Calculations of Analytical Chemistry

> W s^
DO
u< ^ ^D
CD
OU_1 58434 >m XW >
OSMANIA UNIVERSITY LIBRARY,

Call
Accession No.
2<? 8 7
Author
^fitoJk*. JT
stufned
.*:>
last
'S'^^jfttf&jL J
on
cy
before the date
marked below.
INTERNATIONAL CHEMICAL SERIES

Louis P. HAMMETT, PH.D.,
Consulting Editor
*
*
CALCULATIONS OF ANALYTICAL CHEMISTRY
The quality of the materials used in the manufacture of this book is governed by continued postwar shortages.
SELECTION OF TITLES FROM THE
INTERNATIONAL CHEMICAL SERIES

Louis
P.
HAMMETT, PH.D.,
Prcmedical
Consulting Editor
Introduction to Quantitative Analysis Quantitative Analysis
A msden
Physical
Mahin
for
Chemistry Students
Demonstrations Chemistry Aithur and Smith

Booth and Damerell Quantitative Analysis.
Arthur Lecture
in
General
Mittard Physical Chemistry for Colleges
Moore
History of Chemistry
Semixuicro Qualitative Analysis
Briscoe Structure and Pioperties of Matter Coghill and Stvrtevant An Introduction to the Preparation and Identification of Organic Compounds
Crist
Morton in Organic Technique Laboratory Chemistry The Chemistry of Ileterocyclic
Compounds
Norris
Experimental Organic Chemistry The Principles of Organic Chemistry
Parr
Analysis
of
Laboratory Course in General Chemistry
Fuel,
Gas,
Water,
and
Lubricants
for Physical
Daniel*
Mathematical Preparation Chemistry
Reedy
Elementary Qualitative Analysis Theoretical Qualitative Analysis

Rieman, Neuss, and Naiman
Quantitative Analysis
Daniels, Mathews, and Williams
Experimental Physical Chemistry
Desha
Organic Chemistry
Dole
Robinson and Gilliland
The Elements
of Fractional Distillation
Experimental and Theoretical Electrochemistry Eastman and Rollefson Physical Chemistry

Optical Methods of Chemical Analysis
Glasatone, Laidler,
Schoch, Felting, and Watt
General Chemistry
Snell
and Biffen Commercial Methods

Introduction
to
of Analysis
Steiner
Chemical
Thermo-
The Theoiy
Griffin
of
and Eyring Rate Processes
dynamics
Still well
Crystal Chemistry
Stone,
Technical Methods of Analysis
Hamilton and Simpson

Calculations of Quantitative Chemical Analysis
Dunn, and McCullough Experiments in General Chemistry

Colloid Chemistry
Thomas
Hammett
Physical Organic Chemistry Solutions of Electrolytes
Timm
General Chemistry An Introduction to Chemistry
Watt Laboratory
Henderson and Fernelius

Inorganic Preparations
Huntress
Problems
Leighou
in Organic
Chemistry
Experiments in General Chemistry and Qualitative Analysis
Chemistry of Engineering Materials Long and Anderson Chemical Calculations
William* and Homerberg Principles of Metallography
Woodman
Food Analysis

FORMERLY PUBLISHED UNDER THE TITLE
by LEICESTER
F.
HAMILTON,
S.B.
Professor of Analytical Chemistry Massachusetts Institute of Technology
and STEPHEN G. SIMPSON, PH.D.

Associate Professor of Analytical Chemistry Massachusetts Institute of Technology
Fourth Edition Third Impression
McGRAW-HILL BOOK COMPANY, NEW YORK AND LONDON

1947
ING.

Formerly published under the
title
COPYRIGHT, 1922, 1927, 1939, 1947, BY THE
McGRAw-HiLL BOOK COMPANY,
INC.
PRINTED IN THE UNITED STATES OF AMERICA

All rights reserved. This book, or parts thereof, may not be reproduced
w, any form without permission of

the publishers.
PREFACE
book has been clfanged from Calculations of Chemical Quantitative Analysis to Calculations of Analytical Chemistry because the subject matter has been expanded to cover the stoichiometry of both qualitative and quantitative analysis. In order to include calculations usually covered in courses in
title of this
The
qualitative analysis, some rearrangements of material have been made, new sections have been added, and chapters dealing with
equilibrium constants and with the more elementary aspects of Alanalytical .calculations have been considerably expanded.
together, the number of sections has been increased from 78 to 114 and the number of problems from 766 to 1,032.
The
greater part of the book
of quantitative analysis. amperometric titrations
is still devoted to the calculations Short chapters on conductometric and and a section on calibration of weights
have been added, and many other changes and additions have been made at various points in the text. A section reviewing the use of logarithms has been inserted, and a table of molecular weights covering most of the problems in the book is included in
the Appendix. It is felt that every phase of general analytical chemistry is adequately covered by problems, both with and without answers,
and that most of the problems require reasoning on the part of the student and are not solved by simple substitution in a formula.
LEICESTER F. HAMILTON STEPHEN G. SIMPSON
CAMBRIDGE, MASS.,
February, 1947.
CONTENTS
PREFACE
PART
CHAPTER
1.
I.
GENERAL ANALYSIS
MATHEMATICAL, OPERATIONS
1
I.
Factors Influencing the Reliability of Analytical Results
2.
3.
4.
Deviation Measures as a Means of Expressing Reliability

Significant Figures as a
...
Means
of Expressing Reliability
Rules Governing the Use of Significant Figures in Chemical

putations
Com3 6 7
5.
Conventions Regarding the Solution of Numerical Problems Problems 1-18

Rules Governing the Use of Logarithms Method of Using Logarithm Tables
.
....
6.
....
.
9
13
7.
8.
Use
of the Slide
Rule
14
15
Problems 19-24
CHAPTER
9.
II.
CHEMICAL, EQUATIONS
16
10.
Purpose of Chemical Equations Types of Chemical Equations
16
17
18
11. lonization of Acids, Bases,
and Salts
12. Ionic
13.
Equations Not Involving Oxidation
Oxidation
Number
20
21
14. Ionic
Oxidation and Reduction Equations
Problems 25-43
24
CHAPTER
15.
III.
CALCULATIONS BASED ON FORMULAS AND EQUATIONS

of a
16.
17.
Mathematical Significance Formula Weights
Chemical Pôrmula
28
28 29
Mathematical Significance of a Chemical Equation Problems 44-70
32
CHAPTER IV. CONCENTRATION OF SOLUTIONS

^
18.
19.
Methods
of Expressing Concentration
36
3f>
Grains per Unit Volume

vii
CONTENTS
20. Percentage Composition.
21. Specific Gravity
.
.
36 36 37 37
38
Milliequivalents,
22.
23.
Volume Ratios
Molar and Formal Solutions
Weight and Normal Solution
24. Equivalent 25. Simple
Calculations Involving Equivalents,
and
39
43
Normality Problems 71-86
CHAPTER
26.
V.
P]quiLiBRiUM CONSTANTS
Law
of
Mass Action
46 47 48 49
50
Buffered Solution
27. Ion 28. pll
Product Constant of Water
Value
Problems 87-94
29. lonization 30.
Constant
Common
Ion Effect.
52
31. lonization of Polybasic Acids
53 55 56
57
60'
32. Activity
and Activity
Coefficients
33. Dissociation Constants of
Complex Ions
Problems 95-128
34. Solubility
Product
35. Fractional Precipitation
62
64
Problems 129-159
36. Application of Buffered Solutions in Analytical
Chemistry
67
37. Control of Acidity in 38. Separations
Hydrogen
of
Sulficie Precipitations
68
by Means
Ratio
Complex-ion Formation
69
71
Problems 160-178
39. Distribution
73
74
Problems 179-185
CHAPTER VI.
OXIDATION POTENTIALS
40. Relation of the Electric Current to Oxidation-reduction
("Redox")
76
Reactions
41. Specific Electrode Potentials
76
for Half-cell Reactions
42. Rules for Writing
Equations
79
.
43. Oxidation-reduction Equations in 44. Relation
Terms
of Half-cell Reactions.
80
83
between Electrode Potential and Concentration

Extent to Which an Oxidation-reduction Reaction
45. Calculation of the
Takes Place
86
CONTENTS
46. Calculation of Equilibrium
ix
. .
Constant from Electrode Potentials
87
88
Problems 186-218
PART
47. Sensitiveness of the
48. 49.
II.
GRAVIMETRIC ANALYSIS
VII.
CHAPTER
Method
THE CHEMICAL, BALANCE

93
94
Chemical Balance
of
Swings
Conversion of Weight in Air to Weight in Vacuo
95
97
50. Calibration of
Weights Problems 219-240
99
CHAPTER
51
.
VIII.
CALCULATIONS OF GRAVIMETRIC ANALYSIS
Law
of Definite Proportions Applied to Calculations of Gravimetric
Analysis
52.
102
104
Chemical Factors
53. Calculation of Percentages
105
Problems 241-266
54. Calculation of
106 109
Atomic Weights
a Factor Weight Sample
Problems 267-275
55. Calculations Involving
109
110
112
Problems 276-284
Volume of a Reagent Required for a Given Reaction
13
Problems 285-304
57. Indirect Analyses
116
118
121
Problems 305-331
CHAPTER IX.
58.
ELECTROLYTIC METHODS
125
126
Decomposition Potential
59. Analysis
by Electrolysis Problems 332-359
130
CHAPTER X. CALCULATIONS FROM REPORTED PERCENTAGES

60. Calculations Involving the Elimination or Introduction of
a Con135
stituent
61. Cases
Where Simultaneous
Volatilization
and Oxidation or Reduction

136 138
Occur
Problems 360-380
62. Calculation of
Molecular Formulas from Chemical Analyses
....
141
63. Calculation of Empirical
Formula
of a Mineral
144
x
64. Calculation
CONTENTS
of
Formulas of Minerals Exhibiting Isomorphic Re145
placement
Problems 381-424
147
PART
III.
VOLUMETRIC ANALYSIS
153 153
CHAPTER XI. CALIBRATION OF MEASURING INSTRUMENTS

65.
66.
Measuring Instruments in Volumetric Analysis Calculation of True Volume

Problems 425-435
155
CHAPTER XII. NEUTRALIZATION METHODS (AOIDIMETRY AND ALKALIMETRY)

67. Divisions of Volumetric Analysis
68.
158
158
160
Equivalent Weights Applied to Neutralization Methods
Problems 436-456
69.
Normality of a Solution Problems 457-466
Made by Mixing
Similar
Components
161
162
70. Volume-normality-milliequivalent Relationship
163 163
164
.
71. Adjusting Solution to a Desired Normality
Problems 467-480
72.
Volume and Normality Relationships between Reacting Solutions

Problems 481-492
Determination of the Normality of a Solution
166
166
73.
168
169 170
74. Conversion of
Data
to Milliequivalents
Problems 493-514
75. Calculation of Percentage Purity 76. Volumetric Indirect
from
Titratioii
Values
173
176
Methods
Problems 515-532
77.
177
Problems in Which the Volume of Titrating Solution Bears a Given

Relation to the Percentage
180
181
Problems 533-545
78. Determination of the Proportion in
in a
Which Components Are Present

183 184
186
Pure Mixture
79. Analysis of
Fuming
Sulfuric Acid
Problems 546-564
80. Indicators
188 189
81. Equivalence Point

82. Determination of
pH
Value at the Equivalence Point Degree of Hydrolysis of a Salt
191
196
CONTENTS
Problems 565-591
84. Titration of
xi
196 199
Indicators
of
Sodium Carbonate
Use
of
85. Analyses Involving the

