' ? 0*8\ 



£ 



Ml O « 



S 



o cK **> t*» Cn 
N d t>»»A 6\ 



I vc d 



HI Tj-« o 



V?:, 



do bo 9s ^ CTs ' 
d c^ r« ciod ! 



»o O 



vd d ^f 



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00 ci f*) 



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60 

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^1 



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 s''. 

Filter Presses. 
Filterpresses 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 




Fig. 27. 

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 2. e., 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 water to be filtered, another reservoir or tank 
M, in which the floating material (orfibers 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 which it is mixed with the chemicals in 
solutions the latter being pumped into B from Fby 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 Jjy 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 
InsL of Naval Afchitects. 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., /. Soc. Chem. Industry, a» 
12-21. 

'• The Porter-Clark Process" (for softening water.) By J. H. Porter. 
/. Soc. Chem. Industry 3f 5i-55« 

"Suggestions on Boiler Management." By VeroC. Driffield, f. 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 lO, 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. 1 15 

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 8140 ^^^^ ^^^^^^^ 

34 
Suppose the lead button from one gram of coal weighed 31.05 

gram, then — ^ X31.05 = 7420.9 calories per kilo, or 13357. 7B. 

34 
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 analj'sis, thus 

Carbon 94.43 per cent. 

Ash 5-57 " " 

lOO.OO " " 

^'^^ 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 RestUts 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 



ii6 



QUANTITATIVE ANALYSIS. 



M 



.1 I 



8 i J ^ 

Kig. 30. 

granulated cupric oxide for a dis- 
tance of about thirty cm., and at ^ a 
plug of asbestos ; place the tube in 
a combustion furnace Cy connect it at 
d with the drying apparatus « , and at 
d with calcium chloride tube € filled 
with CaCl,, 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 ofiF 
the gas, and continue the aspiration 
of air until the tube is nearly cold. 
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 A ; at ^ is a coil of platinum foil. 
The calcium chloride tube e (Fig. 
31) is now accurately weighed, as 
well as the potash bulbs /,* 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 ^ to ^ is 
also at that temperature. 

After the complete combustion of 



1 The latter one-third full of KOHlsolulion sp. gr. 1.27. 



HEATING POWER OF COAL AND COKE. II7 

the carbon of the coal, which is indicated by the absence of 
black particles in the porcelain boat, turn ofif 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 as 0.500 gram. 
Calcium chloride tube -f- H,0 = 36.5118 grams. 

=a 36.4025 »• 

H,0= 0.1093 " 
0.109 gram H,0 = 0.0121 gram H. 
0.0121 X 100 ^ ^^^ ^^ ^^^^ hydrogen. 

0.500 
The potash bulbs and CO, »» 34-9554 grams. 
= 33.3200 ** 



1.6354 " 
^•6354 grams CO, «» 0.4460 gram C. 
0.4460x100 ^ g^^ ^^^^ ^^^^ 
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 -f- residue (ash) = 8.9693 grams. 

= 8.9460 " 

Ash ^ 0.0233 " 
o.oa33Xioo ^ ^ gg ^^^ ^^ 

0.500 

b. The nitrogen determination is made as follows : 

Select a combustion tube about sixty cm. long and two and 

five-tenths cm. diam<eter, drawn to a point at one end and open 

at the other end (Fig. 32). 




Pig. 32. 



Il8 QUANTITATIVK ANALYSIS. 

At a place three grams of crystallized oxalic acid, then a few 
layers of freshly ignited soda-lime, and at d 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 r 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 ||-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) 

HjSO^ solution taken = 15 cc. 

Normal soda solution required to neu- ) ^ . ^/-« ^^ 

tralize free acid / — ^4-7€>» cc. 

(One cc. NaOH solution neutralized one cc. H,S04) 0.232 cc. of HjSO* 
solution neutralized by the ammonia. 

If one cc. HjSO^ solution = 0.049 grani HjSO^ : : 0.232 cc. := 0.0113 
gram H3SO4. 

o.oii3gram H^SO^ = 0.00392 gram NHj. 

= 0.00322 ** N. 
0.00322 X 100 ^ ^^^ p^^ ^gjj^ nitrogen. 
0.500 



HEATING POWER OF COAL AND COKE. 



119 



The method of Kjeldahl can also be used for the determina- 
tion of nitrogen in coal. Consult '* Contribution a T 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 100.00 

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 ** 



0.061 X 100 



Loss (moisture) 0061 



= 3.05 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 

Ash 4.53 

Total 100.00 

The calorific power of the coal is calculated from the follow- 
ing data : 



I20 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. y. U.") is the heat required to 
raise the temperature of one pound of water i^^F., at its temper- 
ature of maximum density, (39.1").' 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 
and 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 345ck> 
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 is'^C. unite to form 
nine kilos of steam which escapes at lOo"* 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 is"* 
C. when the product of combustion escapes as steam at lOo"* 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. —0.25a 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 i*C, one pound calorie = a.2046 B. 
T. U. = I calories. 

The heat of combustion of carbon, to CO,, 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 i*C. by the complete combustion of one pound of carbon, or the 
number of kilograms of water that can be raised iX.. by the combustion of one kilo- 
gram of carbon. [Kent]. 



HBATING POWER OP COAL AND COKE. 121 

tial temperature of the hydrogen is other than is^'C. 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. 
Lct//'= ** ** ** hydrogen ** " 

LctC^=s ** •* '* oxygen ** '* 

Let 5= " " " sulphur '* ** 

Then : 

„ ,. 8140 C + 3450o(/^— ) -h 2220 5. 
Heating power « j^^ 

_ (8i40 X 86.49) + 34500 (2.36 — 0.345) H- 2220 X 0.18 
100 

^704028 -h 69517.5 + 399.6 
100 

= 7739*4 calories per kilo of coal. 

Where the products of combustion of hydrogen escape as 
steam at lOo^'C, the formula will be : 

8140 r-h 28901 (jy— O) + 22205— 622W 

Heating power « — 

W « moisture of the coal. 

Then: 

8140 X 86.49-h 28901 (2.36— o.345)H-222oX 0.18—622X3.05 
"* 100 

^ 704028.6 -h 58235.5 -h 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. 
I " ** hydrogen " ** water " 8.00 ** ** " 

I ** ** sulphur " ** sulphur dioxide '* i.oo ** *' ** 

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 

** '* " ** nitrogen 

" ** hydrogen " 11.84 

** ** sulphur dioxide'* 0.36 

** *' ** " carbon dioxide ** 0.54 

•* ** air ** 0.82 



is 0.74 cubic meter at i6.67°C 
" 0.84 



One kilo of carbon requires 11. 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' 1 1.6 kilos of air or 9.5 cubic meters. 



i.o kilo carbon 
1 1. 6 kilos air 

(2.6 



Carbon i.oo kilo 
. / Oxygen 2.66 kilos 
^^ \ Nitrogen 8.94 '* 

Total 12.60 ** 



Products of . 
combustion ' 



8.94 
12.60 



66 kilos CO, 

" N 



One kilo hydrogen requires for combustion 34.8 kilos of air, 
or 28.58 cubic meters: 



1.0 kilo hydrogen Hydrogen i.o kilo 

^ ■ 



, combustion 



9. kilos H2O 
26.8 *' N 

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 OP COAL AND COKE. 1 23 

Combustibles in the Coal. 

Carbon = 86.49 V^^ cent. ^ 10.2 kilos of air or 8.32 cubic meters. 

Hydrogen = 2.36 ** ** = 0.82 " '* *' ^* 0.67 

Snlpbnr = 0.18 ** " = o"oo7 " ** ** ** 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 
16.67** C., or by 536.5 (degrees C.) if the water is supplied at 
loo'^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 ftom water supplied at 62° F., and by 
dividing by 956.7® F. when the water is supplied at 212® P. 

The evaporative value of one kilo of the coal will therefore 
be, theoretically, assuming the water to be supplied at 16.67*^0. 
(62** F.) , and the steam generated at atmospheric pressure : 

Carbon, 86.49 X 8140 -«- 100 = 7040.28 calories. 

Hydrogen, (2.36 — 1x34500-) -^100= 695.17 
Sulphur, o.i8 X 2220 -7- 100= 4.00 •* 



7739-45 
7739.45 -«- 620= 12.48 kilos of water evaporated per kilo of coal. 



124 



QUANTITATIVE ANALYSIS. 







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HEATING POWER OF COAL AND COK£. 1 25 

If the water be supplied at ioo'*C., 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 
o£F 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. E. 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 13*83 per cent. 

" ** " "radiation 2.64 '* " 

*' ** " ** moisture 0.08 ** " 

ToUl 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 per 
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 
Barms, 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 
oithe platinum, thereby materially reducing tKe 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 E, 
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. 



CALORIMETJRY, 



12.7 



means of a battery. 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 



QUANTITATIVK 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- 




Fisr. 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 Specific Water equivalent 

Material. grams. heat. in grams. 

Brass of calorimeter 703.07 0.094 66.088 

Steel of calorimeter 31323.25 0.1165 387.157 

Porcelain 134.078 0.179 24.0 

Platinum 21 .3 0.0324 0.68 

Lead 9.0 0.0314 0.282 

Glass of thermometer 12.69 0.17968 3*ii4 

Mercury of thermometer . . . 25.03 0.03332 0.833 

Oxygen 29.1205 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- 6 ve at- 
mosphc res 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=L water equivalent of calorimeter shell and appendages. 
/ = final temperature of water in calorimeter. 
/, = initial ** *' ** ** 

/, = initial temperature of cold water added. 
Jf^= weight of water in calorimeter at beginning of ex- 
periment. 
w = weight of cold water added. 
Then we have : 

(^, - i) IV+ (A - 0^ = (^-^J«;, 
Or, 

^,— / . 
The results of twenty-five determinations gives a mean of 
4^9-97* or practically 490. 

Method of Making a Determination 7vith 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 bum 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) 



I30 QUANTITATIVE ANAI.YSIS. 

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 closedand theshell placed in 
the calorimeter, which has been previously partially filled with 
about 2,400 grams of water. The thermometer and agitator are 
adjusted, and (he 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 P, 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 : 
Let Q = calorific power of the coal. 

J =z observed rise of temperature. 

X = correction for radiation. 

P = weight of water taken in grams. 

P=z 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 

e=(J + ;r)(/>+/>)-(o.23/+I.6/). 

Example Skotving 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. I3I 

The pressure of oxygen = 25 atmospheres. 
The law of variation of temperature in the calorimeter before 
combustion is expressed by X^ = O, 

The law of variation during subsequent period is 

X^ = 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 -f 490), 

=s 7,386.8 calories. 
7,386.6 — (0.0345 + 0.04) = 7,386.72 " 
-*- 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 7971 " '* *' 

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. Stevens' Indicatory April, 1895, 
p. 133-148. 

•' Zur Werthbestimmung der Brennstoffe." (Verfahren und Calorime- 
ter von Mahler, Bunte, Fischer, Scheurer-Kestner), Stahl und Eisen, 13, 

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. 




Weight. 



Part of glass cylinder in \ ^^^ ^^ ,^«.«« w « ^^^^q 
conuct with the water I 9"« gr*™" X °-i9768 



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: 

Par 
c< 

Glass bell jar 75- 381 

Brass base 99-^53 

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 iS'iti 

Mercury of thermometer. 9.583 

Glass of thermometer .... 7.350 

Total 220.478 



Specific 
heat. e 


Water 


quivalent 


X 0.19768 = 


182.245 


X 0.19 = 


14.313 


X 0.09391 = 


9.377 


X 0.09515 =r 


6.294 


X 0.09391 = 


2.001 


X 0.09512 = 


2.930 


X 0.331 = 


0.552 


X 0.331 = 


0.591 


X 0.324 = 


0.490 


X 0.333 = 


0.319 


X 0.19 = 


1.396 




THE THOMPSON CALORIMETER. 1 33 



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 /. 

Let /j = 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 t^. 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 — ^) = r. Expressing this in a formula 

2000 (/ — (4 + 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) ^ 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 {aV) . 

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 h) should not be projected too low into 
the bell jar until the volatile hydrocarbons are consumed ; the 
residual fixed carbon is more difficult to bum. 

The oxygen supply tube should consequently be projected so 
as to deliver the oxygen immediately over the platinum cruci- 
ble, and to more effectually bum 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 bum 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 fOAL CALORIMETER. 1 35 

the theoretical heating value being : 

(8140 X 84.8) + (34500 X 2.42—0.4) + 2220 X 0.62 _ 

100 — 7 3 

calories per kilo of coal. 

The test of the coal by the Thompson calorimeter gave as fol- 
lows: 

Amonnt of coal taken as 0.445 gram. 

Temperature of water and apparatus (initial) 18.95° C. 

Maximum temperature " •* 20.45° C. 

Final temperature (used for correction of radiation) 20.40° C. 

Correction for radiation | ^0-45 — 2040 _ ^.025° 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.' 

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 COAL CAIX)RIMETER. I37 

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 ^-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 pulverised 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 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. 

Rbsults of Tests with the Barrus Coai, Calorimeter. 
Cumberland Coals, 



^ a 



Kind of coal : Mine or locality 



s^ 



I- 



9 

lO 

II 

12 

13 
U 
15 
i6 

17 



George's Creek 

(( c< ..,,* 

n «< 

<( M .....,,., 

(f (i 

'* " (American Co.) 

" (Md. Coal Co.) 

*' *' (G. C. Coal and Iron Co.) 

George's Creek. 

Eureka 

George's Creek 



8.2 

6.1 
6.6 
8.6 

6.5 
7.0 
5.0 
5.1 

6.1 

5.1 

7-5 

5.1 

5.4 

8. 

4.4 



13.868 
14,058 
14,217 
13.925 
12,874 
12,921 
i3»36o 
13*487 
13,656 
13,424 
13,534 
13,745 
13,617 
13,653 
13,427 
12,973 
13.923 



B. T. U. 
i< (< << 



(C €1 <( 



ft (( (( 



it If <( 



(€ ti «• 



CI it <t 
<C tt <( 



f< <f f( 



carpenter's coai, calorimeter. 



139 



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 Chemischc 
Technologic der Br ennstoffe, von Dr. Ferdinand Fischer, p. 401- 

CARPENTER'S COAL CALORIMETER. 

R. C. Carpenter' 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 





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.) 



I40 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 iu 
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 isplaced ; 
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 coai, cai^orimrter. 



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 difl&cult 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. 40. 

References, — *' Uber die Bestimmang des Heizwerthes der festen Brenn- 
materialien und Bericht iiber die wichtigere neure Litteratur dieses 
Gebietes ;*' von Knorre, Die Chetnische Industrie y 17, 93. 

"Etadesur les combustibles et la combustion,*' Vivien, La Sucrarie 
indigene, 44> 261. 

Determinatio7t of the heating power of coal by the use of large 

amounts of coal either {a) in specially constructed apparatus 

for the same^ or (d) under boilers in actual practice. 

Apparatus for determining the heating value of Fuel, by Wm. 
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 loo two-inch tubes. The lower cylinder is com- 



. a 
hi « . 

i'l g 

f • 5 1 S at -S 




5 ?! 



a ^ « V - 






550 -2 



•==^n 



^ if U 4; 



dp 



^S9 



< 



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 



HBATING 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 ANAI^YSIS. 

surface about looo 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. 
RtsuM^ OF Tests Upon Babcock & Wim:ox Boilers.* 



Name of coal. 



Anthracite 1 

ton,Va. Se^- ' ^°t ^'^ ^"^ ^"^ ^^-^ 4-32 "32 1242 272 44» 
bitum |. 

Jackson, O., nut 8 48.0 3358 9.6 32.1 4.1 1 8.93 9.88 262 460 

Castle Shan*n ) 

Pa. } nut. i \ 42i 69.1 4784 10.5 27.9 4.13 10.00 II. 17 416 570 

lump. J 

Cardiff, lump .. 6} 21.2 1564 11. 7 26.7 3.69 10.07 "-40 136 189 

1 Trans. Amer. Soc. Mechan. Engineers, 4, 367. 

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 TBST. 145 

Approximatb Hbatinc Value op Coals. (Kent.) 



■o-d 



«t «i • s-o"S «t ~1 SI'S 
'i si ^^ 4 si -&. 

100 14500 15.00 68 15480 16.03 

97 14760 15.28 63 15120 15.65 

94 15120 15.65 60 14580 . 15.09 

90 15480 16.03 57 14040 14.53 

87 15660 16.21 54 13320 13.79 

80 15840 16.40 51 12600 13.04 

72 15660 16.21 50 12240 12.67 

The use of the table may be shown as follows : 

Given a coal containing moisture two per cent., ash eight per 
cent., fixed carbon sixty-one per cent., and volatile combustible 
matter twenty-nine per cent., what is its probable heating 
value ? 

Deducting moisture and ash we find the fixed carbon is 61.90 
or sixty-eight percent, of the total fixed carbon and volatile 
combustible matter. 

One pound of coal dry and free from ash would, by the table, 
have a heating value of 15480 thermal units, but as the ash and 
moisture having no heating value, are ten per cent, of the total 
weight of the coal, the coal would have ninety per cent, of the 
table value, or 13932 thermal units. This divided by 966, the 
latent heat of steam at 212° F., gives an equivalent evaporation 
per pound of coal of 14.42 pounds. 

The heating value that can be obtained in practice from this 
coal would depend upon the efi&ciency of the boiler, and this 
largely upon the difl&culty of thoroughly burning the volatile 
combustible matter in the boiler furnace. If a boiler efficiency 
of sixty-five per cent, could be obtained, then the evaporation 
per pound of coal from and at 212'' F. would be 14.42 X 0.65 =^ 

9.37 pounds. 

(10) 



146 QUANTITATIVB 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 Pocahontas, 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^ P. per 
ponnd combustible, maximum in boil- 
er te?t9 15.1 12.5 ii.o lo.o 8.3 7.0 

Boiler efficiency, per cent 80.0 76.0 69.0 66.0 60.0 55.0 

Loss, chimney radiation, imperfect com- 
bustion, etc 20.0 24.0 31.0 34.0 40.0 45.0 

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 unbumed 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 



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 
nnfavorable 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 i= 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-^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 
100 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 wit^ approximate accuracy by the method 
described below. Data given : 
I. Analysis of the Coai«. Cum- 2. Analysis op thb Dry Chimnby 

BBKLAND SBMI-BiTUMINOUS. GaS BY WbIGHT. 

Carbon 80.55 per cent. c. o. N. 

Hydrogen 4.50 ** CO, 13.6 3.71 9.89 

Oxygen 2.70 ** CO 0.2 0.09 o.ii .... 

Nitrogen 1.08 " O 11.2 .... 11.20 .... 

Hoisture 2.92 " N 75.0 75.0 

Ash 8.25 ** 

Total loo.o 3.80 21.20 75.0 

100.00 ** 



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 P^^ 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 — 3.8 = 26.32 pounds. Since 
the carbon burned is 80.55 — 2.0 = 78.55 per 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 — o~J ■=" 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 bum 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 -r 0.23 = 1.45 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 -r 
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 : 

Per cent. 

of heat 

Heat value of 

unitB. the coal. 

21.3 pounds dry air X (560^ — 60° F.) X sp. heat 0.238 2534.7 17.80 

0.15 poand vapor in air X (560° — 60"^) X sp. heat 0.48 36.0 0.25 

0.029 pound moisture in coal heated from 60^ to 212^ P. 4.4 0.03 

" " evaporated from and at 212° ; 0.029 X 966 28.0 0.20 

" ** steam (heated from 212^ F. to 560°) X 348 

X 0.4B 4.7 0.03 

0.405 pounds water from H in coal X (560^—60°) X 0.48 97.2 0.68 
0.0237 pound carbon burned to carbon monoxide, loss 

by incomplete combustion, 0.0237 X (14544 — 

4450 239.2 1.68 

0.02 pound coal lost in ashes ; 0.02 X 14544 290.9 2.04 

Radiation and unaccounted for by difference 71 2.1 5.00 

3947.8 27.71 

Utilized in making steam, equivalent evaporation 

10.66 pounds from and at 212° per pound of coal 10295.7 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 
ofi a portion of the grate surface and build a small fire in the 
remainder, and drive this fire with just enough draught to keep 
tip 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. 



I50 QUANTITATIVE ANAI^YSIS. 

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. 

{b). 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 £, 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 
Tiolent, and care must be exercised that small amounts of acid 
only be admitted at a time from B until all action of the acid 
apon 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. 
6, 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 dryness 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, vnthfiure rubber stopper, through 

the latter passing a thistle tube with stop-cock for the delivery 

of the acid, as required. Fig. 43. 

^ is a flask with rubber stopper. The glass tubing must not 

reach below the neck of the flask. This flask should be large 

^ TVanjr. Amer. Inst, Mining Engineers ^ 3, 334. 



SUI^PHUR 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 / with an aspirator and slowly draw air 
through the apparatus ten minutes. 

Transfer contents of bottles c, d, ^, 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 ^lution 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 Ptt,, ii, 251, 1895, 



SULPHUR IN STEEI* AND CAST IRON. 1 55 

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- 
plied from overhead aspirator bottles and suitable rubber con- 
nections 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- 
phide, the iodine solution is run in from a burette, stirring gen- 
tly, till a blue color is obtained, the solution is then stirred vig- 
orously, 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 
of 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, 33» 61. 

" Wiborgh*8 Colorimetric Method,**/- Anal. Chem., 6« 301. 

" Sulphnr Determinations in Iron and Steel,** by different methods. 
By L. S. Clymcr, /. Anal. Chem., 4, 318. 

*' Cadmium Chloride as an Absorbent of Hydrogen Sulphide' '(Sulphur 
in Iron and Steel). By Prank 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., I5» 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 oi pig iron in fine borings, 
are transferred to a No. 3 beaker' 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 STKSI*. 1 57 

In all determinations of this element, the ignited and weighed 
silicon dioxide must be white in color and a fine non-coherent 
powder. 

J^eferences : ** Irregular Distribution of Silicon in Pig Iron." By 
J- W. Thomas, /. AnaL Chem., 3» 148. 

" Silicon in Pig Iron.'* By Clemens JoneSj/. Anal, Chem,, 3» 121. 

"The Influence of Silicon on the Determination of Phosphorus in 
lron.»» 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, 
^he determination of carbon in iron and steel has probably 
received more attention in later years from chemists than any 
^ffler subject in analytical chemistry. 
To secure a method at once complete and rapid whereby car- 
" Varying in amounts from four per cent to o.ooi per cent, in 
erent irons and steels could be accurately determined has 
^ ^ €iesideratum, 
, ^^^^sses that are satisfactory for special grades of irons or 

^^rely can be relied upon in general practice. 
v3^ Vinportant has this subject become to the metallurgical 
^^^\d that committees acting in union from Sweden, England, 
^^d America' 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. 

Per cent. 

English committee i •414 

Swedish committee i .450 

American committee* • •• 1.440 

The English and Swedish committees have not yet selected 

V. Am. Chem. Soc,, 15, 449. 



No. 2. 


No. 3. 


No. 4. 


Per cent. 


Per cent. 


Per bent. 


0.816 


0.476 


O.151 


0.840 


0.500 


0.170 


0.807 


0.452 


0.160 



158 QUANTITATIVE ANAI.YSIS. 

the method to be adopted as standard in carbon determinations, 
but the American committee have rendered their report suggestr 
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* 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. 

Reg^ault' 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.' 

Prom this period, the methods for total carbon can be included 
in two general classes : 

First dass, — Combustion of the carbon in the powdered iron 
directly. 

Second dass, — Separation of the carbon from the iron by chem- 
ical means and combustion of the carbon. 

. Deville and Wohler* 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' by 
which the powdered iron is treated directly with chromium tri- 

lAnn. phys. chem., 1838. 

* Ann. chim. phys., 1839, 107. 
>y. prakt, Chem., 1840, 247. 

« Ztschr. anal. Chem., 8, 401. 

* Oestericher Zeitschrift f&r Berg und HuUenwesen, r88j, 39a. 



CARBON IN IRON AND STBBI<. 1 59 

oxide and sulphuric acid and the carbon oxidized to carbon 
dioidde, 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. 

XlUgren' dissolved the iron with solution of copper sulphate 
and oxidized the carbon to carbon dioxide by heating with 
chromium trioxide and sulphuric acid. 

Eggertz* dissolved the iron with bromine or iodine, and the 
separated carbon was ignited with chromate of potash. 

Langley' modified Ullgren's method by ignition of the carbon 
in ox3'gen 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 
add passing an electric current at the same time and ignited the 
carbon in oxygen.* 

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.^ 

Eggertz's method for combined carbon*, 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.'' 

Boussingault" decomposed with mercuric chloride and oxi- 
dized the carbon to carbon dioxide. 

Wiborgh* 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. 

^ Ann.de Chem. u Phar., 194, 59- 

• Dingler's Pidyteckniskes Journal y 170, 350. 
^American Chemist, 6, 365. 
^Ann.phys, Chem., XK4, 507. 

• Ckem. Newst »5, 301, 

• Ckem, News, 7, ^54. 

^ Engineering and Mining Journal, sx, 151. 

• Dingler's P&lytech.J., 197, 25. 

• Dingler's Polytech. /., s6s, 502. 



l6o QUANTITATIVE ANAI.YSIS. 

Experience has shown that the methods of UUgren, Lang- 
ley, Richter, and Wiborgh give the best resnlts 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 UUgren or Langley methods, somewhat modi- 
fied. The UUgren 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' (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 
100 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, Pig. 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 Jj-tube, 
and is made slightly acid with sulphuric acid. 

C and D contain granulated calcium chloride free from lime. 

£ and /^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 ANAI^YSIS. 

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 f and /^+CO, 65.700 

Tubes E and F 65.002 

CO, ;... 0.698 

CO, : C : : 0.698 : x = 0.1904. 

0.1904X100^ 3 j8 p^^ ^^^^ ^„b^„ 
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 Eggertz 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. i . 1 2) 
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 £ and F+ CO, = 66.053 grams. 

Tubes^andF = 65.621 *' 

CO, = 0.432 ** 
C = 0.1178 gram. 

Graphitic carbon = 1.96 per cent. 

Combined carbon = 1.22 ** 

Total carbon 3.18 " 



CARBON IN IRON AND STEEL. 163 

Method of Langley 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, -Fand G. 
Heat is gradually turned on in the furnace and increased until 

the carbon is completely burned to carbon dioxide. Turn off the 

^eat, disconnect the oxygen tank and slowly aspirate air through 

tie apparatus by means of an aspirator. 
After cooling thirty minutes weigh the tubes E and F and 
<^aJculate the result as given previously. 

ft will be noticed that no Liebig's potash bulbs are used. I 
^^e obtained better results by the use of soda lime in y-tubes 
aa by the potash bulbs, and in general practice they will be 
^^^ much more convenient and less liable to variation in 

. ^^ use of the double chloride of copper and ammonium as a 
^^ ^X\\^ for the iron has been quite general in this country. The 

^^etican Committee on Standard Methods of Iron Analyses 
. ^jjjd that, contrary to the usual practice, this solvent must not 
^ 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- 



I 




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. 




Figr. 46. 

For rapidity of execution and simplicity of apparatus (Fig. 
44) » Ijprefer the former. 

Wiborg's method,' 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 

1/. ScK.lCkem. Industry, 6, 748. 



1 66 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 cr3'stallized 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. 1 67 

drop by drop into A through B, the cock of the latter is 
closed, that marked i? 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 H 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, H 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^r 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^r cent, of carbon, but weighs only 0.000 1 
gram. 

G. Lunge' 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 diflferent tubes. Three stand- 
ard steels are required, one containing one per cent, combined 
carbon, for tool steels, etc., one coptaining 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*) of carbon, but less than 0.75 per cent, (o.i X V)- 
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* 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 Okem Nean^ 47, 285. 




170 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 cohit 
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 Jthat 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,C; but microscopical investigations have further 
proven ^he 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. 

(d) 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,„C. 

(c) Normal carbide of iron, Fe,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 OP IRON. I7I 

(2) Diffused carbide of iron occurring in normal irons in the 
forms of small ill-defined striae and granules. 

(5) Crystallized Fe,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„C. This substance is decomposed by the most dilute acids, 
and at 400** C. it is decomposed into Fe,C and free iron with 
evolution of heat. One of the most remarkable properties of 
this compound is its capacity for permanent magnetism. 

(f) 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^^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 sp6culaire) 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,C, and which Howe also calls 
cementite. Osmond believes that cementite of iron of cementa- 
tion (de racier poule) can now be identified w^ith 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 substance with 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,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. 1 73 

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 crj'stalline 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 
iron with 0.45 per cent, carbon is heated to 82^'' C. and then 
quenched at 690® C, is relief polished, nodules in relief, de- 
pressed tatters or tongues (lambeaux), and between the two 
intercalations of varying breadth and medium hardness are 
developed. Etch polishing proves that the hard nodules are 
maVtensite, 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 
produce an irregular marbleized appearance ; they are almost 
amorphous, slightly granular and warty. Tincture of iodine 
in 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. 

(b) 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. 

{b) 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 £isen, No. 21, 18^. 

'• Microphotography of Iron." By F. Osmond, Paris. /. Iron and 
Steel Inst,, 1890, No. i. 

" Microphotography of Iron.*' By A. Martens, Berlin. St€thl und 
Eisen, No. 20, i8gS' 

** On the Influence of Carbon on Iron.*' By John Oliver Arnold, Bir- 
mingham, England. 



CARBON COMPOUNDS OF IRON. 1 75 

** Report of the French Commission on Testing Materials.'* Minist^re 
des Travaux Publics, Paris, 1892 and 1895. 

** Testing of Materials." By R. A. Hadfield. /. Iron and Steel Inst., 
i8g4, N6. 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. NewSy a6, 139. 

** On the Estimation of Carbon in Pig Iron." By Charles H. Pierce. 
Ckem. News, a8, 199. 

'•Colorimetric Carbon Estimation." By Fred P. Sharpless. /. Anal. 
Chem.y a, 55. 

"A Funnel for Filtering Carbon." By Thomas M. Drown. /. Anal. 
Chem., a, 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. L. de Konick. 
Ztschr. anal. Chem,, 1888, 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." /. Anal. 
Chetn., 6, 402. 

*' Notes on Carbon in Experimental Standards." By P. W. Shimer. 
y. 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., a, 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., la, 303. 

"Apparatus for the Determination of Carbon in Iron and Steel by 
Measurement of the Evolved Carbon Dioxide." By Reinhart. Stahl 
und Risen, la, 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. 



176 QUANTITATIVE ANALYSIS. 

XX. 

Determination of Phosphorus in Cast Iron and Steel. 

The molybdate method, as described by Troilius,' gives 
uniform and satisfactory results. It is as follows : Five grams 
of drillings are dissolved in a No. 4 GriflSn'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^PjO,), which may 
have been formed by the strong heating into orthophosphoric 
acid (H.POJ. 

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. 1 77 

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 diflSculty. 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, but now allowed to run intoa 100 cc. 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 



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 loo** 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 acidsolu- 
tion are required for the complete precipitation of one-tenth 



PHOSPHORUS IN CAST IRON AND STEEL. 



179 



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 g^am 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 Penn. R. R. Co., Dudley and Pease, 
J.Anai.Chem.,7,i<A. 



l8o 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** P., 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-raolybdate 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. 



I8l 



ber 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. Figr. 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), 



l82 QUANTITATIVE ANALYSIS. 

and filter. Add the filtrate to one liter of nitric acid (sp. gr. 
1.20). 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 g^ams 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 96.76 
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 X0.0190), 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. 1 83 

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,, x, 370. 

" Note on Percentage Composition with Table for Phosphorus." By 
William St G. Kent. /. AnaL Chem., i, J64. 

"The Elimination of Arsenic in Phosphorus Determinations.'' By P. 
D. Campbell. J, Anal, Chem,, a, 370. 

" Determination of Phosphorus in Iron and Steel." By Porter W. Shi- 
mer. /. Anal. Chem,^ a, 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.y 4f 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/ 

Classijicatian 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)00o 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, 11, 1894, 88. 



1 84 QUANTITATIVE ANAI.YSIS. 

Class VIII. Carbon 0.910 i.o per cent. 

Class IX Carbon i.ooto i.io per cent. 

Class X Carbon i . 10 to i . 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. 1 85 

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- 



1 86 QUANTITATIVE ANALYSIS. 

larly good at the amount of excitation to which field magnets are 
usually subjected. 

Mr. Ir. 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 ; * phosphorus 0.03 
per cent, to 0.04 percent. ; manganese 0.35 per cent, to 0.50 per 
cent. ; silicon 0.025 P^r 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 STEEI,. 



187 




OB 
OB 
^*» 

O 

^*» 
o 

9 



8 

p. 

09 



9^ 
o 

D 



1 88 QUANTITATIVE ANALYSIS. 

XXII. 

Determination of Aluminum in Iron and Steel. 

The direct determination of aluminum in iron and steel is 
somewhat difficult, especiall}' if the amount of aluminum be 
small. 

Drown* 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 loo 
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 mercury washed with water until the last traces of the 
solution have been removed from it. 

After filtering, to remove any flakes of manganese dioxide 

ly. Anal. Appl. Chem., 5, 631. 



ALUMINUM IN IRON AND STEEL. 1 89 

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 Al,0,.P,Oj. It is more nearly expressed by the 
formula 7A1,0,.6P,0„ 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 teken. 


Per cent, of alumi- 


Percent, of alumi- 


Grams. 


num added. 


num found. 


5 


0.39 


0.36 


5 


0.39 


0.38 


5 


0.39 


0.38 


5 


0-39 


0.38 


5 


0.39 


0.37 


5 


0.043 


0.045 


5 


0.043 


0.041 


5 


0.043 


0.049 


5 


0043 


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 per cent, of aluminum. It might be thought 
that the process would be simplified by reducing the iron to the 
state of protoxide, and then precipitating alumina as basic ace- 
tate, subsec^ently 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. 



V 
I90 QUANTITATIVE ANALYSIS. 

Method of Camot. 

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 ioo° C. for an hour to render the silica insoluble. Dis- 
solve in hot dilute hydrochloric acid, filter from the silica, dilute 
to about lOO cc. w^ith cold water, neutralize as before, add a 
little hyposulphite in the cold, then a mixture of two grams of 
sodium phosphate and two g^ams of sodium acetate, boil until 
all smell of sulphurous acid has disappeared, filter, wash, ignite, 
and weigh as Al,0,.P,Oj, which contains «2 2.1 8 per cent, of 
aluminum.* 

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, i88g, 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. 

ly. Anal. Chem., 5, 178. 




NORDHAUSKN OIL OF VITRIOL. . I9I 

Select a small picnometer (Fig. 51), weight about eight 
grams, and determine its weight with g^eat 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- 
* i^«f-5i- 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^s 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 ;r = H,SO, in the acid. 
j/=SO, ** ** ** 
X -^y =. 100. 

80 , 
-^+j.= 86.2 

98 ;c + 98J/ = 9800. • 

80 JT -|- 98 J/ = 8447.6 ' 

iSx =1352.4 



192 QUANTITATIVE ANALYSIS. 

-^ = 75-1 per cent, of H,SO, in the acid, 
loo — 75.1 = 24.9 per cent, of SO, in the acid. 
J/ = 24.9 per cent of SO, in the acid. 
75.1 + 24.9^ joo 

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 twice 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 d 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. 1 93 

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,0,. 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 crj'stallized ferrous sulphate in 1600 cc. 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.oii gram of iron, that is, it 
will oxidize the amount of ferrous sulphate to ferric sulphate 
that corresponds too.oii 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 

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 ANAI.YSIS. 

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.* 

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. 1.20). 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, 8a. 



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 slowly, 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.* 

References: * * Colorimetric Estimation of Manganese in Steel.** By 
B. W.Chccver,/. AnaL Chem,, x, 88. 

" Volumetric Determination of Manganese.'* By J. Pattison,/. Chem. 
Soc, 35. 365. 

" Method for the Rapid Determination of Manganese in Slags, Ores, 
Etc." By F. G. Myhlertz,/. AnaL Chem., 4f 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- 
^ams 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., 189a. 
s Method of von Schulx and I«ow. 



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 the 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. 
Sodium Cyanide as a Component of Potassium Cyanide. 
The valuation of potassium cyanide for commercial purposes, 
is 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 percent.," 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, sufl&cient 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,. 

These determinations gave a method of obtaining the propor- 
tions of potassium and sodium in the weighed alkaline sulphate 
as follows : 

94.2 parts KjO require 80 parts SO, for K^SO^ 
62.0 •' Na,0 " 80 •* SO5 " NajSO* 

Let G = weight of sulphates. 
•* jr= " ** K,0. 
" ^= *' " Na,0 

80 80 

Or, G =^x -^y -f- 0.85 x + 1.29 j/ 
;ir-|-^=G^^SO, 

_ 1.85 S O3 — 0.85 G 

y - 0.4387 

;r = C?-(SO»-h>) 

Having obtained the values of potassium oxide and sodium 
oxide, they are calculated to potassium and sodium. These 
weights are multipliedby 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 CYANIDS. 1 99 

Amount of salt taken for analysis, 1.519 grams. 

Platinum capsule and alkaline sulphates 46.625 grams. 

" 44.573 " 

K,S04-|-Na,S04 2.052 " 

Crucible and BaS04 25.165 *' 

22.306 *' 

BaSO^ 2.859 " 

Equivalent to 0.981 gram SO,. Cyanogen by titration was 42.33 per 
cent. 

Na,0 = 1.85 (0.981) - 0.85 (2.05a) ^ ^^gj 
0.4387 
~ 0.120 gram sodium, or 7.90 per cent. 
K,0 = 2.052 — (0.981 -I- 0.161) *» 0.910 gram. 
= 0.755 gram potassium, or 49.70 per cent. 