86. Relation of Titration
Two
199
Volumes to Composition
Sample
204
205
Problems 592-606
87. Analysis of
Phosphate Mixtures
207 209
Problems 607-612
CHAPTER XIII. OXIDATION AND REDUCTION ("REDOX") METHODS (OXIDIMETRY AND REDUCTIMETRY)
88.
Fundamental
Principles
of Oxidizing
211
89. Equivalent
Weights
90. Calculations of Oxidation
and Reducing Agents and Reduction Processes
211
216
217
Problems 613-630
91. 92.
Permanganate Process Bichromate Process

Problems 631-682
219 225
93. Ceric Sulfate or Cerate Process
226
227
94. lodimetric Process
234
Problems 683-712
238
CHAPTER XIV. PRECIPITATION METHODS (PRECIPITIMETRY)

95. Equivalent
Weights in Precipitation Methods Problems 713-734
243 245
CHAPTER XV. COMPLEX-ION FORMATION METHODS (COMPLEXIMETRY)

96. Equivalent
Weights Problems 735-751
in
Complex-ion Methods
249
252
PART
IV.
ELECTROMETRIC METHODS
255
CHAPTER XVI. POTENTIOMETRIC TITRATIONS

97. Potentiometric Acidimetric Titrations
98. Simple Potentiometric Titration Apparatus 99. Quinhy drone Electrode
256
257
100. Glass Electrode

101. Potentiometric
258
"Redox"
Titrations
259
261
261
102. Potentiometric Precipitation Titrations
Problems 752-775
xii
CONTENTS
CHAPTER XVII.
CONDUCTOMETRIC TITRATIONS
266
266 267 270
271
103.
Conductance
Conductometric Acidimetric Titrations
104. Mobility of Ions
105.
106. Conductometric Precipitation Titrations

107.
Conductometric Titration Apparatus
Problems 776-789
272
CHAPTER XVIII.
108. Principle of
AMPEROMETRIC TITRATIONS
275
an Amperometric Titration Problem 790
278
PART
Fundamental Laws
V.
GAS ANALYSIS
CHAPTER XIX. CALCULATIONS OF GAS ANALYSES

109.
279
281
110. Gas-volumetric 111. Correction for
Methods
Water Vapor
282 283 284 286
112. Calculations of Gas- volumetric Analyses
Problems 791-813
113. Absorption 114.
Methods
Combustion Methods
Problems 814-836
287
292
PART
VI.
COMMON ANALYTICAL DETERMINATIONS

"PROBLEMS ON SPECIFIC GROUPS AND DETERMINATIONS
A. Qualitative Analysis 309
310
311
PART
vii.
Silver
Group Hydrogen Sulfide Group
Ammonium
Sulfide
Group
Alkaline Earth and Alkali Groups
312
Anion Groups
B. Quantitative Analysis
313
Water
Sodium, Potassium
313 313
Ammonium, Ammonia, Nitrogen

Silver,
314 315 315
Mercury, Gold, Platinum
Halogens, Cyanide, Thiocyanate, Halogen acids
CONTENTS
Barium, Strontium, Calciuirif Magnesium
Limestone, Lime, Cement
Iron,
xiii
163
317
317
.
.
Aluminum, Titanium
Cerium, Thorium, Zirconium, Uranium, Beryllium, Bismuth, Boron Copper, Lead, Zinc, Cadmium, Brass
Tin, Antimony, Arsenic, Bronze
320
321
323
Tungsten,
Carbon, Carbon Dioxide,
Silicon,
Molybdenum
324
Chromium, Vanadium Manganese

Cobalt, Nickel
325
327
329
Phosphorus Sulfur, Selenium

General and Miscellaneous Analyses
329
331
335
APPENDIX
365 379
INDEX
PART I GENERAL ANALYSIS

CHAPTER I MATHEMATICAL OPERATIONS
Factors Influencing the Reliability of Analytical Results. Analytical chemistry is ordinarily divided into qualitative analysis
1.
and quantitative
analysis.
A compound or mixture is analyzed by
qualitative analysis to determine what constituents or components are present; a compound or mixture is analyzed by quantitative analysis to determine the proportions in which the constituents or components are present.
Calculations in qualitative analysis are limited mostly to those pertaining to equilibrium constants and simple weight and volume
Calculations in quantitative analysis are more exand are based upon numerical data obtained by careful measurement of masses and volumes of chemical substances. From the numerical data obtained from these measurements the desired
relationships.
tensive
proportions can be calculated. It is found; however, that duplicate analyses of the same substance, even when made by experienced
analysts following identical methods, rarely give numerical values which are exactly the same. Furthermore, the discrepancy between results is found to depend upon the method used, and an analytical result obtained by one procedure may differ appreciably from a similar result obtained by an entirely different procedure. The most important factors which thus influence the
precision of analytical results are the following: (1) the manipulative skill of the analyst; (2) the experimental errors of the procedure itself, such as the slight solubility of substances assumed
to be insoluble or the contamination of precipitates
assumed to
be pure;
(3) the accuracy of the measuring instruments used; and (4) fluctuations of temperature and barometric pressure. In order, therefore, that a numerical result obtained from chemical meas-
urements may be of scientific or technical value, the observer should have at least a general idea of its reliability.
l
In this connection, there should be kept in mind a distinction between accuracy and reliability. The accuracy of a numerical result is the degree of agreement between it and the true value;
the
reliability or precision of
it
a numerical result
is
the degree of
agreement between
tially
and other values obtained under substan-
Thus, suppose duplicate determinations of the percentage of copper in an ore gave 52.30 per cent and 52.16 per cent, and suppose the actual percentage was 52.32. It can be assumed that the analyst would report the mean or
the same conditions.
average of the two values obtained, namely 52.23 per cent. This differs from the true value by 0.09 per cent, which represents the
absolute error of the analysis. Expressed in parts per thousand, the error would be 0.09/52.32 1,000 =1.7 parts per thousand. This is known as the relative error of the analysis.
it
Since in most chemical analyses the true value is not known, follows that the accuracy of a given determination is seldom
known. We can speak only of the precision or reliability of the numerical results obtained. 2. Deviation Measures as a Means of Expressing Reliability.
a result is known as measure which is of in careful and chemical work is particular importance physical the deviation measure. Suppose, for example, repeated independent readings of a buret gave the following values:
its precision
The numerical measure

measure.
of the reliability of type of precision
(a)
(6)
(c)
43.74
(/)
(p)
43.75
43.76 43.76
43.75
43.76
43.73
(h)
(i)
(d)
(e)
43.75
43.77
The most probable value
obviously the mean, 43.753, which is obtained by dividing the sum of the readings by the number of readings taken. The deviation of each measurement
is
tor this reading
from
this
mean, regardless
(a)
(6)
(c)
of sign, is
shown
(/)
(g)
in the following:
0.013
0.007
0,003
0.003
0.007
0.007
0.003
(h)
(i)
(d)
(e)
0.023
0.017
MATHEMATICAL OPERATIONS
The mean
deviation, or average of these nine values, is 0.0092
and
represents the
reading differs measure of the reliability of a single observation. It is more important, however, to know the reliability of the
amount by which an average single independent from the most probable value; it is therefore a
mean than that of a single observation. It can be shown that the reliability of a mean or average value is numerically equal to the average deviation of a single observation divided by the square In the above, the root of the number of observations taken.
= 0.0031, and the value average deviation of the mean is 0.0092/V9 0.0031. for the reading may be expressed as 43.753 (It is
measmeasurements are involved in a comures.) putation, it is possible to calculate from the deviation measure of each measurement the deviation measure or precision measure of the final result and thus obtain a numerical measure of the probable reliability of that result. For methods of such calculation the student is referred to Goodwin's Precision of Measuresignificant figures in all deviation
customary to use only two
When
several such
ments.
Figures as a Means of Expressing Reliability. In most chemical analyses relatively few independent readings or
3. Significant
are not often used.
determinations are made, so that numerical precision measures In such cases the reliability or precision of a
numerical value is best indicated by the number of significant figures used in expressing that value. It is true that this method
of expression gives only
an approximate idea
of the reliability of
result,
but the importance
of the retention of the proper
number
of significant figures in analytical data cannot be overemphasized. numerical result expressed by fewer or more significant figures
than are warranted by the various factors involved may give to an observer an impression nearly as erroneous as would be given by a result which is inaccurate. 4. Rules Governing the Use of Significant Figures in Chemical
Computations. The following definitions and rules are suggested by those given in Goodwin's Precision of Measurements: A number is an expression of quantity.
A figure,
7, 8, 9,
or digit,
is
any one
of the characters 0, 1,2, 3, 4, 5, 6,
which, alone or in combination, serve to express numbers. significant figure is a digit which denotes the amount of the
quantity in the place in which it stands. In the case of the number 243, the figures signify that there are two hundreds, four
and three units and are therefore all significant. The charIt may be used as a significant is used in two ways. acter
tens,
be used merely to locate the decimal point. It is a significant figure when it indicates that the quantity in the place in which it stands is known to be nearer zero than to any other value. Thus, the weight of a crucible may be found to be 10.603 grams, in which case all five figures, including the zeros, are significant. If the weight in grams of the crucible were found to be 10.610, meaning that the weight as measured was nearer 10.610 than 10.609 or 10.611, both zeros would be significant. By analysis, the weight of the ash of a quantitative filter paper Here the zeros are not significant is found to be 0.00003 gram.
figure, or it
may
but merely serve to show that the figure 3 belongs in the fifth place to the right of the decimal point. Any other characters
except digits would serve the purpose as well. The same is true of the value 356,000 inches, when signifying the distance between
two given points as measured by instruments which are accurate

zeros are not significant. In order to avoid confusion, this value should be written 3.56 X 10 5 inches. If the distance has been measured to the nearest 100 inches, it
to three figures only.
The
should be written 3.560 X 10 6 inches. Rule I. Retain as many significant figures in a result and in data in general as will give only one uncertain figure. (For very
accurate work involving lengthy computations, two uncertain figures may sometimes be retained.) Thus, the value 25.34, representing the reading of an ordinary buret, contains the proper number of significant figures, for the digit 4 is obtained by esti-
mating an ungraduated scale division and is doubtless uncertain. Another observer would perhaps give a slightly different value for
the buret reading
e.g.,
25.33 or 25.35.
All four figures should

figures, in-
be retained. Rule II. In rejecting superfluous and inaccurate

crease
is
by
the last figure retained
if
the following rejected figure
number Thus, 16.279, the new value becomes 16.28. Rule III. In adding or subtracting a number of quantities, extend the significant figures in each term and in the sum or dif5 or over.
in rejecting the last figure of the
ference only to the point corresponding to that uncertain figure occurring farthest to the left relative to the decimal point.
For example, the sum of the three terms 0.0121, 25.64, and 1.05782, on the assumption that the last figure in each is uncertain, is
0.01
25.64
1.06
26.71
uncertain figure (the 4) in the hundredths place, the following figures being unknown. Hence, it is useless to extend the digits of the other terms
it is
Here
seen that the second term has
its first
beyond the hundredths place even though they are given to the ten-thousandths place in the first term and to the hundred-thousandths place in the third term. The third digit of the third term The fallacy is increased by 1 in conformity with Rule II above. of giving more than four significant figures in the sum may be shown by substituting x for each unknown figure. Thus,
0.0121*
1.05782
26.7 Ixxx
In multiplication or division, the percentage precision of the product or quotient cannot be greater than the percentage precision of the least precise factor entering into the computation. Hence, in computations involving multiplication or division, or both, retain as many significant figures in each
factor
Rule IV.
and
in the numerical result as are contained in the factor
having the largest percentage deviation. In most cases, as many significant figures may be retained in each factor and in the result
as are contained in the factor having the least
figures.
member of significant
For example, the product of the three terms 0.0121, 25.64, and 1.05782, on the assumption that the last figure in each is
uncertain,
is
0.0121
for, if
25.6
1.06
0.328
the
first
term
is
in the last place, it
assumed to have a possible variation of 1 has an actual deviation of 1 unit in every

its
121 units, and
percentage deviation would be y^r
100
0.8.
Similarly, the possible percentage deviation of the second
term
would be
*- QO
,, X
100
100
0.04,
and that
first
of the third
term would be
0.0009.
The
lUOj/o^
term, having the largest per-
centage deviation, therefore governs the number of significant figures which may be properly retained in the product, for the
product cannot have a precision greater than 0.8 per cent. That is, the product may vary by 0.8 part in every hundred or by nearly 3 parts in every 328. The last figure in the product as expressed with three significant figures above is therefore doubtful, and the proper number of significant figures has been retained. Rule V. Computations involving a precision not greater than one-fourth of l.per cent should be made with a 10-inch slide rule. For greater precision, logarithm tables should be used. If the old-style method of multiplication or division must be resorted to, reject all superfluous figures at each stage of the operation. Rule VI. In carrying out the operations of multiplication or division by the use of logarithms, retain as many figures in the mantissa of the logarithm of each factor as are properly contained in the factors themselves under Rule IV. Thus, in the solution of the example given under Rule IV, the logarithms of
the factors are expressed as follows:
log 0.0121
log 25.64 log 1.05782
= = =
8.083
1.409
10
0.024
9.516
10
log 0.328
Conventions Regarding the Solution of Numerical Problems. In the calculation of numerical results from chemical data which have been obtained under known conditions and by known methods, little difficulty should be experienced in forming an approxi5.
mate estimate
of the reliability of the various factors
and
of the
In the case of numerical problems which are unaccompanied by any data to show the conditions under which the various measurements were made or the precision of the values given, the retention of the proper number of significant figures in
results obtained.
ment.
the final computed results may be a matter of considerable judgIn such cases the rules listed above are subject to modi-
but in any case the need for a certain amount of common sense and judgment in using them in no way detracts from their
fication,
value.
In the solution of problems in this book, it may be assumed that the given data conform to Rule I, above. In problems containing such expressions as "a 2-gram sample/ "a 25-ml. pipetful," or "a tenth-normal solution/' it may be assumed that the weight of the sample, the volume of the pipet, and the normality of the
.
solution are
known
to a precision at least as great as that of the
other factors involved in the problem. It should also be remembered that the atomic weights of the elements are known only to a limited number of significant figures and, in the absence of further data, it may be assumed that the values ordinarily given in atomic-weight tables conform to Rule I above, in that the last figure in each is doubtful. It follows, therefore, that the same attention should be paid to the precision of the atomic and molecular weights involved in computations as to that of any other data.
happens that independent calculations from given data give results which disagree by only one qr two units in the last This is usually due to the fact that significant figure retained. have been at different stages of the operations rejected figures involved; but this is usually of no importance, since, when properly
It often
expressed, the last significant figure in the result
is
doubtful
anyway.
Analytical determinations are usually done in duplicate. In most of the problems in this book, however, data apparently covering only one determination are given. It may be assumed
that such values represent determinations.
mean
values obtained from duplicate
Problems
1.
How many
Three.
significant figures are implied in the value 2.20
10""9 ?
In
the value 5,000.002?
In the value 2.010

Four.
10 5 ?
Ans.
2.
Seven.
as
is
Calculate the molecular weight of OsCl 4 to as high a degree of precision warranted by the atomic weights involved.
332.0.
Ans.
8
3.

Express the velocity of light, 186,000 miles per second, in such a way as it has been measured to the nearest 100 miles per second.
1.860
to indicate that
Ans.
4.
106 miles per second.
Samples were sent to seven different chemists to be analyzed for percentage of protein. The values reported were 43.18, 42.96, 42.88, 43.21,
What is the mean value, the average deviation of a single value from the mean, and the deviation of the mean? If the correct percentage is 43.15, what is the relative error of the mean in parts per thousand?
43.01, 43.10, 43.08.
Ans.
6.
43.060,0.094,0.036.
2.1.
.
An ore actually contains 33.79 per cent Fe 2 O 8 Duplicate determinations and 34.02 per cent, and the mean of these is reported. By how many 33.80 give do the duplicate results differ from each other? What is thousand parts per
the
mean
value?
What
is
the absolute error?
What
3.5.
is
the relative error in
parts per thousand?
Ans.
6.
6.5.
33.91 per cent.
0.12 per cent.
Two
analysts, working independently, analyze a sample of steel
and
re-
port the following results:
ANALYST A:
Sulfur
ANALYST B:
Sulfur
0.042 per cent 0.041 per cent

in
By how many parts per thousand do the check values agree Each man uses a 3.5-gram sample weighed to the nearest tenth
analyst
each case?
Is
of a gram.
justified in his report?
Do
No.
his figures necessarily indicate greater
ability as
an analyst?
24 parts, 24 parts.
Ans.
7.
No.
It is necessary to solve the following:
4 - (0.0021764 X 0.0121) (1.7 X 10~ ) 0.00047) each term being uncertain in the last significant figure. Should you use arithmetic, logarithms, or a slide rule in the multiplications? What is the
(1.276
final
answer?
Slide rule.
7.5
Ans.
8.
10~4
0.1133, respectively,
buret,
value which has been found by duplicate analyses to be 0.1129 and is to be multiplied by 1.36 ml. as measured by an ordinary
and the product is to be subtracted from the value 0.93742 which has been very accurately measured. Express the result by the proper number
of significant figures.
Ans.
0.784.
9. If in
allowable, to
10.
the analysis of a given substance a variation of 0.30 per cent how many milligrams should a 10-gram sample be weighed?
is
value
How many significant figures are implied in the value 16.00 X 103 ? In the value 1.60 X 10~2 ?
16
103 ?
In the
11.
In the following multiplication the

is
factors
uncertain.
How
rejected as superfluous? correct number of significant figures.
last figure in each of the three in the product as given should be many figures Express the product in such a way as to indicate the
2.0000
0.30
500
300.00
12. Calculate the molecular weight of
warranted by on astronomy gives the polar diameter of the earth as 7,900.0 book 13. A miles. To what precision of measurement does this number imply? If the measurement had been made only to the nearest 10 miles, how should the value be expressed to indicate this fact?
cision as is
to as high a degree of prethe atomic weights involved.
Hf (NO 8)4
Assuming each term to be uncertain in the last figure given, solve the of significant figures: following and express the answer to the correct number
14.
(1.586
16.
29.10)
[162.22(3.221
1Q-4)]
0.00018
A sample of pure anhydrous BaCl
for analysis.
nations
2 containing 65.97 per cent Ba is given One analyst obtains 65.68, 65.79, and 65.99 for triplicate determiand reports the mean value. By how many parts per thousand does
each result
what
differ from the mean? What is the absolute error of the mean, and the relative error (parts per thousand) of the mean? 16. The percentage of carbon in a sample of steel is found to be 0.42 per The calculations involve only multiplication and division. To how cent. many decimal places would you weigh out a 1-gram sample in order to duplicate
is
the result?
sample of limonite was analyzed by 12 students at different times The values obtained for the percentage of iron during the college year.
17.
were: 34.62, 34.42, 34.60, 34.48, 33.71, 34.50, 34.50, 34.22, 34.41, 35.00, 34.65, 34.44. What is the mean value, the mean deviation of a single result, and the deviation of the mean? If the correct percentage is 34.75 what is the absolute
error of the
18.
mean and what
is its
relative error in parts per thousand?
sample of material was sent to two chemists.

CHEMIST A
30.15
Each used the same
method and reported the
results of four analyses, as follows:
CHEMIST
30.251
30.15
30.007
30.101 30.241
30.14
30.16
Calculate in each case the
conditions being equal,
6.
mean value and its deviation measure. which mean value is the more reliable?
Other
In calculations of and division where quantitative analysis involving multiplication four-significant-figure accuracy is required, four-place logarithms
Rules Governing the Use of Logarithms.
10
should be used; in calculations where two- or three-significantfigure accuracy is sufficient, a slide rule should be used. Grammarschool methods of multiplication and long division should not be
employed. Although the theory and use of logarithms are ordinarily covered in preparatory and high schools, the following outline is given as a review of the essential points in this phase of mathematics. 1. The logarithm of a number is the exponent of the power to which some fixed number, called the base, must be raised to equal
the given number.
Thus, suppose
ax
then x
is
=n
the logarithm of n to the base a and
may
be written
x = loga n
2.
The base
in the
common system
term log, without subscript, is arithm in this system. Hence,

10 10
1
and the commonly used to denote a logof logarithms

is 10,
10 2
103
= =
2
1,
log 1 log 10 log 100
=0
- 1 =2 -3 = -1 = -2 = -3
10,
100,
1000,
log 1000 log 0.1 log 0.01

log 0.001
etc.
lO-Ô.l,
10~
10~
3
= =
0.01,
0.001,
It is evident that the logarithms of all
numbers between
and 10 and 100 and 1 and 0.1 and

1
10
will
will
100
0.1
1000 will
will
0.01 will
be be be be be
etc.
plus a fraction 1 plus a fraction
2 plus a fraction 1 plus a fraction 2 plus a fraction
3. If
a number
is
not an exact power of
10, its
common logarithm
can be expressed only approximately as a number with a continuing decimal fraction. Thus,
36= ioi--or
log
36=
1.5503----
11
The integral part of the logarithm is called the characteristic; the decimal part is called the mantissa. In the case just cited, the characteristic is 1; the mantissa is .5563. Only the mantissa
a logarithm is given in a table of logarithms (see next section) the characteristic is found by means of the next two rules.
of
4.
;
The
1 is 1 less
than the number of
characteristic of the logarithm of a number greater than digits to the left of the decimal point.
of log 786.5 is 2; the characteristic
For example, the characteristic

of log 7.865 is 0.
5.
The
tween
characteristic of the logarithm of a decimal number beand 1 is negative and is equal in numerical value to the
number
decimal.
of the place occupied
by the
first significant figure of
the
is
For example, the characteristic

of
of
log 0.007865
-3.
6.
The mantissa
teristic
may
always positive; the characbe either positive or negative. For example,

is
a logarithm
log 36.55 log 0.08431
= +1 = -2
+ +
.5629
.9259
1.5629
This last logarithm is more conventionally written as 2.9259 with the understanding that only the 2 is negative. Another common method of expressing this logarithm is 8.9259 10. 7. The mantissas of the common logarithms of numbers having the same sequence of figures are equal. For example,
log 2.383 log 23.83
log 0.002383
= =
0.3772
1.3772
3.3772 (or 7.3772

is
10)
cologarithm of a rocal of that number. It

8.
The
number
is
the logarithm of the recipfound by subtracting the logarithm
of the
number from
zero.
For example,
log 7. 130
colog 7.130
or
= =
0.8531
0.0000 1.1469
0.8531
10.0000
0.8531
colog 7.130
10
9.1469
10
12
9.