Resulting : 

Sodium 7.90 per cent. 

Potassium 49.70 " '* 

Cyanogen 42.33 " ** 

Undetermined 0.07 ** ** 

Total xoo.oo ** *' 

Equivalent to : 

Sodium cyanide 16.90 per cent. 

Potassium cyanide 82.83 ** ** 

Difference .^ 0.20 ** '* 

Undetermined 0.07 ** ** 

Total 100.00 '* ** 

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 : 

:jK,Fe(CN),= 8KCN+ 2FeC, + N, 
2Na,Fe (CN),= 8NaCN+ 2F6C, + N, 



200 QUANTITATIVE ANALYSIS. 

lOO pounds of potassium f errocyanide» 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 100 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 117 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.* 

SiO, 20.0 to 26.0 " 

AljOj 5.otoio.o '* 

Fe,0, 2.0 to 6.0 " 

MgO 0.5 to 3.0 *' 

SOj o.5to 2.0 " 

1 E. Candlot : J^tude practique sur U Ciment de B^nrtland, (Paris, 1886). 



PORTI.AND CEMENT. 20l 

After manufacture it is practically Ca,SiOj, 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.* 

Calcium carbonate (CaCO,), 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 ivitkout 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.y May, 1886. 



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PORTLAND CEMENT. 203 

Weight of SiO, X 100 . o--rw 
^ = per cent. SiO,. 

( I ) Crucible -|- SiO, 11.205 grams. 

Crucible 10.721 ** 



Si02= 0.484 
0.484 X 100 



2 
Weight A1,0, X 100 



= 24.20 per cent.SiOj. 
: per cent. Al^Og in the insoluble residue. 



(i ) Crucible + AljO, > 10.743 grams. 

Crucible 10.721 ** 

AljOs = 0.022 ** 

0.022 X 100 ^ A , ^ 
=1.10 per cent. Al^Oj. 

Weight of FcaO, X 2.5 X 100 . r^ r^ 
2 1_» 2 = per cent. Fe,0„ 

(2) Crucible + Fe,0, 10.745 grams. 

Crucible 10.721 '* 

Fe,Oj = 0.024 ** 
0.024 X 2.5 X 100 



-= 3.00 percent. Fe,03. 

: per cent. Al^Og. 



2 
Weight of A1,0, X 2.5 X 100 
2 

(2) Crucible -|- A1,0, 10.762 grams. 

Crucible 10.721 " 



AlaOj = 0.041 
0.041 X 2.5 X 100 



= 5.12 per cent. AljOj. 
int. AljOj. 
! per cent. CaO. 



2 
5.12 + i.io == 6.22 per cent. Al^Og. 
Weight of CaO X 2.5 X 100 
2 

(5) Crucible H- CaO 11.2223 grams. 

Crucible 10.7210 '* 



CaO = 0.50x3 ** 

0.5013 X 2.50 X 100 , - ^ ^ ^ 

-^ — ^ ^ = 62.67 per cent. CaO. 

(7) Crucible -I- MgO 10.725 grams. 

Crucible 10.721 " 

I 

MgO = 0.004 '* 



204 QUANTITATIVE ANALYSIS. 

(8) 
^loS.S!.Mgs\ } +Pl««-» di8h=33.8oso grams. 

Platinum dish =33.7550 '* 

= 0.0500 (Total sulphates) '* 
( MgS04,K,S04,NaiS04). 
Crucible -|- Mg,P,OT ^ 10.729 grams. 
Crucible • = 10.721 ** 

0.008 " 
Mg,Ps07=o.oo8 gms.=o.oo8 MgSOiX 2 = 0.0176 (MgS04) ** 

0.0324 (K,S04+Na,S04) ** 
K^PtCl, = 0.0232 = 0.0082 K,S04 X a = 0.0164 (KjSO*; '' 

0.0160 CNa,S04) 
0.0176 MgS04 » 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 100 . », in, 

-— — ^- = 1.22 per cent. MgO. 

0.0164 KaS04 = 0.0088 KjO then gi ^Q^ ^ ^'5 .Xjoo ^ ^ j^p^,. ^^^^ ^^q 

0.0160 Na,S04 =0.0069 Na,0 then?-^^— -^•^--— = 0.86 per cent.Na,0. 

(S08).Crucible H- BaS04 10.729 grams. 

Crucible 10.721 " 

BaS04 = 0008 ** 

SO, = 0.0027 " 

0.0027X 5 X 100 



= 0.67 per cent. SO,. 

RESUME. 

SiO, 24.20 per cent. 

AljO, 6.22 

Fe,0, 3.00 

CaO 62.67 

MgO 1.22 

K,0 1. 10 

Na,0 0.86 

SO, 0.67 

Total 99.94 " 

The following well known brands of Portland cements were 
analyzed in my laboratory by above method. 



PORTLAND CEMENT. 205 

Burham'8. Dyckerhoff's. Saylor's. 

SiO, 21.70 per cent. 19.05 per cent. 21.25 per cent. 

AljOj 6.82 *' 7.90 ** 4,21 

Fe^Og 2.37 •* 4.48 '• 8.25 

CaO 62.26 " 63.62 ** 61.25 

MgO 1.48 ** 1.87 '* 1.50 

K^O 1.84 " 0.88 *• i.oi 

Na,0 0.98 •* 0.36 " 0.99 

SOs 1.20 '* 0.94 " 1.38 

CO, 1.30 

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.' 

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 : * 

12345678 

CaO 61.99 62.89 63.71 63.27 65.59 59-96 64.51 60.81 

SiO, 23.69 22.80 25.37 19-80 22.85 23.70 22.38 22.63 

Fe,Oj 2.71 3.40 *3.I4 3.22 2.76 3.15 2.24 a.42 

AljO, 8.29 7.70 4.31 6.73 5.51 8.20 9.45 7.06 

MgO 0.47 1.20 1.25 2.02 1.24 i.oo ... 2.89 

Alkalies 0.95 1.30 0.84 1.48 0.92 1.05 ... 2.83 

SOs 0.69 0.71 0.87 1.08 1.69 0.88 1.44 0.47 

CO, 0.27 0.23 ... 0.26 ... 0.33 

Insoluble 0.44 1.38 ... 0.80 

» The Mechanical Testing, 

The method recommended for use in this country by the 
American Society of Civil Engineers is as follows : 
(i) Determination of fineness. 

(2) Liability to checking or cracking. 

(3) Tensile strength. 

^ Quant. Ckem. Anal., p. 259. 

^ Der Fforiland-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. loo 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 injh 
thick, with thin ed^es. 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' 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 weight, 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 



taming 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 arid 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 Porti^nd 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. 

Oneyear,(i day in air, the remainder in water), from 200 to 350 pounds' 

per square inch. 

1 In resrai'd to modification of these conditions required for tensile strength, consult 
TVuni. Amer. Soc. of Civil Engineers, August, 1891, p. 285. 



2o8 



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. 



209 



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 ^itreighing 
beam. 

{d) 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. 

(d) The arrangement of the ** grips'* to hold the briquette is 
such that they are always swung from pins, thus giving the test 




Fig. 53. 

upon the cement when the briquette is on a dead straight line. 

Directions for Testing Portland Cement According to the Official 

German Rules} — The quality of a mortar made with cement 

depends not only on the strength of the cement itself, but also 

I Portland Cement^ by Gustav Grawitz. 



2IO 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 lesting Station at Berlin, is produced by .washing and 
drying quartz sand, which must be clean as possible, and after- 
wards be sifted through a sieve 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). The residue remaining in this 
sieve is the standard sand for experiments, the coarsest and 
finest particles having been eliminated. It is absolutely neqes- 
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 testing. \ The sand must be clean and drj', 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 
Pig 54. equal force on both sides during ten to fifteen minutes 
to insure the escape of confined globul^ 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- 




Pig. 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 Baileyi" 



PORTLAND CEMENT. 



' Fairbanks ' 



213 
previously- 



machine in use in England, and the 
described. 

No 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 sufl5- 
cient to determine the value of a cement. The machines for ten- 
sile strength are the *'Faija,'* (Fig. 56), the ''Reid and Bailey," 
(Figs. 57 and 58), 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 Proceedinfirs of the Institution of Civil En^nccrs, 75, 225, 226. 



214 QUANTITATIVE ANALYSIS. 

Faija has determined this variatiou with esitreme care, the re- 
sults 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. Bohmk. 

Averagrc tensile streng^th 
Age of briquettes. per square inch. Number of tests. 

7 days 767 pounds 10 

28 •* 895 *• 10 

E. J. DeSmkdt, 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 diflSculties of this nature the Vereins. 
deutsche Portland Cement Fabrikanten have modified the rules 



2l6 



QUANTITATIVE ANALYSIS. 



in the construction of the briquettes so that two methods are ac- 
ceptable : 

First, the ;iormal 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. 



217 



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. 



Fisr. 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. 



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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 : * 

First. Analysis to determine the chemical composition. 

Second. The determination of density. 

Third. The determination of fineness. 

1 E. Candlot, Ciments et Chaux Hydrauligues, 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 chauss^es 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, 

(d) With a movable reservoir i?, 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 F, the 
other to the support Af^ 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 il/ is 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-^, which is transferred to the sup- 
port M, 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 / 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 [fecole 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 Cashing 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. 

ipartcementl ^^ ,. ^g .. 

3 parts sand / 

Crushing Strength. 

7 days. a8 days. 

Neat cement 250 kilos. 350 kilos, 

ipartcementj ^^ .. ^8^ » 

3 parts sand y 

To convert kilos per square centimeter to pounds per square inch, the equivalents 
used are : one kilo = 3.204 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 '*B6hme,'* Fig. 66, the ** Tet- 
majer,'* as improved by Prof. Amsler-Laffon,* the ** Brink and 
Hubner,*'* the **Riehle,*' the ** Fairbanks," the "Olsen'' and 
the ''Bailey.'* 

Variation in volume (expansion or contraction) — The method 
of Faija,' the one generally used for this purpose, is as follows • 

1 Consult : Schweizer Bauzeit, January 12. 1889. 

> Description of the *' Suchier," " B5hme," and ** Brink and Huber" machines will 
be found in Dn- Portland Cement und seine Anwendunju^en im Bauwesen, Berlin, xSqa. 

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 Paija'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. 

virater 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 
iio° C; the space above the water is therefore filled with the 
vapor rising therefrom, and is at a temperature of about ioo° 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 no 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 2,000-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 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 tx> 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. 

Resumi: 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, Chem. 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 :* 

/Vrj/.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 : /. Am Chem. Soc., 17, 125. 



228 QUANTITATIVE ANALYSIS. 

Second. The copper is separated from tnanganese 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 filtrate 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. 1.2 1. 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 NICKEI.. 229 

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, which 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 sufii- 
cient to clear the solution, cool until cold, and transfer to a cylin- 
der or flask graduated to iii.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 no® 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 iii.i cc. The gradu- 
ated apparatus should be carefully calibrated and compared be- 
fore using. 

Sodium phosphate solution, made by dissolviiig 200 grams of 
the ordinary crystallized disodium hydrogen phosphate in 1S60 
cc. of water. Ten cc. of the solution contain one gram of the 



DETERMINATION OF NICKEL. 23 1 

crystallized salt, and it requires seventy cc. to precipitate one 
gram of iron as ferric phosphate. 

Sodium acetate solutiofiy 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. 

Cupric ferrocyanide 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^.* The manipulation of the appa- 
ratus is as follows : 

Remove the funnel cap c^ 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 with 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 g is slowly lowered until the surface of 
the water therein is on an exact level with o on the tube ib, 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 loo cc. immediately in contact with the stop-cock b. 

Having thus obtained loo 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,). 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. 

I The water used in this apparatus should contain loo 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 h and immediately close the latter. 
Allow the gas to stand in the tube ih 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 0.0 

After removal of carbon dioxide 11.2 

or 1 1.2 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 ii.2cc. 

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;* to do this, open the three way cock e, open a, 
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 commencemeut 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 fl, then close a, lower/, raises, open b, placingthe gasin 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 
ahy absorbing all traces of hydrochloric acid gas. Repeat with 
this once. Return the gas to hi, allow to stand fifteen minutes, 
then take the reading : 

Previous reading 19.6 cc. 

After using Cu,Cls solution 20.7 '* 

CO I.I " 

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 1 1 .2 per cent, by volume. 

Oxygen 8.4 " " ** *' 

Carbon monoxide i.i '* '* " " 

Nitrogen 79.3 * 



t * <' 



Total loo.o 



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.* 

To convert percentages by volume to percentages by weight 
proceed as follows : 



liter of oxygen 
'* *' hydrogen 
** ** nitrogen 
" '* air 

*' " carbon dioxide 
" ** carbon monoxide 
'* *' methane 
'* *' acetylene 
Then 11.2 cc. carbon dioxide 

8.4 " oxygen 

I.I *' carbon monoxide 
79.3 " nitrogen 



gas weighs 1.430 grams. 

*' 0.0895 

" 1.255 

" 1.293 

- 1.996 

" 1.251 

** 0.7151 

* " 1.252 . 

gas weighs 0.02202 g^am. 

** '* o 01201 '* 

" 0.00138 " 

0.09952 '* 



1 00.0 



M t 



* O.I349I 



If the 100 cc. of gas weighs 0.13467 gram, then 
0.02202 X 100 



The carbon dioxide = ■ 



The oxygen = 



0.13491 

0.01200 X 100 

0.13491 



= 16.32 per cent, by weight. 
= 8.97 per cent, by weight. 



The carbon monoxide = — ^ 1.02 per cent, by weight. 

0.13491 ' 

The nitrogen = —^^ = 73.69 per cent, by weight. 

^ 0.13491 



Total 100.00 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. 

1 " '* '* " '* " " *' 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 t in a cut of the dividing panel, and at 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 U 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 
thoroughly 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, Z>, E and 
F are filled with glass tubes. Since the mark m is above the 
place of connectiqn, the latter is always moistened by the re- 
spective liquid and therefore can easily be maintained air tight. 
The other end of the U 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 .r and 
the rubber bag G, and . 1 10 cc. potassium hydroxide 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 



Z40 QUANTITATIVE ANALYSIS. 

are closed, the stop-cock c turned horizontal and the bottle /., 
containing distilled water, raised so that the water fills the bu- 
rette Ay 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 j, so that potassium hydroxide solution 
rises to the mark w, 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 watej^ is placed in the 
tube By loose cotton placed in both sides, the stopper reinserted 
and connected with the tube n. After filling the burette A with 
water to the loo 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 Cten 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 ^ 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 w, 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 Z>. 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 lOO cc. gives the 



ANALYSIS OF FLUE GASES. 241 

amount of carbon dioxide. The gas is now passed into the ves- 
sel ^ in the same manner as in Z>, 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 /'the 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.' 

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 BzpcrimenU at Mimich : Bayxixhes Industrie und Getuerbeblatiy 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.,' 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 ^ ;tr in per cent. 

temperature of discharged gases ^ 7'( Celsius scale), 
temperature of draught at g^ate ^ /, 
then the loss of T with the coals as fuel equals : 



K=o.65- 



CO, 



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 : 



■»! 


ril 


II 






















I'U 














J 










w 














/ 








il 


w 


y 












/ 








1 


y 


A 












f 






fi- 


1 


\i 


VS 


k 








J 








4P. 


\ 


\ 





^ 


k 






/ 








iffi 


1 


N 


N 


N 




s 




) 












V 


\ 


\ 








L^ 






1 1 






\ 


N 




■^ 




' — ' 


-^ 




K 




^ 


^ 














— 


1^ 


• 













^ ' 1 


-J. 




L 


1 


^^* 


7^ 


^'" ' 


z 


^^ ^*' 


'■ ^ 


^^^ u 




^ ^ ^ ^ -^ "- 


' y^-^ 




* y'Sfe^^^ 


^ ^ ^& ^ ^ 


_ ^^^^^ 


^ I f 



• «M fM M «■ 



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. 

COAI< 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.* 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. ^ 

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 ^ with the levelling tube a, which at 
the bottom is similarly fastened into the base at e. The tube 
fl at A 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 r-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 Chemiich-Uchnische Analyse, Post, pp. 117, 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 
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. 




FifiT. 74- 



248 



QUANTITATIVE ANALYSIS. 




FifiT. 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^ 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 w, 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 capillar^'- 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 ^, 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 
^ 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 
> [3 is avoided. Above the globe b, filled 

|ni 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 
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. 77. 




Fiif . 7«. 



GAS ANALYSIS. 25 1 

one for the determination of oxygen in the gas, the other for the 
determination of the carbon di^^e.^'^---^'^>«^'(j(l co. 

This pipette is charged with alkaline pyrogallate solution for 
the former and with cuprous chloride solution for the latter de- 
termination. 

The bulb a next the capillary tube is filled with a solution of 
alkaline pyrogallol, the bulb b partially filled with the same 
solution, the bulb c is empty or nearly so, and the bulb d con- 
tains distilled water. The alkaline pyrogallol solution is made 
by dissolving one part of a twenty-five per cent, pyrogallol solu- 
tion in water, in six parts of a sixty percent, solution of caustic 
potash. 

In order to illustrate the working of the Hempel apparatus, 
an analysis is here given of a gas containing carbon dioxide, 
oxygen, carbon monoxide, ethylene, methane, hydrogen, and 
nitrogen'. A sample of this gas, 100 cc, is collected and meas- 
ured in the gas burette. The carbon dioxide is first absorbed 
by passing the gas into the potassium hydroxide pipette, Fig. 
76, containing a solution of one part potassium hydroxide* in 
two parts of water. Agitate the gas and potash solution, 
and after waiting five minutes pass the gas back into the 
measuring burette and determine the carbon dioxide absorbed. 
The contraction produced gives directly the percentage of car- 
bon dioxide, since 100 cc. were used at starting.* 

The oxygen is next absorbed in the compound pipette. Fig. 
78. The absorption is complete in about five minutes. The 
amount of oxygen absorbed is now measured.^ 

Some chemists prefer to use stick phosphorus for the absorp- 
tion of oxygen. The phosphorus pipette is shown in Fig. 79. 
The bulb b, contains pieces of phosphorus inserted through the 
opening at k^ which is closed by a rubber stopper. The bulb b, 
and the capillary tube c^ are filled with water, likewise a portion 
of a,. 

After the absorption of the oxygen the next step is to absorb 
the acetylene by means of disulphuric acid in the pipette. Fig. 

1 Potassium hydroxide purified by alcohol cannot be used. 
1 Sulton's Vol. Anal., p. 522. 

s Chromous chloride may also be used for the absorption of oxygen, even in the 
presence of hydrogen sulphide and carbon dioxide. Liebig's A nnalen, aaS, 112. 



252 



QUANTITATIVE ANALYSIS. 




Fig. 79. 

77! The absorption is complete in a few minutes, but the re- 
maining gas, previous to measuring, should be passed into the 
potassium hydroxide pipette twice, in order to free the gas from 
fumesof sulphurtrioxide. Allow the gas to stand in the graduated 
burette five minutes before taking measurement of volume. The 




Fig. 80. 



GAS ANALYSIS. 



253 



carbon monoxide is next absorbed by means of a solution of 
cuprous chloride (CUgCl,) in hydrochloric acid* in the compound 
pipette, Fig. 80. 

Complete absorption of carbon monoxide is somewhat slow. 
Fifteen minutes should be given for this with frequent agitation of 




Fig. 81. 

the gas with cuprous chloride solution . The gas is then passed into 
the potassium hydroxide pipette to absorb fumes of hydrochloric 
acid before it is transferred to the measuring burette, where after 
waiting five or ten minutes the volume can be measured. The 
residual gas now contains hydrogen, methane, and nitrogen. 

The hydrogen is determined by passing the gases over palla- 
dium sponge in the palladium tube E, Fig. 81. 

An improved form is shown in Fig^ 82. 



^~\f^ 



Fig. 82. 
1 Prepared by dissolving sixty grams of Cu,0 (red oxide of copper), in 400 cc. of 
hydrochloric acid, sp. gr. 1.19. One cc. of this fresh solution will absorb twenty cc. of 
carbon dioxide. 



254 



QUANTITATIVE ANALYSIS. 



The palladium tube is kept at a temperature not exceeding 
loo** C, either by using a minute flame as shown in Fig. 8i, or 
by immersing the tube, Fig. 82, in a beaker of water at the re- 
quired temperature. Under these conditions the combustion of 
hydrogen proceeds without the combustion of any methane. 
The gas is passed and repassed through the tube slowly at least 
three times, the palladium tube during the whole operation be- 
ing connected with an ordinary absorption pipette filled with 
water, Fig. 81. 

1. I 




Fiir. 83. 

Finally the gas is transferred to the measuring burette and the 
volume determined. As the hydrogen has burned to water by 
uniting with the occluded oxygen in the palladium sponge, the 
diminution in volume represents the amount of hydrogen in the 
gas directly. The residual gas now contains methane and 
nitrogen. Of this gas ten cc. are now taken and the rest allowed 
to escape, or if necessary can be collected and saved in a pipette. 

To the ten cc. of the gas in the burette ninety cc. of air are 
added and this mixture of air, methane, and nitrogen passed 
into the explosion burette, Fig. 83. 

The gases are thoroughly mixed and then exploded. The 



GAS ANALYSIS. 255 

current required to do this is generated by a dip battery of four 
cells connected with a small induction coil, and with the explo- 
sion pipette by the platinum wires kk. Fig. 83, which are fused 
into the pipette. After the explosion the gases are led into the 
potassium hydroxide pipette to absorb the carbon dioxide formed 
by the combustion of the methane. One volume of methane re- 
quires four volumes of oxygen for its combustion, producing one 
volume of carbon dioxide and two volumes of water. One-third 
of the loss of volume, after the explosion and measurement in 
the burette, gives the volume of methane in the ten cc. of the 
gas. This amount subtracted from ten cc. gives the amount of 
nitrogen in the ten cc, and these amounts must be calculated 
back into values of the total amount of gas left in the burette 
before mixing with air. 

The following analysis of a sample of carburetted water gas 
will indicate the working of the method. 
100 cc. of the gas taken. 

Before use of KOH loo.o cc. 

After ** " *• 96.2 •* 

CO, = 3.8 " 

No oxygen present. 

Before use of H^SjO, 96.2 cc. 

After ** •• •' 81.6 " 

(Illumiiiants,) CjH^; etc. = 14.6 " 

Before use of CiisCl^ solution 81.6 cc. 

After ** •' ** " 53.6 *• 

CO = 28.0 ** 

Before use of Palladium tube 53.6 cc. 

After " *• *• " 18.0 " 

H = 35.6 *• 

CH^ + N remaining = 18 cc. 

Ten cc. taken + ninety cc. air. After explosion in the explo- 
sion pipette (Fig. 78) and measurement after absorption of car- 
bon dioxide formed, the volume was 71.8 cc, which corresponds 
to 28.2 cc of absorption or nine and three-tenths cc. of methane. 
If ten cc of the gas gave nine and three-tenth cc of methane. 



256 QUANTITATIVE ANALYSIS. 

eighteen cc. of the gas (amounts remaining before mixing with 
air) will give 16.7 cc. of methane. 

Calculated to 18 cc 

The volume of gas before adding air 18.0 cc. 

** ** ** ** after explosion and absorption(N) 1.3 ** 

CH4=:i6.7 ** 
Re$um6 : 

Carburettcd water Kras. By volume. 

CO, 3.8 percent. 

Cllluminants) CjH^, etc 14.6 '* '* 

CO 28.0 " " 

H 35.6 - " 

CH, 16.7 " ** 

N 1.3 ** " 

Total loo.o ** " 

and by weight : * 

CO, 9.6 per cent. 

(Illuminants)C,H4, etc 23.7 ** " 

CO 45.1 " " 

H 4.1 " " 

CH, 15.4 ** " 

N 2.1 " " 

Total 100.00 ** ** 

Some chemists prefer to determine the hydrogen and methane 
by explosion, instead of using the palladium tube for the hydro- 
gen. In this case suppose a partial analysis of gas gave as fol- 
lows (100 cc. of gas taken) : 

Carbonic acid 2.2 per cent. 

Oxygen 0.0 '* '* 

Illuminants 12.8 * * " 

Carbon dioxide 24.2 ** " 

39.2 " " 
The remaining constituents being (in the 60.8 cc. gas left) 

methane, hydrogen and nitrogen. These are treated as follows : 
Fifteen cc. of this residual gas are taken and mixed with 

eighty-five cc. of air. This is then passed into the explosion 

1 For method of calculatioti see Analysis of Chimney Gases, p. 237. 



GAS ANALYSIS. 257 

burette containing water previously saturated with the gas. It 
is well shaken to insure thorough mixture of the air and gas, 
and then exploded by means of a spark from the induction coil. 
After fifteen minutes the reading is taken : the latter being 77.4 
cc. or 22.6 cc. contraction. (100 — 77.4= 22.6.) 

Methane produces an equal volume of carbon dioxide by com- 
bustion ; therefore, if the carbon dioxide produced be measured 
by absorption with potassium, hydroxide, the amount represents 
the methane. Pass the gas into the potassium hydroxide 
burette and determine carbon dioxide. 

77.4 cc. — 73 cc. = 4.4 cc. methane in the fifteen cc. of the gas 
mixed with the air, or in per cent, of 100 cc. of original gas : 
15 cc. : 60.8 : : 4.4 : x or 17.83 per cent, methane. 

The hydrogen is determined as follows : 

Let C= contraction (15 cc. gas + 85 cc. air) after explosion. 
•* Z? = CO, = CH, in 15 cc. of gas. 

Then^=i£zi4^ = ^^'^-^1'^ = ?Z:^ = 9.2 percent.' 
3 3 3 

hydrogen in fifteen cc. of the residual gas, or 32.07 per cent, 
hydrogen in the 100 cc. of the original gas. 

By adding together all of the constituents determined, and 
subtracting this amount from 100, the residue is nitrogen. Thus 
the complete analysis will be : 

CO, 2.20 per cent. 

Illuminants 12.80 " ** 

O 0.00 " ** 

CO 24.20 " •• 

CH, 17-83 ** " 

H 37-95 " " 

N 5.02 ** " 

Total 100.00 " '* 

1 Consult Gasometrische Methoden, K. Bunsen, and edition, pp. 4^1. 
(17) 



258 QUANTITATIVE ANALYSIS. 

XXXI. 

Heating Value of Combustible Gases. 

In the calculation of the fuel value of gases, the method as 
given by H. L. Payne' will be found accurate and convenient. 
Since the results of gas analyses are stated volumetrically the 
calculation of a number of analyses is greatly facilitated if the 
calories per kilo are converted into heat units per volume, and 
custom requires results to be stated in ** B. T. U.'* per cubic 
foot of gas. Calories per kilo, multiplied by f (the ratio of 
the Fahrenheit thermometer degree to the Centigrade) will give 
British thermal units per pound. Dividing this result by the 
number of cubic feet of each gas per pound will give ** B. T. U." 
per cubic foot. To calculate the cubic feet per pound of gas the 
following fundamental relations are used : 

I pound = 453-59 grams. 

I meter = 39.37 inches. 

1728 (cubic inches to one cubic foot) divided by (3.937)*=: 
28.317 ; therefore one cubic foot = 28.317 liters. From this is 
obtained: ** B. T. U." per cubic foot = Calories per kilo X 

_9_ ^ ^ '3^7 X ^jjg ji^^j. weight in grams of the gas in ques- 
5 453-59 
tion. 

The following table contains the liter weights as determined 
by actual weight of some of the gases : 

Gas. Grams per liter. 

H 0.0895 

O .' 1 .430 

N 1. 257 

Air 1.293 

CO 1. 251 

CO, 1.966 

CH, 0.7155 

C,H, 1.252 

For the other hydrocarbons and gases not given above, we 
may substitute in the formula in place of liter weight the ex- 

ly. Anal. Chem., 7, 230-235. 



HBATING VALUE OP COMBUSTIBLB GASES. 259 

pression (molecular weight ^_0£8950 \ ^his formula then 

\ 2 1.007 ' 

may be reduced to the following form: ** B. T. U." per cubic 

foot= calories (per kilo) X 'nolecular weight ^ ^^^^^^ ^^^^ 

2 
is comparatively simple and can be used in all cases without 
very serious error. 

Applying this formula to the different combustible gases we 
obtain 

Table of Hbating Values op Gases. 

One kilo of H eyolyes upon complete combustion 34»50o calories, or 
62100 B. T. U. per pound, or 348 B. T. U. per cubic foot at 0° C. and 760 
mm. pressure. 

One kilo of CO evolves upon complete combustion 2,487 calories, or 
4,476 B. T. U. per pound, or 349 B. T. U. per cubic foot at 0° C. and 760 
mm. pressure. 

One kilo of CH4* (methane) (marsh gas) evolves upon complete com- 
bustion 13,245 calories, or 23,851 B. T. U. per pound, or 1,065 B. T. U. per 
cubic foot at o^ C. and 760 mm. pressure. 

One kilo of C,H, (acetylene) evolves upon complete combustion 11,925 
calories, or 21,465 B. T. U. per pound, or 1,555 B. T. U. per cubic foot at 
o^ C. and 760 mm. pressure. 

One kilo of C^H^* (ethylene) (olefiant gas) evolves upon complete 
combustion 11,900 calories, or 21,440 B. T. U. per pound, or 1,673 B. T. U. 
per cubic foot at cP C. and 760 mm. pressure. 

One kilo of CsH« (ethane) (ethyl hydride) evolves upon complete com- 
plete combustion 12,350 calories, or 22,230 B. T. U. per pound, or 1,858 
B. T. U. per cubic foot at 0° C. and 760 mm. pressure. 

One kilo of CjHg (propane) (propyl hydride) evolves upon complete 
combustion 12,028 calories, or 21,650 B. T. U. per pound, or 2,654 B. T. U. 
per cubic foot at o^ C. and 760 mm. pressure. 

One kilo of C,Hc '(propylene) evolves upon complete combustion 11,900 
calories, or 21,420 B. T. U. per pound, or 2,509 B. T. U. per cubic foot at 
o^ C. and 760 mm. pressure. 

One kilo of C4H10 (quartane) (butane) evolves upon complete combus- 
tion 1 1,850 calories, or 21,330 B.T, U. per pound, or 3,447 B. T. U. per 
cubic foot at o^ C. and 760 mm. pressure. 

One kilo of C5H1, (quintane) (pentane) evolves upon complete combus- 
tion 11,770 calories, or 21,186 B. T. U. per pound, or 4,250 B. T. U. per 
cubic foot at o^ C. and 760 mm. pressure. 

I The heat values in calories of CH4 C«H« are taken from Thomson's Thermo- 

dumie Untersuchungen. 

s The ** illnminants " in water g^as are (often) taken as a mixture of C,H4 and CsH«, 
and the B. T. U. per cubic foot as 2,000, which is about the mean of the two gases. 



26o QUANTITATIVE ANALYSIS. 

One kilo of C^llu (sextane) evolves upon complete copibustion 11,620 
calories, or 20,916 B. T. U. per pound, or 5,012 B. T. U. per cubic foot at 
cP C. and 760 mm. pressure. 

One kilo of CeH^ (benzene) evolves upon complete combustion 10,250 
calories, or 18,450 B. T. U. per pound, or 4,010 B. T. U. per cubic foot at 
o^ C. and 760 mm. pressure. 

One kilo of CioHg (naphthalene) evolves upon complete combustion 
9,620 calories, or 17,316 B. T. U. per pound, or 6,176 B. T. U. per cubic 
foot at cP C. and 760 mm. pressure. 

To calculate the heat units of a gas from its analysis, multi- 
ply the per cent, of each constituent by its number as given in 
the above table, and the sum of the products will represent the 
British thermal units evolved by the combustion of one cubic 
foot of the gas. Ordinary gas analysis includes as combustibles 
only hydrogen, carbon monoxide, methane, and "illuminants," 
the latter term representing the hydrocarbons that are deter- 
mined by absorption in fuming sulphuric acid or bromine. 
This has proven to be a very trustworthy value where the hy- 
drocarbons are derived chiefly from the decomposition of mineral 
oil, but if produced by the distillation of coal, this value is too 
low, owing to a larger percentage of benzene vapors contained. 

The experimental conditions necessary to give these theoreti- 
cal results are that the gas be measured at 32** F. and 760 B. and 
is burned with exactly the proper quantity of oxygen, and that 
the products of combustion are reduced to the initial tempera- 
ture, the water being all in the liquid state. It is superfluous 
to say that this cannot actually be done ; but as the whole mat- 
ter is a theoretical discussion, it is decided to adhere to the sci- 
entific standard, and to state results in accordance with its defi- 
nitions. 

But in order to obtain figures which shall more nearly agree 
with practice, many persons have preferred to make their calcu- 
lations under certain assumed conditions. This plan is not 
without merit, since by it a somewhat better idea of the true rel- 
ative values of fuel constituents is obtained, similar conditions 
affecting different gases unequally. The following examples 
illustrate this : 

The temperature for standard gas measurement in this coun- 
try is 60° P., and this point is usually assumed as the initial 



HEATING VALUE OF COMBUSTIBLE GASES. 26 1 

temperature. As a final temperature in this case let the tem- 
perature of the steam be lOO pounds absolute pressure per 
square inch (328** F. ) , a point considerably lower than the average 
chimney flue heat. Under these conditions combustion taking 
place in air, not in oxygen, we must add the heat brought in by 
the gas and air at 60° F. and subtract the heat carried away by 
the products of combustion at 328* F., and since the volume of 
gas is greater at 60** than at 32°, we correct for this by multi- 

4Q2 4Q2 

plying the result — -^ — r or -^^— . 
^ ^ ^ 492 + 28 520 

The composition of air is : 

By volume. By weigbt. 

O 20.92 per cent. 23.134 per cent. 

N 79.08 " " 76.866 " " 

Hence 4.78 volumes of air contain one volume of oxygen, or 
one volume of oxygen is accompanied by 3.78 volumes of nitro- 
gen. 

The specific heats of the several gases are as follows : 

Gafi. Sp. heat. 

H 3.4 

O 0.22 

N 0.24 

Air • 0.24 

CO o. 25 

CO, 0.22 

CH4 0.60 

'* lUuminants " 0.41 

It will be more convenient in these computations to make use 
of the so-called ** volumetric *' specific heats, /. e,, the heat 
necessary to raise the temperature of one cubic foot of gas from 
32" F. to 33° F. 

Gas. Vol. sp. heat 

H 0.019 

N 0.019 

0.019 

Air 0.019 

CO ■.... 0.019 

CO, 0.027 

CH4 0.027 

" Illuminants ** 0.040 






262 QUANTITATIVE ANAI.YSIS. 

Then: 

2H + O + 3.78 N = H,0 + 3.78 N ; or i cu. ft. H + 2.39 cu. ft. air = 
I cu. ft. steam + 1*89 cu. ft. N. 

The heat gained or brought in is as follows : 

H = I X 0.019 X [28= (60^-32^')] = 0.53 B. T. U. 
Air = 2.39 X 0.019 X 28 = 1.27 " ** " 

Total gain 1.80 */ " " 
The heat lost or carried away by the products of combustion 
is as follows : Water at 32* F. converted into steam at 328" F. 
absorbs 1,182 B. T. U. per pound, and one cubic foot of hydro- 
gen produces when burnt 0.0502 pounds of water. 

Steam = 0.0502 X 1182 = 59.4 p. T. U. 
N = 1.89 X 0.019 X 296 =s 10.6 " •* •* 



Total loss = 70.0 *• 
Subtract gain = 1.8 ** 






Net loss = 68.2 ** ** ** 

348 B. T. U. less 68.2 B. T. U. leaves 279.8 B. T. U. and cor- 
rected for volume gives 264 B. T. U., a loss of tyventy-four per 
cent. 

In the case of carbon monoxide no water is produced by 
combustion and the former value is consequently much less 
affected. 

One cubic foot of carbon monoxide -|- 2.39* cubic foot of air=: 
one cubic foot carbon dioxide +1.89 cubic foot nitrogen. Heat 
gained or brought in by carbon monoxide and air, the same as 
hydrogen and air in the previous case, one and eight-tenths 
B. T. U. 

Heat lost: 

COj = I X 0.027 X 296 = 8.0 B. T. U. 
N as above =s 10.6 '• " ** 

Total loss 18.6 " " '* 
Subtract gain 1.8 " *' *' 

Net loss 16.8 '* *' *• 
349.5 B. T. U. less 16.8 B. T. U. leaves 332.7 B. T. U. 

1 Refer to sample in hydrogen combustion. 



HEATING VALUE OF COMBUSTIBLE GASES. 263. 

This corrected for volume gives 315, a loss of only ten per 
cent. 

For marsh gas, i cubic foot CH^ +4(2.39 cubic foot air) = 
one cubic foot CO, + 2 cubic feet steam +4(1.89 cubic feet 
N). 

Heat gained : 

CH4 = I X 0.027 X 28 (60°— 32^) = o 8 B. T. U. 
Air = 4 X 1.27 B. T. = 5.1 " " " 

ToUlgainas 5.9 *' ** ** 

Heat lost : 



CO, = I X 0.027 X 296 (3280—32^) = 8.0 B. T. U. 
Steam = 2 X 59.4 B. T. U. = 118. 8 

N = 4 X 10.6B. T. U. = 42.4 



(€ < 
«f « 



Total lossss 169.2 ** * 
Subtract gain = 5.9 ** * 

Net loss = 163.3 " * 

1065 B. T. U. less 163.3 B. T. U. leaves 901.7 B. T. U. 

This corrected for volume gives 853 B. T. U.( 901.7 X ^^ ) 

\ 520 / 

a loss of twenty per cent. 

For ** illuminants" fifteen per cent, is taken as a fair loss, and 
the values are : 

32- p. initial. 6o* initial. Loss in 

Gas. 32* F. final, 328* final. per cent. 