The
antilogarithm of
is
the
number that has
for a
logarithm. For example,

log 7.130
=0.8531
antilog 0.8531
10.
7.130
of the
The logarithm
log (7.180
of
logarithms of
its factors.
a product is equal to the sum For example,
586.3)
= =
log 7.180
0.8531
+ log 586.3 + 2.7681
3.6212
is
equal to the 'logarithm of the numerator minus the logarithm of the denominator; it is also equal to the logarithm of the numerator plus the cologarithm of the denominator. For example,
log
11.
The logarithm
of
a fraction
7 180
log 7.180
log 586.3
= or
0.8531
2.7681
2.0850 (or 8.0850

log 7.180
10)
7 ISO
log
= = =
+ colog 586.3
(or 7.2319
0.8531
+ 3.2319
2.0850 (or 8.0850
10)
10)
The use
of cologarithms is particularly
advantageous when the
multiplication and division of several factors are involved in the same mathematical process. This is shown in the example at the end of this section.
a quantity is equal to the logarithm of the quantity multiplied by the exponent of the power. For example, 3 = 3 X log 71.80 log 71. 80 = 3 X 1.8531
12.
The logarithm
of
any power
of
13.
5.5593
of a quantity is equal to the by the index of the root. For
The logarithm
of
any root
logarithm of the
quantity divided
log
example,
^002 = Y 2 X log 5.002

= 2 X 0.6992 = 0.3496
7.
13
precision of or-
Method
of
Using Logarithm Tables.
The
dinary chemical analytical work is seldom great enough to permit the retention of more than four significant figures in the numerical
data obtained and in the calculations made from such data. Hence a four-place logarithm table such as is given in the back of this
entirely adequate. use the logarithm table in finding a mantissa proceed as follows: First find the first two digits of the number in the column headed " natural numbers," then go to the right until the column
book
is
To
reached which has the third digit of the number as a heading. To the number thus found add the number which is in the same horizontal line at the right-hand side of the table and in the column
is
of proportional parts
headed by the fourth
the number. 236.8

is
Thus the number
significant figure of representing the mantissa of log
3744, and the logarithm is 2.3744. Antilogarithms may be looked up in the antilogarithm table in the same way. Only the mantissa is used in looking up the num-
3729
15
ber; the characteristic is used merely to locate the decimal point. Thus the sequence of digits in the number having a logarithm of
1.8815
is
7603
+9=
7612, and the actual
number
is
76.12 as de-
termined by the given characteristic of the logarithm. In actual calculations from analytical data the essential purpose of the characteristic in a logarithm is to locate the position of the decimal point in the final numerical value obtained. Since in most cases a very rough mental calculation is all that is needed to establish the position of the decimal point, the use of characteristics can be dispensed with. The retention of characteristics is, however, helpful in serving as a check on the other method. Calculations of quantitative chemical analysis in which logarithms are of value seldom involve operations other than those of
multiplication
and
i
division.
i
v ^ * LxAMPLE.-Calculate
SOLUTION:
by logarithms: 0tQ05164 x 136>6Q
-xi
9.827
50.62
-
Method
(without using cologarithms)

log 9.827 log 50.62
= = Sum =
0.9924
1.7044
2.6968
14
= = Sum = = log numerator = log denominator Difference =

log 0.005164 log 136.59
antilog
3.7129
or
7.7129
10
2.1354
T.8483
2.1354
9.8483
or
10
10
2.6968
1.8483
12.6968
9.8483
10
2.8485
705.5.
2.8485
Ans.
Method
(using cologarithms)
= = log 50.62 = colog 0.005164 colog 136.59 = Sum = = antilog

log 9.827
0.9924
1.7044
or
0.9924
1.7044
2.2871
2.2871
3.8646 2.8485
705.5.
7.8646
12.6485
10 10
Ans.
is saved by omitting all above problem and merely
As previously mentioned, much time

characteristics in the solution of the
writing down the mantissas of each logarithm or cologarithm. The location of the decimal point is then determined by a simple
mental calculation on the original expression. Thus, inspection shows that the two factors in the numerator of the above expression give a result approximating 500 and that the factors in the denominator give a result approximating 0.7. The answer must therefore be in the neighborhood of 700, which establishes the position of the decimal point. 8. Use of the Slide Rule. The slide rule is essentially a logarithm table, mechanically applied. On the scales used for multiplication and division the numbers are stamped on the rule in positions
proportionate to their logarithms. Multiplication by means of the rule is merely a mechanical addition of two logarithms; divi-
a mechanical subtraction of two logarithms. Manuals covthe proper use of a slide rule are readily obtainable and are ering usually provided by the manufacturer of the rule.
sion
is
The student of quantitative analysis should be proficient in the use of a slide rule, particularly in the processes of multiplication and division. The slide rule saves a great deal of time in making
minor calculations and
tions
is
an excellent means
made by
logarithms.
of checking calculathe Although precision of the ordinary
10-inch slide rule
is
15
it is
limited to three significant figures,
sug-
gested that slide-rule accuracy be permitted in solving quiz problems and home problems, even though the data given may theoretically require four-significant-figure accuracy.
is
the problems are understood than to give practice in fundamental mathematical

operations.
The purpose of more to make sure that the methods of calculation
Most laboratory
figure accuracy,
calculations, however, require four-significant-
and four-place logarithms are necessary.

Problems
19.
(6)
Using four-place logarithms determine the following:

(c)
(a)
log 387.6,
(/) anti-
log 0.0009289,
colog 52.61, (d) colog 0.06003,
(e)
log 4.1733, (g) aritilog 7.2068
antilog 2.4474,
10.
Ans.
(a)
2.5884,
(b)
4.9679 or 6.9679
0.0001490,
(g)
10,
(c)
2.2789 or 8.2789
10,
(d) 1.2216, (e) 280.2, (/)
0.001610.
20.
Using four-place logarithms

(6)
calculate
the
following:
(a)
226.3
0.00002591,
of 0.09508.
0.05811
64.53,
(c)
fourth power of 0.3382, (d) cube root
Check these to three

0.005864,
(6)
significant figures with

(c)
slide rule.
Ans.
(a)
0.0009005,
0.01308, (d) 0.4564.
Locate 21. Using four-place logarithms find the value of the following. the position of the decimal point by mental arithmetic and also by the proper use of characteristics. Also check the answer to three significant figures with
slide rule.
0.0046191
51.42
287.7
0.84428
Ans.
0.03061.
22.
(6)
Using four-place logarithms determine the following:

colog 0.9566, (d) colog 718.1, - 10. antilog 6.0088
(c)
(a)
log 0.005903,
(e)
antilog 3.6482,
log 67.84, (/) anti-
log 2.0696, (g)

23.
Using four-place logarithms

0.1869
-5-
calculate
the 'following:
(a)
33.81
362.4, (c) cube of 0.09279, (d) square root of 0.0009915, (6) 0.5546. Check these to three significant figures with a slide rule.
Using four-place logarithms find the numerical value of the following expression. Locate the position of the decimal point by the proper use of Also check the answer to characteristics and check by mental arithmetic.
24.
three significant figures
by means
1.864
of
slide rule.
5987.9
0.006602
0.4617
1053.3
CHAPTER
II
CHEMICAL EQUATIONS
Purpose of Chemical Equations. When the nature and composition of the initial and final products of a chemical reaction are known, the facts can be symbolized in the form of a chemical
9.
properly written, the equation indicates (1) the nature of the atoms and the composition of the molecules taking part in the reaction, (2) the relative number of atoms and moleequation.
cules of the substances taking part in the reaction, (3) the proresulting substances, the proportions by volume of all gases involved. These four principles applied to reactions which go to completion serve as the foundation of quantitative chemical analysis. Before the
When
portions
(4)
by weight
of the interacting
and
and
calculation of a chemical analysis can be made, it is important to understand the chemistry involved and to be able to express the
reactions in the form of balanced equations. 10. Types of Chemical Equations. The determination of the
nature of the products formed by a given reaction involves a knowledge of general chemistry which, it is assumed, has already been acquired from previous study, but the ability to write and balance equations correctly and quickly is acquired only by considerable practice. The following discussion is given to help the student attain this proficiency, especially in regard to equations involving oxidation and reduction, which usually give the most
trouble to the beginner. With equations expressing the reactions of (1) combination, (2) decomposition, and (3) metathesis, it is seldom that much
about equality between the atoms and molecules of the reacting substances and those of the products, for little more is involved than purely mechanical adjustment of the terms and an elementary knowledge of valence. As examples of the above types of chemical change in the order
difficulty is experienced in bringing
given, the following equations
may be
1ft
cited :
CHEMICAL EQUATIONS
(1)
(2) (3)
17
2HgO -> 2Hg + O2

FeCl 3
+ 3NH OH -* Fe(OH) + 3NH C1

4 3
Equations expressing reactions of oxidation and reduction, although usually somewhat more complicated, offer little additional difficulty, provided that the principles underlying these types of chemical change are thoroughly understood. The above equations are molecular equations. For reactions
taking place in aqueous solution (such as the third case above) equations are usually better written in the ionic form. To do so
correctly requires a knowledge of the relative degrees of ionization of solutes and the correct application of a few simple rules.
11. Ionization of Acids, Bases, and Salts. Although the theory of ionization should be familiar to the student from his previous
study of general chemistry, the following facts should be kept in mind because they are particularly important in connection with
writing equations: " " Strong acids include such familiar acids as HC1,
2
H S0 HN0
4,
HBr, HI,
4.
3,
HC103 HBr0 3 HIO 3 HC1O 4 and

,
,
HMnO
These
acids in solution are 100 per cent ionized, although at ordinary concentrations inter-ionic effects may give conductivities corre-
sponding to an apparent degree of ionization a little less than 100 per cent. In ionic equations (see below) strong acids are written in the form of ions.
"Strong" bases include NaOH, KOH, Ba(OH) 2 Sr(OH) 2 and Ca(OH) 2 These bases in solution are 100 per cent ionized and
,
,
.
in ionic equations are written as ions.
with very few exceptions, are completely dissociated into simple ions in solution, and in ionic equations are written as ions. Two common exceptions are lead acetate and mercuric chloride. Many acids and bases are ionized in solution to only a slight degree at ordinary concentrations. Table IX in the Appendix lists most of such acids and bases ordinarily encountered in anaSalts, lytical chemistry, and the student should familiarize himself with the names of these substances and have at least a general idea ol
the magnitude of the degree of ionization in the case of the
mon
common
ones.
Certain acids contain more than one hydrogen replaceable bj
18

acids).
a metal (polybasic
in steps,
It will
be noted that these acids ionize
and the degree
of ionization of the first
hydrogen
is in-
variably greater than that of the others. Phosphoric acid, for example, is about 30 per cent ionized in tenth-molar solution to ~~ = + and 2 PO 4 ions give ions, but the concentration of HPO 4 S ions is is much less, and that of PQ 4 small. Sulfuric acid is very ~ 100 per cent ionized into H+ and HSO 4 ions, but the bisulfate + ions and ion is only moderately ionized further to
give
SCV*
ions.
Equations Not Involving Oxidation. Most of the reactions of analytical chemistry are reactions between ions in solution. For this reason, although the molecular type of equation
12. Ionic
is
serviceable as a basis for quantitative analytical calculations, the so-called ionic equation is usually easier to write and is generally better.
In writing ionic equations, the following basic rules should be observed

:
Include in the equation only those constituents actually taking part in the chemical reaction. EXAMPLE I. The addition of a solution of sodium hydroxide
1.
to a solution of ferric nitrate results in a precipitation of ferric hydroxide. The ionic equation is as follows:
Fe+++
+ 30H- -> Fe(OH)
*
3
The sodium
ions from the sodium hydroxide and the nitrate ions from the ferric nitrate do not enter into the reaction and hence
are not represented in the equation.

2.
its
cases where a reac,tant or product exists in equilibrium with constituent ions, express in the equation that form present in
In
greatest
amount.
weak acids, weak bases, and the slightly ionized should salts be written in the molecular form. Substances of this most often encountered in analytical chemistry are the type 2 O, 2 3 O2 4 OH, 2 S, 2 C0 3 2 following: HF,
It follows that
HC H
,
Pb(C H
2
HgCl 2 The last Appendix).

3 2) 2 ,
NH H H H P0 H C O and H SO
,
,
,
HNO
3 4 2 2 4 2 3 (see Table IX, three of these are borderline cases since they
It is desirable to underline formulas of precipitates. The use of downward-pointing arrows is equally satisfactory. If desired, formulas of gases
may
be overlined or denoted by upward-pointing arrows.
CHEMICAL EQUATIONS
are ionized to a moderate degree to give hydrogen ions
19
and
lead into
H PO4~, HC2 O4~,

2
and
HSO ~
3
ions, respectively.
"
acetate
and mercuric chloride may be dissociated

1
The salts somewhat
[e.gr., Pb^HaC^)" in the former case] but are relato give the metal ions. They are therefore ionized tively usually written in the molecular form. EXAMPLE II. The addition of an aqueous solution of ammo-
complex ions
little
nium hydroxide
to a solution of ferric nitrate results in a precipitation of ferric hydroxide. The ionic equation is as follows:
Fe+++
+ 3NH OH -> Fc(OH) + 3NH +

4
3 4
hydroxide is ionized into ammonium ions and hydroxyl ions, the ionization is comparatively slight and only the undissociated ammonium hydroxide molecules
In this case, although
are expressed in the equation. 1 EXAMPLE III. The addition of a solution of hydrogen sulfide to an acid solution of copper sulfate gives a precipitate of copper
sulfide:
ammonium
Cu++
+ H S -> CuS + 2H
2
'
fact that the original solution is acid docs not require that hydrogen ions be on the left-hand side of the equation. The equa-
The
tion merely indicates that the solution becomes more acid. EXAMPLE IV. When a solution containing lead nitrate is treated
with sulfuric acid, a white precipitate of lead sulfate is obtained. This precipitate dissolves in a solution of ammonium acetate, and the addition of a solution of potassium chromate then causes a
yellow precipitate to appear.
actions are
The
ionic equations for these re-
+ HS0 ~ -> PbS0 + H+ PbSO + 2C H - - Pb(C H O + S0 Pb(C H O + CrO -* PbCr0 + 2C H O

Pb++
4
4
2) 2
2) 2
As a matter
4
tration of
tion of
NH OH exists at
is
3
of fact, it
ammonia
not entirely certain that an appreciable concenThe equilibrium existing in an aqueous solumore generally and better expressed as follows:
is
all.
2
NH + H O
<=>
[NH OH
4
(?)]
NH +
4
Here again, the concentration of OH"~ is relatively low, and the equation for the above reaction can therefore be written
3NH + 3H O -> Fe(OH) + 3NH +

3
20

V.
Silver chloride dissolves in
is
EXAMPLE
of ammonia.
an aqueous solution
The equation
:
written as follows (see
Example
II
and
or
footnote above)
AgCl AgCl
+ 2NH OH -> Ag(NH

4
3) 2
+ 01- + H
+ 2NH - Ag(NH
3
3) 2
+ 01is
>
The
silver
ammino ion,
its
like
most complex ions,
only very slightly
dissociated into
constituents:
Ag(NH 3
+ 2
Ag+
+ 2NH
3.
EXAMPLE VT. A nitric acid solution of ammonium molybdate ((NH 4 ) 2 MoO 4 added to a solution of phosphoric acid results in
]
the precipitation of
3
ammonium phosphomolybdate.
4
12MoOr + H P04 + 3NH

Note here that
sponding 24
+ 21H+ ->
(NH 4 ) 3 P0 4 .12Mo03 + 12H2O
molybdate ions only 3
of the corre-
for every 12
ions present enter into the reaction. nitrate ions of course take no part in the reaction.
13. Oxidation
ammonium
The
Although the term "valence" usually refers to the degree of combining power of an atom or radical, it is likely to be applied somewhat differently in the various branches of chemistry. For this reason, in inorganic chemistry the term "oxidation number" is to be preferred in expressing state of
oxidation.
Number.
already familiar with the general aspects of the periodic table and with the combining power of the elements he has thus far studied. It will be recalled that (1) the oxidation number of all free elements is zero, (2) the oxidaIt is
is
assumed that the student
tion
+1 (except in the case of the relatively rare metallic hydrides), (3) the oxidation
of
number
of
hydrogen
in its
compounds
is
number
(4) the oxidation
sodium and potassium in their compounds is +1, and number of oxygen in its compounds is 2 (with
few exceptions).
oxidation numbers of the elements of a given compound is zero, the oxidation number of any element in a compound can usually be readily calculated from those of the other elements making up the compound. Thus, the oxidation
Since the algebraic
sum of the
number
of Cl in
HC1O 3
is
+5, since +1
+5+
[3
(-2)]
0.
In
number of the C10 3 radical is 1, since it is combined with the +1 hydrogen. The oxidation number of S 2 in
this case the oxidation
CHEMICAL EQUATIONS
is
21
14.
+12 since Na2 = +2 and

number
of
sulfur
atom
7 oxygen atoms = therefore has an oxidation number of +6.
Each
it
The
bears.
oxidation
an ion
is
Thus, the oxidation number

is
the same as the charge of the nitrate ion (N0 3 ~)
is
1, that of the sulfate ion (SC^) S phate ion (P0 4 ) is -3.
-2, and that
of the phos-
A few
the
sum
give trouble. Thus, in the compound of the oxidation numbers of the carbon and nitrogen
cases
may
HCNO
atom
is obviously +1, but this would be true if C = +4 and N = 3,. or C = +3 and N = -2, or C = +2 and N = -1, etc. However, since the oxidation number of carbon is so often +4 (e.g., GO 2 > and that of nitrogen is so often -3 (e.g., NH 3 ), these would be-
the most likely oxidation numbers to take.
compound like Fe 3 O 4 shows an apparent fractional oxidation number for the metal constituent, in this case 2%. Actually two of the iron atoms have an oxidation number of +3, and one iron atom has an oxidation number of +2. This is called a mixed
oxide (FeO.Fe2 3 ). A similar case is the salt oxidation number of each sulfur atom is 2^.
of the
Na S O6
2 4
the average,
In so-called per-oxy acids and salts of these acids, one (,or more) oxygen atoms has an oxidation number of zero. For example, in hydrogen peroxide, H 2 2 the oxidation number of one oxygen atom is 2; that of the other is 0. Sulfur forms analogous
,
per-sulfur acids. 14. Ionic Oxidation
and Reduction Equations. In the case of oxidation-reduction equations the two rules given in Sec. 12 should It will be found convenient in most cases to also be observed.
Write the formula of the oxidizing agent and of the reducing These should conform agent on the left-hand side of the equation. to Rules 1 and 2.
a.
write equations systematically according to the following steps:
Write the formulas of the resulting principal products on the These should likewise conform to right-hand side of the equation.
b.
Rules
c.
and 2. Under the formula of

1
the oxidizing substance, write the
number
its
expressing the total change in oxidation

stituent elements.
the
number
of all of
con-
Under the formula of the reducing substance, write number expressing the total change in oxidation number of its
constituent elements.
22
d.

Use
the number under the formula of the oxidizing agent in the as the coefficient for the reducing substance; use the number equation under the formula of the reducing agent in the equation as the coefficient for the oxidizing substance.
e.
Insert coefficients for the principal products to conform

step.
to the
preceding
f.
If possible, divide all the coefficients by the greatest
common
divisor,
or, if necessary, clear of fractions by multiplying all the
by the necessary factor. g. If the reaction takes place in acid solution, introduce the formulas HÔ and //+ in amounts necessary to balance the atoms of
coefficients
oxygen and hydrogen on
the reaction takes place in basic solution,
HtO and OH"

and hydrogen.
h.
If introduce the formulas in amounts necessary to balance the atoms of oxygen
the
two sides of the chemical equation.
charge on each of the two sides of the equation. They should be the same. EXAMPLE I. When a solution of chlorine water is added to
Check
the equation
by determining the
total net ionic
a sulfuric acid solution of ferrous
sulfate,
the iron
is
oxidized.
is
The
step-by-step formulation of the equation for this reaction

STEP
a,
as follows:
6
c
d, e
Fe ++ Fe++
1
+ +
+
RESULT C1 2 -> Ke +++ C1 2 -> Fe^ +

2
+ + +
Cl~ Gl~
2FeV
C1 2 -> 2Fe 4++
2C1~
/
g
None None
4+ = 4 +
a dilute nitric acid solution of stannous chloride is treated with a solution of potassium dichr ornate, tin is oxidized (from 2 to 4) and chromium is reduced (from 6 to 3). Neglecting the partial formation of complex ions (e.g. Slide") the
II.
EXAMPLE
When
development
STEP
a, 6
of the equation is as follows:

RESULT
c
e
Sn ++ Sn+ +
2
+ +
Cr2 Or -> Sn++++ Cr2 O 7 - -> 811++++

34-3
Cr
rf,
/
g
6Sn++ 3Sn+ + 3Sn++
+ 2Cr,O7- -* 6811++++ + + Cr O ~ -> 3Sn +++ + + + Cr O ~ + 1411+ -> 3Sn++++ +

2
7 2
2Cr+ ++
+ 7H O
2
18+ = 18+
CHEMICAL EQUATIONS
Note that
would tion would
23
in writing this equation in the molecular form one be at a loss to express the products correctly. The quesarise
whether to write stannic chloride and chromic nitrate or stannic nitrate and chromic chloride. As a matter of ionized fact, none of these is formed since the salts are completely
in dilute solution.
hydrogen sulfide is bubbled into a dilute sulfuric acid solution of potassium permanganate, the latter is reduced (to manganous salt) and a white precipitate of free sulfur
EXAMPLE
III.
When
is
obtained.
STEP
a, b
MnOr + H S MnOr + H S
2
RESULT -> 2
Mn++ + S
->
Mn+ + +
5
d, e
2MnOr +
5HiS -> 2Mn++
5S
58
/
g
None
2MnOr + 5H S + 6H+ - 2Mn++ + 4+ = 4+

2
8II 2
EXAMPLE
clichromatc.
TV.
In the presence
of sulfuric acid
will
potassium permanganate solution
an excess of oxidize a chromic salt to
RESULT
t-
Mn++
3Mn + 6Mn +
f
+ 6Mn ++ +
EXAMPLE
of
22TI-
V.
When
metallic
alkali,
aluminum
is
a nitrate in caustic
is
the latter
added to a solution reduced and ammonia,

is
gas
evolved.
STEP
a, 6
RESULT
Al
Al
3
+ N0 - - AlOr + NH +N0 - -A10- +NH,

3 3
d, e
8A1 8A1
+ 3NOr 3
8A1O2
+ 3NH
2
f
g
None
+ 3NO - + 5OH- + 2H O 8- = 8-
SAlOr
+ 3NH
24
EXAMPLE VI. Solid cuprous sulfide is oxidized by hot concentrated nitric acid forming a cupric salt, sulfate, and 2 gas*
N0
STEP
*. b
RESULT
c
d, e
+ NO CujS + NO
CutS
3
- Cu++ - Cu++
+ SO - + NO + SO ~ + NO
4 4
2 2
1 1+1+8 - -* 10NO 2Cu ++ CuaS + 3
+ SOr + +
10NO2
g h
CuzS
10NO 3-
None 12H+ -* 2Cu++
SO4-
2+ = 2+
Problems
+ 10NO + 6H O
2 2
is the oxidation number of each of the elements (other than = and hydrogen oxygen) in each of the following: (a) N2 O3 (6) SbS 3 (c) H 4 P2OS (d) K 2 Pt(N0 2 ) 4 (e) S 8 (/) Co(NH 3 ),+++; (g) Cu 3 [Fe(CN) 6 ] 2 (h) NaCHO2 ?
26.
What
+3; (b) +3, -2; (c) +3; (d) +1, +2, +3; (e) 0; (/) +3, -3; (O) +2, +3, +2, -3; (A) +1, +2. 26. What is the oxidation number of each of the elements (other than hydrogen and oxygen) in each of the following: (a) MnO2 (6) A12 (SO4) 3 (c) NaCu(CN) 2 (d) (VO) 3 (PO 4 ) 2 (e) Fe(ClO 3 ) 3 (/) HAsOr; (?) CdS 2 O 6 .6H 2O; (h) (UO2 )(C1O 4 ) 2 .4H 2 O?
(a)
;
Ans.
Ans.
(a)
+4;
(g)
+5;
(/)
+5;
(6) +3, +6; (c) +1, +1, +2, -3; +2, +5; (h) +6, +7.
(d)
+4, +5;
(e)
+3,
27. State the oxidation