H 348.0 B.T.U. 264B. T. U. 24 

CO 349-5" " '* 315" " ** 10 

CH4 1065.0" " '* 853." " ** 20 

lUuminants 2000.0 ** ** ** 1700 ** ** ** 15 

Natural gas has been taken as a standard for heating gases 
with a valuation of 1000 B. T. U. per cubic foot. 

At ninety-four per cent. CH^, which is not far from the aver- 
age, it will show by calculation 1000 B. T. U. per cubic foot and 
hence the numerical result obtained by this method for any fuel 
gas will indicate also its standing in that scale. 

Referring to the analyses of gas given on page 256, the ** B. 
T. U." per cubic foot are as follows : 



264 QUANTITATIVE ANALYSIS. 

Products op Combustion Condbnsbd. 

CO 28.0 per cent. X 3495= 97.86 B. T. U. 

CO, 3-8 

(Illuminatits)C,H4, &c.... 14.6 ** ** X 2000.0= 292.00 " ** ** 

'h 35.6 «* " X 348.0=123.88*' " ** 

CH4 16.7 ** *' X 1065.0 = 177.85 ** " " 

Total = 691.59*' " " 

The ** B. T. U.'* per cubic foot of gas will be as follows: 

Products op Combustion in Vapor at 328° F. 

CO 28.0 per cent. X 315= 68.20 B. T. U. 

CO, 

(lUuminants) CjH* 14.6 " " X 1700 = 248.20 " " " 

H 35.6 " " X 264= 63.98" " " 

CH, 16.7 " " X 853 = 142.45" " " 

N 

Total = 552.83 " '• " 

In determining the B. T. U. per pound or of calories per kilo, 
the analysis of the gas by weight is taken and not by volume, 
as just instanced. 

The B. T. U. per pound of the gas would be : 

Products op Combustion Condensed. 

CO 451 per cent. X 4476 = 2018.6 B. T. U. 

(lUuminants) C,H4, &c 23.7 " " X 21440 = 5081.2 " " " 

CO, 

H 4.1 " " X 62100 = 2546.1 " " " 

CH4.... 15.4 *' *' X 23851 = 3673.0 " " " 
N' 

Total = 13318.9 " " " 

and where the products of combustion are in vapor at 328"* F., 
as follows : 

CO 45.1 per cent. X 3402.0 = 1534.3 B. T. U. per pound. 
(Illuminants) C,H4 23.7 " " X 18224.0 = 43190 " " " " 

CO, 

H 4.1 " " X 47196.0=1935.0*' ** " " 

CH4 15.4 *• *' X 19081.0 = 2938.4" ' 

N 

Total = 10726.7 " " " " 



HEATING VALUE OF COMBUSTIBI.E GASES. 265 

MANUFACTURE OF WATER GAS. 

Nearly all of the carburetted water gas in the United States is 
made either by the Lowe process or the Wilkinson process, 
probably four-fifths by the former. 

Briefly stated, the Lowe water gas system consists in the de- 
composition of steam at a high temperature by incandescent car- 
bon, thereby producing hydrogen and carbon dioxide : 2H,OH- 
C=2H,H-CO,. 

In an excess of carbon, the carbon dioxide saturates itself 
with another carbon atom, forming carbon monoxide (CO, -f- C 
= 2CO, making the finished product 2H, + 2CO) . 

In practical working the reduction of carbon dioxide to mon- 
oxide is never quite perfect, the unpurified gas usually contain- 
ing about three per cent of carbon dioxide, to be extracted (as 
in coal gas) by lime purification. 

As the gas, in the process of manufacture, passes from the 
generator to the carburetters, it is enriched by means of crude 
oil or cheaper distillates : hence the name carburetted water 
gas. 

The generator, carburetter, and super-heater are cylindrical 
steel shells, thickly lined with special fire blocks, between 
which and the metal are annular spaces packed with non-con- 
ducting material. The generator is usually supported on short 
columns, as illustrated, leaving cartage room under the hopper- 
shaped ash-pit. The grate, controlled by the several cleaning 
doors, is located slightly above the ash-pit, and the fire is 
charged with coke through the door in the extreme top. 

The generator is connected, both above and below the fuel- 
bed, with the top of the carburetter, the bottom of which leads 
laterally into the adjoining super-heater. The carburetter and 
super-heater, often referred to as the fixing-chambers,'* are filled 
with checker work, and affording such an enormous heating 
surface that even the heaviest distillates can be permanently 
gasified at the low temperatures necessary to the highest illumi- 
nating effect. The enriching oil is introduced at the top of the 
carburetter. 

The oil heater is a simple and practical arrangement for pre- 

1 Humphreys & Glasgow : •• Carburetted Water Gas," 1895. 



HEATING VAXUE OP COMBUSTIBLE GASES. 267 

heating the oil on its way to the carburetter by means of the hot 
gas escaping from the super-heater. 

Operation, — A fire is started in the generator, which is then 
deeply charged with coke and opened to the blast. The air 
enters in large volume below the grate and quickly kindles the 
fuel, while the hot products resulting from the partial combus- 
tion pass forward through the carburetter and super-heaterand, 
after parting with their sensible heat, escape into the stack. As 
soon as these generator gases have sufficiently warmed the 
checker- work, supplies of secondary air are admitted to the topof 
the carburetter and the bottom of the super-heater respectively, 
and the combustion regulated to give the requisite temperatures 
in the two vessels simultaneously. The generator fire being in 
proper condition, and the carburetter and super-heater at the 
desired temperatures, the apparatus is ready for gas making. 
The blasts are shut o£F one by one, beginning with that of the 
super-heater ; the stack valve is closed ; steam is admitted 
under the fuel bed, and having traversed it, passes as water gas 
into the top of the carburetter. At this point the oil is intro- 
duced, and encountering the heated checker-work is vaporized 
and ultimately gasified in presence of the hot water gas. This 
process continues until the temperatures of the fire and the 
checker- work are sufficiently reduced. The oil is then shut off; 
next the steam ; and the stack valve being opened the blasts are 
again admitted and the energy of the fire and the checker-work 
recuperated as first described. The generator is supplied with 
fuel at intervals of from forty-five to sixty minutes, and cleaned 
usually once during each shift. The gas passes from the seal 
through the scrubbers and condensers and is subsequently de- 
prived of its carbon dioxide and treated for its slight sulphur 
impurities in the manner common to coal gas. 

Uncarburetted water gas has the following composition :* 

H 49»32 percent. 

CH, 7.65 " " 

CO 37.97 " •" 

CO, 0.14 " ** 

N 4.79 " " 

O 0.13 ** " 

Total 100.00 ** " 

^ Kitig'8 Treatise on Coal Gas, 3, 362. 



208 



QUANTITATIVE ANALYSIS. 



and after carburetting 

H 38.05 per cent. 

CH4 11.85 " 

CO 29.40 ** 

O o.io " 

CO, 0.10 '* 

N 3.71 *' 

Illuminants 16.79 ** 

Total 100.00 ** ** 

The heating power of the uncarburetted gas per cubic foot 
would be : 



H ... 
CH,. 
CO. 



Products condensed. 
0.4932 X 348.0 = 171.63 B. T. U. 
0.0765 X 1065.0 = 81.47 " *• *• 
0.3797 X 349-5^ = 132.72 ** '* " 



Total 385.82 *' ** ** 

and the heating power of the carburetted water gas per cubic 
foot would be : 

Products condensed. 

H 0.3805 X 348.0 = 131.31 B. T. U. 

CH4 0.1 185 X 1065.0 =126.20" ** «' 

CO 0.2940 X 349-56 = 102.77" " " 

CO, 

O 

N. 

Illuminants.. 0.1679 X 2000.0 =335.80 " " " 

Total 696.08 " " " 

An analysis of a sample of London (£ng.) coal gas gives the 
following : 



H 

CH, 

CO 

C,H, 

N 

O 

CO, 

Aqueous vapor. 



27.70 per cent. 
50.00 " 

6.80 " 
13-00 ** 

0.40 " 



0.10 
2.00 



Total 100.00 



HEATING VALUE OF COMBUSTIBLE GASES. 269 

The heating power will be, per cubic foot, 

Products condensed. 
H 0.2770 X 348.0 SB 96.39B.T.U. 

CH4 0.5000 X 1065.0 =532.50 ** *' '* 

CO 0.0680 X 34956= 23.77 ** ** ** 

CjH^ 0.1300 X 1673.0 =217.49** '* •' 

Total 870.15" ** " 

and when the products of combustion are in a state of vapor (for 
instance 328** F.) the heating power per cubic foot will be : 

H 0.2770 X 264= 73.12 B. T. U. 

CH4 0.5000 X 853 = 426.50 '* ** *« 

CO 0.0680 X 315= 21.42" 

C,H4 0.1300 X 1400 = 182.00 ** 






Total 703.04** " " 

There are few complete analyses of purified coal gas known,' 
I. e., Heidelberg gas by R. Bunsen, Konigsberg gas by Bloch- 
mann, and Hannover gas by Dr. Fischer. 

Heidelberg Kdnigsberg Hannover Hannover 

gas. gas. gas. gas. 

I. II. 

CfHg 1.33 0.66 0.69 0.59 

CjH, 1. 21 0.72 0.37 0.64 

CjH^ 2.55 2.01 2.11 2.48 

CH4 34.02 35.28 37.55 38.75 

H 46.20 52.75 46.27 47.60 

CO 8.88 4.00 11.19 7.42 

COj 3.01 1.40 0.81 0.48 

O 0.65 .... trace 0.02 

N 2.15 3.18 i.oi 2.02 

Total 100.00 100.00 100.00 100.00 

In the Wilkinson process the water gas is made by the com- 
bined generator and retort process. (A full description of a recent 
pkmt will be found in the The American Gas Light Journal, 67, 
399, 401. 

An analysis of a sample of Wilkinson water gas, made by the 
writer,' gave as follows : 

1 Wagner's Manual of Chemical Technology, (13th edition, 1893} p. 39. 
s Wood's '* Thermodynamics, Heat Motors, and Refrigerating Machines, 3rd edition, 
pp. a6o-fl6i. 



270 



QUANTITATIVE ANALYSIS. 



H 39.50 per cent. 

Heavy hydrocarbons, ^ „ „_^^«^«\ a.a^ t* 

lUnminants. ^»^« ^^^^ »«« | 6.60 

CH, 37.30 - 

CO 4.30 " 

N 8.20 ** 

O 1.40 " 

Impurities (H,0, CO, H,S) 2.70 ** 

100.00 
One cubic foot containing 755.31 B. T. U. products condensed. 
G. Lunge' gives an analysis of ** Tessie du Motay" gas, as 
follows : 



CO, 

lUuminants. 
O 

CO 

H 

CH, 

N 



14.3 per 


cent. 


0.6 






27.7 






28.8 






25.5 






3-1 







Total loo.o " " 

containing 827.62 B.T. U. per cubic foot, products condensed. 

For complete details regarding the manufacture of coal gas 
consult King's Treatise on Coal Gas,'' edited by Thomas New- 
bigging, London. 

Producbr Gas. 



Confltituents. 

CO 

H 

CH, 

CO, 

N 



Sieman's 
ffas. 

•• 23.7 

.. 8.0 

.. 2.2 

.. 4.1 

.. 62.0 



Anthracite 
producer gas. 

27.0 

12.0 

1.2 

2.5 
57.3 



Soft coal pro- 
ducer gas. 

27.0 

12.0 

2.5 
2.0 

56.5 



100.00 



100.00 



The heating power of the Sieman's producer gas will be 
134. 1 B. T. U. per cubic foot: of the anthracite producer gas 
153.7 B. T, U.. P^r cubic foot, and of the soft coal producer gas 
168. 1 B. T. U. per cubic foot (products of combustion con- 
densed). 

1 ** Wassergasfabnkatioii in New \orlc, " ZeitscAri/'t fur angewandU Chemie, 1894, pp. 
137-142. 



HEATING VALUE OF COMBUSTIBLE GASES. 27 1 

OIL GAS. 

Oil gas is usually formed by vaporization of mineral oil at 
high temperatures. Two processes are in use : the ** Pintsch" 
and the ** Keith," the former probably representing ninety per 
cent, of the production of oil gas. 

For a description of the ** Pintsch'' oil gas apparatus consult 
Wagfur^s Chemical Technology (edition of 1892), p. 80, also 
/. Soc, Chem, Industry, 69 March, 1887. In the manufacture of 
Pintsch oil gas, in the United States, '* mineral seal" oil is often 
used. This oil is a petroleum product having a specific gravity 
of about 0.840, flashing point 266** F., and fire test 31 1"* F. 

Several analyses, by the author,* of this oil give carbon 83.30 
per cent., hydrogen 13.20 per cent., the remainder being oxy- 
gen, nitrogen, etc., and the analysis of the gas therefrom gave : 

CO 0.5 per cent. 

CH, 57.7 " " 

H 3.4 " '' 

{Benzene vapor, C^Hg \ 
Propylene CjH^ X • 38.1 •* *• 

Ethylene CH^ j 

The heating power would indicate 1582 B. T. U. per cubic 
foot, products condensed. 

W. Ivison Macadam, F.C.S.,/. Soc. Chem, Industry, March, 
1887, tabulates the results of a series of his tests upon the 
Pintsch and Keith oil gas, as follows : 

Paraffin Oil into Gas. 

Averagre AvcragTC 

of trials with of trials with 

Keith's Pintsch '8 

apparatus. apparatus. 

Specific gravity of the oil 0.875 0-877 

Weight of one gallon of the oil 8.758 lbs. 8.779 Ihs. 

Number of gallons per ton of 

oil 255.76 255.15 

Flashing point 289*^ F. 295° F. 

Burning point 347"' P. 354° F. 

Gas from one gallon of oil • • • • 84.93 c. ft. 90.03 c. ft. 

" ** " ton ** *•.... 2i,720c.ft. 24,757 c. ft. 

Candle power of gas 61 .38 candles. 60.82 candles. 

Illuminating value of i cubic 

foot in grains of sperm 1473 grs. 1459 grs. 

Illuminating value of- 1 ton in 

lbs. of sperm 4570 lbs. 5160 lbs. 

1 Transactions Amer. Society Mechanical Engineers, 14, (189a) 355. 



272 QUANTITATIVE ANALYSIS. 

Average Average 

of trials with of trials with 

Keith's Pintsch's 

apparatus. apparntus. 

Illuminating value of i gallon 

in lbs. of sperm 17.876 lbs. 20.198 lbs. 

Heavy hydrocarbons absorbed 

by bromine 39.05 38.20 

Carbon dioxide 0.27 0.08 

Dihydric sulphide Decided. None. 

Oil gas, compressed to six or eight atmospheres, in iron cylin- 
ders, is extensively used for the lighting of railway carriages. 
When more pressure, say ten atmospheres, is used the gas loses 
hydrocarbons which settle out, and this loss in illuminants may 
cause twenty per cent, loss in the illuminating power of the gas. 
References. ^Oss Manufacture and Analysis. By W.J. Atkinson Butter- 
field, P.C.S., London, 1896. 

Methods of Gas Analysis. By Dr. Walther Hem pel, translated by Prof. 
L. M. Dennis, N. Y., 1892. 

Oil Gas. By W. A. Noyes, W. M. Blink, and A. V. H. Mory, /. Am. 
Chetn. Soc.t x6, 688. (A report of a very complete test of an oil gas plant). 
Technische Gasanalyse. By C. Winkler. 
Chemisch-Technische Analyse. By Dr. Julian Post, Braunsweig, 1890. 

NATURAI, GAS. 

The increased use of natural gas' in the metallurgical indus- 
tries in the states of Pennsylvania, Ohio, and Indiana, has given 
this subject an enhanced value. 

The composition of the gas is not uniform and consequently 
the heating power varies. Chemists are not in agreement with 
the statements of the results of analyses, as the following com- 
parisons show : 

Analysis of Natural Gas, by Dr. G. Hay, for thb Natural Gas 

Commission.' 

CO, 0.00 per cent. 

CO i.oo *• 

Heavy hydrocarbons 0.50 ** ** 

CH4 95.20 •* •• 

H 2.00 " ** 

1.30 *• " 

N 0.00 '* •* 

100.00 •' *' 
B. T. U. per cubic foot = 1036.87. 

^ For the history of the development of natural gas in Pennsylvania, consult Tmms- 
actions A mer. Institute Mining Engineers, 14. 423-439. 
a Engineering and Mining Journal^ 39, 247. 



HEATING VALUE OP COMBUSTIBLE GASES. 273 

S. A. Ford (chemist to the Edgar Thomson Steel Works) 

reports analyses of natural gas, as follows : 

No. I. No. a. No. 3. No. 4. No. 5. No. 6. 

CO, • • • • 0.80 0.60 0.00 0.40 0.00 0.30 per cent. 

CO i.oo 0.80 0.58 0.40 i.oo 0.60 ** 

1. 10 0.80 0.78 0.80 2.10 1.20 •• 

CjH^-.. 0.70 0.80 0.98 0.60 0.80 0.60 " 

CjHe... 3.60 5.50 7.92 12.30 5.20 4.80 " 

CH4... 72.18 65.25 60.70 4958 57-85 75.16 •* 

H . ... 22.02 26.16 29.03 35.92 9.60 14.45 ** 

N 0.00 0.00 0.00 0.00 23.41 2.89 " 



Total- 99.30 100.81 99.99 100.00 100.00 100.00 " ** 

Nos. 1-4 are analyses of gas from the same well, made at in- 
tervals of two months. Nos. 5 and 6 are from two different 
wells in the East Liberty District, Pa. 

W. A. Noyes* gives the analysis of a sample of natural gas, 
from New Lisbon, Ohio, as follows ; 

CH4 67.00 per cent. 

C^H, II. 10 ** " 

CO2 1.20 " ** 

0.90 ** •* 

N 19.80 '* " 



Total 100.00 •* " 

The number of B. T. U. per cubic foot amounting to 917. 

The percentage of nitrogen in the gas being exceptionally 
high, the heating power is correspondingly reduced. 

Another analysis (Taylor, Trans, Amer, Inst. Mining Eng,, 
18, 881) is reported as follows : 

CO 0.50 per cent. 

H 2.18 ** *' 

CH4 92.60 ** ** 

CjH^ 0.31 *' " 

CO, 0.26 " " 

N 3.61 •* •* 

0.34 '* •* 



Total 99.80 * 

Each cubic foot containing 1000.52 B. T. U. 

1 Proceedings Amer. Asso. Advancement qf Science, 1893, p. 106. 
(18) 



274 QUANTITATIVE ANALYSIS. 

The most complete investigation regarding the chemical com- 
position of natural gas, has been made by Prof. F. C. Phillips 
for the Geological Survey of Pennsylvania.* 

Analysis of Frbdonia Natural Gas. (Phillips.) 

N 9.54 per cent. 

CO, 0.41 " ** 

C,H4, etc 0.00 " " 

CO 0.00 ** " 

Free hydrogen 0.00 ** *• 

. NH, 0.09 ** *' 

Hydrocarbons of paraffin series 90.00 ** ** 



Total 100.00 ** ** 

Sheffield gas. Wilcox guB. Kane gras. 

N 9.06 9.41 9.79 per cent. 

CO, 0.30 0.21 0.20 ** " 

O trace trace ... ** ** 

H 0.00 0.00 0.00 " ** 

CjH^, etc 0.00 0.00 0.00 ** ** 

CO 0.00 0.00 0.00 ** ** 

Paraffins 90.64 90.38 90.01 " " 



Total .. 100.00 100.00 100.00 ** " 

A practical test of the fuel value* of natural gas has been car- 
ried out by the Westinghouse Air-brake Co., of Pittsburgh, Pa. 
Taking the usual ** best*' quality of Pittsburg coal, it was found 
that its evaporating duty in a particular boiler was 10.38 pounds 
of water per pound of the solid fuel. With the same boiler 1.18 
cubic feet of natural gas evaporated one pound of water ; whence 
it follows that one pound of coal is equivalent to 12.25 cubic feet 
of gas, or that 1000 cubic feet of the gas were as good as 8if| 
pounds of coal. According to calorimetric tests, 55.4 pounds of 
coal contain the same number of heat units as 1000 cubic feet of 
the natural gas. 

I Report on the Chemical Composition of Natural Gas," F. C. Phillips, /. />T(ii«A/fie 
Institute, 134, 242-256, 358-375- 

^Journal Iron and Steel Inst., 1887, 366^18. "Fuels." Mills and Rowan, p. 292. 



PRACTICAL PHOTOMETRY. 275 



XXXII. 

Practical Photometry. 

The illuminating value of any source of light is determined by 
comparing it with some source of light of known value. The 
illuminating value of gas is measured by comparing a flame that is 
burning at the rate of five cubic feet an hour with a standard 
sperm candle that is burning at the rate of 120 grains an hour. 

The amount of light received by any object will vary inversely 
as the square of the distance, of that object from the source of 
illumination, hence, if the light whose power is to be determined 
illuminates body at X inches to the same degree that a standard 
candle would illuminate that same body at Finches, the illumi- 

nating power of that light will be-r^ candles. 

In constructing a photometer this single principle is kept in 
view, and all the refinements are to eliminate errors in judgment 
and to allow for the variations in the rate of combustion of gas 
and sperm. 

The accompanying illustration shows the form of photometer 
known as the Bunsen, which is the one most commonly used in 
Germany, England, and America. 

It consists first of a table which carries the apparatus and 
on which the distance between the lights is accurately laid off and 
marked by two lines. This distance is generally 60 inches, but 
2 meters and 100 inches are also used. In case either light is 
changed or moved for any reason, it may easily be put back in 
place by placing it centrally over the line indicated on the table. 
To facilitate the adjustment two plumb-bobs are hung over each of 
the lines at the ends of the table, so it is easy to see whether the 
flames are properly centered in one direction. In the other direc- 
tion they are centered by sighting along the bar. The bar is 
placed at right angles to the two lines laid out on the table and 
centrally between them. It is laid out in inverse squares so that 
** i'' is in the center. If the length of the bar is Kand the dis- 

tance from the candle is X, the candle-power is — ^^ . The 

mark that indicates four candle-power is twice as far from the 



276 



QUANTITATIVE ANALYSIS. 




PRACTICAL PHOTOMETRY. 277 

light to be measured as it is from the candle, 9 is three times as 
far, etc. 

The bar should be made so that it may be raised or lowered at 
pleasure, and be planed to a thin edge on top so that no light will 
be reflected from it on the disk. On the bar is a sight-box in 
which a paper disk is placed at right angles to and centrally over 
the bar. There are several kinds of disks used, but the one most 
commonly preferred in this country is made by taking a piece of 
white sized paper of medium thickness, and cutting out of the 
center a many-pointed star about an inch and a half in diameter 
outside the points. This paper with the star cut from the center 
is then placed between two pieces of tissue paper and the three 
held together either by placing between pieces of glass or else by 
being fastened with thin starch water. At the back of the sight- 
box are two mirrors, so placed that the observer may stand in 
front of the bar and see both sides of the disk. On the front of 
the sight-box a hood is so placed as to partially screen the eyes of 
the observer from the lights. 

At one end of the bar is the light to be tested. This is con- 
nected to a pipe sealed in mercury, so that it may be moved back 
and forth or raised and lowered at pleasure . It is usually arranged 
with a micrometer cock so that the rate of flow maybe regulated 
as closely as may be necessary. 

At the other end of the bar is a candle balance. The balance 
is usually arranged for two candles and all readings are multiplied 
by 2. This balance is so constructed that the position of the 
candles may be adjusted vertically or horizontally. 

This end of the bar is so arranged that the candle balance may 
be removed and a standard burner put in its place. The standard 
burner commonly used is a Sugg Argand burner, size D. This is 
covered with a thin sheet metal chimney one and seven eights 
inches diameter. This chimney has an opening on one side ^ 
inch high and one and one half inches wide. On the opposite 
side the chimney is cut away to prevent light, being reflected 
through the slot in front. The standard burner, like the one 
through which the gas is tested, is so arranged that it may be 
adjusted in all directions. 

A meter to measure the gas is necessary. As gas is burned 



278 QUANTITATIVE ANALYSIS. 

at the rate of five feet an hour when being tested, the meter is so 
geared that one of the hands makes a complete revolution each 
time a twelfth of a foot of gas passes. A clock is attached to 
the meter with a large second hand, so when the meter hand 
mentioned and the second hand move together, gas is passing 
at the rate of 5 feet an hour. In addition to these hands are 
one indicating feet and one minutes. Some meters are furnished 
with a third set of hands reading feet and hundreds. 

The meter has a thermometer to show the temperature of the 
gas and a universal level so that it may be properly leveled. On 
the side is a glass gauge and a mark indicating the height of the 
water, which should always be constant. 

The pipe connections to the meter are so arranged that open- 
ing a cock will allow the gas to pass around instead of through 
it. This permits the operator to start or stop the meter at pleas- 
ure without interfering with the light. 

A pressure gauge connected with the various parts of the ap- 
paratus enables the operator to ascertain the pressure of the gas 
at different points. One of these connections is to the pipe a 
short distance below the test burner. This gives the pressure 
near the point of ignition. The pressure is read in inches and 
fractions of an inch of water. 

A gas governor is connected before the inlet to the meter, 
which reduces the pressure to about an inch and a half of water. 
Beyond the meter is a smaller governor which reduces the pres- 
sure to about nine-tenths of an inch and prevents alteration of 
the flow of gas due to the irregularities in the meter. 

Black screens are arranged to screen the eye of the observer 
from the light. These are sometimes fixed and at others set on 
the bar. The latter arrangement is preferable, as they may be 
moved to suit different positions of the sight box. 

For testing gas of not over eighteen candle power the Standard 
London Argand burner is used. For higher candle power gas 
the ordinary sawed lava tip is best. The latter is commonly 
known as the batwing burner. 

The photometer should be set up in a small, light-proof room 
with dead black walls. The latter can be hung with black vel- 
vet or painted with glue and lampblack. Great care should be 



PRACTICAL PHOTOMETRY. 279 

taken to insure proper ventilation without draft. The tempera- 
ture of the room should be kept as near 60** F. as possible, and 
the air should not be allowed to become vitiated by the products 
of combustion. The table should be set so that readings may 
be taken from both sides of the bar. 

MANNER OF USING THE PHOTOMETER. 

When one starts to use a new photometer, or one with which 
the experimenter has not previously worked, the instrument 
should be carefully verified. 

First, make sure that the lines defining the distance between 
the lights are the proper distance apart and parallel, and that the 
bar is perpendicular to and midway between them. Next 5iee that 
the bar is level. The disk must be at right angles to the bar, 
and the small pointer under the sight box in line with the disk. 
The two mirrors should be made of the best plate glass and well 
silvered. They should be kept clean. The disk should exactly 
bisect the angle made by the mirrors. The bar should be veri- 
fied so that the operator may be sure that it is properly divided, 
and the meter should be tested with a meter prover. In testing 
the meter be sure that the temperature of the room, of the water 
in the meter, and of the water in the prover are the same. The 
pressure gauge should be verified by a U-shaped water gauge. The 
knife edges of the candle balance should be clean and sharp, and 
the lever should be free to move without rubbing. The weight 
for the candle balance should be weighed on an analytical bal- 
ance to be sure that it is correct. 

For testing coal gas no choice is allowed in the burner, but 
when water gas or any high grade gas is to be tested it is neces- 
sary to get a burner suited to the gas. The most suitable burner 
can be quickly determined by experiment, and the greatest effi- 
ciency is usually obtained with a burner of such size that the gas 
is almost on the point of smoking. When the photometer light 
is burned continually, as is usually the case in gas works, the 
tip on the flat-flame burner should be changed at intervals of two 
or three weeks. Care should be taken that the tip is smooth. 
Any tips that are chipped on top or rough in the slot should not 
be used. 



28o QUANTITATIVE ANALYSIS. 

In preparing for a test, the burner and candles should be 
placed in their proper positions and at such a height that the 
center of the flames will be on a level with the center of the 
disk. The height of the candle flame is taken when the candle 
end of the balance is down. The gas should be burned, long 
enough to be sure that the apparatus is cleaned out and thaf 
fresh gas is being burned. Before starting it is necessary to con- 
trol the pressure under the burner so that it will not vary during 
the test. The governor on the outlet of the meter will do this if 
it is in order. If the pressure varies, the governor must be cleaned 
before starting the test. During the test the pressure gauge 
must be shut off, as in case there is change of pressure it will 
store or give out enough gas to vitiate the result. The meter 
should be level and the water at the proper height. 

The wicks of the candles should never be touched. The 
candles are lighted and allowed to burn until the wick curls over 
to the edge of the flame and bums away as the candle is consumed. 
The end of the wick should glow. No test should be started 
until the wicks are bent over and the ends are glowing. The 
candles should always be burned eight or ten minutes before 
starting a test. A common practice which gives good results is 
to allow the candles to burn eight or ten minutes and then ex- 
tinguish them for two or three minutes. The candles are then 
relighted and allowed to bum about two minutes before starting 
the test. They are commonly placed in the holders in such a 
way that the ends of the wicks are as far away from each other as 
possible. 

When the apparatus has been brought to the proper condition 
for testing, the flow of gas is adjusted to as near five feet an 
hour as possible, and the meter is allowed to run until the twelfth 
of a foot hand points to o, when it is by-passed. The clock is 
stopped at o. The candles are counterbalanced by the sliding 
weight on the balance lever until the weight almost carries the 
lever down. In a few seconds the candles burn sufficiently to 
allow the balance to fall, and at that instant the meter and clock 
should be started. As soon after as possible the 40-grain weight 
should be dropped into the scale pan, which brings the candles 
down again. The operator should always move about the room 



PRACTICAL PHOTOMETRY. 28 1 

deliberately so as to avoid as far as possible creating currents of 
air. The candle flames must be still before beginning to take 
readings. 

A reading should be taken every minute for ten minutes. 
When the screen is apparently illuminated equally on both sides 
ft should be moved a little to the right and to the left, and in 
each case the illumination on that side should increase. Five 
readings should be taken on one side of the bar and the sight- 
box turned around and five taken from the opposite side. In 
case the bar is accessible from only one side, the readings should 
be made with one eye and the screen turned in the sight-box 
after half have been completed. This will eliminate the errors 
due to possible difference in eyes and in the sides of the screen. 

The last reading should be taken during the first half of the 
tenth minute and the times noted when the candle balance falls, 
and when the gas hand completes its tenth revolution. The tem- 
perature of the gas and the reading of barometer should also 
be noted. After this the candles may be (extinguished. They 
should be blown out and the ends of the wicks extinguished with 
a piece of sperm. The wicks should never be touched with any- 
thing else. 

If the candle balance falls in less than 9^ or more than 10^ 
minutes, or, if the gas hand takes less than 9^ or more than 10^ 
minutes to make 10 revolutions, the test should be discarded. 
Long practice has shown that within these limits the light given 
by the candles varies approximately with the consumption of 
sperm and that given by the burner approximately with the gas 
consumed. 

If the candles take X seconds to burn 40 grains and the gas 
hand Y seconds to make 10 revolutions, the average read- 
ing multiplied by 2 should be multiplied by ^^ X — y- or-p^. 

This will give the candle-power of the gas uncorrected for tem- 
perature and pressure. 

The standard of pressure is 30 inches of mercury and the 
standard temperature is ^ Fahr. To correct the pressure multiply 
by 30 and divide by the barometric reading. In correcting for 



282 . QUANTITATIVE ANALYSIS. 

temperature the gas is assumed to be a perfect gas saturated with 
water-vapor. The following is the formula for correction for 
pressure and temperature : 
_ 17.64 (h — a) 

''" 460 + / 

n = the number by which the observed volume is to be 
multiplied to reduce it to 30 inches and 60®. 

h = the height of the barometer in inches. 

/=the temperature Fahrenheit. 

a = the tension of aqueous vapor at /**. 

The table on the opposite page will facilitate corrections for 
various pressures and temperatures. 

Inasmuch as a flame is not perfectly transparent, a test made 
with it at right angles to the bar does not give the mean of the 
light that is emitted horizontally. The richer the gas the greater 
is the difference between the candle-power measured on the flat 
and on the edge of the flame. A gas that gives 25 candles measure- 
ment flat will not give over 19.5 candles measured on the edge. 
When the flame is at an angle of 10 degrees with the bar it gives 
almost as much light as when it is measured at 90 degrees. 

The best photometers are made so that the burner may be 
turned on its axis and the light measured at all angles. 

When it is desired to measure the light emitted by a burner at 
various altitudes, mirrors are used to reflect the light to the disk 
as the latter is kept vertical and in the same horizontal plane as 
the standard burner. In such cases it is necessary to test very 
carefully the amount of light absorbed by the mirrors at all angles. 

There is a popular impression that photometrical work is not 
accurate and therefore not to be depended upon, but, if care is 
taken by the operator in his work, and all the apparatus is 
properly adjusted, the error will be less than i per cent. By- 
taking the average of a series of measurements the error can be 
reduced to a point where it is inappreciable. 



PRACTICAL PHOTOMETRY. 

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283 



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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 -5 thence into 
a case surrounding the stem of a suitable burner C, onwards to 
a metal casing or jacket enveloping the calorimeter D, then 




Figr. 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 



CAlrORIMETER 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 promptlj' turned to waste. 

The collected water is next measured, anditsweightcalculated, 
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 twenty 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 prodiuts 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 /% 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. .^J 

Temperatureof the "body"' (d) -. 63.795° 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 

(«—£/) 2.185 X 0.025 X 1278 = 0.698° gain. 

(^— ^) 3-295 X o.oi X 12.78 =0.421° loss. 

•0.2770° gain. 
• 23.228 -|- 7.67—0.28 a= 177.88 -f- 0.2452 ^ 725.3 heat units at 60° F. and 
thirty inches barometer. ' ' • * 

The coal gas of London, Eng., with an illuminating power of 
sixteen to seventeen candles, has a colorific po^^er 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 tie 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 ^ows the instrument to consist 

1 . Cold water inlet. 

2. Strainer. 

3. Overflow to caloribiete; 

4. Upper container. 

5. Waste overflow. 
6 and 7. Pall pipe andjoint. 

8. Drain cock. 

9. Adjustment cock. 

12. Cold water thetmonieter. 

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. 
33. 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. hAi 

38.3 



Air jacket. 




39. Test hole in air jacket. 
43. Hot water thermometer, 

of a coQ^ustion chamber surrounded by a water jacket, the latter 
filled wijh a great many tubes. To prevent loss by radiation 

V. Soc. Chem. Ind.July, 1895, 63a. 



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 betw^|^he gases and the water, 
but the two move in opposite dir^^^^, during which process 
all the heat generated by the flaml^Pfransferred 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 loo 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.S, 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, w>., 43.8** — 17.2** = 26.6"* C. The calculation is as fol- 
lows : 

where H-=. the calorific value of one cubic foot of gas in calories. 

W-=. the quantity in liters of the water heated. 

7"= the difference in temperature between the two thermome- 
ters in degrees C, and C= the quantity in cubic feet of gas 
used, then 

^_ 2X26.6 _ calories or 604 (152 X 3.968) *' B. T. U." 
0-35 
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 g^oss 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 Resum^ of Tests upon London Coal Gas. 



g g-2 






«2 



is iS Rs •-! ^4« Ell-Si: st «s 
{iz h! {it sS o^i is*i 5|; o|| 3« 15 _ 

o o o P. oS 08 ^.a t5 o p. 

Pirst day.. 21.0° 15.322 26.113 10.79 0.0407 ... 25.7 165.3 15.4 149.9 
Second** .. 22.5° 12.9 27.68 14.780.0584 ... 27.4 165.9 iM 148-5 
Third ** .. 17.5° 13.71 28.6 14.89 0.1103 17.5 26.43 164.8 15.86 148.94 
Fourth" .. 17.5^ 13.75 28.53 14.78 0.1103 17.4 26.43 165.6 15.86 149.74 

Bxperiments 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, 2.20 per cent, (by volume). 

Illuminants^CjHjV 12.80 " ** ** 



|C,H 



% 



O 0.00 

CO 24.20 

CH, 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 ** * * ** 

Petroleum from E. Galacia 10005 " ' * ** 

Petroleum from W. Galacia 10235 ** '* ** 

Crude shale oil from Autun (France) 9950 " ** ** 

Dr. Paul estimates the evaporative power of liquid hydrocar- 
bons as the sum of the carbon and hydrogen present, on the 
basis that when oxidized with the theoretical proportion of air, 
each pound of carbon evaporates 11.359 pounds of water at 
iS-S"* C., and each pound of hydrogen 41.895 pounds of water at 
15.5** C, into steam at 100** C. The following table gives the re- 
sults obtained : 



Carbon. 
CjHeO (Phenol).... 76.6 
CjHgO (Cresol).... 77.77 
CioHg (Naphthalin). 93.75 
CuHio (Anthracine) 94.38 

CsH,o (Xylol) 90.56 

C9H1, (Cumol) 90.00 

CoHi, (Cymol) 89.55 



Hydrogren. Oxygen. 



6.49 
7.41 
6.25 
5.62 

9-44 
10.00 

10.45 



17.00 
14.82 



Evapora- Evapora- 
tion power tion datv 
in pounds in pounac 
of water of water 
at 100' C. at 15.5' C. 

12.24 10.50 



I3-00 
15.43 
15.24 
16.58 
16.78 
16.94 



II. 16 

13.07 
13.26 
14.24 
14.41 
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. 

HeatuniU. Atioo'C. At 15.5' C. 

Total heat of combustion 14500 15.0 lbs. . . lbs. 

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 lbs. • . lbs. 

Intent heat of water vapor 8695 ..." .. " 

Available heat 53337 

Waste heat of furnace gases 1 1520 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 Bightv-Six Per Cent., Hydrogen 
Fourteen Per Cent. 

Total heat Equivalent evaporation 

of com- of water, 

bustion. At loo' C. At 15.5* C. 



C = 0.86 X 14500 12470 B. T. U. 

H=:O.I4 X 62032 8684 



21 154 21.9 lbs. 18.8 lbs. 
Heat unita in fur- 
Purnace gases. nace gases. 

CO, r 3.i61bs. 411B.T.U 

Water vapor 1.26 " 359 ** 

N 11.45 '* 1683 ** 

Surplus air 14.37 " 2124 ** 2.2 lbs 

30.24 ** 4577 '* 4.8 '* 

Total heat of combustion 21 154 " 

Latent heat of water vapor 1217 '* 1,3 lbs 

Available heat 19937 ** 

Waste in furnace gases 4577 " 4.8 *' 

Effective heat 15360 ** 15.8 ** 13.6 lbs. 

Theoretical evaporating power .... 21.9 '* 



294 



QUANTITATIVE ANAI^YSIS. 



Hydrocarbon Containing Carbon Sbvrnty-Five Pkr Cent., Hydro- 
gen Twenty-Five Per Cent. 



C «« 0.75 X 14500 • 
H = 0.25 X 62032 . 



Pumace ff^ces. 

CO, 2.75lb8. 

Water vapor 2.25 ** 

N • 13.39 " 

Surplus air 17.39 ** 

35.78 

Total heat of combustion 

Latent heat of water vapor 



Total heat 
of com- 
bustion. 

10775 B.T.U. 

15508 

26283 " 
Heat unit* in fur- 
nace srasct' 
358 B. T. U. 
641 
1968 
2483 " 

5450 
26283 
2174 " 



Equivalent evaporation 
of water. 
At ioo» C. At 15.5* C. 



27.1 lbs. 23.1 lbs. 



2.6 lbs. 



2.2 lbs. 



Available heat 24109 

Waste in furnace gases 5450 



Effective heat • 



18659 



5.6 



19.3 



16.5 lbs. 



Theoretical evaporating power .... 27.1 ** 

The theoretical evaporative efficiency of different combustibles 
is estimated by Rankine from their chemical composition as fol- 
lows : 

E=i 15C + 64H — 80, and to calculate the quantity of air 
required for combustion, /i = 12C + 36H — 4JO, from which 
the following table is derived. 



Description of fuel. C. 

Charcoal 0.93 

Coke 0.88 

Coal 0.87 

Coal 0.75 

Ethylene, CjH^... 0.75 
Acetylene, C4H,.. 0.85 

Peat, dry 0.56 

Wood, dry 0.58 



1 composition. 






Evaporation due U> 


H. 


0. 


A. 


E. 


c. 


H-^ 


0.00 


0.00 


II.5 


14.0 


14.0 


0.00 


0.00 


0.00 


10.6 


13.2 


13.2 


0.00 


0.16 


0.00 


15.75 


22.7 


12.7 


10.00 


0.15 


0.00 


15.65 


22.5 


12.66 


9.84 


0.05 


0.04 


12.0 


15.9 


13.02 


2.85 


0.05 


0.05 


10.6 


14.I 


n.25 


2.85 


0.2s 


0.00 


18.8 


27.3 


11.25 


16.05 


0.14 


0.00 


15.43 


22.1 


12.9 


9.2 


0.06 


0.31 


7.7 


lO.O 


8.5 


1.5 


0.05 


0.40 


6.0 


7.5 


7.5 


0.00 



UQUID FUEI.. 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 : 
Let E be the corrected and reduced evaporation. 
e = the weight of water evaporated. 
7*, = the standard boiling point (212 F.). 
Tt = the temperature of the feed water. 
7i = the actual boiling point observed : then 



■='1 



z._, ,, I 7;-7;+o.3(7;-r.) 



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 e£Eiciency of a fumance 

, _ , £"( available) 
would be — Ewr-rrr"^- 
E (total) 

The loss of units of evaporation by waste gases Rankine gives ; 

Loss by chimney = -i+iH 7; (F^) 

where i + A' equals the weight of burnt gas per unit of fuel and 
7^ (F) the temperature of the chimney gases above that of the 
atmosphere. 

For ordinary coal i + yi' 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 : 

Oxyffenper 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^ 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.^ 

I ** bituminous'* ** 10.14 

I ** oil36^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 dr^wn 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 filled a glass tube 
betit at right angles, for conveying the gas, first through a cal- 
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.' 

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 ANAI.YS1S. 

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 j-^ 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 suflSciently 
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 

Founds. Pounds per ton. 

(The weight of) fI?'i"T^L^n f Si%T miS ^ 



L tamed. 



of tar and liquor 

from a ton of 

coal. 



and this amount divided by 76,800 gives the gallons of tar and 
liquor produced per ton.' 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.' 

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). 

1 NewbiflTffing's Handbook for Gas Engineers, p. 57. 
s 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 : ^ 

Let A represent silica in combination with bases of the clay. 

Let B represent hydrated 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 -^ + -ff + C 
Now transfer it in small portions at a time to a boiling solution 
of sodium carbonate ( i : 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 everj'^ 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 y4 + -5 + C The difference will be the 
weight of A or silica in combination with bases in the clay. 

If the weight of ^4 + ^ + 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 oi 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 -^ + -ff + Cin one gram. 

1 Prom Freseniui, Quant. Anal., Cairn's, p. 68. 



ANALYSIS OF CLAY, KAOLIN, FIRE SAND, ETC. 



301 




CL p 




ft P 




S 3* ^ 




«-»• rt- sr 




i'-"!- 




S C3- 




5 ^ CI* 




one aci 

excess 

washed 




CL 


» 


^ 


ft 


rt '^ o> 




Itrat 
sod 
11. 


':? 


c "^ 


3. 


2 3 


p 


1' 


i: 


Sg^ 


or 




'^ 


o* ::; 


J* 


0- s- 




" /— V 


> 


^'5* 


!? 


n> 


b 


2L S2 


r 


c 0' 


5- 


a § 


-^ 


-^ 




^. 


N 


S*B 


**• 

3 


=: S 


<^ 


S-g- 


1^ 


C^ 8 


«^ 


ISS 


1 


3 ><* 




» 


8* p 


t\ 




§• 


Cfl •— » 








?s 




s < 








£•? 




rt- 




sodi 
ered 




^i 





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- 
fiuonc 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 o£f 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,PtCl, 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 drj^ness, ignited to 
constant weight as sodium sulphate, and then calculated to Na,0. 

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, dr>' and ignite and fuse this 
titanic oxide with about twelve times its weight of acid sodium 
sulphate ; allcJw 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). 



ANAI^YSIS OF CLAY, KAOLIN, FIRE SAND, ETC. 303 

Water of Hydration. 

Take two grams of the clay, dried at 100** C, transfer to a 
covered 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 Representativb Fire Clays. 

I. 2. 3. 4. 5. 6. 7. 8. 9. 

SiO, (com'd) 50.46 50.15 56.42 65.10 39.94 .... 40.33 29.67 44.20 

Al,Oj 35.90 35.60 26.35 22.22 36.30 0.72 38.54 20.87 39-U 

H,0 12.74 13.61 10.95 7.10 14.52 0.35 13.00 8.61 14.05 

K,0 0.48 0.18 0.42 0.14 0.66 1.55 0.25 

^flf O 0.07 .... ..•■ .... .... .... .... .... 

CaO 0.13 o.ii 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,0, 1.50 0.83 1.33 1.92 0.46 0.18 0.90 1.45 0-45 

SiO,(frce) 4.90 98-31 5-15 3Mi 0.20 

Moisture 2.80 2.18 3.26 0.90 

TiO, 1. 15 1. 14 1.05 

SOj >.. 0.14 

Org. matter 0.58 

Total 100.75 100.67 100.63 99.60 99.18 99.92 99.24 100.00 100.24 

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,'** 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. 

1 Used in xnakinsr 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 ph3'sical 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 
Riehlfe U. S. Standard Automatic and Autographic Testing 
machine is used for this purpose.* (Fig. 90). . 

Crcshing Strength of Various Building Stones. 

Ultimate crushlnsr itrength. 

Pounds per Tons per 

square inch. square foot 

Kinds of stone. Minimum Maximum. Minimum. Majdmum. 

Granite 12000 210C0 860 1510 

Trap rock of N. J 20000 24000 1440 1730 

Marble 8000 20000 580 1440 

Limestone 7000 20000 500 ■ 144a 

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. 

Absorptivb Power op Stone, Brick and Mortar. 

Ratio of absorption.! 

Kind of material. Maximum. Minimum. 

Granite i — 150 o 

Marble i— 150 o 

Limestone i — 20 i — ^500 

Sandstone i — 15 1—240 

Brick 1—5 I-— 50 

Mortar i — 2 i — 10 

1 Thus, if 150 units of dry srranite weigrb after immersion in water 151 units, the ab- 
sorption is one in 150 and stated i— 150. 

3 For description of this apparatus consult The Digeitqf Physical Tests and Laboratory 
Practice, Vol. i, p. 248 (July i^). 



3o6 



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. 



ANAI^YSIS OF CLAY, KAOLIN, FIRE SAND, ETC. 307 

Bauschinger ( Mechanisch-technischen Laboratorium, Miin- 
chen).' 

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. 

h. 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 — lo** to —15** C. 

1 standard Tests and methods of Testing Materials : Titans. Amer. Society Mech. Engi- 
neers, 14, I29i. 



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 quantity 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 \^ight 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 th^ presence of soluble salts, 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 comers lying 
innermost in the brick are knocked o£f. 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- 
bumed clay, for which purpose unbumed 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- 



3IO 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 H. Lynwood Garrison, Trans, Amer, Soc. Civil Eng., 33, 88. 



AI^LOYS. 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 suflSciently 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 100 - ^ _ 
s= 80 per cent. Cu. 

Porcelain crucible + ZnO 17-655 grams. 

Porcelain crucible 17.605 •* 

ZnO =s 0.050 " 

0.050 X 65 ^ _ 0.040 X 5 X loo 

— ^~ — = 0.040 Zn, — — ^ ' = 20 per cent. 

ol I 

Cu 80 per cent. 

Zn 20 ** 

Total 100 " 

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, 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 -h SnO, 16.6743 grams. 

Porcelain crucible .* 16.52^ *' 

SnOj== 0.1523 
Sn = 12 per cent. 

Platinum cone + Cu 28.1 15 grams. 

Platinum cone 27.995 " 

Cu= 0.120 

Cu = 60 per cent. 

Porcelain crucible + ZnO 17-6750 grams. 

Porcelain crucible 17.6052 " 

ZnO= 0.0698 ** 
Zn = 28 per cent. 



ALLOYS. 313 

Resum6 : 

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* or "Sterro*' *. 60 38.2{i.8Fe)* 

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 MetalJ* 

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. 
s Method of B. M. Bruce, modified. 



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,S,. The 
Gooch crucible containing the Sb,S, + 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,S, X 0.71390 = Sb. 

The filtrate from the Sb,S, 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, 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, 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 fron^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. 



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3l6 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. Oxides found. Metals found. 

Sn 1. 162 \ f Sn 1. 154 

Sb 1.312 / 3-131 \ sb 1.309 

Examples of Ai^loys of the Second Class. 

Iron. Tin. Antimony. Lead. Copper. Zinc. Bismuth. Phos. 

Babbitt metal 45-5 i3-oo 40 i-S 

Britannia metal 90.0 10.00 

Pewter •••• 89.3 7.1 1.8 1.8 

Argentine 85.5 14.5 

Ashbury metal 77.8 19.4 2.8 

Soft solder 50.0 .... 50.0 

Anti-friction metal 40.0 5.0 55.0 

Tobin bronze 0.2 0.9 .... 0.4 61.2 37.3 

Phosphor-bronze* lo.o .... 9.5 79.70 0.8 

Deoxidized bronze.. 0.20 12.40 .... 2.2782.67 2.45 ...• 0.005 

Magnolia metal 4.75 15.0 80.0 trace .... 0.25 > . . . 

Rose metal 22.90 .... 27.10 50.0^ 

Camelia metal 0.55 4.25 .... 14.75 7o«2o 10.20 

Ajax metal 10.98 .... 7.37 81.28 0.37 

Car-box meul 0.61 .... 14.38 84.33 o-68 

Parson's white metal .... 86.00 i.oo 2.00 2.00 27.00 

'* B " alloy, P. R. R.' 8.00 .... 15.00 77.00 trace 

Third Class Comprises : 

Aluminum bronze Al 7.3, Si 6.5, Cu 86.2 or Al 10, Cu 90 

Ferro-aluminum Al 1.23, Fe, etc. 99^73 or Al 12.50, Fe, etc., 87.50 

Ferro-tungsten Fe 43.4, W53.1, Mn 3.5' 

German silver Cu.50, Ni 14.8, Sn 3.1, Zn 31.9 

Rosine t; Ni 40, Ag 10, Al 30, Sn 20 

1 Detailed instructions for the determination d| phosphorus in phosphor bronse will 
be found in The American Engineer and Railroad ^umal, 68, rzS. 

S This alloy, accordingr toC. B. Dudley {J. Franklin Inst., March, 1892, p. 168). is the 
best bearing metal known. 

• Consult experiments on ferro-tungsten ; J. S. DeBenneville, J Am, Chem. Soc., 16, 
303. 



ALLOYS. 317 

Metalline Co 35, Al 25, Cu 30, Fe 10 

Aluminnm '* bourbounz " Al 85.74, Sn 12.94, Si 1.32 

Silicon bronze Fe, etc. 86.59, Si 13.41* 

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,, 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 water, 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. 

DeterminaHon of Manganese in Manganese Bronze* Dissolve 
five grams of drilling in nitric acid of 1.20 sp. 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 without 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, 

^ Consult I>etermination of Silicon in Ferro-silicons ; its Occurrence in Graphitoidal 
Silicon, by H. J. Williams, Trans. Amer.Inst, Min. Eng,y 17, 542. 
> Jesse Jones, J. Am. Chem. Soc., 15, 414. 



3l8 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 0.00 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. (=1 gram of sample) filteredo£f 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. 3L9 

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 Al,0,. The weight obtained multiplied by 0.534 X 
100 == percentages of Al. This amount subtracted from 100 
per cent, gives the percentage of iron. (Phillips.) 

Germah 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,' 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 W6hler*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 

I Ber. d. Cfum. Ges., J J, 2478, /. AnaL Chem., 4, 83. 

s Communicated to the author by G. W. Thompson, Chemist National Lead Co.. N.Y. 



320 QUANTITATIVE ANAI^YSIS. 

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 alloj'^ 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,S„ 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. 

For copi)er, treat the alloy with dilute nitric acid in a porce- 
lain dish and evaporate to dryness ; 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 Erlenmeyer 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^ , 

One gram of the finely divided alloy is dissolved by boiling in 
from seventy to lOO 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- 

1 Method of G. W. Thompson. 



ALW)YS. 321 

tion of the alloy is diificult 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 
flow into the beaker with rest of the chloride. Fitially 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 1 10° 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 oxalid 
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 pifecipitated 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 water-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 off ; 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 liberate 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,S„ 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.' 

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 water-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 antiipony. Antimony in 
solders may 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., f. 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. W. Richards,/. Am, Chem. Soc, 16, 541. 

** Materials of Engineering." By R. H. Thurston, Part III. 

"The Testing of Materials of Engineering." By W. 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 grams of the tin plate, cut into strips two 
to three cm. long by three to five mm. wide, are placed in a dry 

^ Consult Am. Engineer and R. R. Journal, 8, iH^ 128. 
* Consult/. Am. Chem. Soc., x6, 541. 



324 QUANTITATIVE ANAI<YSIS. 

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 unduly 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 fubes 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 dr>' chlorine and 
the minimum temperature possible.—/. Soc. Chem, Ifid., i8g^^ 
p. 822. 

The Analysis of Tin Plate for Tin, Lead, Iron ayid 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, 1. 10 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 5.3S 
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 sufl&ciently 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 
teme plate used for roofing : 

I. II. III. IV. v. VI. VII. VIII. IX. 

Tin ..• 1.58 2.08 2.40 3.37 1.60 2.54 1.97 1.96 2.56 

Lead 7.97* 7.13* 8.89 11.98 2.48* 7.48* 8.12* 7.09 10.23* 

Iron 89.84 90.23 88.10 84.18 95.31 89.35 89.29 90.55 86.64 

Manganese 0.36 0.31 0.31 0.35 0.36 0.38 0.37 0.32 0.32 

Carbon I 

Phosphorus 

Sulphur ... '■°-^5 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 

Silicon, etc j 

100.00 100.00 99.95 100.13 100.00 100.00 100.00 100.17 100.00 

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. + SnCl, = 
2FeCl, + SnQX,),— Proceedings Eng, Society of Western Pa,, 82, 
182. 

XL. 
Chrome Steel.* 

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, J, — 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. P. Hart, Jr., and J. Calisch : Stevens Indicator, 9, 49-6s* 



CHROME STEEI,. 32? 

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. Louis 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. fiask 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 fiask 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 I 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. 



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CHROME STEEL. 329 

-chromate. Evaporate this to dryness with hydrochloric acid in 
slight excess, and treat residue with hot water. 

Filter off any insoluble residue (generally silica), add five cc. 
hydrochloric acid to the filtrate, then sodium sulphite until the 
yellow color disappears, and heat to boiling. The chromium 
trioxide is reduced to chromic oxide. To the boiling solution 
add ammonium hydroxide in slight excess, boil five minutes, 
filter, wash well, dry, ignite and weigh as chromic oxide, con- 
taining 68.62 per cent, chromium. 

Manganese Determination, — Dissolve five grams of the steel 
in 150 cc. of nitric acid (sp. gr. 1.20). Boil until the bulk is 
about 100 cc. Add a few crystals of potassium chlorate whereby 
the manganese separates as manganese dioxide, insoluble in 
strong nitric acid. Boil for a few minutes, add fifty cc. cold con- 
centrated nitric acid, filter on an asbestos filter, wash three 
times with concentrated nitric acid, and four times with cold 
water. Place the asbestos filter containing the precipitate into 
a beaker, add an excess of hydrochloric acid and boil until all 
the chlorine is driven off. Dilute with water, filter off the 
asbestos, wash well, add ten cc. acetic acid to the hot filtrate 
and neutralize with ammonium hydroxide. Boil, allow the basic 
acetate of iron to settle. Filter into a flask and to the filtrate 
add a few cubic centimeters of ammonium hydroxide and then, 
carefully, sufficient bromine to precipitate the oxide of manga- 
nese. Cork and allow to stand twelve hours, filter, dry, ignite 
and weigh as Mn,0^ containing 72.08 per cent, of manganese. 

Silicon Determination, — Five grams of the steel are dissolved 
in thirty cc. dilute sulphuric acid (one part sulphuric acid to 
two parts water). When solution is complete, add strong nitric 
acid until no more effervescence occurs. Evaporate to dryness, 
moisten with hydrochloric acid and dissolve in excess of boiling 
water. Filter off the silica, wash with dilute hydrochloric acid 
and hot water, dry, ignite and weigh as SiO, containing 46.7 per 
cent, of silicon. This process is used when tungsten is absent. 

Determination of Tungsten, — Dissolve five grams of the steel 
in a three-inch porcelain evaporating dish with twenty cc. hydro- 
chloric acid (strong) and fifty cc. of strong nitric acid, and 
evaporate to dryness. 



330 



QUANTITATIVE ANALYSIS. 



The presence of tungsten is at once indicated by the yellow- 
color of the tungstic acid (WO,), which separates with the silica. 
Add fifty cc. water, ten cc. hydrochloric acid, warm and filter ; 
wash with water acidulated with hydrochloric acid to prevent 
any tungstic acid passing through the filter. 

The tungstic acid is then dissolved on the filter in hot 
ammonium hydroxide and is thus separated from the silica. 
The filtrate is concentrated so as to allow of its being transferred 
into a weighed platinum crucible, in which it is evaporated to 
dryness, ignited and weighed as WO,. 

Carbon ^phosphorus Bjid sulphur are determined by the usual 
methods in steel analysis. 

The following analyses, made in the laboratory of the Insti- 
tute, show the composition of some of the varieties of chrome 
steel : 

No. I Steei.. 

C 1. 1077 per cent. 

P 0.0354 ** •* 

Cr 0.7563 '• " 

Si 0.J292 '* ** 

S 0.0065 " '* 

Mn 0.0219 " " 

Fe (difference) 97-9430 " *' 



100.0000 



No. 3 STEEL. 

C 0.7253 per cent. 

P 00186 '* 



Cr 

Si 

S 

Mn 

Fe (difference) 



0.5127 

0.1754 

0.0052 

0.0103 

985525 



"Magnet Steel." 

C 0.9571 per cent. 

P 0.0522 ** 

Cr 0.4940 " 

W 0.6186 " 

Si 0.0550 ** 

Mn 0.0167 *' 

S 0.0043 " 

Fe (difference) 97.8021 " 



100.0000 



CHEMICAL AND PHYSICAL EXAMINATION OF PAPER. 33 1 

** Rock Drill'* Steel. 

C 0.8508 per cent. 

P 0.0218 " 

Cr 0.5455 " 

Si 0.1246 " 

S 0.0057 '* 

Mn 0.0112 ** 

Fe (difference) 98.4404 •* 



100.0000 



XLI. 
The Chemical and Physical Examination of Paper. 

This subject may be conveniently divided into eight sections : 
First, — Determination of the nature of the fiber. 
Second. — Microscopical examination. 
Third, — Determination of free acids. 

Fourth, — Determination of the nature and amount of the sizing 
used. 

Fifth, — Determination of the amount of ash and its analysis. 
Sixth, — Determination of the weight per cubic decimeter. 
Seventh. — Determination of the thickness of the paper. 
Eighth. — Determination of the absolute breaking strength. 

First. — Determination of the Nature of the Fiber, 
The introduction, in late years, of the various kinds of wood 
fibers in the manufacture of paper has rendered the chemical 
examination of the same exceedingly difficult. 

This is more especially so where the wood fiber has been sub- 
jected to chemical treatment, as in the ** sulphite process*' or 
the *• soda process," before being incorporated in the paper. 

Nearly all of the chemical reactions for the recognition of the 
wood fibers in paper produce certain colors with the various 
resins in the wood when the reagent is added. While the fiber 
prepared entirely by the ** mechanical" process can be indicated 
without difficulty, even when mixed with cotton and linen in 
various amounts, the conditions are greatly altered when the 
wood fiber has been subjected to bleaching and chemical treat- 
ment, since the latter removes much of the resinous matters of 
the wood and increases the difficulty of the qualitative examina- 
tion. 



332 QUANTITATIVE ANALYSIS. 

The chemical reactions of the fibers produced from the various 
woods used in paper-making, pine, poplar, and spruce, are 
identical, qualitatively, with the following reagents. 

1 . Hydrochloric acid and phloroglucin produce a red color 
with ** mechanical'* wood pulp. 

2. Aniline sulphate produces a yellow color. 

3. Naphtylamin and hydrochloric acid produce an orange yel- 
low color. 

4. Anthracene hydrochlorate produces a red color. 

5. Phenol Hydrochlorate produces a bluish-green color. 

6. Concentrated hydrochloric acid produces a violet color. 

7. Pyrrol and hydrochloric acid produce a purple red color. 

8. Pyrogallic acid and zinc chloride produce a dark violet 
color. 

9. Nitric and sulphuric acids produce a red color. 

10. Haematoxylin solution produces a red color. 

11. Alcoholic solution of cochineal produces a blue violet. 
Where the wood pulp is composed entirely of *' mechanical" 

wood fiber the above reactions are very marked, and by the aid 
of the microscope, the varieties of wood can be determined. 

Wood pulp produced by the *' soda*' or by the *' bi-sulphite'* 
process gives a much weaker reaction with the chemical reagents 
used for identification, and in many instances where the pulp 
has been used many times in paper-making will give no color 
reactions sufficient for recognition. The amount of ** mechanical 
fiber" in a mixture of '^chemical fiber," linen fiber, cotton fiber 
and ** mechanical" fiber in a paper can be determined as follows: 

The sample of paper is first boiled in water, then in alcohol, 
and afterwards digested with ether. After drying, a solution of 
chloride of gold is added. 

Linen, cotton, and ** chemical" wood fiber have no reducing 
action upon the solution of gold ; but the mechanical wood fiber 
immediately reduces gold from the solution, this action being 
due to the ligno-cellulose remaining in the mechanical wood 
fiber. 

100 grams of mechanical wood pulp, under above conditions, 
will reduce 14,285 grams of gold.* 

1 Handbuch der Technisch-Chem. Untersuchungen (Bollby). 6th Auf.. page zoo;. 



CHEMICAL AND PHYSICAL EXAMINATION OF PAPER. 333 

If a sample of paper be submitted for examination as to the 
fibers used in its manufacture, the following preliminary work 
is requisite : The rosin, sizing, filling, etc., in the manufactured 
paper must first be removed. Cut the paper into small pieces, 
place them in a beaker and digest with a solution of caustic 
soda (one part caustic soda to thirty of water) , at a moderate 
heat for ten minutes. Pour off the liquid, replace with dou- 
ble the amount of distilled water, and warm ten minutes ; pour off 
this liquid, and repeat once. Now place the paper in a solution 
composed of one part of hydrochloric acid and fifteen parts of 
distilled water and digest ten minutes. Wash a number of times 
with distilled water, until washings are no longer acid ; then 
dry. 

Suppose the sample of paper so treated to be composed of a 
mixture of **mechanicar* chemical wood fiber, linen, and cotton 
— a mixture to be found in many samples of good quality of 
writing-paper. 

A sample of the dried paper is tested with solution of gold 
chloride. If no reduction of gold takes place, the indications 
point to the absence of mechanical wood fiber. This, however, 
is not absolute, since, if the paper has been made from ** cut- 
tings,'* ** old paper stock,*' etc., etc., the mechanical wood pulp 
might have been treated quite a number of times by chemicals 
in the production of the finer quality of paper, and its ligno- 
cellulose destroyed or modified in such a way as to nullify the 
gold test. 

Generally speaking, however, the reduction of the gold 
chloride is indicative of the presence of mechanical wood 
fiber.* « 

R. Benedikt* gives a method for the determination of mechani- 
cal wood fiber in paper, dependent upon the methyl numbers of 
lignin contained in it. This process has been tested by W. 
Herzberg* with the result that preference is given to the use of 
gold chloride solution. 

^"Ueber die quantitative Bestimmung des Holzschliffs im Papier."von Rich. Godeffroy 
und Max Conloa ; Mittheilungen aus dem R. K. Technologischen Gewerbe museum in 
Wien. x888. 

3 Mitteitungen aus dem Kdniglichen technischen Versuchsaustalten zu Berlin, 1892, 
p. 54. 

s Chem Zig.^ 15, 201. 

4 Mitt. K&nig. tech. Versuchs., 1891, 44—50- 



334 QUANTITATIVE ANALYSIS. 

If the amount of mechanical wood fiber in a paper amounts to 
about ten per cent., Gottstein* states that the fibers may be 
counted under the microscope, after the fibers have first been 
made visible by a treatment with an alcoholic phloroglucinol 
solution and hydrochloric acid. Fifteen per cent, or more of the 
mechanical wood fiber in the mixture renders the test valueless. 
If chemical wood fiber be present in a paper with mechanical 
wood fiber, no color tests for the former are positive in the pre- 
sence of the latter, since the mechanical wood pulps possess'a 
greater tinctorial power. 

Should mechanical wood fiber be absent, however, a solution 
of resorcin can be applied to a properly prepared sample of the 
paper. Chemical wood fiber produces a violet color, whereas 
cotton and linen are without action. 

A solution of phenol also produces a violet color under similar 
conditions. 

Second, — Microscopical Examination . 

By careful manipulation of the microscope, the fibers of linen, 
cotton, and the various woods can be recognized. 

The distinction must be noted here, however, that the fibers 
from paper, no matter what the source, do not have the appear- 
ance under the microscope that they possessed before the me- 
chanical and chemical treatment required in the manufacture of 
paper. 

The chemical process in paper-making is very severe upon the 
various fibers, since they are subjected to beating and cutting 
in the ** beating-machine," to protracted maceration in strong 
alkali, to digestion in boiling water, to bleaching with chloride 
of lime, are loaded with various clays, and finally are sized, and 
often burnished. 

This difference between linen fibers before and after treatment 
is shown in Figs. 92 and 93. 

A comparison shows not only a radical change in the form of 
the fibers, but a difference in the transparency, due to removal 
of soluble portions of the fiber. 

Poplar wood fiber (Fig. 94) made by chemical process, under 

1 Papier-ZeituDg, 1884, 432. 



CHEMICAL AND PHYSICAL EXAMINATION OF PAPER. 335 

the microscope resembles the fibers of linen more than does any 
of the wood fibers. It, however, has one distinguishing charac- 
teristic, even among the disinteg^rated pulps, that is, the tangen- 




Fig. 92. 



Pig. 93- 




Fig. 94- Fig. 95. 

tial fragments have among them particles bearing a grate, or 
screen-like, appearance, as shown in Fig. 95. 

The coniferous woods used in paper-making show peculiarities 
in structure entirely different, under the microscope, from linen 
and cotton, the most distinctive one being the small circular 



336 



QUANTITATIVE ANALYSIS. 



** pits'' or spots along the center of each fiber. A section of 
spruce wood, composed of fifteen or more fibers, is shown in 
Fig. 96. 

After pulping and making into paper, spruce fiber has the ap- 




Fig. 96. 



Fig. 97- 




Fig. 98. Fig. 99. 

pearance, under the microscope, shown in Fig. 97. It still re- 
tains the peculiar circular markings, and is readily distinguishd 
from the linen paper fiber, Fig. 93, or frofn cotton fiber, Fig. 98. 
In Fig. 99 is shown the peculiar *' center-marking" of conif- 




CHEMICAI, AND PHYSICAI, EXAMINATION OF PAPER. 337 

erous fiber, as taken from a sample of writing paper sold as linen 
paper, but shown by both chemical and microscopical examina- 
tion to be composed largely of spruce fiber and linen.' 

The microscope will thus determine the differences between 
the various fibers used in paper-making, and, by properly ar- 
ranged apparatus connected therewith, the percentage of each 
variety of fiber. 

According to the German official directions, the sample of 
paper, after removal of sizing, etc., is to be steeped in a solution 
of one-fifth gram of iodine and two grams of potassium iodide ^ 
in twenty cc. of water and then examined under the microscope. 
The fibers may be conviently divided into three groups : 

1. Linen, hemp, and cotton. 

2. Wood-cellulose (** chemical*' wood fiber), straw-cellulose, 
and esparto. 

3. Ground wood-cellulose and jute. 

After treatment with the above solution, the fibers of group i 
are stained brown, those of group 2 are not colored, whilst the 
strongly lignified fibers of group 3 are colored yellow. But it 
has been found that this method is somewhat defective ; the 
cellulose of group 2, for example, being invariably to some ex- 
tent stained, whilst the members of group i are so deeply colored 
that it is almost impossible to distinguish their structural char- 
acters. After many experiments, the following method was 
found more satisfactory. 

The paper is placed on the object-glass of the microscope and 
treated with iodine solution, the unabsorbed iodine removed by 
means of filter paper, and the paper covered with sulphuric acid 
dilute. The solution of iodine in potassium iodide should be of 
such a strength that a layer of three cc. thickness should be of 
ruby-red color and quite transparent. The paper is now removed 
and boiled with a solution or dilute potassium h^'droxide, washed 
thoroughly, and replaced on the object-glass. The color reac- 
tions are as follows : 

I . Cotton, linen, and hemp take a violet-red or wine-red color. 

1 The niicro>photograph9 used in this article are from Bpecimens made during an 
inyeatigation upon fibers of papers by Charles S. ShulU and the writer in 1893, and rep- 
resent the fibers magnified 200 diameters. 



338 QUANTITATIVE ANALYSIS. 

2. Well bleached wood-cellulose and ordinary bleached straw- 
cellulose are colored gray-blue or pure blue, without any tinge 
of red. 

3. Unbleached or imperfectly bleached wood fiber absorbs very 
little iodine and remains colorless. 

4. Strongly lignified fibers, such as ground wood-cellulose 
and raw jute, are colored yellow. 

The numbers of each variety of fiber are now carefully counted 
by means of the microscope and an eye-piece micrometer ruled 
in squares. This chemical treatment and microscopical ex- 
amination is to be repeated upon at least fifty different pieces of 
paper from different parts of the sample, and an average taken. 
By this means approximate percentages of ^each variety of fiber 
in the paper can be stated.* 

Third, — Determination of Free Acids in the Paper. 

Free acids in the paper may be : 

1 . Chlorides, from the hypochlorites used in the bleaching, 
and which have not been removed by the * * anti-chlor. ' ' 

2. Sulphuric acid, from acid alums used in the sizing. 

Free acids are exceedingly injurious to the paper, producing 
gradual deterioration in the breaking strength, and also produc- 
ing brittleness. 

The amount of chlorides can be determined as follows : 

Take five-tenths gram of the paper, cut into small portions, 
and digest with fifty cc. of boiling distilled .water for two 
minutes, then filter. The filtrate is acidified with a few drops 
of nitric acid, and the amount of chlorine determined by a one- 
tenth normal silver nitrate solution. 

The free sulphuric acid determination requires the determina- 
tion of the combined sulphuric acid in the alum, since in the 
titration with soda solution the combined acid, as well as the 
free, is indicated. The combined acid is determined indirectly 
and then substracted from the total acid, the difference being 
the free acid, thus : If the alum used is potash alum, the per- 
centage of potash should be determined, and then the amount 
of sulphuric acid and alumina calculated from the formula of 
the alum (anhydrous) K,A1,(S0,),. 

ly. Soc. Chem. Ind., 8. 564. 



CHEMICAL AND PHYSICAL EXAMINATION OF PAPER. 339 

If soda or ammonia alum be used, the determination of the 
soda, or ammonia, will be required. Where no clay has been 
used in the paper, the alum can be determined* instead of the 
other base, and the sulphuric acid necessary to form the alum 
calculated; this latter is then deducted from the total acid. 
Total acid is thus determined: 

Two grams of the paper are cut into small pieces and digested 
with 200 cc. of boiling distilled water for three minutes, then 
filtered and a few drops of solution of litmus added. A solution 
of tenth-normal soda is gradually added from a burette, until 
the red color of the solution turns to blue, when the amount of 
alkali used is noted and calculated to sulphuric acid. 

From the total amount of sulphuric acid is subtracted the, 
combined sulphuric acid already determined in two grams of 
paper. This latter amount is found by determination of any 
of the bases, alumina, potash, soda, or ammonia, and calculation 
of the required acid necessary to form the alum used in the paper. 

If aluminum sulphate, Al,(SOJ„ be used instead of alum, 
then the free acid and combined acid will be the same in amount, 
since aluminum sulphate is an acid salt, and titration with the 
soda solution will give the amount directly. 

Fourth. — Determination of the Nature and Amount of Sizing 
Used, 

A paper sized with rosin, when extracted with absolute alcohol, 
gives a solution j^hich, poured into excess of water, yields a 
milky turbidity due to precipitated rosin.* Another test is based 
on the Raspail reaction, rosin giving, with sugar solution and 
sulphuric acid, a violet-red color. The sugar may be omitted, 
as enough is formed for the reaction by the action of the 
sulphuric acid on the cellulose of the paper. 

The presence of animal size is detected by treating the aqueous 
extract of the paper with tannin. The following fundamental 
distinction between papers sized with rosin and gelatin is found 
to exist. In the former the rosin is distributed uniformly 
throughout the substance of the paper, while in the latter, 
whether the sizing has been performed in the pulp or sheet, it is 

^ Basic sulphate of alumina forms an exception. Perg^uson : Basic sulphate of 
alumina,/, Am. Chem. Soc., z6, 153. 

> W. Hextzberg : Mitt. Konig. Tech. Versuchs, 3, 107 ; /. Soc. Chem. Ind., 9. 99. 



340 QUANTITATIVE ANALYSIS. 

always found exclusively on the surface of the finished product. 
This peculiar property of gelatin can be shown by saturating a 
plaster-of- Paris slab with gelatin solution colored suitably, and 
breaking it when dry, on which it will be found to be colored to 
a trifling depth, the inner part being white. On these facts the 
following test is based : A half-sheet of paper is repeatedly 
crumpled and unfolded , and when the surface has been thoroughly 
chafed, is smoothed out and written upon : if it is sized with 
rosin, the inscribed characters are but little blurred ; while, if 
animal size has been used, they run freely, and are visible from 
the opposite side of the sheet. Leonhardi has modified this test, 
removing the doubtful element introduced by the manual use of 
pen and ink. A pipette, of which the exit is ten cm. above the 
paper, and which delivers drops weighing 0.03 gram each, is 
filled with a solution of ferric chloride containing 1.531 per cent, 
of iron. A single drop is allowed to fall and to remain on the 
paper for the same number of seconds that one sq. m. of the paper 
weighs in grams, when it is removed by blotting paper, and the 
under side of the paper brought in contact with a plug of wad- 
ding wet with a weak solution of tannin : the production of a 
black color proves the iron solution to have penetrated, and, 
therefore, shows the sizing to be of animal origin. 

Schuman*s method for the determination of rosin in paper is 
as follows : Two grams of the paper are cut into fine pieces 
and digested below boiling fifteen minutes with a five per cent, 
solution of sodium hydroxide, and filtered. 

The filtrate is made acid with dilute sulphuric acid, the rosin 
separating and rising to the surface of the liquid. This latter is 
filtered upon a weighed filter, dried at loo"* C. to constant weight, 
and its weight carefully determined. 