(6)
number
2 7
;
of each element in the following: (a)
2 7
N 0;
2
(c)
.
H Se;
2
(d)
Mn O
(e)
HCN;
of
;
(/)
K Fe(CN)
4
(g)
Na2Cr2O
<A)
(NH 4) 2SO4
28. State
(a)
(g)
the
;
oxidation
number
2
each
element
;
in
2
the
2 7
;
K Mn0
2 2
(6)
2
IIC1O4
(h)
Na2S O.,.5H O;
Fe(CN)
6
(d) Pb 3 O 4 (c) Mg P 2 O 7 NH2OH; (t) IIN 3

;
.
(e)
K II Sb O
2
following:
(/)
Na
S2
29. State the oxidation

(6)
B
;
(c)
number of each element in the following: (a) A1O2 ~; Cu(NII 3 ) 4 ++; (d) Ag(CN) 2-; (e) SnS 3 ~; (/) MgNH 4 AsO4
2
4
(g)
Na B
2
7;
(h)
HC O -;
(0
WF -.
8
;
30.
(a)
(/)
Give the oxidation number of each element in the following: 2 PtCl c (c) K 3 Co(NO 2 ); (d) SbOCl; (e) HC 2 H 3 O2 (b) (UO 2 ) 3 (PO 4 ) 2 LiH; (g) Bi(OH)CO3 (h) Hgl.HgNHJ; (0 Fe 4 [Fe(CN) 6] 3
31.
in (a)
Na 2 S4O6
The
How do you account for the unusual average oxidation number of sulfur (c) Na S O ? (6) FeS
;
32.
duction.
HO
2
and
following unbalanced equations do not involve oxidation and reConvert them into complete, balanced ionic equations. Introduce other constituents wherever necessary. Substances are in solution
unless underlined.
(a)
(6)
A1C13
Fe2 (SO4) 3
+ NaOH -> NaAlO + NH OH ->Fe(OH)

2
4
CHEMICAL EQUATIONS
(c)
26-
(d)
(e)
(/)
(g)
(h)
+ NH OH - Cu(NH,) SO K Cd(CN) + H S -Cd FeCl + K Fe(CN) -> Fe [Fe(CN) H PO + (NH Mo0 + HNO -> (NH ),PO .12MoO, Na AsS + H SO ->As S + 1I S Na,Sb0 + II SO + H S -> Sb S
CuSO
2
3
6l3
4) 2
HC1
0)
33.
->
U0 C1
2
HC H O + PbO 2
3
Pb(C2 H 3O2 ) 2
The
reduction.
following unbalanced equations do not involve oxidation and Introduce the necessary constituents and convert to complete,
balanced, ionic equations.

(a)
(&)
(c)
Substances are in solution unless underlined.
(d)
(e) (/)
to)
(K)
()
34.
+ KOH -> KiPbOi NH OH - Ag(NII,) Cl + AgCl H H SnCle + S -8nS, Sb S + (NH S -> (NH^jSbSi Hg(N0 + KI -> K HgI Na SnO + HC1 + H S -> SnS UO SO + KOH->K U O Pb(C H O + K CrO - PbCrO + KC H,O2
Pb(OH) 2
2 4
2
4) 2
3) 2 3
2) 2
Balance the following oxidation and reduction equations: ++ H + - Fe +++ + Cl" + H 2O ClOr (a) Fe ++ -> Mn++ + CrOr MnO2 Cr H^ 2
(6)
(c)
(d)
(e)
(/)
+ + + +H + ++ -> aH+ Mn C1 H O MnOr + + + + MnO ~ + H S + H+ -* Mn++ + S + H O I0 - + I- + H + -> I + II MnO ~ + S O - + H+ - Mn++ + S O - + H O

-'-
36.
Complete and balance the following ionic oxidation-reduction equations:

(a)
(6)
(c)
(d)
(e) (/)
to)
(K)
+ H+ -* Mn++ + I + H O -* Cr+++ + S + H O Cr + H S + H+ ZnO + H Zn + OHAsO - + Zn + H + -> AsH + Zn++ + H O BrOr + I" + H+ -* Br~ + I + H O NOr + Al + OH- + H O -* NH + AlOr Cr +++ + NaA + OH- - CrOr + Na+ + II O Al+ ++ + S ->A1(QH) + 8 + S0
MnOr +
2
7
I-
36. The following unbalanced oxidation-reduction equations represent Convert them to balanced ionic reactions taking place in acid solution.
equations, introducing
(o)
(6)
(c)
H + and H O wherever necessary. Cr O - + NO - Cr+++ + NO ~ - Cr O + SO Cr +++ + S -* Mn++ + O H O MnOr +

2 2
26

(d)
(e)
+ BiO -> MnO ~ VO ++ + MnOr -> VOr + Mn++ + Zn -> U+ ++ + + Zn++

Mn++
2
37. The following equations involve oxidation and reduction. They represent reactions taking place in the presence of acid. Convert them to balanced
ionic equations, introducing II +
(a)
(fe)
(c)
(d)
(e)
(/)
(flf)
H O wherever necessary. Cr O + I- -> O+++ + I MnO - + H C O -> CO Cr+++ + Bi0 -> Cr O U++++ + MnOr - UO + + + Mn++ U0 - + H+-lKV-+ + Ot - -> I I- + Fe(CN) + Fe(CN) S S 0r + I, + Iand
2
38. Write balanced ionic; equations for each of the following reactions taking place in acid solution unless otherwise specified. Introduce hydrogen ions and water or hydroxyl ions and water wherever necessary, (a) Bichromate reduced by sulfite giving chromic salt and sulfate; (6) chromic salt oxidized
by
free chlorine to give chromate and chloride; (c) chromite oxidized in alkaline solution with sodium peroxide to chromate; (d) lead peroxide oxidized by
and free oxygen; (e) cupric salt and and metallic copper; (/) manganous salt and chlorate giving a precipitate of manganese dioxide and chlorine dioxide gas; (</) cobaltous chloride in alkaline solution with hydrogen peroxide
permanganate giving mangaiious
salt
metallic
aluminum giving aluminum
salt
to give a precipitate of cobaltic hydroxide.
what
39. Express the following reactions in ionic form, and in each case state fraction of the nitric acid employed serves for oxidation:
(a)
(6)
(c)
(d)
(e)
(/)
(g)
+ HNO - Cu(NO + NO + H O Zn + IINO -* Zn(NO + NO + H O Cu S + HN0 -> Cu(NO + NO + II SO + H O Cu S + HNO -* Cu(NO + NO + S + H O FeS + HNO -* Fc(N0 + S + NO + H O FeS + HNO -> Pe(NO,) + NO, + H SO + H O Sn + HNO + H O ->H SnO + NO + H O
Cu
3
3) 2
3) 2
3) 2
3) 2
3) 3
40.
Write balanced ionic equations for the following reactions taking place
in solution:
(a)
(6)
(c)
(d)
(e)
(/)
+ metallic aluminum + sodium hydroxide aluminate + hydrogen gas + ammonia. chromic salt + oxygen gas. Bichromate + hydrogen peroxide + acid chromic salt + iodine. Chromate + iodide + acid manganous salt + sulfate. Permanganate + sulfite + acid iodide sulfate + Cupric cuprous iodide precipitate + free iodine. cobaltous salt + oxygen gas. Cobaltic oxide + acid
Nitrate
>
>
>
>
>
>
CHEMICAL EQUATIONS
(g)
27
solution)
>
Manganous
salt
permanganate
(in
neutral
manganese
mercurous
dioxide precipitate. (h) Mercuric chloride chloride precipitate

41.
+ stannous chloride + + H SnCle

2
hydrochloric acid
nitric acid is
Write balanced ionic equations for the following reactions in which used as an oxidizing agent. Introduce H + and H2O where
necessary.
(a)
(6)
(c)
(d)
(e)
(/) (g)
(fc)
(0
42.
+ HN0 - Cu++ + NO Zn + (very dilute) HNO - Zn++ + NH^ Fe++ + HNO - Fe +++ + NO Cu S + HNO -> Cu++ + SO - + NO Cu S + HNO - Cu ++ + S + NO FeSj + HNO -> Fe +++ + SOr + N0 Sn + HNO -. H SnO + NO FesP + HNO - Fe+++ + HiPOr + NO +++ + HiSiO + NO FeiSi + HNO - Fe
Cu
3 3
2 2
3 3
in solution.
(a)
Write balanced ionic equations for the following reactions taking place Introduce H 2O and other simple constituents wherever necessary.
+ H S0 - CuSO + (NH SO -+ AgCN (precipitate) (6) NuAg(CN), + HNO -> H Cl S + Ag S (precipitate) (f) Ag(NH KCN S0 + + NII OH -> K Cu(CN) + KCNO (d) Cu(NH K Cd(CN) SO + KCN (e} Cd(NH Cl + HC1 - CoCl (/) Co(NH 43. Balance the following molecular equations: (a) Se Cl + H O H SeO + IIC1 + Se; (b) RuQ + 1IC1 - H RuCl + C1 + H O; (c) Ag AsO + Zn + II,SO - AsH t + Ag + ZnSO + II O; (d) Ce(IO + H (^ O Ce ((J O + I + CO (e) Fe(CrO + Na CQ + O - Fe O + Na CrO HCu(NH,)S0 4
3) 2 2
4) 2
3) 4
3) 4 3) 6
>
3) 4
4) 3
2;
2) 2
CO
(fusion).
CHAPTER
III

15.
Mathematical Significance of a Chemical Formula.
The
law
of definite proportions states that in
any pure compound the
proportions by weight of the constituent elements are always the same. A chemical formula therefore is not only a shorthand method of naming a compound and of indicating the constituent
elements of the compound, but it also shows the relative masses of the elements present. Thus the formula Na2 SO 4 (molecular weight = 142.06) indicates that for every 142.06 grams of pure anhydrous sodium sulfate there are 2 X 23.00 = 46.00 grams of sodium, 32.06 grams of sul= 64.00 grams of oxygen. The percentage of fur, and 4 X 16.00 2 X 23 00 X sodium in pure anhydrous sodium sulfate is therefore ^ 100 = 32.38 per cent. A gram-molecular weight of a substance 16. Formula Weights. is its molecular weight expressed in grams. Thus, a gram-molec'
ular weight (or gram-mole, or simply mole) of Na 2 SO 4 is 142,06 mole of nitrogen gas (N 2 ) is 28.016 grams of the element. grams.
formula weight (F.W.) is that weight in grams corresponding to the formula of the substance as ordinarily written. In most
cases it is identical to the gram-molecular weight, but occasionally the true molecular weight of a compound is a multiple of the weight expressed by the formula as ordinarily written in a chemical
In practically all the reactions of analytical chemistry, however, it can be assumed that the value of the formula weight and that of the mole are the same. The gram-atom or gram-atomic weight is the atomic weight of
equation.
the element expressed in grams (e.g., 40.08 grams of calcium; 14.008 grams of nitrogen). A gram-ion is the atomic or formula weight of an ion expressed in grams (e.g., 40.08 grams of Ca++; 62.008 grams of NO 3~).
28
CALCULATIONS BASED ON FORMULAS AND EQUATIONS 29

one thousandth of a mole; a milligram-atom is one thousandth of a gram-atom. A formula weight of hydrated ferric sulfate, Fe2 (SO4 )3.9H 2 0,
millimole
is
for example, is 562.0 grams of the salt. It contains 2 gram-atoms of iron (= 117.0 grams), 21 gram-atoms of oxygen (= 33G grams), 9 formula weights (9 F.W.) of water, 3,000 milligram-atoms of
sulfur,
17.
and in solution would give 3 gram-ions of sulfate. Mathematical Significance of a Chemical Equation.
chemical equation not only represents the chemical changes taking place in a given reaction but also expresses the relative quantities of the substances involved. Thus, the molecular equation
H S0 + BaCl
2 4
-*
BaS04 + 2HC1
acid,
not only states that sulfuric acid reacts with barium chloride to
give
barium
sulfate
and hydrochloric
but
it
also expresses
the fact that every 98.08 parts by weight of sulfuric acid react with 208.27 parts of barium chloride to give 233.42 parts of barium sulfate and 2 X 36.47 = 72.94 parts of hydrogen chloride, these
numerical values being the molecular weights of the respective compounds. These are relative weights and are independent of the units
If a weight of any one of the above four substances is the known, weight of any or all of the other three can bo calculated by simple proportion. This is the basis of analytical computations.
chosen.
EXAMPLE
I.
sample of pure lead weighing 0.500 gram
is
dissolved in nitric acid according to the equation
3Pb
+ 8HN0 - 3Pb(N0
3
3) 2
+ 2NO + 4H
How many
How many grams 3 are required? pure of Pb(NO 3 ) 2 could be obtained by evaporating the resulting solution to dryness? How many grams of NO gas are formed in the
grams
of
HNO
above reaction? SOLUTION: Atomic weight of lead = 207 Molecular weight of HNO 3 = 63.0 Molecular weight of Pb(NO 3) 2 = 331 Molecular weight of NO = 30.0 (3 X 207) grams of Pb react with (8 X 63.0) grams of HNO 3 (3 X 207) grams of Pb would form (3 X 331) grams of Pb(NO3 ) 2 and (2 X 30.0) grams of NO
,
30

of
Hence 0.500 gram

0.500
Pb would
-
require
& v (\1 O = X tC o X
405 gfam of
HNO
'
and would form

0.500
X X
o 9
X
nn
799 gram of
Pb(N03 ) 2
and
0.500
v O X
*m =
0.0483 gram of
NO
grams of H 2 S would be required to precipitate the lead as lead sulfide from the above solution? How many milliliters of H2S under standard temperature and pressure would be required for the precipitation? (A gram-molecular standard conditions 22.4 liters. under of a occupies gas weight
EXAMPLE
II.
How many
See Sec. 110.)
SOLUTION:
Pb++
+HS2
PbS
+ 2H+
= 207 H 2 S = 34.1
Atomic weight
of lead
" "
Molecular weight of 207 grams of Pb 4 4 require 34.1 grams of of Pb ++ Hence 0.500
HS
2
gram
0.500
34.1 grams of
requires
*? 0.0822
gram
of
H S.
2
Ans.
HS
2
Volume
of
HS2
occupy 22,400 ml. under standard conditions OR99

-
22,400
54.1 ml.
EXAMPLE
III.
In the reaction expressed by the equation:
2Ag2 C0 3 -> 4Ag

(a)
+ 2C0
how many gram-atoms of silver can be obtained from 1 F.W. of silver carbonate, (6) how many gram-atoms of silver can be obtained from 1.00 gram of silver carbonate, (c) how many grams
of silver carbonate are required to give 3.00 grams of oxygen 2 ) are produced from gas, (d) how many moles of gas (CO 2
+
1
50.0 grams of silver carbonate, and of gas (C0 2 O2 ) are produced from
(e)
how many
milliliters
millimole of silver car-
bonate?

SOLUTION:
(a)
31
2 F.W.
(6)
4 gram-atoms Ag 1 2 gram-atoms Ag. Molecular weight Ag2 CO 3 = 276 1 1 HA fin

>
Ag2 CO 3 F.W. Ag2 CO 3
1.00
gram Ag2 CO3 =
0.00363
(c)
-^~X X
276
KKO
^
>
0.00363 F.W.
Ag2C08
0.00726 gram-atom Ag.
Ans.
1
2 moles Ag2 C03 (= 2 (= 32 grams)

3.00 grams
= 552
grams) give
mole
O2 =
3.00
-^d
51 .7
grams Ag2 C03
Ans.
2)
(d)
2 moles
Ag2 CO 3
(= 552 grams)
50
3 moles (O2
+ CO
50.0 grams
(e)
Ag2 C0 3 =
-^ X 3 = 0.272 mole gas.
Ans.
1
1
mole Ag2 CO 3 > 1^ moles gas mole gas (standard temperature and pressure) = 22,400
mfflimole
mL
Ag2 CO3 = 1^ X = 33.8 ml.
of gas.
Ans.
EXAMPLE
2
TV.
In the reaction expressed by the equation

2
MnO + 2NaCl + 3H SO
or
2
-> MriSO 4
+ 2NaHSO +
4 2
C\ 2
+ 2H O
2
MnO + 2C1- + 6H+ ~> Mn++ + C1 + 2H O

2
(a)
how many
,
gram-ions of
Mn++
mole of MnO 2 (6) how many from 5.00 grams of MnO 2 (c) how many millimoles
,
can be obtained from 1 milligrams of MnSO 4 can be obtained

of
MnO
are
required to give 100 ml. C12 (standard conditions), and (d) if 1.00 gram of NaCl, and 5.00 grams of 1.00 gram of 2 SO 4 2
MnO
is
are used, which
the limiting reagent, and how many
milliliters
of C1 2 (standard conditions) are evolved?
SOLUTION (a) 1 mole

:
(b)
MnO 1 gram-ion Mn++ " > 0.001 gram-ion Mn 4 Ans. 1 millimole MnO 1 mole Mn0 (= 86.9 grams) -> 1 mole MnS0 (= 151 151 5.00 grams MnO = 5.00 X SJTS oO.u
2
>
1
".
grams)
8.69 grams
MnSO
4.
Ans.
32

100 ml. C1 2
1
(c)
=
ZZ.4
=
=
1
4.47 millimoles C12

2
2.
millimole Cl2
100 ml. C1 2
(d)
MnO 4.47 millimoles MnO

millimole
2
Ans.
1.00
gram
MnO =
no ~~ =
i
(\r\
0.0115 mole
1.00
gram NaCl -
00
^-,
~
1
00
oo.o
0.0171 mole
5.00 grams
H SO
2
X12OU4
^^ =
1
sir? yo. 1
0.0510 mole
According to the equation these substances react in the molar

ratio of 1:2:3, or 0.0115:0.0230:0.0345.
The NaCl
is
therefore
the limiting reagent and the other two are in excess.
2 moles NaCl ->

0.0171 mole
mole C1 2 = 22,400 ml. C12

'
NaCl ->
* 71
Zi
22,400
192 ml. C1 2
Ans.
Problems
How many grams of potassium and of carbon are contained in gram of K4Fe(CN) .3II O; (6) 1 F.W. of KHC H O ?
44.
6 2
4
(a)
0.211
Ans.
46. lead.
(a)
0.0782 gram, 0.0360 gram;
(b)
39.1 grams, 48.0 grams.

3
A certain weight of lead phosphate, Pb (PO contains 0.100 gram of How many grams of phosphorus are present? What is the weight of the
4) 2 ,
lead phosphate?
What
is
the percentage of oxygen present?

15.8 per cent.
of
Ans.
46.
0.00997 gram.
0.131 gram.
How many grams of oxygen are present in 1.00 gram following: (a) Fe O (b) BaSO (c) Fe(NO .6H O?
2
each of the
3,
4,
3) 3
Ans.
47.
(a)
(a)
0.300 gram,
(b)
0.275 gram,
(c)
0.686 gram.
of the following:
What is the percentage by weight of sulfur in each BiA, (b) Na 2 S2 O3.5II2O, (c) K2 SO4 .A12 (SO4 ) 3 .24H2 O?
(a) 18.7
Ans.
per cent,
(b)
25.8 per cent,
(c)
13.5 per cent.
48. Ignition of anhydrous magnesium ammonium phosphate forms magnesium pyrophosphate according to the equation: 2MgNH 4 PO 4 > Mg2 P2 O7 + 2NH 3 H2O. Calculate: (a) number of formula weights of Mg2 P2O7 produced from 1.00 F.W. of MgNH 4PO 4 (b) number of grams of NH 3 produced
same time, (c) number accompanying the formation of

at the
of milliliters of
1
NH
2 2
3 7.
(standard conditions)
millimole of
(c)
Mg P O
Ans.
(a) 0.500, (b) 17.0
grams,
44.8 ml.

What is the weight of the constituent elements in 0.717 gram of AgN03 ? Ans. Ag = 0.455 gram, N = 0.059 gram, O = 0.203 gram.
49.
60. Calculate the number of pounds of materials theoretically necessary for from CaO and 2CO3 (6) BaSO 4 the preparation of 1.00 pound of (a) from Na2S04.10II2 and BaCl2 .2H2 O.
KOH
Ans.
(a)
(&)
CaO = 0.500 pound, K CO3 = 1.23 pounds. Na2SO4 .10H2 O = 1.38 pounds, BaCl2 .2H2O =
2
1.04 pounds.
Balance the following equation and also write it as a balanced ionic BaSO 4 Calculate from it the followBaCl2 - A1C13 equation: A1 2 (SO 4 )3
51.
number of gram-ions of Al" "*" contained in 1 gram-mole of A1 2 (SO4)3, ++ (b) number of gram-ions of Ba reacting with 1 .00 gram of A1+ *~+, (c) number of grains of BaSO 4 obtainable from 2.00 grams of A1 2 (SO 4) 3 .18II 2 O, (d) number of grams of BaSO 4 produced by mixing solutions containing 3.00 grams of A12 (SO4 ) S and 4.00 grains of BaCU.
1
1
"
ing: (a)
Ans.
52.
(a) 2, (b) 0.0556, (c)
2.10 grams, (d) 4.48 grams.
From
the reaction: 4FeSa
10 2 -*
2Fe 2 O 3
+
(d)
8SO2
calculate the fol,
lowing: (a) number of moles of FeS2 required to form 1 F.W. of Fe 2 O 3 (b) number of grams of oxygen required to react with 2.00 moles of FeS 2 (c) number
,
of millimoles of
SO2 equivalent to 0.320 gram of O2

176 grams,
(c)
conditions) accompanying the formation of 0.160 grain of
volume of SO2 (standard Fe 2O3

.
Ans.
53.
(a) 2, (b)
7.27, (d)
89.6 ml.
Complete and balance the following ionic equation for a reaction taking ~" ^Fe ++ ^ + Mn 4 +. Calculate Fe+ + + MnO4 from it the following: (a) number of gram-ions of Mn ++ produced from 1 gramion of Fe++, (6) number of millimoles of Fe 2 (SO 4 ) 3 .9H 2 O obtainable if 1 millimole of KMnO4 is reduced, (c) decrease in the number of gram-ions of H 4
place in the presence of acid:
"
accompanying the formation of 1.00 gram of Fe "*, (d) number of grams of Fe 2 (SO 4) 3 obtainable by mixing solutions containing 1.00 gram of FeSO4 .7II 2O, 0.100 gram of KMnO4 and 1.00 gram of H 2 SO 4
. ,
4"1
Ans.
64.
(a)
5 , (b)
2%,
of
(c)
3
0.0286, (d) 0.633 gram.
What weight
ing to the equation:
NH is required to dissolve 0.120 gram of AgCl accord+ + Cl~? AgCl + 2NH -> Ag(NH
3
3) 2
Ans.
0.0285 gram.
66. How many grams of 2 S are required to precipitate the bismuth as Bi 2 S 3 from an acid solution containing 100 mg. of dissolved bismuth?
Ans.
0.0244 gram.
66. How many grams of 2 SO4 are required to dissolve 0.636 gram of 2H 2 SO4 - CuSO4 SO2 metallic copper according to the equation: Cu 2H2 O? How many milliliters of gas are evolved (measured under standard
conditions)?
Ans.
1.96 grams.
224 ml.
34
67.