Starch was used, formerly, as a sizing for paper, but in recent 
years it has been largely replaced by rosin size. It can be de- 
tected as follows : 

The paper is cut into small portions and is digested with boil- 
ing water for fifteen minutes, then filtered. To the filtrate is 
added a drop of a dilute solution of iodine. A blue coloration is 
indicative of the presence of starch. 

The quantitative determination is dependent upon the conver- 



CHEMICAL AND PHYSICAL EXAMINATION OF PAPER. 341 

sion of Starch into glucose by means of dilute sulphuric acid, 
and estimation by means of Pehling's solution. 

Ten to fifteen grams of the paper are digested with 250 cc. of 
distilled water, to which has been added two per cent, of 
sulphuric acid. Two or three hours* heating at 100"* C. is suffi- 
cient to convert the starch into glucose, the exact point being 
determined by taking a drop of the solution and adding thereto 
one drop of the dilute iodine ; if no blue color is shown, the 
conversion is complete. 

The solution is now made alkaline with soda, diluted with 
water to 500 cc, and two samples each of 150 cc. taken, filtered, 
washed well and treated with Fehling's solution,' as usual in 
the determination of sugars. Sadtler states as follows regarding 
this test : 

** In carrying out the gravimetric method the Fehling's solu- 
tion remains in excess (indicated by the blue color of the solu- 
tion after boiling) , while the cuprous oxide is carefully filtered 
off and further treated. ' * 

The procedure is as follows :* 

** Sixty cubic centimeters of the mixed Fehling's solution and 
thirty cubic centimeters of water are boiled in a beaker, and the 
solution containing the maltose added thereto and the mixture 
again boiled. It is then filtered with the aid of a filter-pump, 
upon a Soxhlet filter ( asbestos layer in a tared funnel of narrow 
cylinder shape) , quickly washed with hot water, and then with 
alcohol and ether, and dried. The asbestos filter, with the 
cuprous oxide, are now heated with a small flame, while a cur- 
rent of hydrogen is passed into the funnel, so that the precipi- 
tate is reduced to metallic copper It is allowed to cool in the 
current of hydrogen, placed for a few minutes over sulphuric 
acid, and then weighed.*' 

Fifth, — Determination of the Ash, 

Three grams 'of the paper are transferred to a weighed plati- 

1 Tollen's formula for Pehling'9 solution is as follows : 54.639 grams crystallized 
copper sulphate are dissolved in 500 cc. water. 173 grams Rochelle salts and sixty grams 
Aodium hydroxide are dissolved together in 500 cc. of water. Kqual volumes of these 
solutions.are mixed when required for use. Ten cc. of this Pehling's solution correspond 
to 0.0607 gram maltose— or 0.0765 gram starch. 

^Sadiler: Industrial Organic Chemistry, p. 152. 



342 QUANTITATIVE ANALYSIS. 

num crucible and ignited until all carbonaceous matter is con- 
sumed. The amount of ash is indicative of the use, or not, of 
mineral filling, such as Carolina kaolin, to increase the weight 
of the paper. After the correct determination of the amount of 
the ash, it should be transferred to a 3-inch porcelain capsule, 
and the scheme on the opposite page used for its analysis. 

It is always advisable to test some of the ash, before its 
analysis, by fusing a portion on charcoal with sodium carbonate. 
By this means, lead or chromium can be detected, and then 
properly separated in the analysis of another portion of the ash. 
If clay, in appreciable quantities, is found, it will be necessary 
to add ten per cent, of its weight as water, since most clays 
contain from eight to twelve per cent, of water, which, in the 
above instance, would have been driven off during the ignition 
of the paper to determine the per cent, of ash. If much iron be 
found, Prussian blue, Indian red, Venetian red, or ochre may 
have been used. If the color of the ash is blue, ultramarine is 
present ; if white, silica, or a fine quality of clay, or calcium sul- 
phate, or agalite' may be present ; the chemical analysis readily- 
showing the one used as a filler. 

If the ash found is very small in amount, it will be necessary 
to subtract the amount of ash corresponding to the variety of 
fiber or pulp with which the paper is made, to exactly determine 
the amount of ash belonging to the added materials. 

Ash in Commbrcial Pulps. 

Sulphite 0.48 per cent. 

Sulphite, bleached 0.42 '* •* 

Soda 1.54 " 

Soda, bleached 1.40 ** " 

Straw 2.30 ** ** 

Straw, bleached 1.34 '* ** 

Ground wood (pine) 0.43 ** *' 

Ground wood (fir) 0.70 ** '* 

Ground wood (aspen ) 0.44 ** ** 

Ground wood (lime) 0.40 ** '* 

Linen 0.76 " 

Linen, bleached 0.94 ** " 

Cotton 0.41 " " . 

Cotton, bleached 0.76 ** ** 

1 A variety of talc— silicate of magnesium— in a finely powdered condition ; it has a 
very extensive use as paper filler. 



CHEMICAL AND PHYSICAL EXAMINATION OF PAPER. 343 



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344 fiUANTITATIVE ANALYSIS. 

Ash in Fibbrs. 

Cotton O.I2 per cent. 

Italian hemp 0.82 ** " 

Rhea 5.63 

Best Manilla hemp i .02 

Sulphite fiber 0.46 

Pine Flemish flax 0.70 

China grass 2.87 

Jute 1.32 

Esparto 3-5o-504 

Soda fiber i.oa-2.50 

Sixth, — Determination of the Weight pet 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.* 

Seventh, — Determination of the Thickness, 

The thickness of paper can be accurately determined by the 
apparatus, a sketch of which is shown in Pig. 100. 

By means of a delicate spring, a lever, s^, is held against ^,, 
touching jj only at one point. 5, carries a toothed segment, 
which moves a pointer, z, along an arc divided into 500 parts. 
One division represents 0.002 mm. of thickness of the paper tested. 

Eighth. — Deterfnination 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.* The tensile strength 
of the sheet, both across and parallel to the web, is determined 
separately, and the average values recorded. To ascertain the 

1 I^itfaden f Ur Papier-ptiifung, W. Uerzberg, Berlin, 1888. 

3 Verhandlung des Vereins surBcfdrderung^des Gewerbefleisses in Prcussen, 1885. 



CHEMICAI. AND PHYSICAL EXAMINATION OP 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 : 
180 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 
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 



QUANTITATIVE ANALYSIS. 



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 
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. 

lOI.) 

1 . The driver. 

2. Apparatus for mounting. 

3 . Apparatus for transmission of power. 
4. Apparatus for 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, *, 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 /, 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, 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^ s^. 

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 /, which is fastened to the bed rf, at the other by the car- 
riage w, and passes through the shell t. 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 180 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 QUANTITATIVK 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 / 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 ofif 
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 /, 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 aiJd 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. 

Let X = unknown tearing length. 

G=^ wt. of the torn strip (in 0.18 mm. length), in grams. 

K= no. of kilos necessary to tear strip. 

Then^=^ or x=^/r.> 

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. 
I Papicr-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 

Toilei 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 friee 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 Analyst, xx, 47. 



350 



QUANTITATIVE ANALYSIS. 



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352 QUANTITATIVE ANALYSIS. 

Water. 

For the determination of water, the method of Lowe is 
employed.' 

From eight to ten grams of the soap, ( wh ich has been reduced to 
very .fine shavings, and represents an average sample) , is weighed 
out between watch-glasses and heated in the air-bath, at first 
from 6o**-7o'' C, to avoid melting, then at ioo**-io5° C, to con- 
stant weight. In selecting the sample in this, as well as in all 
subsequent determinations, it is essential that an average speci- 
men be obtained, since the content of water in the different parts 
of the bar varies considerably. 

This is best effected by cutting away about one-third from the 
end and evenly scraping the cut surface of the remainder until 
a sufficient amount is obtained for analysis. 

If the determination of free alkali is of considerable importance, 
the soap should be dried in an atmosphere free from carbon di- 
oxide. The loss at 105° C. represents the water together with 
other 'volatile constituents, such as alcohol and essential oils, 
which may be present. 

Unsapanified Matter. 

For the determination of unsaponified matter,* the soap, which 
has been dried in the manner indicated, is extractedin a Soxh- 
let extraction apparatus with petroleum ether, which, for this 
purpose, should boil below 80** C, and should leave no residue 
upon evaporation. After th$ extraction is complete, the petro- 
leum ether is distilled off, the residue dried at 100® C and weighed. 

In a boiled, well-made laundry soap, there should be no- 
unsaponified matter unless the same has been added subsequently. 

In addition to unsaponified fats, foreign matters aire sometimes 
found in the petroleum ether extract, such as a soft paraffin (so- 
called** Mineral Soap Stock"), waxes, hydrocarbon oils, phenol, 
etc. If waxes are found to be present, the dried soap should 
be extracted with boiling toluene, which dissolves the same 
better than petroleum ether. 

1 J. F. Schnaible,/. Anal, chem., 4, 147-156. 

3 Allen : Commercial Organic Analysis. Vol. a. 



SOAP ANALYSIS. 353 

Total Alkali, Fatty Acids, 

The dried soap thus freed from unsaponified matter is next 
dissolved in hot water, preparatory to determining the total 
alkali and fatty acids. A pure soap dissolves completely in hot 
water, and no ordinary product should leave more than a slight 
residue. If the article examined is a ** scouring soap'*, the in- 
soluble residue will be found to contain quantities of fine sand 
and sometimes talc. The residue, if appreciable, should be 
washed by decantation, and eventually brought upon a filter with 
hot water, dried at loo'' C, and weighed, after which, if desired, 
it can be subjected to further examination. 

To the aqueous solution is added an excess of half normal sul- 
phuric acid setting free the fatty acids which rise to the surface. 
The beaker or vessel in which the precipitation was effected is 
next cooled with ice-water. When the fatty acids,* have solidi- 
fied, it is best to decant the liquid, remelt with hot water two or 
three times to remove any enclosed mineral acid, again cool, fil- 
ter, and wash with cold water until the washings are no longer 
acid, as shown by litmus. 

The filtrate from the insoluble fatty acids contains the total 
alkali now present as sulphate, the excess of sulphuric acid and 
any glycerol which may have been present in the soap, if 
saponification was effected in the cold. The acid liquid may 
further contain a small amount of soluble fatty acids. It is first 
titrated with half normal potassium hydroxide using methyl 
orange as indicator.* From the original amount of sulphuric 
acid added and the number of cc. half normal potassium hy- 
droxide required to neutralize the excess of the same, the total 
alkali of the sample can be determined. 

It is calculated to Na,0. After the liquid has been rendered 
neutral to methyl orange (which indicates the mineral acid), 
phenolphthalein is added and more potassium hydroxide is run in. 
The number of cc . of potassium hydroxide required for neutralizing 
to phenolphthalein corresponds to soluble fatty acids and is cal- 

(C H COX 
p'tt**qqJO, in the absence of 

1 Bulletin No. 13, Pt. 4. P- 456, U. S. Dept. Ag^r., Chem. Div. 

2 Allen : Com. Or%, Anal., a, 260. 




354 QUANTITATIVE ANALYSIS. 

more definite knowledge as to their nature. The solution is now 
concentrated and tested for glycerol, which may be determined 
by evaporating to dryness and extracting with ether-alcohol 
mixture', or else by oxidizing to oxalic acid by means of per- 
manganate' (not always applicable).' 

In soaps containing silicates of the alkalies (a not unusual 
constituent) , the gelatinous silicic acid which separates on the 
addition of sulphuric acid remains with the fattj'^ acids on filtra- 
tion. To separate the fatty acids from this as well as other 
impurities, proceed as follows : 

The funnel containing the filter with the fatty acids is placed 
in a small beaker and heated in an air bath (Allen's method). 
As the filter dries, the fatty acids pass through it and collect in 
the beaker below, while all impurities (silicic acid, talc, etc.) re- 
main on the filter. Of course it is necessary to wash the filter, 
which remains saturated with the fatty acids, with hot redistilled 
alcohol or petroleum ether, or else exhaust in an extraction 
apparatus. The alcohol or petroleum ether is distilled o£f and 
the residue treated in the same way as the main quantity of fatty 
acids. 

In determining the fatty acids in a soap, it is frequently con- 
venient to extract with ether in a separatory funnel.* To do 
this the soap solution is placed in the funnel and shaken with 
sulphuric acid and ether. The separated acids are at once dis- 
solved in the ether. The aqueous solution may be drawn off 
below, the ethereal solution washed with water, the ether evapo- 
rated, and the residue dried at loo** C, and weighed. 

Since the fatty acids exist in the soap as anhydrides and are 
weighed as hydrates, it is necessary to multiply the weight found 
by the factor 0.97, which gives the weight of fatty anhydrides. 
The fatty acids, after having been weighed, may be titrated with 
half normal potassium hydroxide, and from these data may be 
ascertained what portion of the total alkali exists in combination 
with the acid as soap. 

1 Chem. Ztg., 8. 1667. 

a Chem. Ztg., 9, 975. 

> Allen : Com. Org. Anal.. 3, ago. 

4 Chem. News, 43, 218. 



SOAP ANAI.YSIS. 355 

Free Alkali, 

To determine the per cent, of free alkali' in soap, a separate 
^rtion is weighed out and extracted with neutral alcohol in an 
•extraction apparatus. The caustic alkali is determined in the 
alcoholic solution by titrating with half normal hydrochloric 
acid, using phenolphthalein as indicator. If, however, the soap 
contains unsaponified fat, as is frequently the case if made by 
the so-called ** cold-process,** this method cannot be used, since 
in alcoholic solution unsaponified fat would be readily saponi- 
fied by the free caustic alkali present. In such a case the soap 
must first be dried in an atmosphere free from carbon dioxide 
at loo® C.,the unsaponified matter extracted with petroleum 
ether, and finally the soap dissolved in alcohol and the free alkali 
determined in the alcoholic solution as before. The sodium car- 
bonate, sodium silicate, borax, and every thing insoluble in alco- 
hol, remains behind in the extraction tube and may be dried at 
loo"* C. and weighed. If considerable, it may be further treated, 
as follows : 

First, it should be exhausted with boiling water ; one-half of 
this solution is then titrated with half normal hydrochloric acid 
using methyl orange ^s indicator. The amount of acid required 
corresponds to carbonate, silicate and borate. In this solution 
sulphates may also be determined and starch and gelatine tested 
for. The other half of the solution is examined qualitatively 
for carbonate, silicate and borate. If there remains a considerable 
residue insoluble in water, it may be dried at loo** C, weighed 
and further examined. 

ReHn, 

Resin is a very common constituent of soaps, the resinates of 
the alkalies having a similar action to soaps, and the cheapness 
of the material often suggesting a partial substitution of it for 
the natural fats and oils. 

As a qualitative test for resin, Gottlieb's* method is reliable 
and easily made. 

The soap is dissolved in water and heated to boiling. A strong 
solution of magnesium sulphate is added until the fatty acids are 

1 Allen : Com. Ox%. Anal., 3, 251. 

SBenedikt : Analyse der Pette u. Wacbsarten, p. 121. 



356 QUANTITATIVE ANAI.YSIS. 

completely precipitated. The magnesium resinates remain in 
solution. After boiling two or three minutes, the solution is 
filtered and the hot filtrate acidified with dilute sulphuric acid. 
In the presence of resin the liquid becomes turbid, due to the 
separated resin acids. The boiling should be continued for one- 
half hour, to make sure that the turbidity is due to resin acids 
and not to volatile fatty acids. One method for the quantitative 
determination of resin in soap is that of Hiibl,' as follows : 

One-half to one gram of the mixture of fatty and resin acids 
is heated in a closed flask on the water-bath with about twenty 
cc. of alcohol to complete solution. The acids are neutralized 
with alkali, using phenolphthalein as indicator. The alcoholic 
soap solution is then poured into a beaker, the flask rinsed with 
water, the solution diluted to 200 cc, and silver nitrate added 
to complete precipitation. The precipitate (consisting of the 
silver salts of the resin and fatty acids) must be protected 
from sunlight. It is filtered, washed with water, dried at 100** 
C, and extracted in a Soxhlet tube with ether. The silver 
resinates dissolve in the ether, while the silver salts of the fiatty 
acids remain behind. The ethereal solution, as it leaves the 
extraction tube, should be yellow or light brown in color, but 
not dark brown. It is filtered, if necessary, and the filtrate 
shaken with hydrochloric acid in a separatory funnel. The re- 
sulting ethereal solution of the resin acids is filtered from the silver 
chloride, washed with water, and the filter and separator rinsed 
with ether, the ether distilled off, and the residue dried at 100® C. 
As the resin is weighed in the hydrated form, its weight must 
be multiplied by the factor 0.9732 to obtain the weight of the 
anhydride. 

Twitchell's method for the determination of resin in a mixture 
with fatty acids depends upon the formation (in alcohol solution) 
of the ethereal salts of the latter when treated with hydrochloric 
acid, resin being unacted upon. The gravimetric method is as fol- 
lows :* Two or three grams of the mixture of fatty acids and 
resin are dissolved intentimestheirvolumeof absolute alcohol and 
dry hydrogen chloride is passed through in a moderate stream, 

1 Benedikt. p. 125. 

V- Anal. Appi. Chem., 5, 379; Vulti : School of Mines Quarterly, 13, 249. 



SOAP ANAt,YSIS. 



357 



the flask being placed in a vessel with water to keep it cool. 
The gas is rapidly absorbed, and after about forty-five minutes 
the ethereal salts separate and float on the solution. After 
waiting for half an hour longer, the liquid is diluted with five 
times its bulk of water and boiled until the acid solution is clear, 
the ethereal salts, with resin in solution, floating on top. To 
this is added some light petroleum, and the whole transferred to 
a separatory funnel, the flask being washed out with light petro- 
leum. The acid liquid is then run off, and the petroleum ether so- 
lution washed once more with water and then treated in the funnel 
with a solution of a half gram of potassium hydroxide and five cc. 
•of alcohol in fifty cc. of water. The resin is immediately saponi- 
fied, and the two layers separate completely. The resin soap 
solution can then be run off, and the resin recovered, as usual 
by the addition of an acid. The first stages of the volumetric 
method are similar to those of the gravimetric, with the excep- 
tion that the contents of the flask are washed into the separating 
funnel with ether instead of light petroleum, and the ethereal 
solution is then thoroughly washed with water until all soluble 
acidity is removed ; fifty cc. of neutral alcohol is then added, and 
the solution titrated with standard solution of sodium hydroxide. 

It is frequently of interest 
to know the origin of the {^p 
fatty acids of a soap which 
is, however, in many cases, 
a problem not easily solved. 
The only clues are to be 
sought in the specific grav- 
ity, combining weight, 
melting and solidifying 
points, and iodine number 
-of the fatty acids. 

The values for the specific 
^ravitiesin column III page 
358, were obtained with a 
Westphal and a Reimann's 
balance plummet, with a 
thermometer of a range 95° — loi 
ing figure. 




Fig. 102. 

C, as shown in accompany- 



U 

< 

Cm 

a 



e8 
Cm 



09 

C 

o 



> 



o 

6 

U 

•d 

c 

*3 
o 

43 

43 



fi 
«> 

^ 

H 









•1»H 



25 



•»PP» 



•1«d 






••pp» 



■IBd 



11 









V 

9i 



•n>P« 



IBd 



•«pp» 



•;»H 



f|PPB 



•1«H 



-sppB 



•1«d 



ag^ OS ox 



•BPPB 

A;bh 



IBH 



.a?>- 






11 



§ 4! -5 '2 -g 



o 
•9 



ooo6iN.6o ooco6o>^4-t*)6 oooo 



** " d "^ 









§^0«^® O O OSD O O O O OW O ^VOVO 






^J5J!f?feqgio :u?qq«?22:q«2 oq«oq 






= g = = = = =! 



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: rt I e?S" • irt 



: :5q: 
' -9) = 



:^^ 



}3_K 



oooooo 00000000K.0 00^0 



000000 oooooooo«o OOmO 



|!!!!l isll!!!! IffI 



■Irtif! !!!i!!l8l fW 




ddddd 6 6 6^666666 6666 



y 6 6 6 6 6 6 6 6Sb6 6 6 6 6 6 6 6 6 6 



^5 d d o o' o* o . d d d 6 d 6 • d 6 6 6 



^ovooooo ooo^oooeoS? 0^0 




? 



# 



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 i;i 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 conclusionmay be 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 :' 
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 100 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,0), 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. 

/ Alkali, combined \ © ._ << << 

\ assoap,Na20 / ^'5" 

Alkali free» as NaOH 0.20 •* " 

" Na,COs 020 " " 

Insoluble in H,0 0.20 " " 

Fatty anhydrides 52.32 " ** 

Resin 19-45 *' " 

Total 100.00 " " 

Washifig Powders. 
The washing or soap powders contain besides powdered soap, 
a large percentage of sodium carbonate, usually in the form of 
dried soda crj'stals. 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 



^2 ^ ^ CTj o 



1? 



5 



2J 
o 



o 



o o 






a: 

o 




O MVO M 

"8 8 8.^ 



8> S 

61 b 

O ON 



3. 

a 
S 



Origin. 



Fatty and resin 
anhydrides. 



> 

s. 

GO 
GO 



0) 

O 



■^ "Si a\ 



■^4 



Ov 00 

8? ^ 



Soda (Na«0)exist 
ing as soap. 



8 



000 M 

p b-^ b 



o 

8x 



Silica. 



OJ o 



o o 



i 52 



o 



Soda as silicate. 



58 



8 


p 

M 




S5 

M SO 




a 




8^ 


p 

•si 


Sodium carbonate 
and hydrate. 




£ 


i 




Si; 


p 


p 


1 


Sodium chloride. 


. p 


p 
00 


p 


P P 

M M 


p 


p 

M 


P 


Sodium sulphate. 


p p 


p 


p 

s 


pp 
83. 


p 

M 


p 

M 





Lime and iron 
oxide. 



Crt M C 



% 



Water. 



8vO >0 Q >AnO ^ 



8 8 



Total. 



: o 



3 o 00 



Patty and resin 
acids. 



362 QUANTITATIVE ANALYSIS. 

mixing, the somewhat stiff material is drawn off into coolings 
frames.' The cold and hard soap thus formed is then finely 
ground.* 

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 sodiunx 
carbonate. 

References, — "Die Darstellungder Seifen, Parfumerien und Cosmetica.'* 
By C. Dcite, 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^y 14, 623. 

" Soap Powders." Seifen^ Oel und Fell Industrie ^ 3> 973. 

''Oils, Fats, Waxes and their Manufactured Products." By Alder 
Wright, F.R.S., 1894. 

'* Oils, Fats, and Waxes." By Dr. R. Benedikt and Dr. J. Lewkowitsch» 
F.C.S., 1895. 

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. 41a. 

2 SdfHitJSc American Suppl., 1893, p. 1473.3. 



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* 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. ofjL 
paraflSn oil and ten per cent, 
of residuum . Durand Wood- 
man* gives an analysis of a 
crude petroleum from Ohio. 
300 cc. of the oil were [taken __ 

and eighteen distillates each of ^'^ Fi^i^. 

fifteen cc. (five per cent, of total) were obtained. The results in 
detail were as follows : 




Number of distillate. 
I 



2 . 

3- 

4- 

5- 
6. 

7- 
8. 

9- 
10. 
II . 
12. 

13- 
14. 

II: 



•F. 
160 
200 
210 
250 
263 
277 
348 

354 
370 
400 
427 



l^::::::::::::::::: 

Residuum 

ly. Am. Chem. Soc., 13, 168. 
s Ibid, IS, 180. 



476 
486 

40O 
466 
450 



70.5 
65.0 
61.0 

57.5 
54.0 
52.0 
48.0 

45-0 
430 
41.0 
40.0 
40.0 

39-0 
40.0 

390 
40.0 
41.0 
41.0 



Per cent 

5 
10 

15 
20 

25 
30 
35 
40 

45 
50 

60 

65 
70 

25 
80 

85 

90 

100 



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 lo.o per cent. 

Illuminating oil 60.0 " " 

Lubricating oil I5«5 *' ** 

Tar and Residuum 14.5** " 

ToUl 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 the 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 i i.o per cent. 

Illuminating oil 64.0 ** *' 

Lubricating oil 10.3 '* ** 

Residuum 14.7 *' ** 

Totat 100.00 " ** 

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, 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, SoP 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 OP PETROLEUM. 365 

2. Illuminating oils. The various varieties of kerosene, boil- 
ing points 150** to 300** C. 

3. Residuum, (tar, etc.) boiling point 300*0., 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.* 

The-manufacture of vaseline, petrolatum, cosmoline,etc., from 
the tarry residuum (vacuum process,) has increased largely in 
the last few years.* 

In the oil trade the principal mineral oils obtained from petro- 
leum are as follows : 

Benzenes and naphthas, 62**, 65°, 75®, 88^, 90°Baumfe. 

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^ Blackreduced 
(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 7 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. p. Peckham : Report on Petroleum, p. 165. 

s 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.' ■ 

XLIV. 
The Examination of LrUbricating Oils. 

The generally accepted conditions of a good lubricant are as 
follows : 

ist. 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 : 

I St. 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. 

7th. Acidity. 

Sth. Maumen6'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-five cc.) 
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 ANAI^YSIS. 

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 
per cent, 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 Maumenfe'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 



\ 




Fig. 106. 

The liquid fatty acids are 



Fig. 105. 

a small glass tube, sealed at one end. 
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 



370 



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. 

Patty acids. Melting point. Congealing point. 

Cotton-seed oil 33.0^ C. 30.5° C. 

Olive *' 26.0 21.0 

Rape-seed *' 20.0 12.0 

Castor " 13.0 30.0 

Sesam^ ** 26.0 32.0 

Cocoanut '* 24.5 24.0 

Lard 44.0 39.0 

Tallow 45.0 42.0 

Wool-fat 42.0 40.0 

Palm oil 48.0 43.0 

Specific Gravity, 
In the chemical laboratory the hydrometers used are generally 
marked with the specific gravity direct. In the oil trade, how- 



THE EXAMINATION OF LUBRICATING OILS. 



371 



ever, and in general commercial practice the Baum6 
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 
60*" F.,the readings are too small. Suppose an oil reg- 
isters 28° Baumd at 72** F., we make use of the table, 
on p. 372, and find the corrected reading to be 27.2*" 
Baum^. 

To convert this into specific gravity the following 
table is used : 



10 
II 

12 

13 

14 
15 
16 

17 
18 

19 

20 

21 
22 



a" 
02 bo 



■3a 

lit 


M 


ll 


S.S 
CO bo 


ii 

III 


II 


23 


0.9150 


36 


0.8433 


49 


0.7821 


24 


0.9090 


37 


0.8383 


50 


0.7777 


25 


0.9032 


38 


0.8333 


51 


0.7734 


26 


0.8974 


39 


0.8284 


52 


0.7692 


27 


0.8917 


40 


0.8235 


53 


0.7650 


28 


0.8860 


41 


0.8187 


54 


0.7608 


29 


0.8805 


42 


0.8139 


55 


0.7567 


30 


0.8750 


43 


0.8092 


56 


0.7526 


31 


0.8695 


44 


0.8045 


57 


0.7486 


32 


0.8641 


45 


0.8000 


58 


0.7446 


33 


0.8588 


46 


0.7954 


59 


0.7407 


34 


0.8536 


47 


0.7909 


60 


0.7368 


35 


0.8484 


48 


0.7865 


70 


0.7000 



Tig. 109. 



1. 0000 
0.9929 

0.9859 

0.9790 

0.9722 

0.9655 

0.9589 

*5-9523 

0.9459 

0'9395 

0.9333 

0.9271 

0.9210 

and we find that 27.2'' Baum6 are equal to 0.8928 
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 1° Baum^ for every 
10** F. above 60** F., and add i** Baumfe for every 10° 
F. below 60** F. 



372 QUANTITATIVE ANALYSIS. 

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THE EXAMINATION OF LUBRICATING OILS. 373 

gM ^ W « CI « M r0c0C0r0e0'^^^'^^lOtOln^^0v0^0 r^t^ 

? • 



^ fcM M dKq^oq rs-s© "o-^copi w m o o crvopvo »o^« moq t>.^cf 



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374 QUANTITATIVE ANAI.YSIS. 

Thus, if the hydrometer, when placed in the oil, reads 26* 
Baumfe and the temperature of the oil 80® F., the correct reading 
will be 24** Baum6 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) 

I<et A — M=i C. (0.927 — 0.915 = 0.012) 
M — B = D, (0.915 — 0.890 = 0.025) 

Then ^ . ^^ = per cent, of A I — — ^ ) » 
C+D ^ ^0.037/ 

and 

C , „/O.OI2^ 



, = per cent, of B(— ) . 



C + n-''--- Vo.o37>' 

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 centSi are read on 
abscissa line 67.5 (or 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. iii) 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 I^UBRICATING OILS. 375 

urn 




: 1 ! II 


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""".r*"'^ ; 




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::::: : iC 




j~ — r " r ■ " 


, HTl^'' 


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^Hl--, ..., -L. 1 ,11.^'^ .f 


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■ ■ I 1 ■ I 




■*" T , + -1 


4 I J.- ^r^ I j ^ ' 4 


t , : i 




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80 90 100 




Fij^. III. 



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 OP LUBRICATING OILS. 



377 



Gay-Lussac, 4** C = 



100 



ioo + « 



= specific gravity. 



170 
Beck, 12.5° C. = ^-T- — = specific gravity. 

_ . o^ 136.8 .^ ' . 

Cartier, 12.5 C.= — — — j — = specific gravity. 
126.1 + ^ r & .7 

Baum6 hydrometer, at is'* C.= — ^—i — = sp.gr. 



Brix hydrometer, Fischer 
hydrometer at 15.6° C. 



400 
■ 1 — =sp. gr. 

400 + « ^ ^ 



n = degrees indicated upon the spindle. 

TABI.E 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 o-9i5 ** 

Lard oil 0.915 ** 

Tallow oil 0.903 " 

Menhaden oil 0.928 " 

Rape-seed oil 0.916 " 

I Rosin oil 0.980101.05 " 

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, Ghent, 
Ind,, IX, 297. 

*'On the Chemistry and Analytical Examination of Fixed 
Oils." By Alfred H. Allen, F.C.S., /. Soc. Chem, Ind., 2, 49- 



5-73. 



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 



378 



QUANTITATrVB ANALYSIS. 



■I ■mill 



ICX3 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- 
p 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 beV- 
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-parafi&n, of good quality, 

does not show any material 

^^' "^- difference in its consistency 

at 25** C. or io° C, but a radical change would be indicated at 

id'' 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 ANAI^YSIS. 

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 

XXXlardoil 3 

American sod oil r 

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 T2 

Extra bleached winter white menhaden oil 11 

Bank oil 4 

Straits oil 7 

Sea elephant oil 5 



THE EXAMINATION OF LUBRICATING OILS. 38 1 

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 Degrad 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. November i to April i. 

Tallow oil, S^' 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 caroil " '* ** " " '* ** '* 

Chicago, Burlington & Quincy Railroad Co. Black Engine 
oils : 

Summer oil must flow at 15^ C. and above. 
25° oil " " " i°C. " 

15" oil " " •* 9^0. ** 

Zero oil " " " 15^0. ** 

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,/, is the oil cooling chamber, in which is the glass 
receiver, adjusted to a rocking shaft, ^, to facilitate the introduc- 



382 



QUANTITATIVE ANALYSIS. 



tiou 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 filled 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. ii6. 



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, y, 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 OltS 



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. 117. 



Seconds at 
15* C. 



Seconds at ComparatiYe Comparative 



75' C. 



thickness 

with water 

at 15* C 

18.0 

21.6 

9.6 

203.0 

0.0 



thickness 
with water 
at 7.5' C. 

22.4 

31.5 
II.9 

377-0 
0.0 



Colza oil 162.0 222.0 

Olive oil 195.0 284.0 

Hemp-seed oil 87.0 107.0 

Castor oil 1830.0 339o.o 

Distilled water 9.0 9.0 

The Pennsylvania Railroad Co. viscosity tests are made as fol- 
lows: 

A 100 cc. pipette of the long bulb form is regraduated to hold 
just 100 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 
m 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 difi&cultto clean, and are not as convenient 
as the Engler or Redwood viscosimeters. 

Engler'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 ; a, d, ther- 
mometers ; ^ 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. 118. 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. 

Engler 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 i30seconds, 




Pig. 1x9. 

the ratio is determined by -^ = 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* 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^. lao. Pig. lai. 

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 filled with the oil which is taken for the 
standard, such as rape oil or lard oiK 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, /, /. 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. 

ly. Soc. Chem. Ind., 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 B^ 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, E, 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. 




Aa.BMk]r.(.C«.il T. 



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. Z> is a thermometer, and records the 
temperature of the water-bath. 




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, Z>, 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 ANAI^YSIS. 



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 




«B.»L««n«A,¥. 



feT. PAUL Rr. CO. 

GIBBS' VISCOSIMETER. 
Fiff. 124. 

dirt have become lodged in the coil. This materially interferes 
w^ith 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 OIW. 39 1 

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, (9, Pand 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 7" is one-sixteenth inch. 

The following table shows the result of viscosity tests upon 
various oils made with this instrument. 



392 



QUANTITATIVE ANAI^YSIS. 



VISCOSITIES OF VALVE OILS AND STOCKS. 



Gravity. 



Flash. 
F. 



Per cent 

mineral 

oil. 



Viscosities 



250* F. 300* F. 350* F. 400' F 



Nat. Refg Co., Loco. 

Cyl 

Nat. Refg Co., German 

Perfection valve oil . . . 

**(another) 

41 It << 

Vacuum valve oil 

C.,M. &St.P.valveoil 
Extra lard oil (average 

of 3 samples) 

St d Oil Co., No. I stock 
*< 2 " 

" 4 - 



26.8 
25.8 
26.0 
25.7 
25.9 
25.2 
26.4 



525° 
550 
510 
undet 
510 
535 
485 



27.0 

273 
27.8 
26.2 



520 
510 
490 
525 



75.7 
7.00 

54.7 

65.0 

undet. 



100 
100 
100 
100 



38 sec. 

43 
35 
34 



32 

33 



25 

46 

47 
46 



23 
32 
32 
30 
33 



26 
28 
25 
24 
23 
27 
23 

21 
26 
26 
25 
27 



21 
23 



20 
22 
22 

21 
23 



Viscosities expressed in seconds for 50 cc. 



VISCOSITIES OF CAR AND ENGINE OIL. 





Gravity. 


Flash. 
F. 


Per cent 

mineral 

oil. 


Viscosities. 




75- F. 


no' F. 


150* F. 


National Refg Co., car oil. . . 
Relief Oil Works, " ... 

(^fll^nfl CAT oil ..< 


30.8 
304 
28.5 
28.2 
28.7 
27.8 

265 
30.1 
26.5 


200^ 

200 

160 

165 

155 

Ts 

260 
210 
385 


100 
100 

90 

90 

90 

90 

91.9 

91.0 
100 
100 


223 

163 
102 

83 
102 

88 
234 
257 
130 
740 


68 
61 
•54 
50 
54 
52 

113 


41 


<< «i ti 


34 

37 
54 


<( << (1 


14 II II 


II II II 


11 II II 


Relief Oil Works, engine oil. 
National Refg Co., " 


Viscosities expressed 


in seco 


nds for 50 cc. 








THE EXAMINATION OF LUBRICATING OILS. 



393 



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. ) 

,»a5^»W404SSOMe0 68TOT5 80 95 9 88 10 




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 ^hnf ^^ ^° 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. Lew', 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. : Firsts 
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 

1 Ding. poly. J. ^ 1891, 2S0. 




AM.dC.MOTieO.N.Y. 



Pig. 126. 



396 QUANTITATIVE ANALYSIS. 

at the moment its volume is read in the receiving flask, a notable 
diflFerence 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 twentj^-five cc. of the oil have been delivered 
from-^ 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 ^. 

None of the oil in tube from e to af passes into A during the 
delivery of the twenty-five cc. through g, since the tube/^ d is 
only partially emptied of its oil, the level of the oil in A after 
the deliveryof the twenty-five cc. still remaining above the point 
where the tube /enters A, 

Second, — Oftentimes the samples of oil sent for examination 
do not exceed loo cc. in bulk, an amount entirely too small if 
other tests are to be included. 

Man}'^ forms of viscosimeters require loo cc. of oil for the vis- 
cosity test, and not a few fifty cc. 

I have found twenty-five cc. to be ample, provided the aperture 
at g is small enough to prevent a too rapid delivery of the oil 
and consequently render close readings and comparisons diflScult. 
By making this orifice three sixty-fourths inch, sufl5cient time is 
secured to obtain accurate results. 

If the operator prefers not to use the graduated tube/^af to 
measure the oil, a receiving flask, properly marked, can be 
placed under ^, as in other forms of viscosimeters. 

The plan suggested by Schublerthat viscosities should be com- 
parable with water is the only proper one and in the following 
determinations of viscosity the comparison is included : 



THE EXAMINATION OF LUBRICATING OILS. 



397 



Seconds 


Seconds 


atdo'Cs 


at 50* C a 


68* F. 


I2a' F. 



Seconds 
at loo' C. 
=ar2'F. 



Seconds 
at 150* C. 
SB 30a' F. 



Seconds 
at 200* C. 
=392' F. 



Water 

Prime lard oil 

No. I ** " 

XXX *' *• 

Prime neat*s foot oil 

White " ** »• 

Pure hoof oil 

Oleo oil 

Horse oil 

Gelatine oil 

Rosin oil, ist run 

** 2d " 

•* 3d " 

Dog-fish oil (Pacific) 

Right whale oil ( Pacific) • . • 

Natural bow head oil (Pacific) 

Bleached whale oil 

Natural winter ) 

Sperm oil (Pacific) j 

Bleached sperm oil (Pacific)* 

Natural spring sperm oil • • • • 

Bleached spring sperm oil • - • 

Natural winter whale oil (Atlan- 
tic) 

Bleached winter whale oil (At- 
lantic) 

Extra bleached winter whale oil 
(Atlantic) 

Natural spring whale oil (Atlan- 
tic) 

Bleached springj whale oil •• 

Porpoise head oil 

Sea elephant oil 

Bank oil 

Prime crude menhaden oil. . • 

Brown strained ** ** ... 

Light ** " "... 

Natural winter menhaden oil 

Bleached " " 

Extra bleached winter white 
menhaden oil 

Castor oil 

"White seal** castor blown oil. 

Prime quality summer white 
cotton-seed oil 

Prime quality winter white 
cotton-seed oil 

Herring oil (Pacific) 

Rape oil 

Olive oil 



51 
55 
70 

73 
60 

70 

72 
300 

64 
solid. 



70 
75 
50 
58 
47 
52 

33 
29 
30 
32 

53 

43 

55 

57 
52 

34 
51 
39 
39 
42 
40 
41 
34 

39 
730 



51 
56 

63 



29 
30 

31 
28 
28 
30 
30 

solid. 

23 
22 
26 
27 
27 
27 
22 

22 
22 
22 

26 

26 



26 
26 

36 
30 
24 
24 
24 

25 

24 
24 

.11 

26 

26 

26 

24 



18 
18 
18 
19 
19 
17 

solid. 
19 
15 
15 

]l 

18 
18 

16 

16 

16 

17 

18 

18 

18 
18 
16 
17 
17 
17 
18 

17 
17 
17 

17 



18 
18 
20 
18 



16 
16 
16 
16 
16 
16 
16 
16 
360 
^5 
14 
14 
16 

II 

16 
15 

'5 
16 

15 
16 



15 
16 

16 
16 

'5 
16 
16 
16 
16 
16 
16 
16 

16 

17 
20 

15 

!l 

16 
16 



35 



15 



15 



15 
20 



15 
15 



A chart of a few of the above oils is shown on the following page. 



398 



QUANTITATIVE ANALYSIS. 



Viscosity Tests. 

a— Prime lard oil. f --Castor oil. 

*— Prime neat's foot oil. >— '* White seal" castor-blown oil. 

<f— Rosin oil (second run). m^Prime qual. summer white cotton-seed oil . 

#— Bleached whale oil (Pacific). »— Rape oil. 

/— Spe rm oil ( Pacific) . o— Olive oil . 

^—Natural winter whale oil (Atlantic), p—** Degras" oil. 
A— Porpoise head oil. r— Rosin oil (first run). 

x--Oelatine oil. 




*9j9pBJpa93 999Jj99a 



THE EXAMINATION OF LUBRICATING OILS. 399 

An examination of these tables and curves brings prominently 
forward the following facts : 

That at high temperatures the variation in the viscosity of sim- 
ple oils is very slight. 

That ** blown** oils, and ** gelatine** oils, which are manufac- 
tured especially to give ** body** to compounded oils fail in their 
• purpose at high temperatures. 

This is shown especially in Fig. 127, by the curves of the com- 
pounded oil, for instance, which at 20^ C. remains solid, like- 
wise at 50*" C. and 100** C, but at 150** C. (302'' F.) it indicates a 
viscosity of 360 seconds, and at 200 C, a viscosity of 35 seconds. 

This ** gelatine** oil is generally a compound of aluminum 
oleate, lard and petroleum. 

Castor oil shows the highest variation of any of the simple 
oils, while sperm oil shows the least, and it is probably this 
property of the latter that has given it the reputation as the 
standard oil in lubrication. 

Of the animal oils, lard oil ranks first in lubrication, followed 
in order by neat's foot, horse oil and tallow oil. 

Generally speaking, the marine oils are the better lubricants, 
with the exception that acidity often rapidly forms in them, and 
so renders them valueless for the lubrication of many forms of 
machinery. The order of their value would be sperm oil, por- 
poise head oil, bleached menhaden oil, whale oil, dog fish oil, 
sea elephant oil and herring oil. Of the vegetable oils, rape oil 
is the recognized standard in lubrication. Its use for this pur- 
pose is very limited in this country, though in Germany and 
Russia large amounts are annually consumed. 

Olive oil, while a good lubricant, is too high in price and its 
place has been taken in later years by refined cotton-seed oil. 
This latter oil, while seldom used alone in lubrication, is added 
to lard oil in proportions varying from twenty to fifty per cent., 
producing a mixture that lubricates nearly as well as pure lard 
oil, though acidity more rapidly develops than in lard oil alone. 
Castor oil is largely added to other oils to give high viscosity at 
ordinary temperatures, and to produce ** body,** which it loses at 
high temperatures. Its use for this purpose still continues in Eng- 
land, while in this countr>' its application is limited. 



400 



QUANTITATIVE ANALYSIS. 



The so-called ** seal castors'' and ** blown oils*' are made from 
cotton-seed oil, and are used in place of ** gelatine" oil to pro- 
duce high viscosity, at a much lower cost than ** gelatine" oil. 

'*The Doolittle torsion viscosimeter"* recently introduced, 
(1893) is used in the railroad laboratories of the Philadelphia 
and Reading Railroad Co. It is briefly described as follows : 

A steel wife is suspended from a firm sup- 
port and fastened to a stem which passes 
through a graduated horizontal disk, thus 
measuring accurately the torsion of the 
wire. The disk is adjusted so that the 
index point reads exactly zero, thus 
showing that there is no torsion in the 
wire. 

A cylinder two inches long by one and a 
half inches in diameter, having a slender 
stem by which to suspend it, is then im- 
mersed in the oil and fastened by a thumb- 
screw on the lower part of the stem to the 
disk. The oil is surrounded by a bath 
of water or paraffin wax according to the 
temperature at which it is desired to take 
the viscosity. This temperature being 
obtained while the disk is resting on its 
supports, the wire is twisted 360** by means 
of the knob at the top. The disk being 
released, the cylinder rotates in the oil by 
: virtue of the torsion of the wire. 

The action now observed is identical with 
that of the pendulum. 
If there was no resistance to be overcome, the disk would re- 
volve back to zero, and the momentum thus acquired would carry 
it to 360'' in the opposite direction. What we find is that the 
resistance of the oil to the rotation of the cylinder causes the 
revolution to fall short of 360", and that the greater the viscosity 
of the oil the greater will be the resistance and hence the retarda- 

IJ. Am. Chem. Soc., 15, 173. 




THE EXAMINATION OF LUBRICATING OILS. 4OI 

tion. We find this retardation to be a very delicate measure of 
the viscosity of an oil. 

There are c number of ways in which this viscosity may be 
expressed, but the simplest is found to be directly in the 
number of degrees of retardation between the first and second 
complete arcs covered by the pendulum. For example, suppose 
we twist the wire 360® and release the disk so that rotation 
begins. In order to obtain an absolute reading to start from, 
which shall be independent of any slight error in adjustment, 
we ignore the fact that we have started from 360°, and take as 
our first reading the end of the first swing. Suppose our read- 
ings are as follows : 

Right, 350 ; left, 338 ; right, 328, and keeping in mind the 
vibrations of the simple pendulum we will see at once that we 
have read two complete arcs whose difference is 22** computed as 

follows : 

1st arc, Right 350° + Left 338° = 688° 
2d arc, Left 338° + Right 328° = 666° 

22° retardation 
In order to secure freedom from error we take two tests — one 
by rotating the wire to the right, and the second to the left. If 
the instrument is in exact adjustment these two results will be 
the same, but if it is slightly out, the mean of the two readings 
will be the correct reading. 

It will also be noticed that if the exact retardation due to the 
oil alone is to be obtained we must subtract the factor for the 
resistance due to the air and the wire itself. These are readily 
obtained by allowing the cylinder to rotate in the air and deter- 
mining the retardation exactly as we have done above. This 
factor remains constant for each instrument and is simply de- 
ducted from all results obtained. 

Iodine Absorption, 
The determination of the iodine absorption of an oil is prob- 
ably the most important chemical test for recognition quantita- 
tively in a mixture of animal or vegetable with mineral oils. 
Introduced by Hubl' it has since maintained this position, 

^ Ding, poly, J. ^ 453, 281. 



402 QUANTITATIVE ANALYSIS. 

though Other chemists have introduced the bromine absorption 
and others of similar character. They have not been adopted 
with the confidence of the iodine process. 

Warren' draws attention to the fact that Chateau in his 
Essais PersonnelUsy p. 70, used the iodine absorption in a manner 
similar to Hubl many years previously. 

In a mixture of two fatty oils with a mineral oil, the best re- 
sults are obtained by saponifying and separating the fatty acids 
from the mineral oil. The iodine absorption of the mixed fatty 
acids is then taken, and where the nature of them has already 
been shown by color tests, etc., their proportion can be indicated 
by the following formula : 

100 (I—n) 

x= ^ -, 

m — n 

Where x = the percentage of one fat, 

y= '' ** ** the other, 

/= iodine degree of mixture, 

w= ** ** **fat;r; 

n=z ** ** ** *' y. 

The method is as follows :* 

Twenty-five grams of iodine and thirty grams of mercuric 

chloride are each dissolved in 500 cc. of ninety-five per cent. 

alcohol, uniting the two solutions, and allowing to stand several 

hours before use. 

It is then standardized by tenth normal thiosulphate solution. 

The process of the determination of the iodine absorption of an 

oil is as follows : One-tenth to five-tenths gram of the fat or oil 

is dissolved in ten cc. of purest chloroform in a well stoppered 

flask, and twenty cc. of the iodine solution added. The amount 

must be finally regulated so that after not less than two hours 

digestion the mixture possesses a dark brown tint ; under any 

circumstances it is necessary to have a considerable excess of 

iodine (at least double the amount absorbed ought to be present) , 

and the digestion should be from six to eight hours. Some 

potassium iodide solution is then added, and the whole diluted 

with 150 cc. of water, and tenth normal thiosulphate delivered 

1 Ckem. News, a6. i88. 

3 Sutton : Volumetric Analysis, 343. 



THE EXAMINATION OF LUBRICATING OILS. 403 

in till the color is nearly discharged. Starch is then added, and 
the titration finished in the usual way. 

If more than two fatty oils are present in a mixture with 
mineral oil, the method of Warren' can be used. 

The following determinations of the iodine absorption made in 
my laboratory are indicative of the variations of the absorption 
by the different oils : 

Prime lard oil 76.4 77.2 

No.i ** " 69.8 69.9 

XXX ** " 65.1 65.6 

Oleo oil $1.6 $1.6 

Prime neat's foot oil 80.1 82.0 

Horse oil 82.3 82.5 

Natural bow-head whale oil 130.5 131. i 

" winter '* " 121. i 126.0 

Extra bleached winter white oil 124.9 126. i 

Bleached spring *' *' 126.1 126.2 

Crude 'sperm oil 82.3 82.3 

Prime quality winter white cotton-seed oil . . 114.2 114.9 

'* ** 'summer** ** ** ** .. 110.2 110.6 

winter yellow •* ** ** .. 115.9 118.6 

** ** summer *' ** ** *' .. 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 

I Oum. News, 63, 315 : /. Anal, Appl. Chem., 5. 315. 



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 surface of the oil once every minute beginning at lOo' F. 

Oils that flash below no** 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, Z?, 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 ofiBcially 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, £*, furnishes 
an induction spark that 
passes over the oil. Bat- 
teries for generating the 
current are situated un- 
der the firame, 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 




Pigr. 131. 



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 



4o6 



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. 13a. Pig. 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 OP LUBRICATING OII*S. 



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 




Fiff. 134. 



Figr 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. 



4o8 



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. They should be 




Fig. 136. Fig. 137. 

free from any of the lighter oils (naphtha, kerosene, 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' 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. xo days. 24 days. 

Linseed oil 0.3000 gram. 0.0050 gram. 

Olive oil 0.2200 *' 0.0062 ** 

Neat's foot oil 0.1100 *• 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. 

I Analyst t 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 is"* to ais"* 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.)* 

Take two ounces of alcohol and warm tq about 100® F.; 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. 

Maumetu'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 

I Hydrometers and thermometers should be procured through Chas. A. Tagliabue» 
New York. 



THE EXAMINATION OP LUBRICATING OILS. 41I 

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. 

M^,= *» •• ** ** lard 

W^ = weight of mixture. 

/, = temperature of menhaden oil. 

/, = '* ** lard 

/, = '* ** 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 2*" C. 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 : 



412 



QUANTITATIVE ANALYSIS. 



Name of Observer. 



Maumene. 

•c. 



Schaedler. 

•c. 



Archbutt 

•c. 



Allen. 

•c. 



Stillman. 

•c. 



Lard oil 

Tallow oil 

Neat's foot oil 

Oleo oil 

Elain oil 

Sperm oil 

Whale oil 

Menhaden oil 

Doff-fish oil 

Cod liver oil - 

Crude cotton-seed oil. • - 

Rape oil 

Castor oil 

Olive oil 

Rosin oil 

Mineral lubricating oil< 

Earth nut 

Rosin oil 

Sea elephant 



40 

41-43 

45 



102-103 



58 
47 
42 



67 



50 



69.5 
48 

67 
28 



43 
37J 

51 

123-128 



70 

46 
41-45 



47-60 



41 



38i 
45-47 
126 

"3 
67-69 

65 
41-43 
18-22 

3-4 
22 



39-5 

39 

40 

37 
48 

128 

80 

no 

74 
60 

45 

42 

10 

3 

10 
65 



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. 

Prom 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* in which barium poly-sulphide 

1 Spon's BncyclopedU. 4. i473*i47S- 



THE EXAMINATION OF LUBRICATING OILS. 413 

zinc chloride, stannic chloride, phosphoric acid and mercuric 
nitrate, insolations, are used, while very interesting, seldom are 
of any advantage over the two tests noted above. Glassner's' 
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 
whole 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. 

y^ Ckem. Cenirbl., 187s, 57' 



414 



QUANTITATIVE ANALYSIS. 





Heidenreich's test. 


Massie's test 




Before sdrring. After stirring. 




T.O f/l oil •••• ■■■••• 


Yellow 


Brown 


Yellow 


Tallow oil 


Yellow. 


Orange. 


Colorless. 


Neat* s foot oil 


Yellowish. 


Red brown. 


Red. 


Oleo oil • 


Colorless 


Orange. 
Brown. 


Pink. 


Slain oil ••••••••> 


Light green (turn- 
ing to brown). 


Orange red. 






Sperm oil 


Brown with pur- 
ple streaks. 
Red violet. 


Reddish brown. 


Red. 


Whale oil 


Violet brown. 


Red. 


Menhaden oil..-* 


Red. 


Brown. 


Dark red. 


Doe-fish oil 

Cod liver oil 


Violet. 


Dark brown. 


Orange. 


Red violet. 


Dark brown. 


Orange red. 


Crude cotton-seed 


Brilliant red. 


Brown. 


Brown. 


Ref 'd cotton-seed . 


Reddish brown. 


Red. 


Orange red. 


H ori^ oil 


Yellow hrovrn 


Brown 


Orange. 
Orange. 
Yellow to 


Oo ctor oil • ••• 


Lgt. yel. to brown. 
Light green. 


Pale broijvti- 


Olive oil 


Greenish to light 
brown. 




greenish. 


Ro^iti oil ..••••••• 


Brown 


Brown 


Orange. 
Reddish. 


Earth nut oil 


Yellow to orange. 


Greenish. 



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* 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' or the process of E. 
Valenta* 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 jtself 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., 34, 347. 

3 Mittheil der Konig. tech. Versuchsanstalten, /^po, 19. 

* Ztschr. anal. Chem*, 35, 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, 100 cc. of an 
alcoholic solution of potash (eighty grams potassium hydroxide to one 
liter alcohol of ninety-eight X)er 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 : 

^=100 (/— «) 
x^^tn — n. 



a. 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^ 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. 

1 Benedikt : Oils, Fats and Waxes, 355. 



4l6 QUANTITATIVE ANAI^YSIS. 

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, Pats 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 OP 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 coefiBi- 
cient of friction. It is equivalent to the tangent of the an^le 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 (p^ and the coefiBicient 

br/. 

/=tan^. (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. Heck el thus describes the Thurston and Henderson- 
Westhoven machines : The primary idea of determining dura- 





Figr. 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- 



4l8 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 puUy, 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 ££. 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, Oy indicates on the scale, Py 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, 
£E, 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, FF, 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, N, is fixed to show 
the degree of heat developed by the friction, and the revolution 
counter, /, actuated through the endless screw, g, records the 
revolutions of the journal, A. The column, A^, through its two 
arms, Z, 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. HI. 

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, 
00, 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, /, in motion which indicates on 
the scale, «, the approximate rapidly of the wheel-rims in kilo- 




Fig. 142. 

Extreme lengrth 7i 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 QUANTITATIVK ANAI^YSIS. 

wheels whereby the rattling of the wheels upon the car track is 
imitated. 

In making atrial, 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 Riehl6, (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, which 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 OF I^UBRICATING 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. 



Baltimorb and Ohio Railroad. 



Subject. 



.189 



Engineer of Tests, 
Dear Sir ; Below please find report from locomotives inspected this day. 



1 


i 

a 
8 

H 


jj 


U 


s 


5 


i 


1 

•c 
< 


i 


a 
2 


II 

n 


ii 


Kind of oil 
used. 


Miles run 
per pint of 
oil allowed 


Miles run 

per pint of 

oil used. 


Number of 

drops per 

minute. 


a 


1 


i 

§ 


•1 
1 


1 
I 





1 


1 





































'Inspector, 



Bai«timorb and Ohio Raii«road. Oppicb op Sdpbrintbnd- 

BNT OP MonVB POWBR. 
(Specifications for Compound Oils.) 

DBTAII« SPBCIPICATIONS. 

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° P. ; 
from May i to October i the flashing point must be above 250° P. 

2. Prom October i to May i it must have a cold test below 15^ P. 

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-flve per cent, of saponiflable ani- 
mal oil. 

3. It must show not more than six per cent, of fat acid or its equivalent. 

4. It must not 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. 



To. 



Chicago, Burwngton and Quincy Railroad Co. Chem- 
ical Laboratory. 

Aurora, III., 18.. 

Supt. M . P. : 

Dear Sir : I have made an examination of sample of above oil, and 
have obtained the following results : 

Flashing point ^F. Ash %. Tar %. 

Burning * ' ^F. Cold test at ^F. 

Specific gravity °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. 



Amount used.« oz. 



Highest reading. 
Lowest " 
Range of " 
Average 



Time run in minutes 

Total revolutions 

Revolutions per minute 

Speed, miles per hour 

Pressure, total lbs 

'* lbs. per sq. inch 

Coefficient of friction 

Lubricating value, with Extra Lard 

Oil as 100 



ist trial. 



Temp. 



Arc. 



2d trial. 



Temp. Arc. 



Temp. 



3d trial. 



Average. 



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 100^ 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.- 

«« 2C® ** ** *• 7xy^ " " 

— 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 //»/, 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 

hurning point not lower than 575^ F., and a specific gravity between 25" 

and 28^ B. Must not undergo a loss greater than one-half (i) 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 g^reenish 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, TVans, 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. Atn, Soc, 
Mech, Eng,, 7. 437- 

" Cost of Lubricating Car Journals.** By L. A. Randolph, Trans. Am. 
Soc, Mech. Eng.j 10, 126-35. 

"Special Experiments with Lubricants.*' By J. E. Denton, Trans, 
Am, Soc, Mech. Eng.^ xa, 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 Carjoumal^ 
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. 

XI.V. 
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. 

/. 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 ILI^UMINATION. 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^ P. 

2 — It must have a fire test not below 150° P. 

3 — It must have a cloud test not above 0° P. ,. 

4 — It must be'a ** water white" in color. 

5— Its gravity must be between 44^ and 48° B. at 60° P. 
300* Fire Test Oil. 
This oil must conform to the following requirements : 

I — It must have a flash test above 250° P. 

2— It must have a fire test not below 300"^ P. 

3 — It must have a cloud test not above 32° P. 

4 — It must be a *' standard white" in color. 

5— Its gravity must be between 38° and 42° B. at 60° P. 

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 iio° 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 iio° 
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, /?, 
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 QUANTITATIVB 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^. 

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 /?, 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 beingr 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. 43 1 

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 lipon 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,* 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 II*I*UMINATION. 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 as 100.00 
»' =s2. *' = 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, arid 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 ANAI.YSIS. 

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 ail 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-pving 
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 
foUowed'ior 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 ofl the superfluous liquid. 
Second, the effect of variation of temperature in the amount of 
vapor absorbed by the air current. As above stat^id, 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 



43^ 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 fprmer 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 spee'd 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 



43^ QUANTITATIVE ANALYSIS. 

duplicate of stationary electric-lighting plants. The engine is a 
15 horse-power Westinghouse automatic, the dynamo a 150 light 
Hdison 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 £'«^i«tf^n«^ (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. 



OIM USED FOR II.LUMINATION. 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 traflSc 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 gasworks 
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 railw^ay 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. 



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XI.VI. 

The Analysis of Lrubricating 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-liabilit3'^ 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 animal 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') 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 as specific gravity of paraffin oil 
;r = 20 per per cent, or \ 
^ s: 80 per cent, or | 
Then i^r-h 1^=0.912 
0.183 -ht J' =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 
r^pe-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, tx) 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 : 

Spbcific Gravity. 

Cotton-seed oil 0.920 to 0.925 

Rape-seed oil o-9i5 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 

Heidbnreich's Test. 

Before stirrinff. After stirring. 

Cotton-seed oil Faint reddish brown Brown. 

Rape-seed oil Yellow brown Brown. 

Massib'sTbst. 

Cotton-seed oil Orange red. 

Rape-seed oil Orange. 

Iodine Absorption. 

Cotton-seed oil 104 to 114 

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 



ANAI.YSIS 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 2d* 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 : 

Wi = proportion of rape-seed oil. 
w^ ^ proportion of cotton-seed oil. 
ze^g^ weight of mixture (20 per cent.) 

/i = temperature of melting point of fatty acids of rape-seed oil. 

/, = temperature of melting point of fatty acids of cotton-seed oil. 

t^ = temperature of melting point of mixed fatty acids. 

• h — h 

Inserting the value : 

2ef . ^ 20 ^3 3Q :_ 14 p^j. cent. 
20—30 

ze/, = 20 ?3lZ?2^ 6 per cent. 
30—20 

Or, 

Paraffin oil 80 per cent. 

Rape-seed oil 14 per cent. 

Cotton-seed oil 6 per cent. 

Total 100 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. 

XLVII. 

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, in the latter, oleate of lime, 
carbonate of lime, and silica are often present in addition to the 
former. 

The following analj'sis of a sample from a locomotive cylinder 

would indicate a simple deposit. 

Moisture 2.28 per cent. 

/^•i 1 ui • ^u /Animal 10.54 

Oils soluble in ether I ^j^^^^^ ^^^^ .. 

Hydrocarbons insoluble in ether 47«97 ** 

Fixed carbon 23.73 ** 

FeO 2.83 

Undetermined 1.42 ** 

Total 100.00 ** 

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. 

^., , ,, . , f Animal 8.15 ** 

Oils soluble in ether { Mj^eral 7.86 " 

Soap 2,10 •* 

Hydrocarbons insoluble in ether i .67 " 

Fixed carbon 2.71 ** 

Oxides of Iron and aluminum 6.81 '* 

SiO, 3.6s 

CaCQ, ; 43.22 

MgCO, 10.17 

Undetermined 0.44 ** 

Total : 100.00 ** 

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 



ANAI.YSIS OF CYLINDER DEPOSITS. 447 

temperature. Oftentimes the statement has been made to me, 
when the deposit was given for analysis, '*A11 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. 

^., , . , . , f Castor oil 26.19 

Oils soluble in ether | ^.^^^^^ ^^ ^^ 

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. ii5. 



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 " 

Oil8 soluble in ether \ ^jneral 19.60 " 

Soap traces 

Fixed carbon 10.90 ** 

FeO 14.01 ** 

Fe 27.85 

PbO 0.82 

CuO 1.07 ** 

Undetermined 0.71 ** 

Total 100.00 ** 

The evolution of hydrogen by hydrochloric acid, from the de- 
posit, after all the oils and fatty 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,* 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. 



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ANAI.YSIS OF CYLINDER DEPOSITS. 45 1 

Where qualitative analysis has shown the deposit to be a sim- 
ple one, the analysis can be stated as follows : 

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Fe 

Totel 

For a complex deposit, the following form can be used : 

Moisture per cent. 

Oils soluble in ether{An^^alj;;;- •••;••• 3^ ^ 

Soap ** 

Hydrocarbons insoluble in ether ••• • ... ** 

Fixed carbon ** 

Fe 

FeO 

CuO 

PbO 

ZnO 

CaO 

MgO 

CO, 

SO, 

SiO„ etc 

Total 

Where the lime and magnesia exist in amounts more than 
necessary to combine with^the carbon dioxide and sulphur tri- 
oxide present, the excess may have united with oleic acid to form 
soaps insoluble in water, but soluble in ether. 

In some instances the lead oxide and zinc oxide will be found 
only in the ether soap solution (3), as lead and zinc oleates, but 
in others, while they undoubtedly first existed as oleates, they 
had become decomposed, and the lead and zinc oxides woiildbe 
found in section (8) of the above scrheme. 

The following is an analysis of a cylinder deposit, ** Mica 
Grease'* having been used as a lubricant : 



452 QUANTITATIVE ANALYSIS. 

Moisture 11.23 P^i" cent. 

{Animal 9>05 ** 

Mineral 6.28 - 

Soap (CaO + MgO united with fatty acids) . . 43.90 ** 

Fixed carbon 6.33 " 

Oxides of iron and aluminum 6.59 ** 

CaO 3.15 

MgO 2.19 ** 

CO, 6.27 

Silica and mica 5.01 *' 

Totel 100.00 '* 

References .'-^''TYl^ Production of Paraffin and Paraffin Oils." By R.H. 

Brunton, C. E., Proc. Inst, Civ. Eng,, 66, 180-237. 
** The Russian Petroleum Industry." By Boverton Redwood, F.C.S., 

/. Soc. Chem, Ind,, 4* 70-82. 
** On the Testing of Lard for Cotton-seed Oil and Beef Stearin." By 

John Pattison, F.I.C.,/. Soc, Chem. Ind,, 8, 30-31. 
**The Manufacture of Paraffin Oil." By D. R. Stewart, F.C.S., 

Ibidy 8, 100- 1 10. 
** Wool-Fat, and the Processes of Obtaining It." By H. W. Langbeck, 

Ihid, 9> 35^359- 
"Some Experiments on Petroleum Solidification." By Samuel 

Rideal, F.I.C, Ibid, 10, 889. 
'•The Flashing Test for Petroleum." By F. A. Abel, F.R.S., Ibid^ 

I, 471-478. 
** Report* on Lighting Passenger Equipment." Master Carbuilders* 

Association for 1893. The Railway Car Journal, July, 1894. 



XLVIII. 
Paint Analysis, 

Paint is a liquid preparation having a two-fold use. Pri- 
marily it acts as a protecting coating against the action of the 
weather, and simultaneously as a decorative agent. 

The liquid is usually linseed oil and turpentine and the color- 
ing matter or body some solid pigment, such as finely ground 
red oxide of iron. 

1 This report includes a list of the principal railroads in the United States, and the 
methods used by each for passenger car illumination'; vf>., oil lamps, oil gas nnder 
pressure ('* Pintsch gas "}, or electric light (incandescent), with the conclusion that the 
" Pintsch gas " is rapidly being adopted in preference to oil illumination. 



PAINT ANALYSIS. 453 

It is essential in the production of a good paint that the oil 
used should be one that, upon drying on the surface applied, 
should become hard, lustrous, and somewhat elastic. 

Linseed oil excells all others in use for this purpose, and any 
sophistication thereto only deteriorates the quality. 

Four qualities are essential in a paint: i. Durability; 2. 
Working Qualities ; 3. Drying Properties; 4. Covering Power. 

The following list of pigments, with their chemical composi- 
tion stated, will give an idea of the great variety that can be 
used in paints for outside work. The list would be largely in- 
creased were other pigments included that are used for interior 
decorative work only. 

Red Pigments, — Indian red, Tuscan red (Fe,0,), vermilion 
(HgS), red lead (Pb,OJ, antimony vermilion (Sb,S,). Iron 
oxide, Indian red, and Tuscan red can be analyzed by Scheme 
XIII, p. 29. 

Brown Pigments. — Umbers (Fe,0,, MnO,, etc.)i Van Dyke 
brown, (Fe,0„ carbon), manganese brown (Mn.OJ and sepia. 
The composition of sepia is as follows : 

Melanin 78.00 per cent. 

CaCOj 10.40 

MgCO, 700 

Alkaline sulphates 2.16 ** 

Organic mucus 1.84 ** 

99.40 

White Pigments.— VJhite: lead (2PbC0..PbH,0,), lead sul- 
phate (PbSOJ, zinc white (ZnO), sulphide of zinc, white (ZnS), 
** lithophone." Also the following, added oftentimes as fillers : 
barytes (BaSOJ, **blanc Fixe** (artificial barytes), gypsum 
(CaSOJ, strontium white (SrSOJ, whiting (CaCO,), China 
clay (kaolin), and magnesite (MgCOJ. 

Yellow and Orange Pigments, — Chrome yellow (2PbCrOJ, 
Chinese yellow (PbO.PbCrOJ, zinc chrome (ZnCrOJ, realgar 
(As,S,). •• cadmium yellow** (CdS), **King*s yellow** (As,SJ, 
yellow ochre (Fe,0„ A1,0„ SiO„ etc.), and Siennas (Fe,0„ 
H.0, Mn,0,). 



454 QUANTITATIVE ANALYSIS 

Green Pigments, — Chrome green (Cr,0,), copper green (CuA), 
mineral green (malachite), cobalt green (ZnO, CoO, P,Oj, etc.), 
manganese green (BaO, MnO„ etc. )i emerald green ("Paris 
green/* 7Cu2C,H,0,. 3CuAs,0^) and Brunswick green (com- 
pounded of barytes, chrome yellow, Prussian blue, etc.). 

Black Pigments. — Lampblack (carbon), bone-black (carbon 
and Ca,HPO^), vegetable black, Frankfort black, coal-tar black, 
asphaltum black, and graphite black (C).^ 

Blue Pigments. --HlXxBrn^xine^ (SiO„ A1,0„ Na,0, S), Prus- 
sian blue, Chinese blue, or Brunswick blue, (Fe.C,^N,g), cobalt 
blue or smalts (A1,0,, CoO), Bremen blue (CuH,OJ, and cop- 
per blue (CuO, CO,, H,0). 

The various colored lakes, carmines, aniline lakes, etc., have 
but a limited application in Engineering Chemistry. Their 
methods of manufacture and assay can be advantageously 
studied by reference to **Painters' Colors, Oils, and Varnishes," 
by George H. Hurst, F.C.S., London, 1892, pp. 249-282. 

The analysis of a white paint, ground in oil, as shown in the 
Scheme on page 455, will indicate the method of procedure in 
analyses of this character. Where qualitative analysis has 
shown the presence of a few constituents only, the Scheme can be 
correspondingly modified. 

^ The American Eng^tneer and Railroad Journal, Nov. 1896, p. 315, states: "Graphite 
mixed with an oil is chemically inert and iu drying forms a coat that adheres firmly to 
the metal surface. Its resistance to the action of acids and alkalies has been proven by 
numerous tests much more severe than the conditions of service, and its resistance to 
the penetrations of moisture have been equally satisfactory. Heat does not cause it to 
blister, and we are informed that steel chimneys painted with it have been heated to 
redness withont decolorizing: the paint The paint has been used with success upon the 
hulls and decks of steel steamers, and there seem to be no conditions of service which 
it does not successfully meet." 









[.» Eh?|t 






tin ' — 













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456 QUANTITA.TIVE ANALYSIS. 

Analysis of White Lead Paints.^ 

(Dry, not ground in oil.) 

I. 2. 3- 4- 5. 6. 

PbO 86.35 85.93 83.77 84-42 86.5 86.24 

CO, 10.44 11-89 15-06 14.45 11.3 11-68 

H,0 2.95 2.01 i.oi 1.36 2.2 1.61 

Total 99.74 99.83 99.84 100.23 100.0 99.53 

from which the composition of the white leads can be calculated 

to be : 

1. i. 3. 4. 5. 6. 

PbCO, 63.35 72.15 91.21 87.42 68.36 70.87 

PbHjO, .... 36.14 27.68 8.21 12.33 31.64 28.66 
Moisture •• 0.25 .••• 0.42 0.48 •.•• .*.• 

Total.... 99.74 99.83 99.84 100.23 100.00 99.53 

No. I. English make. Made by Dutch process; of very good quality. 

2Jq 2 " *' *' " *' *' *' " " " 

No. 3. Krems white. Made by precipitation with carbon dioxide. It is 
deficient in body, although of good color. 

No. 4. German make. Precipitated by carbon dioxide ; of good color, 
but deficient in body. 

No. 5. German make. Made by Dutch process ; a good white. 

No. 6. German make. Made by precipitation with carbon dioxide ; 
quality fair. 

Lead white, ground in oil, is a common form in the market. 
It usually contains about eight per cent, of raw linseed oil, and 
has an extended use among painters, as it readily mixes with 
additional oil and turpentine to form liquid paint. 

The brown pigments, composed principally of oxides of iron 
and manganese, can be analyzed by Scheme XIII, p. 29 ; the 
yellows and greens containing chromium require a special pro- 
cess, as follows : 

1 Painters' Colors. Oils and Varnishes. By G. H. Hurst, P.C.S., p. 301 





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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, 2PbC0,+PbH,0,. 

Analysis of Red Chromate 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 : aPbO.CrOa or 
PbCrO* + PbO. 



O 

or- 




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B St 



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460 QUANTITATIVE ANAI.YSIS. 

Chrome green, in which the coloring matter is Cr,0„ 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 : 

Pennsyi^vania Raii«road Company. Motivb Powbr Dbpartmbnt. 
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 (PbCr04pbO), 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 y Altoona^Pa,, Feb, 18, i8gi. 

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. 46 1 

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 : 

Pennsyi^vania 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 x>er 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. 

Altoonay 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 painting the structure 
of the elevated railroads in New York City is given :' 

Boiled linseed oil 9 parts. 

Red oxide of iron finely ground ^\ " 

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.K., Trans. Am. Soc. Civil Eng., 10, 130. 



PAINT ANALYSIS. 463 

White Lead Paint. Olive Color. 
147.42 kilograms white lead. 
79.38 ** ** lime (CaSOJ. 

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.* 

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.' 

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 Enirineers, 15, 429. 
^ Am. Eng. and R. R. Journal, 65, 185. 



464 QUANTITATIVE ANAI^YSIS. 

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, 

Bltu Pigments, Ultramarine beinga silicate, can be analyzed 

by Scheme XIV, page 37. 

Composition of Ui^tramarinb. 

SiO, 49.68 per cent. 

AljOg 23.00 

S 9-23 " 

SO, 2.46 

Na,0 12.50 ** 

H,0 3>i3 " 

Total loooo ** 

Composition of Commerciai, Prussian Bi«ub. 

AljOj 2.45 percent. 

Fe,Oj, 3-31 

CaS044-SiO, 89.86 

CN + S 4- II 

H,0 0.27 

Total 100.00 *• 

Composition of Smalts. 

SiO, 56-4 per cent. 

AlA 3-5 " 

FeA 41 ** 

CoO 16.0 •* 

CaO 1-6 

K:,0 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.' 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 absorptionof 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. E. 
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. I/inton, / Am, Chem, 
Soc, 16, 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, 7^95, 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 FarbstofEen." 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. 

Pyromctry. 

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 :* 

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 i;Ooo° F. 

2. Contraction of clay, as the Wedgewood 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 Nrws, 34. 32a (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. 

ID. 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 Le 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 andNoel'sop- 
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 /<7ttr. Iron atid Steel Inst,, 

i893» P- 340. 

Wiborgh's air pyrometer is fully described in Trans. Am, Inst, 
Mining Eng„ 21, p. 592. 

Hobson's hot-blast pyrometer is largely used for measuring 




Fijf. 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** P., without 
danger of injury. 

Bristol's recording thermometer gives a continuous graphical 
record of temperatures up to 600"* P. 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° P., 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 Pig. 148. 

The calorimeter proper g, is surrounded by the containing 
vessel m, of sheet lead ; the space between^ and m is filled with 



470 



QUANTITATIVE ANALYSIS. 



air but conduction at^ is reduced by a layer of paste-board. 
The cover d admits the thermometer /, 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 balf k is dropped through 
a, at the same instant ^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 5 the 




Fig. 148. 

specific heat of the metal, then the temperature of the heated 
chamber may be found from the following formula : 



= ^(^) + ^ 



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 a3 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 IVin 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 from 32** 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, and 
it increases 0.0003 ^o^ 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 ANAI^YSIS. 

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 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," 
i» 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 JSoc,^ 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. 
Le 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- 




Figr. 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 Nouei p)rrometric 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 



ber C\ creating suction in chamber C 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 
ifthe 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 ^, Fig. 152, communicate 




JA 



476 



QUANTITATIVE ANALYSIS. 




PYROMETRY. 



477 



respectively with the chambers C and C 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 .r4. 

This principle was very fully demonstrated previously by Prof. 
Barus, in U, S, GeoL Survey, BtUletin No. §4, 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 /y into a coil, located 
in chamber B (Fig. 153), thence 
through the second aperture, located 
in the coupler^, 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 -P -P'. 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. 



47^ 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 
Ey and dip into the liquid contained in the jar F, 

The tube / connects through the pipe d with the top of the 
regulator .r4, and shows the amount of suction, as at/. The 
tube /connects by the tube a at ^ 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 /. 

If the water column m 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 if/ until / comes to the exact mark. 

The aspirator D exhausts into the vessel -5, 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'' F., 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 «. 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, /, 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 415° ** 

Boiling-point of sulphur 448^ ** 

Melting-point of aluminum 625° ** 

Boiling-point of selenium 665° ** 

Melting-point of silver 945^ '* 

'* *• gold 1045^** 

*• " ** copper 1054°" 

" '• palladium 1500° *' 

•• " •' platinum i775° *' 

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 
demEinflussvon Wasserstoffund Kieselsaure, Widerstandsanderung von 
reinem Platin und Rhodium mit der Temperatur, Lufttherniometer- 
gefasse aus schwerschmelzbarer Masse.) 

** Sur un Thermom^tre a Z^ro Invariable." M. Iv. 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., 34, 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 lengrth. 

Gram = unit of mass. 

Second — unit of time. 

Dym = unit of force, equal to that force which acting 

on one gram for one second, produces a veloc- 
ity of one centimeter per second. 

£r^. = unit of work, equal to the work done by one 

dyne actiug 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. 



THB BI.KCTRICAI. UNITS. 48 1 

An ordinary sovolt 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. P., 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 \^^ part of the E. M. P. of a 
Clark standard cell at 15*^ C. 

A Daniel cell has an E. M. P. slightly greater than one volt. 

Quantity, — The Coulomfi 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. 
Por ordinary use, the one-millionth part, or micro-farad, is em- 
ployed as the unit. 

Work, — Th^JotUe 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*^0 

Power, — The Watt is the power expended by one ampire 
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. 

Por 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. 

tbousacd 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-amp^res. 

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. 

[ International unit = i. 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 anj'^ part of a circuit, not containing a 
source of E, M, /^, 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, Amn^es - ^^^^ 

Amperes -Qj^^^. 

Joule's Law. — The heat developed in any conductor is 
proportional; 

I St, 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 

C/=o.24X ORt, 
or in units 

Calories = 0.24 (Amperes)* 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 Equfvalents. 

Grams per 
coulomb. 

Hydrogen 0.000010334 

Gold 0.0006791 

Silver 0.0011180 

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 eflSciency 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 (z) Horse-Power as 
In Foot-Pounds. 33,000 (log. 4.518514) foot-pounds per minute. 
550 (log. 2.740363) foot-pouuds per second. 
1,980,000 (log. 6.296665) foot-pouuds per hour. 



484 



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. r.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 8a 

pounds pressure (95 pounds absolute). 
2.2104 (log. 0.344441) pounds steam at 100 pounds 
pressure (115 pounds absolute). 
.002933 (log. 3.467312) pounds carbon consumed per 
minute, or 0.176 (i. 24551) pounds carbon 
per hour. 
.1823 (log. 1.260787) pounds ordinary coal per hour. 
.1169 (log. 7.067815) pounds ^ 0.0157 gftls. 

(log. 2.19590) ordinary petroleum per hour. 
.1276 (log. 7. 1 05 781) 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 (z) Poot-Pound per Second as 

.001818 (log. 3.259594) horse power. 
1.3565 (log. 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 ( 1 15 pounds absolute; per hour. 
One Poot-Pound per Minute ss 

.0000303 (log. 5.481443) H. P. 
.0226 (log. 7.354108) watts. 
.0833 (log. 2.920820) candles. 
•07733 (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. i. 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, 71 U, to Workt 1.41 1 (log. 0.149500 horse power, or 
Light and 1,052.6 (log. 3.022263) watts, or 

Electricity, 3i88o (log. 3.588832) candle power. 

One B. T. U. per Minute = 

.023515 (log. 2.371345) H. P., or 

17-5453 (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. 2.915927) pounds ordinary good coal to 

make it from water at 62^ F., assuming 
no loss ; it contains 
1. 154.5 (log. 3062368) B. T. U., or 
895,892 (log. 5959315) 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. T.655565) H. P., or 
337.6 (log. 2.528304) watts, or 
1,244.5 (log. 3094893) candles. 



486 QUANTITATIVE ANALYSIS. 

One Pound of Steam. 
Steam to Work, At 8o p^uuds pressure (95 absolute) takes 

Light and -0793 (^<>S- 2.899328) pounds carbon, or 

Electricity, .0821 (log. 2.914343) pounds ordinary good coal to 

make it from water at 62^ P., 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 z 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- 19389s) candles. 
Fuels to B. T. U. 15 (log. i.i 76091) pounds water evaporated from 

and at 212° F. 
12.56 (log. 1.099000) pounds steam made from water 
at 62° P., to steam at 100 pounds pressure 
(115 pounds absolute). 
Steam work, 12.61 (log. 1. 10067) pounds steam made from water 

at 62° P. 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. 3 1 6053) pounds water evaporated from 
and at 212^ K. 
I7'325 (log. 1.238673) pounds water from 62° P. 
to steam at 100 pounds pressure (115 
pounds absolute). 
17.40 (log. 1.240050 pounds water at 625 P. to 80 
pounds pressure (95 pounds absolute). 

One Cubic Poot Ordinary Illuminating Gas per Hour ^ 

650 (log. 2.812913) B. T. U. per hour. 
504,400 (log. 5.702775) foot-pounds per hour. 



ENERGY EQUIVAI^ENTS. 



487 



Light to Work. 



B. T, U, 
Electricity^ 
Steam and 
Combustibles. 



Electricity 

to IVork. 

B. T. U, 
Steam, 

Light and 

Combustibles, 



•25475 (log. 7.406110) 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. T. 750585) pounds water at 62" F. to 
steam at 100 pounds pressure ( 1 15 pounds 
absolute). 
LIGHT. 
One Candle Power = 
.00036364 (log. 4.560672) H. P. 
.2713 (log. 1.433411) watts. 

12 (log. 1.079181; foot-pounds per minute. 
720 (log. 2.857332) foot-pounds per hour. 
.015464 (log. 2.189319) B. T. U. per minute. 
.92783 (log. "1.967470) B. T. U. per hour. 
.0008037 (log. 4.905102) pounds steam per hour at 100 
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. T.6512) grains carbon per hour. 
.0000661 (log. 5.820201 ) pounds ordinary coal per hour. 
.0000464 (log. 5.66644) pounds. 
•32475 Hog. 7.511538) grains. 
.001531 (log^ 3.184975) cubic inches. 
0.000006628 (log. S.821342) gallons ordinary kerosene per 
hour. 
.001427 (log. 3.154557) cubic feet ordinary gas per 
hour. 
ELECTRICITY. 
One (I) Watt = 
.0013405 (log. 3.127241) H. P. 

•057 (log. 2.755913) B. T. U. per minute. 
3.42 (log. 0.534064) B. T. U. per hour. 
44.24 (log. 1.645775) foot-pounds per minute. 
2,654.4 (log. 3.423966) foot-pounds per hour. 
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. 3.721 151) cubic feet ordinary illumina- 
ting gas per hour. 



488 QUANTITATIVE ANALYSIS. 

List op the Principal Blbmbnts, with thbir Atomic Weights, Spe- 
cific Gravities and Specific Heats. 

Atomic Specific Specific 

weight. gravity. neat. 

Aluminum 27.50 2.67 0.2143 

Antimony 120.0 6.70 0.0508 

Arsenic 75.0 5.63 0.0814 

Barium i37'0 4.00 0.0470 

Bismuth 208.0 7*67-9*93 0.0380 

Boron ii.o 2.68 0.3660 

Bromine 80.0 3.15 0.0843 

Cadmium 112.0 8.45 0.0567 

Calcium 40.0 1.58 0.1670 

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 0.1070 

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 193*0 22.42 0.0326 

Iron 56.0 7.79 0.1138 

Lead 207.0 11.35 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 = 1.0; 0.3600 

Oxygen i6.o 1. 105 (air = 1.0) 0.2500 

Palladium 106.5 1 1 .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 o. 1776 

Tin iiS.o 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 



TABI.BS. 



489 



CONVBRSION TaBI^ES. 



Found. 


Sought 


Factor. 


Found. 


Sought. 


Factor. 


A1,0, 


Al, 


0.53015 


Mg,P,0, 


2Mg 


0.21883 


NH4CI 


NH, 


0.31882 


Mn,0, 


2Mn 


0.69695 


PtCleCNH,), 


2NH, 


0.07692 


Mn,0, 


3Mn 


0.72084 


PtCl.(NH,), 


N, 


0.06329 


MuS 


Mn 


0.63211 


Pt 


2NH, 


0.17518 


Hg 


HgO 


1.07984 


(NH^XSO* 


2NHa 


0.25815 


HgS 


Hg 


0.86208 


Sb.0, 


Sb, 


0.83366 


MoS 


Mo 


0.49992 


Sb,0, 


Sb, 


0.75046 


NiO 


Ni 


0.78524 


Sb,S, 


Sb. 


0.71438 


NiSO* 


Ni 


0.37849 


A8,0, 


As, 


0.75757 


(NH,),PtCl, 


2N 


0.06329 


As,0, 


As, 


0.65217 


PbSO* 


Pb 


0.68292 


A8,S, 


As, 


0.60928 


Pt 


2N 


O.14414 


BaSO* 


BaO 


0.65654 


Pdl, 


Pd 


0.29448 


BaSO* 


Ba 


0.58790 


Mg,P,0, 


2P 


0.27852 


Bi,0, 


2Bi 


0.89654 


Mg,P,0, 


PA 


0.63756 


KBFI4 


B 


0.08683 


U.PtOn 


PA 


O.I9817 


AgBr 


Br 


0.42556 


(NH4),PtCl, 


Pt 


0.4391 1 


CdS 


Cd 


0.77712 


K,SO, 


K, 


0.44898 


CdSO« 


Cd 


0.53786 


K,S04 


K,0 


0.54075 


CaO 


Ca 


0.71428 


K,PtCl« 


K,0 


0.19404 


CaSO* 


CaO 


0.41 158 


AgCl 


Ag 


0.75275 


CO, 


C 


0.27278 


SiO, 


Si ' 


0.47020 


CaCO, 


CO, 


0.44002 


SiPl* 


Si 


0.57878 


BaCO, 


CO, 


0.22332 


Na,S04 


Na, 


0.32435 


AgCl 


CI 


0.24725 


Na,SO, 


Na,0 


0.43674 


Cr,0, 


Cr, 


0.68483 


NaCl 


Na 


0.39408 


Cr,0, 


2CrO, 


I.31520 


BaSO^ 


8 


0.13755 


CoO 


Co 


0.78696 


BaSO^ 


SO, 


0.34346 


CuO 


Cu 


0.79858 


SrSO* 


Sr 


0.47674 


Cu,S 


Cu, 


0.79827 


Tl,PtCle 


2TI 


0.50046 


CaFl, 


Fl, 


0.48088 


SnO, 


So 


0.78681 


BaSiPle 


6F1 


0.40783 


TiO, 


Ti 


0.60065 


Agl 


I 


0.54031 


UsO, 


3U 


0.84873 


Fe,0, 


Fe, 


0.70000 


Vd,0, 


2Vd 


0.56145 


Fe,0, 


2FeO 


0.89999 


WoO, 


Wo 


0.79310 


LiCO, 


Li. 


0.18944 


ZnO 


Zn 


0.80338 


MgO 


Mg 


0.60375 


ZrO,* 


Zr 


0.73913 


1 Improvements in Methods of Chemical Calculations." Consult J. Anal 
403. 


. Chem,^ I, 










5^ 










C university)) 










V^^cT 


'F0HS^*V,^*^ 





490 QUANTITATIVE ANALYSIS. 

Comparison of Cbntigradb and Pahrbnhbit Dbgrbbs. 



Degrees 


De«rrees 


Centi- 


Pahreu- 


grade. 


heit. 


2500 


4532 


2000 


3632 


1500 


2732 


1200 


1992 


1000 


183a 


950 


1742 


V 


1652 
1562 


825 


1517 


800 


1472 


775 


1427 


750 


1382 


725 


1337 


700 


1292 


675 


1247 


650 


1202 


625 


"57 


600 


zzza 


575 


1067 


550 


1022 


500 


93a 


475 


887 


450 


842 


425 


797 


400 


752 


375 


707 


350 


662 


325 


617 


300 


572 


l^ 


570.2 


568.4 


297 


566.6 


296. 


564.8 


295 


563 


294 


561.2 


293 


559.4 


292 


557.6 


291 


555-8 


290 


554 


289 


552.2 


288 


550.4 


287 


548.6 


286 


546.8 


a85 


545 


284 


543 


283 


541.4 


282 


539.6 


281 


537-8 


a8o 


536 


III 


534.2 


532.4 


277 


530.6 


276 


528.8 


275 


527 



Degrees 


Degree 


Centi- 


Fanret 


grade. 


heit 


274 


525.2 


273 


523.4 


272 


• 521.6 


271 


5198 


270 


518 


a 


516.2 
514.4 


267 


512.6 


266 


510.8 


265 


509 


264 


507.2 


263 


505.4 


262 


5036 


261 


501.8 


a6o 


500 


259 


498.2 


258 


496.4 


257 


494.6 


256 


492.8 


255 


491 


254 


489.2 


253 


487.4 


252 


485.6 


251 


483.8 


250 


482 


249 


480.2 


248 


478.4 


247 


476.6 


246 


474.8 


245 


473 


244 


471.2 


243 


469.4 


242 


467.6 


241 


465.8 


240 


464 


'4 


462.2 


460.4 


237 


458.6 


236 


456.8 


235 


455 


234 


453.2 


233 


451.4 


232 


449-6 


231 


447.8 


230 


446 


229 


444.2 


228 


442.4 


227 


440.6 


220 


438.8 


225 


437 


224 


435.2 


223 


433-4 


222 


431.6 


221 


429.8 



Degrees Degrees 

Centl- Pahren- 

grade. heit 

ato 4a8 

219 426.2 

218 424.4 

217 422.6 

216 420.8 

215 419 

214 417.2 

213 415.4 

212 4i3'6 

211 411.8 

azo 4Z0 

209 408.2 

208 406.4 

207 404.6 

206 402.8 

205 401 

204 399-2 

203 397.4 

202 395.6 

201 393.8 

aoo 39a 

199 390.2 

198 388.4 

197 386.6 

196 384.8 

195 383 

194 381.2 

193 379.4 

192 377.6 

191 375.8 

190 374 

l8q 372.2 

188 370.4 

187 368.6 

186 366.8 

X85 365 

184 363.2 

183 361.4 

182 359.6 

181 3S7.8 

z8o 356 

179 354.2 

178 352.4 

177 350.6 

176 348.8 

175 347 

174 345-2 

17^ 343.4 

172 341.6 

171 339-8 

170 338 

169 336.2 

168 334.4 

167 332.6 



TABLES. 491 
Comparison op Cbnugradb and Fahrenheit DwGKnn^—ConHnued. 

Degrees Desrrees 

Centi- Pahren- 

Srrade. heit. 

58 136.4 

57 134.6 

56 132.8 

55 131 

54 129.2 

53 127.5 

52 125.6 

51 123.8 

50 laa 

49 120.2 

48 1 18.4 

47 116.6 

46 114.8 

45 "3 

44 III. 2 

43 109-4 

42 107.6 

41 105.8 

40 Z04 

39 102.2 

38 100.4 

37 98-6 

36 96.8 

35 95 

34 93-2 

33 91.4 

32 89.6 

31 87.8 

30 86 

29 84.2 

28 82.4 

27 80.6 

26 78.8 

25 77 

24 75-2 

23 73.4 

22 71.6 

21 69.8 

20 68 

19 66.2 

18 64.4 

17 62.6 

16 60.8 

15 59 

14 57-2 

13 55.4 

12 53.6 

II 51.8 

zo 50 

Q 48.2 

8 46.4 

7 44.6 

6 42.8 

5 41 



Degrrees 


Degrees 
Panren- 


Centi- 


grade. 


heit. 


166 


330.8 


165 


339 


164 


327 


163 


325.4 


162 


323.6 


161 


321.8 


z6o 


3ao 


ip 


318.2 


316.4 


157 


314.6 


156 


312.8 


155 


3" 


154 


309.2 


153 


307.4 


152 


305.6 


151 


303.8 


150 


302 


\n 


300.2 


298.4 


H7 


296.6 


146 


294.8 


145 


a93 


144 


291.2 
289.4 


143 


142 


287.6 


141 


285.8 


140 


284 


••$ 


282.2 


280.4 


137 


278.6 


136 


276.8 


135 


^75 


134 


273.2 


133 


271.4 


132 


269.6 


131 


267.8 


130 


266 


;^ 


264 


262.4 


127 


260.6 


126 


258.8 


las 


257 


124 


255.2 


123 


253.4 


122 


251.6 


121 


249.8 


lao 


248 


\\t 


246.2 


244.4 


117 


242.6 


116 


240.8 


"5 


239 


114 


237.2 


113 


23.54 



Degrees 
Centi- 


Degree! 
Pahren- 


grade. 


heit. 


112 


233.6 


III 


231.8 


IIO 


230 


;s 


228.2 


226.4 


107 


224.6 


106 


222.8 


105 


22Z 


104 


219.2 


103 


217.4 


102 


215.6 


lOI 


213.8 


zoo 


212 


p 


210.2 
208.4 


97 


206.6 


96 


204.8 


95 


203 


94 


201.2 


93 


199.4 


92 


197.4 


91 


195.8 


90 


Z94 


87 


192.2 


86 


186.8 


85 


185 


84 


183.2 


84 


181.4 


82 


179.6 


81 


177.8 


80 


176 


^ 


174.2 


172.4 


77 


170.6 


76 


168.8 


75 


Z67 


74 


165.2 


73 


163.4 


72 


161.6 


71 


19.58 


70 


158 


69 


156.2 


68 


154.4 


67 


152.6 


66 


150.8 


65 


149 


64 


147.2 


63 


145.4 


62 


143.6 


61 


14 1. 8 


60 


140 


59 


138.2 



492 



QUANTITATIVE ANAI<YSIS. 



CoBO^ARisoN OP Cbntigradb AND Fahrbnhbit DnOKBVS— Continued. 

Degrees Degrees 
Centi- Pahren- 

grade. heiL 



4 
3 

2 

+ I 
O 

— I 

— 2 

— 3 

— 4 

— 5 

— 6 

— 7 



39.2 

37.4 

3.56 

33.8 

3a 

30.2 

28.4 

26.6 

24.8 

as 

21.2 

19.4 



Degrees 
Centi- 


Desrrees 
Pabren- 


grade. 


heit 


— 8 


17.6 


— 9 


15.8 


— xo 


14 


—II 


12.2 


— 12 


10.4 


—13 


8.6 


— 14 


6.8 


— 15 


5 


—16 


3.2 


z\l 


+ 1-4 


— 0.4 


—19 


— 2.2 



Degrees 
Centi- 


Degrees 
Pahren- 


grade. 


heit 


— ao 


— 4 


—21 


- 5.8 


—22 


-7.^ 


-23 


-9.4 


—24 


— II.2 


—25 


—13 


—30 


—22 


-38 


—31 


-36.4 


—40 


—40 



Stbam Prbssurbs Exprbssbd IN Pounds pbr Squarb Inch and 

ATMOSPHBRBS POR DiPPBRBNT TbMPBRATURBS. 



Pounds 






Pounds 






per 
square 


Atmos- 


Temperature 


per 
square 


Atmos- 


Tempera tun 


inch. 


pheres. 


of steam. 


inch. 


pheres. 


of steam. 


I 


0.07 




33 


2.24 




2 


0.14 




34 


2.31 




3 


0.21 


60^ C. 


35 


2.38 




4 


0.28 


[140° F.] 


36 


2-45 




1 


0.35 




% 


2.52 


128,8° c. 


0.41 




2.58 


[263°F.] 


I 


0.48 




39 


2.65 




0.54 




40 


2.72 




9 


0.61 


86^ C. 


41 


IM 




10 


0.68 


[ 186.8° F. 


42 




II 


0.75 
0.81 




43 


2.92 




12 




44 


2.99 


i35.i°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° P.] 


48 


3.26 




\l 


1. 16 




49 


3-33 




1-23 




50 


340 




19 


1.30 




51 


3-47 


140.6° C. 


2C. 


1.36 




52 


3-54 


[284^ P.] 


21 


1.43 




53 


3.60 




22 


1.50 


112.2^ C. 


54 


3.67 




23 


1.56 


[234° F.] 


55 


3.74 
3.81 




24 


1.63 




56 




25 


1.70 




§ 


3.88 




26 


^V 




3-94 


145.4'* c. 


^Z 


1.84 




§9 


4.01 


[294^ P.] 


28 


1.90 




60 


4.08 




29 


1-97 




61 


4.15 




30 


2.04 


121.4° C. 


62 


4.22 




31 


2.11 


[250.° F.] 


63 


4.28 




32 


2.18 




64 


4.35 





TABLES. 



493 



Stkam Prbssurbs Bzprbssbd in Pounds per Square Inch and 
atmosfhbres for different temperatures— cb»/t»f^^^. 



Pounds 






Pounds 






per 
square 
bich. 


Atmos- 


Temperature 


per 
square 


Atmos- 


Temperature 


pheres. 


of steam. 


inch. 


pheres. 


of steam. 


65 


4.42 




95 


6.46 




66 


4.49 


1491'' C. 


96 


6.53 


163.5° c. 


% 


4.62 


[300.4° P.] 


^ 


6.60 
6.66 


[3»5-3°P.] 


69 


4.69 




99 


6.73 




70 


4.76 
4.B3 




100 


6.80 




71 




lOI 


6.87 




72 


4.95 




102 


6.94 




73 


4.96 




103 


7.00 


166.5° c. 


74 


5.03 


153.1° c. 


104 


7.07 


. [331-7° P.] 


'1 


5.15 


[307.6°F.] 


105 


7.14 




76 


5.17 




106 


7-2£ 




% 


5.24 




\% 


7.28 




5.35 




7.35 




81 


5.37 




109 


7.42 




5.44 
5.51 


156.8° C. 


no 
120 


7.49 
8.17 


169° C. 
[33^2°F.] 


82 


5.57 


[3i4.2°F.] 


130 


8.85 




!» 


5.64 




140 


9.53 


180° C. 


S* 


571 




ISO 


10.21 


[356° P.] 


8s 


5.78 
5-85 
5.92 




160 


10.89 




86 

1 




X 


".57 
12.25 


19CPC. 
[374° P.] 


5.98 


160.2° C, 


190 


12.93 




89 


6.05 


[320° P.] 


200 


13.61 




90 


6.12 




210 


14.29 




91 


6.19 




220 


14.97 


200° C. 


92 


6.25 




230 


15.65 
16.33 


[39*° F-] 


93 


6.32 




240 




94 


6.39 




250 


17.01 


257° C. 



[494.6°F.] 



494 QUANTITATIVE ANAI.YSIS. 

United States System of Measures and Weights Compared 
With the Metric System. 

X. Linear Measure. 

I mile=s8 furlongs=s8o chains=320 perches=s528o feet=i6o9.344 meters. 
I furlong =io chains^ 40 perche8:= 660 feet:= 201.168 ** 
I chains 4 perches^ 66 feet= 20.x 168 " 
I perch ^ 16J feet^ 5.0292 " 
I chain = 100 links. 

I link=7.92 inchesssso.201168 meters. 
I yard =3 feet=36 inches=o.9i44 " 

I foot=i2 inches=o.3048 '* 

I inch =0.0254 '* 

a. Surface Measures. 

I square mile=64o acres. 

I acre=io square chains=i6o square perches=4356o sq. feet=4o.4694 ares. 

3. Measures of Capacity. 

y^.— Dry Mbasurb. 

X bushel=2i5o.42 cubic inches. 

I bushel^the volume of 77.627 pounds of distilled water at 4° C. 

Legal : i liter=o.9o8 quart. 

I bushel=4 pecks=8 gallon8=32 quarts^35. 24229 liters. 

I peck ^2 gallons= 8 quarts= 8.81057 liters. 

I gallon = 4 quarts= 4.40528 liters. 

X quart = 1.10132 liters. 

I cubic foot=7.48gallons=28.3i5 liters^^2.42 pounds of water at 60° F. 

-5— Liquid Measure. 

I gal Ion =23 1 cubic inches. 

I gallonssthe volume of 8.3388822 pounds=58378 troy grains of distilled 

water at 4° C. 

Legal : i liter= 1.0567 quart=o.264i7 gallon. 

I gallon=4 quarts==8 pints=32 gills=s3.78544 liters. 
I quart =2 pints^ 8 gills=o.94636 liter. 
I pint = 4 gills=i. 47318 liter. 
I gill =0. 1 18295 liter. 

4. Weights. 

I grain troy =0.0648004 gram. 

I pound troy =0.822857 pound avoirdupois. 

I pound avoirdupois= 7000 grains troy = 1.2 15279 pounds troy. 



TABLES. 495 

A — Avoirdupois Weights. 

I ton=20 hundred weight=224o pounds= 1016.070 kilograms. 

I hundred weight= 112 pounds= 50.8035 kilograms. 

I pound= 16 ouncess= 256 drams= 768 scruples= 7680 grains= 453.603 grams 

I ounce = i6drams= 48scruples= 48ograin8= 28.350 grams 

I dram = 3scruples== 30grains= 1.772 grams 

I scruple = iograins= 0.5906 gram 

^— -Troy Weight for Drugs. 

I pound = 12 oz. =96 drachms— 288 scruples=576o grains= 373.2503 gms. 

I oz. = 8drachms= 24 scruples— 48ograins= 31.X042 gms. 

I drachm = 3 scruples= 60 grains= 3.888025 gms. 

I scruple = 20 grainssr 1.296008 gms. 

I grain =0.064804 gm. 

C— Troy Weight for Jewei^ and Precious Metals. 

I pound=i2 ounces=24 carats=240 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= i. 55521 gms. 

I grain = 0.0648004 gm. 



Percentages and Gravity of Ammonia. 

Table Showing the Percentages of Ammonia (NH,) in Aqueous 
Solutions of the Gas of Various Specific Gravities. 

Carius. Temperature 15"^ C. 

Specific NH, Specific NH, Specific NH, 

gravity. per cent. gravity. per cent. gravity. per cent. 

0.8844 36 0.9133 24 0.9520 12 

0.8864 35 0.9162 23 0.9556 II 

0.8885 34 O.9191 22 0.9593 10 

. 0.8907 33 0.9221 21 0.9631 9 

0.8929 32 0.9251 20 0.9670 8 

0.8953 31 0.9283 19 0.9709 7 

0.8976 30 0.9314 18 0.9749 6 

0.9001 29 0.9347 17 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 14 0.9915 2 

0.9106 25 0.9484 13 0.9959 I 



496 



QUANTITATIVE ANALYSIS. 



Table Showing the Amount of K,0 in Potash Lye of Different 
Specific Gravities. Temperature 17.5°. 

(Hofiman-Schaedler, ''Tabellen fiir Chemiker," p. 119.} 

specific 
gravity. 

I.I35 
1. 129 
I.123 
I.XI7 
I^II 
1. 105 
1.099 
1.094 
1.088 
1.082 
1.076 
1.070 
1.065 
1.059 

1.054 
1.048 
1.042 

1-037 
1. 031 
1.026 
X.02I 
I.OI5 

Table Showing the Amount of Sodium Oxide (Na,0) in Soda Lyes 

OF Different Specific Gravities. Temperature 17.5°. 

(Hoffman-Schacdier, **Tabellcn fiir Chemiker.") 



K,0 




K,0 




K,0 




K,0 


per 


specific 


per 


Specific 


per 


Specific 


per 


cent 


grravity. 


cent 


gravity. 


cent. 


gravity. 


cent. 


45.0 


1.576 


34.0 


1. 414 


23.0 


1.269 


12.0 


44.5 


1.568 


33.5 


1.407 


22.5 


1.263 


11.5 


44.0 


1.560 


33.0 


1.400 


22.0 


1.257 


II.O 


43-5 


1.553 


32.5 


1.393 


21.5 


1.250 


10.5 


43.0 


1.545 


32.0 


1.386 


21.0 


1.244 


lO.O 


42.5 


1.537 


31.5 


1.379 


20.5 


1.238 


9.5 


42.0 


1.530 


31.0 


1.372 


20.0 


I.231 


9.0 


41.5 


1.522 


30.5 


1.365 


19.5 


1.225 


8.5 


41.0 


I.5U 


30.0 


1.358 


19.0 


I.219 


8.0 


40.5 


1.507 


29.5 


1.352 


18.5 


I.213 


7.5 


40.0 


1.500 


29.0 


1.345 


18.0 


1.207 


7.0 


39.5 


1.492 


28.5 


1.339 


17.5 


1. 201 


6.5 


39.0 


1.484 


28.0 


1.332 


17.0 


1. 195 


6.0 


38.5 


1.477 


27.5 


1.326 


16.5 


1. 189 


5-5 


38.0 


1.470 


27.0 


1.320 


16.0 


I.183 


50 


37.5 


1.463 


26.5 


I.313 


15.5 


1.177 


4.5 


37.0 


1.456 


26.0 


1.307 


15.0 


I.I7I 


4.0 


36.5 


1.449 


25.5 


1. 301 


14.5 


1. 165 


3.5 


36.0 


1.442 


25.0 


1.294 


14.0 


1.159 


3.0 


35.5 


'.435 


24.5 


1.288 


13.5 


1.153 


2.5 


350 


1.428 


24.0 


1.282 


13.0 


1.147 


2.0 


34-5 


1. 42 1 


23.5 


1.275 


12.5 


I.141 


1.5 



Na,0 

per 

cent. 

35.0 
34.5 
34.0 
33.5 
330 
32.5 
32.0 

31.5 
31.0 

30.5 
30.0 

29.5 
29.0 
28.5 
28.0 



Specific 
gravity. 

1.500 

1.492 

1.485 

1-477 

1.470 

1.463 

1.4.55 
1.448 
1.440 

1.433 
1.426 
1.418 
1. 41 1 
1.404 
1.396 



Na,0. 




Na,0 


per 


Specific 


per 


cent 


gravity. 


cent 


27.5 


1.389 


20.0 


27.0 


1.382 


19.5 


26.5 


1.375 


19.0 


26.0 


1.367 


18.5 


25.5 


1.360 


18.0 


25.0 


1.353 


175 


245 


1.345 


17.0 


24.0 


1.338 


16.5 


23.5 


I.331 


16.0 


23.0 


1.324 


15.5 


22.5 


1.317 


15.0 


22.0 


1.309 


14.5 


21.5 


1.302 


14.0 


21.0 


1.295 


13.5 


20.5 


1.288 


13.0 



Specific 

gravity. 

I.281 

1.274 
1.266 

1.259 
1.252 

1.245 
1.238 
I.23I 
1.224 
I.217 
1. 210 
1.203 

1195 
I.188 
1. 181 



NatO. 




per 


Specific 


cent 


gravity. 


12.5 


1.174 


12.0 


1. 167 


11.5 


1. 160 


II.O 


1.153 


10.5 


1. 146 


lO.O 


I.139 


9.5 


X.132 


9.0 


1.125 


8.5 


1. 118 


8.0 


I.III 


7.5 


1. 104 


7.0 


1.097 


6.5 


1.090 


6.0 


1.083 


5.5 


1.076 







TABLES. 






jPECIPIC 


Gravity of Soi^utions of Calcium Chloride at 18.3° 






CSCHIFF.) 






specific 


Per cent. 


Per cent. 


Specific Per cent. 


Per cent 


gravity. 


CaCl,-f6HaO 


CaCl,. 


gravity. CaCl,+6H,0. 


CaCl,. 


1.0039 


I 


0.507 


I -1575 


36 


18.245 


1.0079 


a 


1,014 


I. 1662 


37 


18.752 


1. 01 19 


3 


I.521 


I.1671 


38 


19.259 


I.OI59 


4 


2.028 


I.1719 


39 


19.766 


1.0200 


5 


2.534 


I. 1768 


40 


20.272 


1. 0241 


6 


3.041 


I.1816 


41 


20.779 


1.0282 


7 


3.548 


I.1865 


42 


21.286 


1.0323 


8 


4.055 


I.1914 


43 


21.793 


1.0365 


9 


4.562 


I. 1963 


44 


22.300 


1.0407 


10 


5.068 


1. 2012 


45 


22.806 


1.0449 


II 


5.57s 


1.2062 


46 


23.313 


I. 0491 


12 


6.082 


1.2112 


47 


23.820 


1.0534 


13 


6.587 


1. 2162 


48 


24.327 


1.0577 


14 


7.096 


1. 2212 


49 


24.834 


I.0619 


15 


7.601 


1.2262 


50 


25.340 


1.0663 


16 


8.107 


I. 2312 


51 


25.847 


1.0706 


17 


8.611 


1.2363 


52 


■ 26.354 


1.0750 


18 


9.121 


I.2414 


53 


26.861 


1.0794 


19 


9.625 


1.2465 


54 


27.368 


10838 


20 


10.136 


1.2516 


55 


27.874 


1.0882 


21 


10.643 


1.2567 


56 


28.381 


1.0927 


22 


II. 150 


1. 2618 


57 


28.888 


1.0972 


23 


11.657 


1.2669 


58 


29.395 


I.IOI7 


24 


12.164 


1. 2721 


59 


29.902 


1. 1062 


25 


12.670 


1.2773 


60 


30.408 


I.II07 


26 


13.177 


1.2825 


61 


30.915 


I.II53 


27 


13.684 


1.2877 


62 


31.422 


I.II99 


28 


14.191 


1.2929 


63 


31.929 


1. 1246 


29 


14.698 


1. 2981 


64 


32.436 


1. 1292 


30 


15.204 


1.3034 


65 


32.942 


1. 1339 


31 


I5.7JI 


1.3087 


66 


33.449 


I.I386 


32 


16.218 


1.3140 


67 


33.956 


1.1433 


33 


16.725 


1.3193 


68 


34.463 


1. 1480 


34 


17.232 


1.3246 


69 


34.970 


I.I527 


35 


17.738 


1.3300 


70 


35.476 


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 


1. 1 


1.07335 


lO.o I 


.14315 


19.0 


1. 01450 


1.2 


1.08097 


II.O I 


15107 


20.0 


I.02174 


1.3 


1.08859 


12.0 I 


15931 


21.0 


1.02899 


1.4 


1.09622 


13.0 I 


.16755 


22.0 


1.03624 


1.5 


1. 10384 


14.0 I 


17580 


23.0 


1.04366 


1.6 


I.II146 


15.0 I 


.18404 


24.0 


1. 05 108 


1-7 


I.II938 


16.0 I 


19228 


25.0 


1. 05851 


1.8 


I.12730 


17.0 I 


20098 


26.0 


1.06593 


1.9 


1. 1 3523 


18.0 I 


20433 


26.395 



497 



498 



QUANTITATIVE ANALYSIS. 
Spkcipic Gravity op Gasbs and Vapors. 



Gas or vapor. Formula. 

Acetone C,H,0 

Acetylene C,H, 

Air 

Aldehyde CjH^O 

Ammonia NH, 

Amy lie alcohol CjHuO 

Arsenic AS4 

Arsenious anhydride As,0, 

Arsine AsH, 

Benzene C^He 

Bromine Br, 

Butane C^Hjo 

Carbon bisulphide OS, 

Carbon dioxide CO, 

Carbon monoxide CO 

Carbon oxychloride COCl, 

Carbon ox^^sulphide COS 

Chlorine CI, 

Chlorine cyanide CNCl 

Chloroform CHCl, 

Cyanogen (CN), 

Ethane C,He 

Ether OJl,fi 

Ether acetic C4H8O, 

Ethylic alcohol C,HeO 

Ethylene CjH^ 

Hydrobromic acid HBr 

Hydrochloric acid HCl 

Hydrocyanic acid HCN 

Hydrofluoric acid HF 

Hydrogen H, 

Hydrogen sulphide (sulphuret- 
ted hydrogen) H,S 

Hydroiodic acid HI 

Iodine I, 

Mercury Hg 

Methane CH4 

Methy lie alcohol CH4O 

Nitric oxide NO 

Nitrogen N, 

Nitrous oxide N,0 

Oxygen O, 

Phosphine (phosphuretted hy- 
drogen) PH, 

Phosphorus P4 

Phosphorus pentachloride PCI5 

Phosphorus trichloride PC1| 

Propane CjHg 

Selenium Se, 

Selenium hydride SeH, 







Weight 






of one 






liter in 




Specific 


flrrams at 


Molecular 


f.?^5^: 


ato'C.and 


wcigrht 


760 mm. 


58.0 


2.0025 


2.5896 


26.0 


0.9200 


1. 1650 


... 


1. 0000 


1.29387 
I.9811 


44.0 


1.5320 


88.0 


0.5960 


0.7707 


3.1470 


4.0696 


300.0 


10.3900 


13.4362 


198.0 


3.8500 


7.9105 


78.0 


2.6950 


3.4851 


78.0 
160.0 


2.7700 
5.3933 


6.8697 


58.0 


2.0041 


2.5914 


76.0 


2.6450 


3.4204 


44.0 


1.5290 


1.9662 


28.0 


0.9674 


1.2510 


99.0 


3.4163 
2.0748 


4.4174 


60.0 


2.6828 


71.0 




3.180I 


61.5 


2.1244 


2.7473 


II9.5 


4.2150 


4.4507 


52.0 


1.8064 


2.3360 


30.0 


1.0366 
2.5650 


1.3404 


88.0 


33170 


3.0670 


3.9662 


46.0 


1. 6133 


a.0862 


28.0 


0.9674 


I.25IO 


81.0 


2.7310 


3.5316 


36.5 


1.2474 


I.613I 


27.0 


0.9456 


1.2228 


20.0 
2.0 


0.6930 
0.06926 


0.8060 
0.08958 


34.0 


I.1921 


I.5416 


128.0 


4.4330 


5.7456 


254.0 


8.7160 


I I. 2710 


200.0 


6.9760 


9.0210 


16.0 


0.5560 


0.7155 
1.4483 


32.0 


I.I200 


30.0 


1.0390 


i.'256i7 


28.0 


0.97137 


44.0 
32.0 


1.5269 
1. 1056 


1-9745 
1.4298 


34.0 


I. 1850 


1.5350 


124.0 


4.3550 


5.6318 


208.5 


3.6500 


4.7201 


137.5 


4.7420 


r.^ 


44.0 


1.5204 


158.0 
81.0 


5.7000 


7.0229 


2.7846 


3.601 X 



TABLES. 



499 



Specific Gravity of Gases and VwoviS—Continued, 



Molecular 

Gas or vapor. Formula. weight. 

Silicon chloride SiCl^ 169.5 

Silicon fluoride Sip4 104.0 

Steam H,0 18.0 

Sulphur Si 64.0 

Sulphuric acid H2SO4 98.0 

Sulphuric acid, anhydrous SO, 80.0 

Sulphurous acid, anhydrous***' SO3 64.0 

Tellurium Te, 256.0 

Tellurium hydride TeH, 130.0 





Weight 




of one 




liter in 


Specific 


grams at 


mt 


ato'C. and 


760 mm. 


5.9390 


7.6208 


3.6000 


4.6554 


0.6235 


0,8063 


2.2000 


2.8430 


2.1500 


2.7803 


2.7630 
2.234 


\''^ 


8.9160 


11.5310 


4.5276 


5-8550 



Comparison of the Degrbes of Baum^'s Hydrometer with the 
Real Specific Gravities. 
I. For I^iquids Heavier than Water.* 





Specific 




Specific 




Specific 


Degrees. 


gravity. 




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 -55 1 


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 


1.600 


6 


1. 041 


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 


1.070 


36 


I 310 


62 


1.689 


II 


1.078 


37 


1.322 


63 


1.708 


12 


1.085 


38 


1-333 


64 


1.727 


13 


1.094 


39 


1.345 


6S 


1.747 


14 


I.IOI 


40 


1.357 


66 


1.767 


IS 


1. 109 


41 


1.369 


67 


1.788 


16 


1. 118 


42 


1.382 


68 


1.809 


17 


1. 126 


43 


1.395 


69 


1. 83 1 


18 


X.I34 


44 


1.407 


70 


1.854 


19 


I.I43 


45 


1.420 


71 


1.877 


20 


1. 152 


46 


1.434 


72 


1.900 


21 


1. 160 


47 


1.448 


73 


1.924 


22 


1. 169 


48 


1.462 


74 


1.949 


23 


1. 178 


49 


1.476 


75 


1.974 


24 


I.188 


50 


1.490 


76 


2.000 


25 


1. 197 


51 


1.504 






The Table 


of Comparison of the Degrees of Baumd 


's Hydrome 


terwith the real 



Specific Gravities for liquids lighter than water will be found on page 371. 



500 



QUANTITATIVE ANALYSIS. 



Of the Proportion by Weight op Absolute or Real Alcohol in ioo 
Parts op Spirits of Different Specific Gravities. 
(Mendeli^eff. )* 



Specific 


Per 


Specific 


Per 


Specific 


Per 


il^P'i 


cent 
of real 


gravity. 
ati5*C. 


cent 
of real 


gravity 
ati5*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 


41 


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 


11 


0.9294 


45 


0.8510 


79 


0.9813 


12 


0.9273 


46 


0.8485 


80, 


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 


O.9II9 


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 


91 


0.9665 


24 


0.9097 


58 


0.8176 


92 


0.9651 


25 


0.8983 


59 


0.8149 


93 


0.9637 


26 


0.8960 


60 


0.8120 


94 


0.9623 


27 


0.8937 


61 


0.8092 


95 


0.9608 


28 


0.8914 


62 


0.8063 


96 


0.9593 


29 


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 Absoi,ute or Rbai. Ai^cohol in 100 

Volumes of Spirits of Different Specific Gravities 

AT 15.5° C. (Mendel^eff.)* 



100 volumes spirits. 

Contain 

volumes 

Specific of real 

S^ravity. alcohol. 


100 volumes 

Specific 
gravity. 


spirits. 
Contain 
volumes 
of real 
alcohol. 


100 volumes spirits. 
Contain 
volumes 
Specific of real 
gravity. alcohol. 


I.OCXX) 





0.9604 


34 


0.8950 


68 


0.9985 


I 


0.959' 


35 


0.8925 


69 


0.9970 


2 


0.9577 


36 


0.8901 


70 


0.9956 


3 


0.9563 


37 


08876 


71 


0.9942 


4 


0.9548 


38 


0.8851 


72 


0.9928 


5 


0.9534 


39 


0.8826 


73 


0.9915 


6 


0.9518 


40 


0.8800 


74 


0.9902 


7 


0.9503 


41 


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 


O.861I 


81 


0.9822 


14 


0.9382 


48 


0.8583 


82 


O.98H 


15 


0.9364 


49 


0.8554 


83 


0.9801 


16 


0.9344 


50 


0.8525 


84 


0.9790 


17 


0.9325 • 


51 


0.8496 


85 


(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 


91 


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 


0.91 13 


61 


O.8161 


95 


0.9677 


28 


0.9090 


62 


O.812I 


96 


0.9667 


29 


0.9067 


63 


0.8080 


97 


0.9654 


30 


0.9045 


64 


0.8035 


98 


0.9642 


31 


0.9022 


65 


0.7989 


99 


0.9630 


32 


0.8997 


66 


0.7939 


100 


0.9617 


33 


0.8974 


67 







) Pogg. Annallen, 138, 230. 



502 



QUANTITATIVE ANALYSIS. 



Table Showing Pkrcbntagbs of Rbal Sulphuric Acid (H,S04) Cor- 

RBSPONDING TO VARIOUS SPECIFIC GRAVITIKS OF AQUEOUS 

Sulphuric Acid. 





Bincau; Otto. Temperature 15° C 






Specific 


Per 


Specific 


Per 


Specific 


Per 


Specific 


Per 


gravity. 




gravity. 


cent. 


gravity. 


cent. 


gravity. 


cent 


1.8426 


100 


1.675 


75 


1.398 


50 


1. 182 


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 


1. 159 


22 


1.8384 


96 


1.627 


71 


1. 361 


46 


I.1516 


21 


1.8376 


95 


I.615 


70 


1*351 


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.83I 


92 


1.580 


67 


1.324 


42 


1. 121 


17 


1.827 


91 


1.568 


66 


I.3IS 


41 


I.II36 


16 


1.822 


90 


1.557 


65 


1.306 


40 


1. 106 


15 


I.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 


I.512 


61 


1.272 


36 


1.0756 


II 


1.786 


85 


1. 501 


60 


1.264 


35 


1.068 


10 


1.777 


84 


1.490 


59 


1.256 


34 


1. 061 


9 


1.767 


83 


1.480 


58 


1.2476 


33 


1.0536 


8 


1.756 


82 


1.469 


57 


1.239 


32 


1.0464 


7 


1.745 


81 


1.4586 


56 


I.231 


31 


1.039 


6 


1.734 


80 


1.448 


55 


1.223 


30 


1.032 


5 


1.722 


79 


1.438 


54 


I.215 


29 


1.0256 


4 


1. 710 


78 


J. 428 


53 


1.2066 


28 


1. 019 


3 


1.698 


77 


1. 418 


52 


I.198 


27 


1. 013 


2 


1.686 


76 


1.408 


51 


1. 190 


26 


1.0064 


I 



TABLES. 



503 



Tabi^b Giving thb Pkrcrntages o^ Hydrochw)ric Acid Contained 
IN Aqubous Solutions of thb Gas of Various Spbcipic Gravitibs. 

Ure. Temperature 15° C. 



Specific 


Per cent 


Specific 


Per cent 


Specific Per cent 


Specific 


Per cent 


gravity. 


HCl. 


gravity. 


Ha. 


gravity. 


HCl. 


gravity. 


HCl. 


1.200 


40.777 


I.1515 


30.582 


1. 1000 20.388 


1.0497 


10.194 


1. 1982 


40.369 


I.1494 


30.174 


1.0980 ] 


[9.980 


1.0477 


9.786 


I.1964 


39.961 


I.1473 


29.767 


1.0960 


[9.572 


1.0457 


9.379 


I.1946 


39.554 


1. 1452 


29.359 


I.I939 ] 


[9.165 


1.0437 


8.971 


1. 1928 


39.146 


I.I43I 


28.951 


I.0919 ] 


[8.757 


I.0417 


8.563 


I.I910 


38.738 


I.1410 


28.544 


1.0899 : 


18.349 


1.0397 


8.155 


1. 1893 


38.330 


I.I389 


28.136 


1.0879 3 


[7.941 


1.0377 


7.747 


I.1875 


37.923 


I.I369 


27,728 


1.0859 ^ 


17.534 


1.0357 


7.340 


I.1857 


37.516 


I.I349 


27.321 


1.0838 1 


[7.126 


1.0337 


6.932 


1. 1846 


37.108 


I. 1328 


26.913 


1.0818 ] 


[6.718 


1. 0318 


6.524 


1. 1822 


36.700 


1. 1308 


26.505 


1.0798 ] 


[6.310 


1.0298 


6.I16 


I.1802 


36.292 


1. 1287 


26.098 


1.0778 


[5.902 


1.0279 


5.709 


1. 1782 


35.884 


I.1267 


25.690 


1.0758 J 


5.494 


1.0259 


5.301 


1. 1762 


35.476 


1. 1247 


25.282 


1.0738 ] 


[5.087 


1.0239 


4.893 


1. 1741 


35.068 


I. 1226 


24.874 


1. 0718 ] 


[4.679 


1.0220 


4.486 


I.1721 


34.660 


I. 1206 


24.466 


1.0697 


[4.271 


1.0200 


4.078 


1.1701 


34.252 


I.I185 


24.058 


1.0677 


13.863 


I.OI80 


3.670 


I.1681 


33.845 


I.I164 


23.650 


1.0657 


13.456 


1. 0160 


3.262 


I.1661 


33.437 


I. "43 


23.242 


1.0637 


^3.049 


1. 0140 


2.854 


I.164T 


33.029 


1.1123 


22.834 


1.0617 ] 


[2.641 


1. 01 20 


2.447 


1. 1620 


32.621 


1.1102 


22.426 


1.0597 ] 


[2.233 


1. 0100 


2.039 


1.1599 


32.213 


1. 1082 


22.019 


1.0577 


[ 1.825 


1.0080 


1. 631 


I.1578 


31.805 


1.1061 


21. 61 1 


1.0557 


[X.418 


1.0060 


1. 124 


I.1557 


31.398 


1.1041 


21.203 


1.0537 


1 1. 010 


1.0040 


0.816 


I.1536 


30.990 


1. 1020 


20.796 


1. 0517 ] 


[O.602 


1.0020 


0.408 



5^4 QUANTITATIVE ANALYSIS. 

Percentages and Gravity of Nitric Acid. 

Table Showing the Percentages op Nitric Acid (HNO,) in 
Aqueous Solutions of Various Specific Gra\^ties. • 
Kolb, Ann. Chem. Phys., 4, 136. Temperature 15° C. 



Per cent 


Specific 


Per cent. 


Specific 


Per cent. 


Specific 


Per cent. 


Specific 


HNOs. 


gravity. 


HNO,. 


gravity. 


HNO,. 


gravity. 


HNO,. 


gravity. 


100.00 


1.530 


80.96 


1.463 


59.59 


1.372 


39.00 


1.244 


99.84 


1.530 


80.00 


1.460 


58.88 


1.368 


37.95 


1.237 


99.72 


1.530 


79.00 


1.456 


58.00 


1.363 


36.00 


1.225 


99.52 


1.529 


77.66 


1.451 


57.00 


1.358 


35.00 


I.218 


97.89 


1.523 


76.00 


1.445 


56.10 


1.353 


33.86 


1. 211 


97.00 


1.520 


75.00 


1.442 


55.00 


1.346 


32.00 


1. 198 


96.00 


I.516 


74.01 


1.438 


54.00 


I.341 


31.00 


1. 192 


9527 


I.514 


73.00 


1.435 


53.81 


1.339 


30.00 


1. 185 


94.00 


1.509 


72.39 


1.432 


53.00 


1.335 


29.00 


1.179 


93.01 


1.506 


71.24 


1.429 


52.33 


1. 331 


28.00 


I.I72 


92.00 


1.503 


69.96 


1.423 


50.99 


1.323 


27.00 


I.166 


91.00 


1.499 


69.20 


I.419 


49.97 


1.317 


25.71 


1.157 


90.60 


1.495 


68.00 


1. 414 


49.00 


I.312 


23.00 


1.138 


89.56 


1.494 


67.00 


I.410 


48.00 


1.304 


20.00 


1. 120 


88.00 


1.488 


66.00 


1.405 


47.18 


1.298 


17.47 


1.105 


87.45 


1.486 


65.07 


1.400 


46.64 


1.295 


15.00 


1.089 


86.17 


1.482 


64.00 


1.395 


45.00 


1.284 


13.00 


1.077 


85.00 


1.478 


63.59 


1.393 


43.53 


1.274 


II.41 


1.067 


84.00 


1.474 


62.00 


1.386 


42.00 


1.264 


7.22 


1.045 


83.00 


1.470 


61.21 


1.381 


41.00 


1.257 


4.00 


1.022 


82.00 


1.467 


60.00 


1.374 


40.00 


1.251 


2.00 


1. 010 



Normal Solutions. 

Normal sulphuric acid contains 49.0 grams H^SO^ per liter. One cc. 
contains 0.049 gram H,S04. 

Normal hydrochloric acid contains 36.37 grams HCl per liter. One cc. 
contains 0.036 gram HCl. 

Normal nitric acid contains 63.0 grams HNO, per liter. One cc. con- 
tains 0.063 gram HNOg. 

Normal oxalic acid contains 63.0 grams C,04H,.2Hj,0 per liter. One cc. 
contains 0.045 gram 0,04!!,. 

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,CO, per liter. One 
cc. contains 0.053 gratn Na,COj. 

One-half normal ammonium hydroxide contains 8.5 grams NH, per 
liter. One cc. contains 0.0085 gram NHj,. 



NORMAL SOLUTIONS. 505 

One-ten tb normal potassium permanganate contains 3.156 grams 
KsMn^Og per liter. One cc. contains 0.0008 gram oxygen. 

One-tenth normal potassium bichromate contains 4.913 grams K,Cr,07 
per liter. One cc. contains 0.0049 gram K,Cr,OT. 

One-tenth normal iodine contains 12.65 grams I per liter. Onecc. equiv- 

»i-*«4^ 4./^ / 0.01265 gram iodine. 

aient to -[q Qj^go gjam Na,S,0,.5H,0. 

One-tenth normal sodium thiosulphate contains 24.8 grams 'Sa^Sfig, 

5H,Oper liter. One cc. equivalent to { °:3^ gj^" ^^"-^^ ^^^^ 

One-tenth normal silver nitrate contains 16.966 grams AgNO, per liter. 
Onecc.eq«ivalentto{--76p-Ap 

One-tenth normal sodium chloride contains 5.837 g^ams NaCl per liter. 
Onecc.eqnivalentto{°-gU:S?r- 



For ammonium molybdate solution consult page 177. 
For a magnesia mixture a>nsult page 178. 



Indicators. 

Phenolphthalein — Alcoholic solution i : 30. Colorless by acids ; red 
violet by alkalies ; also by CO,. 

Methyl orange — Water solution i : 1000. Yellow color by alkalies; pur- 
ple red by mineral acids ; not affected by CO,. 

Litmus — Water solution. Blue by alkalies ; red by acids. 

Cochinelle — ^Three parts cochinelle ; 400 parts H,0 ; 100 parts alcohol. 
Violet by alkalies ; yellowish red by acids. 



INDBX. 



Page. 

ABKVS cloied tester for oils 405 

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 406 

Adulterations in soap 349 

Agallte. in paper 343 

Air pyrometer 467 

Air required for combustion of one kilo of hydrogen xaa 

carbon laa 

specific heat of ...*. 361 

thermometer 467 

weight of liter 237 

Ajajc metal, composition of 3x6 

Alcohol, table of specific gravity 500 

Alkaline permanganate solution 74 

Allen's method for determination of PeO in iron ores 32 

scheme for analysis of unsaponifiable matters in soaps 351 

Alloys, analysis of 31X 

Alum, determination of AlfOa in .....w 2 

inpaper 339 

Aluminum, " bourbounc," composition of 3x7 

bronze, composition of 3x6 

analysis of 3x7 

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 xoo*C 293 

Anthracite producer gas, analysis and heating value 270 

Antifriction metal, composition of 3x6 

Antimony and tin, separation of . in alloys 3x4 

quantitative determination of, in alloys 329 

vermilion 453 

Anti-incrustating compound for locomotive boilers 97 

Apparent specific gravity for coke 25 

Approximate heating value of coals 145 

Aqua regia method for determination of sulphur in iron and steel 153 

Archbutt's apparatus for purifying water 107 

Araeo-picnometer 376 

Argentine, composition of 3x6 

Arsenic bronze 3x7 

trioxide solution 195 

Asbestos, use of in mechanical filtration of water 1x3 

paints 4^ 



OI THK ^K 

ukiv£:bsity 

INDEX. ^--=^^2]^- 507 

Ash, determination of, in coal and coke ao 

P«P«r 34X 

AshleBs filters x 

Ashbury metal...- 316 

Asphalt paint 456 

Asphaltum black , 454 

Atomic weights, table of 488 

Available heat of boilers 195 

"B" ALIX>Y. P. R. R., composition of i 

Babbit metal, composition of 3x6 

method of analysis 3x4 

Bacteriological examination of water, references upon 92 

Barrus coal calorimete r '. 1 35 

Baxytesin paint 433 

Basic slag, analysis of 39 

Baum6 hydrometer..... 377 

Beck hydrometer 377 

Beef tallow 358 

Bell metal, analysis of 3x3 

Bettel's method for determination of Ti in iron ores 35 

Bennett drsring apparatus 17 

Benzene, heating power per kilo 259 

Berthelot's bomb xa6 

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 43 

Blast furxmce slag, analyses of 37 

calculation of 48 

table of types of 54 

Blastfurnace, the charging of.... 43 

graphical method 55 

Blown oils • 400 

Bog headcannel coal, analysisof 32 

Bdhme-Hammer apparatus for cement 2x0 

B5hme, Dr., tests upon cement 2x4 

Boiler compound, Chicago, Milwaukee & St. PaulRailway 97 

Boiler scale, composition of 92 

Boilertests X25, X44 

Bone-black 454 

Bone-fat 416 

Brass, analysis of 3x3 

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 2x0 

andsand, preparation of six 

Bristol's recording thermometer 469 

Britannia metal, composition of 3x6 

British teme plate, analysisof 3^ 



508 INDEX. 

Briz hydrometer 377 

Bromine method for determination of tnlphur in iron and steel 150 

Bronxe for bearings, analysis of 313 

Brown's pyrometer ' 469 

Bruce, E. M., Sabbitt metal analysis 3^3 

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 399 

crushing strength of •-• 3<H 

frost test 306 

Bunsen photometer 275 

Bunsen valve la 

Burham's Portland cement, analysis of 205 

Butane, (C4H10), heating power per cubic foot 259 

*'B. &0" R.R., specifications for compound oils 4^3 

CADMIUM chloride solution for determination of sulphur in iron and steel xss 

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 PfOt in 12 

Calculation ot 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 X39 

the Hartley 284 

the Junker 287 

the Mahler 125 

Calorimetry i?5 

Ca melia metal, composition of 3< ^ 

Camp, J. M., iodine method for sulphur in steel i54 

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 Portiand cement 205 

Car-box metal, composition of.v 316 

Carburetted water-gas, manufacture of 2^ 

Camelly's & Burton's pyrometer 47* 

Camot's method for determination of aluminum in steel * • • • • 190 



INDEX. 509 

Carpenter's coal calorimeter 139 

Cartier's hydrometer 377 

Cast steel, determination of sulptanr in 150 

Castile soap, analysis 351 

C. B. & Q. R. R.. specifications for black engrine oil 425 

Cement, Portland, examination of aoo 

Cementite (73 

Centigrade desrrees, table of 490 

Charginsrof blastfurnaces 43 

Chateau's color tests for oils...* 41a 

Chimney erases, 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 338 

method of analysis 326 

Chrome yellow 457 

analysis of 435 

Chromium triozide, determination of , in KsCrsOf 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 

firreen 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, analysisof 39 

Copper-ball pyrometer 469 

Copper, determination of, in alloys 322 

in copper sulphate 2 

by electrolysis 5 

volumetrically 4 



5IO INDEX. 

Copper grreen 454 

Cotton fibers in paper, detection of 337 

CosmoUne 365 

Coulomb, the 481 

Cracking of Portland cement 90^ 

Cresol (CyHtO), evaporative power in pounds4>f water at 100* C 992 

Croasdale Stuart, bibliogrraphy of the electrolytic assay of copper 8 

Crushing strength of coke 34 

Crushing tests of cements aaa 

Cnmol (C«H,a) 99a 

Cumberland semi-bituminous coal, analysis of 147 

Cupric ferrocyanide as indicator 231 

Cuprous chloride solution for absorption of CO 239 

Current, electrical 480 

Cylinder deposits, analysis of 450 

Cylinder oil, specifications for 434 

Cymogene 364 

Cymol 393 

DANFORTH oil 364 

Dasymeter , 342 

Davidson's viscosimeter 387 

Degras oil 416 

"Delta" metal for bearings 3x3 

Denton, J. B., boiler test 325 

Deoxidised ** bronsc,'* composition of 316 

Derveauztbe, purifier for boiler water 105 

Deville, determination of heating power of various petroleums 992 

DeSmedt, S. J., tests upon Portland cement ai4 

"Dinas" fireclay, composition of 303 

Directions for testing Portland cement by method of the American Society of Civil 

Engineers 305 

Directions according to the official German rules S09 

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 453 

Dublin water works, description of the filter beds.' 86 

Dudley & Pease, volumetric method for determination of phosphorus in iron and 

steel 179 

Durability of paints 453 

Dyckerhofi's Portland cement, analysis of 305 

Dyne, the 480 

EAST Liberty, Pa., natural gas, analysis of 273 

Eggerts'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 481 

Elementary analysis of coal iiS 

Elements, listofthe principal 488 

Elliott gas apparatus 335 

Emerald green 454 

Energy equivalents, table of 483 

Engine oil, viscosity of 39a 



INDEX. 511 

Bngler'g method for the examinatton of petroleum 369 

vlscosimeter 384 

Bnglifih specifications for Portland cement 2x3 

Krdman chimney : as 

Brg, the 480 

Bschka-Presenius method, determination of sulphur in coal at 

Esparto, detection of, in paper 337 

Ethane (CaH«), heatings power per cubic foot 359 

Ether petroleum ••• • 364 

Bthylene (0,114). heating power per cubic foot aS9 

European river waters^ composition of 8$ 

BTaporatlve power of coal • ta3 

Evaporation, difference between theoretical and actual xas 

Experimental plant for the sras-producing qualities of coal 197 

PAIJA cement testing machine an 

Fairbank's cement testing machine • ao8 

Farad, the 481 

Fargo, D. T.. analysis of well-water from 99 

Patty acids in soap, determination of 353 

Feed-water heaters 99 

Ferrite • 171 

Ferro-aluminum • 316 

analysis of 318 

Ferro-tungsten 3x6 

Fiber in paper, determination of • 331 

Filter presses 1 < zzx 

Filters, sand 86 

Fineness, determination of, in Portland cement ao6 

Fire clays, composition of various 303 

Fire-proof paints 463 

Fire sand, analysis of 399 

Fire test of oils 404,498,499 

Fisher's coal calorimeter 139 

Fixed carboi^, determination of , in coal and coke. . 19 

Flash test of oils 403,428,499 

Flue gases, analysis of with Orsat-Milencke apparatus 937 

Ford. S. A., analysis of natural gas by 973 

France, specifications for cements requiredin • 219 

Frenc ochre 463 

Frankfort black 454 

Fredonia natural gas, analysis of a74 

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«Ot 190 

Freight car oil, specifications for 494 

Friction, coefficient of 4x7 

Fulton's table of physical and chemical properties of coke a8 

GALENA, determination of lead in 9 

Garrison, H. Lsmwood, microscopical examination of building stones 3 10 

Gas, average production from one ton New Castle coal 999 

coal, analysis and valuation 968 

experimental plant for the determination of the gas-producing qualities of coal 997 

natural, analysis and valuation 379 

oil, analysis and valuation a^i 



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 383 

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 3x6 

Gibb's viscosimeter 390 

Glosway's method for determination of nitrites in water 8x 

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 

Goubertfeed water heater, the 100 

Granite, absorptive power of 304 

crushing strength of 304 

Grant cement testing machine, the 2x3 

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 thermoelectric pile 7 

Guthrie's "entectic" composition of 317 

Gypsnmin paint 453 

HANNOVER coal gas, analysis of '. 369 

Hardness of water, determination of 69 

standards of 73 

Hart, B. P., Jr., chrome steel analyses by 327 

Hartig-Rensch apparatus 346 

Hartley's calorimeter for combustible gases 264 

Hay, Dr. G., analysis of natural gas by 273 

Heat effective, method of calculation for liquid fuels 393 

Heat energy, in blast furnace 42 

Heating power of coal and coke 1x4 

Heating value of combustible gases 358 

hydrogen 259 

Heckel, G. £., description of friction xnachine 4x7 

Heidelberg coal gas, analysis of 369 

Heidenreich's color test for oils 4x2 

Hematite, scheme for analysis of 29 

Hemp fibers, detection of, in paper 337 

He mpel gas apparatus 245 

Henderson-Westhoven lubricant tester 4x8 

Henry, the 48X 

Herrick, W. Hale, apparatus for electrolysis of copper 7 



INDEX. 513 

Hobson's hot blast pyrometer 468 

Holde, method for detection of rosin oil 4^ 

Hoppes feed-water heater, the loi 

Hydration, water of, determination in iron ores 31 

Hydrochloric acid, tableof gravities 503 

Hydrogen, determination of,incoal ■ 1x5 

water gas 115 

heatingvalue of a6i 

specific heat of 361 

weight of one liter 237 

Hydrometry • • 371 

Hygroscopic water, determination of, in coal 1x9 

ILLUMINANTS, valuation of, in gases for heating purposes 359 

Illuminating oils 363 

Indian red 453 

Indicators used in titration 506 

Inductance 481 

Iodine absorption of oils 40Z 

method for determination of tin in tin plate 325 

sulphur in steel 154 

Iron, determination of, in ammonio-ferric sulphate .««•• zi 

carbon in 157 

inironwire « z 

manganese in X99 

phosphorus in X76 

silicon in ■ 156 

sulphur in rso 

in tin plate 3^5 

Iron ores, scheme for analysis of 29 

composition of various 36 

JACKSONVILLK, Pla., analysis of well water from 84 

James River, Va., analysis of water from 84 

Jameson apparatus for making Portland cement briquettes 2x7 

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 

RANK natural gas, analysis of 274 

Kaolin, analysis of 299 

Keith oil gas 27X 

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 X45 

calculations for determination of the various losses of heat in boiler 

practice 147 

classification of iron and steel 187 

Kerosene 3^>426 

Kilo-Watts, definition of 482 

King's yellow 453 

Koppe-Saussure air hygrometer 346 

Krem's white 45^ 



514 INDEX. 

I^AMPBLACK 454 

Irangley'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 4.S3 

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 3R6 

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 1 14 

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 

Lu bricating oi Is, the examination of 366 

Lux's qualitative test for fatty oils in mineral oils 4x4 

MACADAM, W. Ivison, tests upon oil gas 27Z 

Magnesia mixture, formula for preparation 178 

llmitof amount in Portland cement 201 

Magnesium sulphate, determination of SO^ in 8 

Magnesium chloride, corrosive action in boilers 66 

Magnesite 453 

Magnet steel, composition of 330 

Magnetic properties of nickel steel 1S5 

Magnetite, scheme for analysis of 29 

Magnolia metal, composition of 313 

Mahler's calori meter 126 

Manganese, brown 453 

green 454 

colorimetric method for determination of 193 

determination of, in iron and steel 19a 

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 formala for non-inflammable paint 464 

Maasie's nitric acid test for oils 4x3 

Maumene's test for oils 410 

Measurement of electrical energy 483 

Mechanical ener^ developed by the blast furnace 43 

Mechanical testinfir of Portland cement 205 

Medicated soaps 349 

Megrohms 481 

Melting-points of fatty acids 370 

Mercury thermometers for high temperatures 466 

Mesureand Noriel's pyrometer 474 

Metalline, composition of 313 

Methane, determination of, in gases 257 

heating value of 259 

specific heat of 361 

weight of one liter 337 

Metric system of weights and measures, tables of 494 

Metropolitan R. R. formula for paints used 46a 

Mexican petroleum, analysis of 364 

Mica grease 451 

Micro-farad 481 

Michaelis machine for testing Portland cements an 

Microscopical examination of building stones 3x0 

pap**- f. 334 

Midvale Steel Co., classification of steel by X83 

Mill cinder, analysis of 39 

Mineral green '. 454 

soap stock 35a 

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., fireclay, composition of 303 

Munz metal, composition of 313 

Mutton tallow 358 

NAPHTHA group in petroleum, divisions of * 364 

Naphthalene (C,«Ha} , heating value per kilo, per pound, per cubic foot ate 

evaporative power in pounds of water at 100* C . • 293 

Natural gas as the standard of heating value for combustible gases 263 

Nesster 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 

NewUsbon, 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 X85 

Nitrates, determination of , in water 81 

Nitric acid, tables of specific gravities 504 

Nitrites, in water, determination of 8x 

Nitrogen, determination of , in coal X17 

in chimney gases 236 

solubili^ of , in distilled water 237 

specific heat of 261 



5l6 INDEX. 

Nitrogren, weisrlit of one liter 237 

Nordhausen oil of vitriol, determination of SO^ and HtS04 in 190 

Normal solutions 504 

Noyes, W. A., analysis of natural gas 273 

OCKAN waters, composition of 9s 

Oleic acid 409 

Ohm, The 481 

Ohm's law 483 

Oil, acidity of 408 

Oil, American sod 380.416 

bank 380,397 

black engine 425 

blackfish 381 

blown 377 

castor 380, 377 , 39S, 399, 4 1 3 , 4 14 

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 

Danforth 364 

degras 380. 398,4x6 

dog fish 380,412,414 

dolphin 377 

earthnut.... 4za. 414 

elain 380, 414 

engine 381 

freight car 381.434 

gelatine 397.398 

headlight '. 426 

herring 381. 397. 4Q3 

hoof 381, 403 

illuminating 426,427 

kerosene 362 

lard 370, 377, 398. 399. 403. 409. 4", 414 

linseed 358. 409. 453 

marine 399 

menhaden 377,381,412,4x4 

mineral sperm 426 

neat's foot 377. 381, 398, 403. 409. 4". 4U 

oleo 403,412,414 

olive 370.377.381,397.398.403.409.414 

palm 370,358,409 

paraffin 3^,409 

gas 36a 

passenger car 381.423 

porpoise head 397, 398,403 

rape-seed 358. 370. 397, 398, 399. 4", 414 

rosin 377.398,403,412,414 

sea elephant 380,397,412 

sesamd 370 

Smith's Perry 365 

sperm 377. 380. 398, 399. 403, 409, 4", 4^4 

strait's 380 

sunflower 358 

tallow 370,377.380,413,4x4 



INDEX. 517 

Oil, valve 392 

whale 390, 398,403,412,414 

white seat blown 397, 398 

150* fire test 437 

300* fire test 427 

Oils, flash and fire tests of 403 

iodine absorption of 401 

Maumene's test for 410 

specific gravity of 371 

viscosityof 383 

Oil gas, analysis and heating value of 271 

method of manuf actu re 271 

Olefiant gas, heating power per kilo, per pound, per cubic foot 259 

Olive oil soap, analysis of 361 

Olsen cement testing machine ao8 

Organic and volatile matter in water, determination of 83 

Orsat-Miiencke apparatus for analysis of flue gases 237 

Oxygen, determination of . in chimney gases ..* 235 

required to oxidize organic matter tn 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 341 

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, U. L., 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 (CbH ,,) heating power per kilo, pound, and cubic foot 259 

Per cenL 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 (C«H«0), evaporative power of 292 

Phillips, P. C, analysis of natural gas 274 

Phillips, H.- J., determination of hardness of water 70 

Phosphor-bronze, composition of 3x6 

Phosphor-tin, analysis of 319 

Phosphoric acid, determination of, in calcium phosphate xa 



51 8 INDEX. 

Phosphorus, determination of , in iron and steel 176 

phosphor-tin 3x9 

coal and coke a2 

Physical tests of coke 24 

Phjrtosterol 416 

Pintsch oil sras. method of manufacture 271 

" Pittsburg Bituminous'* coal, analysis 23 

Porosityof 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^Og in 14 

Potassium cyanide, sodium cyanide as a component of 197 

Potassium hydrate solution for absorption of COg 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 (CgHg), heating power per kilo, per pound, per cubic foot ^9 

Propylene (CsH«^, heating power per kilo, per pound, per cubic foot 259 

Prussian blue 454« 459i 4*4 

Purification of sewage and of water by filtration 88 

Pyrogallic alkaline solution of *. 239 

Pyrometry t 466 

QU ARTANE (CfHit) heating power per kilo, per pound, per cubic foot 259 

Quintane (CaHji) heating power per kilo, per pound, per cubic foot 259 

Quarts, as a constituent of Portland cement 205 

Quartjrites 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 2x2 

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 

Hilbl'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 377.398.403,412,414,465 

spirit 465 

Rosine metali composition of 3x6 

Rossi, A. J., calculation of blast furnace slagr 48 

Rotary delivery 484 

SAINTIGNON pyrometer 47a 

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 rpsinin paper 340 

Secondary silica 310 

Segar fireclay pyrometer 471 

Sepia 453 

Septometer 386 

Sextane (C«H]4), 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. Fm 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 

oilSf determination of 370 



520 INDEX. 

Specific heats of the elements 4B8 

Specifications for cabin car color 460 

freightcar color 461 

Speculum metal, analysis of 313 

Spiegrelberg's agriution apparatus for determination of phosphorus in steels 179 

Stammer's colorimeter for oils 432 

Standard crushed quartz, for Portland cement briquettes ao6 

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 

mansraneseiu X93i 194 

nickel in 227 

phosphorus in 176 

silicon in 156 

sulphur in 150 

tungrsteniu 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 iron 171 

Suchier machine 222 

Sulphur dioxide, determination of, in Nordhausen oi 1 of vitriol 192 

determination of, in coal and coke 2X 

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 SOg, in HaS^Oy 190 

TABI^E of heating value of solid combustibles 124 

showing the yearly saving effected by the use of the feed water heaters for 

various horse-powers X03 

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 hardnessof 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 

Teztor's method for the rapid dete rmination of manganese 194 

Thermo-electric pile 7 

Theoretical evaporative efficiency of different combustibles 294 

Thickness of paper, determination of 344 



INDEX. 521 

Thompson, Cm scheme for flOAp analysis 350 

Thompson, G. W., analysis of alloys 319 

Thompson's calorimeter 132 

ThSmer compression machine 25 

Th^mer, W., table of constants of fats and fatty adds 358 

Thurston lubricant tester 417 

Tin and antimony, separation of, In alloys 314 

quantitative determination of. in alloys 33 1 

plate, methodof analysis ... 333 

Titanic oxide, determination of, in clays 30a 

iron ores 35 

Tohinbronse, composition of , 316 

Toilet soaps 349 

Tollen's formula for Pehling'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 173 

Tungsten, determination of. in chrome steel 329 

Turpentine 453, 465 

Tuscan red 453 

Twitcheirs method for determination of resin 356 

UHHI^ING AND STEINBART'S automatic indicator for the composition of furnace 

srases 244 

Uehlingand Steinbart's pyrometer 474 

Ullgren's method for the determination of carbon in iron and s^eel 160 

Ultramarine, composition of 454,464 

Umber 453 

Unsaponifiable matterin soaps 352 

Unit current 480 

Unit magnetic pole 480 

Unwin, description of dasymeter 242 

V ALHNT A'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 f abrikanten, rules for testing cement 214 

Vermilion 453 

Viscosity of oils 383 

Viscosimeteri Davidson's 387 

DooUttle's 400 

Bugler's 384 

Gibb's 390 

Lew's 394 

Perkin's 393 

Redwood's 385 

Stillman's 394 

TagUabue's 389 



522 INDEX. 

Viscosity te sts of va rious oi 1 s 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 19s 

WARRKN water filter, description of 86 

Water, ammonia free, methodof 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 2^8 

uncarburetted, composition of 267 

Water gas, method of analysis 245 

manufacture 265 

Watt, the 481 

Wausau water, composition of 9^ 

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 34^ 

Westphal balance 374 

White lead 453 

CO, 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 

Wink ler gas burette 247 

Wisconsiuoil tester 42S 

Wolff's colorimeter 77 

Wood , com position of .«> 295 

Woodman, Durand, analysis of petroleum 363 

Wood cellulose, detection of. in paper 337 

Wool grease 370. 4 16 

Working qualities of paints 453 

Wright's C. R. Alder, scheme for soap analysis 350 

XYLOL (ChHio), evaporative power in pounds of water at 100* C 292 



INDEX. 523 

YELLOW cadmium 453 

Chinese 453 

chrome 453 

King's 453 

ochre 453 

soap 349 

ZKTTLITZ clay, composition of 303 

Zinc, chrome 453 

electro-chemical equivalent 483 

technical determination of, in ores 195 



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