How many
grains of anhydrous chromic chloride (CrCl 3 ) could be ob2 S in the presence of HC1:
tained from 100 mg. of 2 Cr 2 O7 after reduction by Cr2O7 ~ 3H2 S 8H+ -> 2Cr+++ 38 7II 2O?
many
milliliters
(standard conditions) of
+ HS
2
How many grams and how would be required?
Ans.
0.0723 gram, 0.0347 gram, 22.8 ml.
68.
How many
is
What
69.
grams of chromium are present in 0.250 gram of the percentage of potassium in this compound?
K Cr C>7?
2
2
What
aluminum?
60.
(a)
What
contains 0.200 gram of 2 SO 4 .A1 2 SO4.24II 2 O, weight of alum, is the percentage of oxygen in the compound?
What weight of sulfur is present in an amount of 318 mg. of sodium, (fe) 1.00 gram-atom of oxygen?
Na 2 S 2 O3 that
contains
61.
following: (a)
62.
(b)
NH 3 (b) Pb(NO ) 2 (c) What is the percentage of oxygen in FeSO4 .7H 2O, (c) K2 SO4 .Cr 2 (SO 4) .24H 2O?
,
How many
grams
of nitrogen are present in 1.00

3
,
gram FeSO4 .(NH4) 2 SO4 .6H2 O?
of each of the
each of the following:
(a)
H O,
2
63. Ignition of
bismuth basic carbonate takes place according to the follow-
ing equation:
2BiOIICO 3 -> BiA,
+ 2CO + H O.
2
Calculate the following:
(a) number of formula weights of Bi 2 O 3 produced from 1 F.W. of the carbonate, (b) number of millimoles of OO 2 accompanying the formation of 1.00 gram of Bi 2 O?, (c) volume of CO 2 (standard conditions) formed from 0.0200 gram of BiOIICOs, (d) volume of gas (CO2 + water vapor) accompanying the forma-
tion of 1.00 millimole of Bi 2 O 3

1
Convert the following to balanced molecular and ionic equations: Calculate from them the following: 3 ->Fe(NO 3) 2 + AgCl. of of formula number AgCl obtainable from 1 F.W. of FeCl 3 (a) weights ++ of Fe of number '(b) produced per millimole of AgCl, (c) number gram-ions -of grams of Fe(NO 3 )3.6H 2 O obtainable if 1.00 gram-molecular weight of AgNO 3 is used up, (d) number of grams of AgCl obtained by mixing solutions containing 0.700 gram of FeCl 3 and 0.600 gram of AgNO 3 How many grams of which reactant are left over?
64.
eC!3
+ AgNO
*'
66.
2
Assuming that the reaction

3
for the fusion of the mineral
chromite with
Na CO + NaNO takes 13Na CO + 14NaNO 3
place according to the equation:
10Fe(CrO 2 ) 2
,
+
of
5Fe 2 O ?
20Na 2 CrO4
+ 7N +
2
millimoles and
1.00
how many
of
milliliters
(measured at
13CO2 how many 760 mm. and 0C.) of gas

(a) 1.00
are formed from that weight of

Cr,
(6)
Fe(CrO 2 ) 2 containing
gram-atom
gram
Cr?
NH +
67.
How many milligrams of 3 are required to react with 27.2 mg. of T H 3 ->IIgNH 2 Cl Hg 2N the to Cl Hg2 2 according equation: Hg 2 Cl 2 + Cl~? How many grams of free mercury would be formed? 4
66.
NH
HS
How many grams and how many milliliters (standard conditions) of are 2 required to precipitate the arsenic from an acid solution containing a 6H + -> As2 S 3 6H 2O? How 3H 2 S 0.100 gram of Na 3 AsO 3 2AsO 3
:
many grams
of the sulfide
would be formed?

68.
Balance the following equation:
MnOr +
Fe ++
Fe + ++
+HO
2
+ H+ -> Mn++ +
FeS04.7H 2 O
re-
and calculate from
it
the
number
of grains of
that contains 0.250 gram of Mn. ~ 69. Balance the following equation: Cr2 7 Fe++ H+ -> Cr+++ +f+ of Fe If 1.00 gram-molecular weight 2 O. 2 CrO4 is dissolved in water = 2H+ > Cr2 07 = and the solution acidified (2Cr04 2 0), how many grams
quired to reduce that weight of
KMnO4
+H
+ + K +H
"
of
FeSO 4 .(NH 4 ) 2 SO4.6H 2 O would be
required to reduce the
chromium
in the
resulting solution?
70. When used for the oxidizing effect of its nitrate, which is the more economical reagent, potassium nitrate at 65 cents per pound or sodium nitrate at 50 cents per pound? How much is saved per pound of the more economical
reagent?
CHAPTER
IV
CONCENTRATION OF SOLUTIONS
Solution reagents of Expressing Concentration. used in analytical chemistry are usually either (1) laboratory
18.
Methods
reagents the concentrations of which need be known only approximately, or (2) titration reagents the concentrations of which
must be known to a high degree of precision. There are several ways of expressing concentration and it is important to have a In anaclear understanding of just what is meant in each case. of concentration are methods expressing lytical work the following most commonly used. 19. Grams per Unit Volume. By this method a concentration is expressed in terms of the number of grams (or milligrams)
of solute in each liter (or milliliter) of solution.
liter solution of
5-gram-per-
sodium chloride is prepared by dissolving 5 grams of the salt in water and diluting to one liter (not by adding one liter of water to the salt). This method is simple and direct but it is not a convenient method from a stoichiometric point of view, since solutions of the same concentration bear no simple relation to each other so far as volumes involved in chemical reactions are concerned. Chemical substances enter into reaction upon a mole-to-mole basis and not upon a gram-to-gram basis. This method is on a percentage 20. Percentage Composition. in terms of grams of concentration and basis expresses by-weight solute per 100 grams of solution. A 5 per cent of sodium chloride
is
dissolving 5 grams of the salt in 95 which of course gives 100 grams of solution.
made by
grams
of water,
The specific gravity of the solution of a 21. Specific Gravity. of the concentration of the solute in the a measure is solute single
solution.
is
Although occasionally used in analytical chemistry, it a cumbersome method, since it necessitates consulting a table
order to determine
in
the percentage-by-weight
Tables of specific gravities of
common
36
composition. reagents are found in the
37
handbooks and other reference books of chemistry. Tables covering the common acids and bases are also in the Appendix of this Here it will be found, for example, that hydrochloric acid text.
of specific gravity 1.12 contains 23.8
grams
of
hydrogen chloride
in 100
grams
of solution.
22.
Volume
Ratios.
Occasionally in analytical
work the con-
a mineral acid or of ammonium hydroxide is given in terms of the volume ratio of the common concentrated reagent and water. Thus HC1 (1:3) signifies a solution of hydrochloric acid made by mixing one volume of common, concentrated hydrochloric (sp. gr. about 1.20) with three volumes of water.
centration of
a solution made by mixing one used concentrated sulfuric acid (sp. commonly This method of gr. 1.84) with three parts by volume of water. is cumbersome, particularly in work expressing concentrations where subsequent calculations involving the solutions are to be made. A molar solution is one con23. Molar and Formal Solutions. taining a gram-mole of substance dissolved in a liter of solution. This is usually identical to a formal solution which contains a formula weight of substance in a liter of solution (see Sec. 16).
vSimilarly
2
H SO
(l"-3)
signifies
volume
of the
weight of substance dissolved in a liter of water a molar solution, for the resulting solution constitute not does does not occupy a volume of exactly a liter. 1 A liter of molar (M) sulfuric acid solution contains 98.08 grams of 2SO4 a liter
A gram-molecular
of half-molar
49.04 grams does not mean 98.08 grams of the ordinary concentrated sulfuric The concentrated acid contains acid, but of hydrogen sulfate.
(J^M, 0.5M, or M/2) sulfuric acid solution contains In this particular case 98.08 grams of 2S04 of 2 S04.
about 96 per cent of the latter. Since 1 mole of hydrochloric acid reacts with 1 mole of sodium hydroxide, a certain volume of sodium hydroxide solution will be exactly neutralized by an equal volume of hydrochloric acid of the same molar concentration, or twice the volume of hydrochloric acid of one-half the molar concentration of the sodium hydroxide.
Solutions containing a gram-molecular weight of substance dissolved in 1,000 grams of water are useful in computations involving certain physicochemical phenomena. Such solutions are often referred to as molal solutions,
1
but this standard
is
not used in general analytical work.
38

sulfate will neutralize 2 molecules of
One molecule
of hydrogen sodium hydroxide.

2
H S0 + 2NaOH -> Na S0 + 2H
4
2 4
To
neutralize a certain
volume
of
one-half that
tion
volume
of sulfuric acid of the
sodium hydroxide solution, only same molar concentra-
would be required.
Volumetric calculations are therefore
concentrations are expressed in terms of greatly simplified moles of substance per unit volume of solution; for, when so expressed, the volumes of reacting solutions of the same molar concentration, although not necessarily equal, bear simple numerical relationships to each other.
when
EXAMPLE.
SOLUTION:
1
What volume
of 0.6380
solution will neutralize 430.0 ml. of 0.4000
M sulfuric acid?
potassium hydroxide
mole
H S0 ~
2 4
2 moles
KOH
H SO
2
430.0 ml. of 0.4000 molar solution contains
x
0.1720 mole
1
0.4000
2
0.1720 mole
ml.
KOH KOH contains 0.0006380 mole KOH

4
H SO o
0.3440 mole
Volume required = ^ r^rôoT^ = U.UUUoooU
539.3 ml.
Ans.
24. Equivalent Weight and Normal Solution. The equivalent weight of an element or compound is that weight equivalent in
reactive power to one atomic weight of hydrogen.

is
The
milli-
one thousandth of the equivalent weight. The equivalent weight gram-equivalent weight is the equivalent weight expressed in grams;
the gram-milliequivalent weight
1
is
the milliequivalent weight ex-
The application of gram-equivalent weights pressed in grams. to various types of chemical reactions will be taken up in detail in Part III, but simple cases, applying particularly to qualitative
analysis, will
1
be considered briefly here.
The equivalent weight of a substance, like the atomic or molecular weight, merely a number without a unit of weight; the gram-equivalent weight is a definite number of grams. However, when the connotation is clear, the terms
is
equivalent weight" and "milliequivalent weight" are frequently used to signify gram-equivalent weight and gram-milliequivalent weight, respectively.
"
The gram-equivalent weight
of
39
an acid, base, or salt involved a simple metathesis such as a neutralization or precipitation is that weight in grams of the substance equivalent in neutralizing or precipitating power to 1 gram-ion of hydrogen (i.e., 1.008 grams of H+). A normal solution contains 1 gram-equivalent weight of solute in 1 liter of solution, or 1 gram-milliequivalent weight in 1 milliThe normality of a solution is its relation to a liter of solution. normal solution. A half-normal solution therefore contains in a unit volume one-half the weight of solute contained in its normal N, or solution, and this weight may be expressed as 0.5 N, N/2. The concentration of a normal solution is expressed simply
in
as N.
Since the concentrations of solutions used in precise volumetric analysis are usually found experimentally, the concentrations can-
not often be expressed by whole numbers or by simple fractions. They are more likely to be expressed as decimal fractions, e.g., 0.1372 N.
26. Simple Calculations Involving Equivalents, Milliequivalents, and Normality. The use of equivalents, milliequivalents, and
normality
is
so extensive in analytical chemistry
are so fundamental that a clear understanding of at this time. More detailed discussions applying particularly to
and the terms them is essential
quantitative analysis will be given in Part III. Let us consider here only the simplest reactions between common acids, bases, and salts, and as an example let us take sulfuric
A mole, or gramand a molar solution molecular weight, of 4 is 98.08 grams, 2 of the acid therefore contains this amount of pure hydrogen sulfate in a liter of solution. Since 98.08 grams of H 2 SO4 has a neutralizing power equivalent to 2 gram-atoms (2.016 grams) of hydrogen as an ion, the gram-equivalent of H 2 SO4 as an acid is 98.08/2 = 49.04 grams, which is equivalent in neutralizing power to 1 gram-atom (1.008 grams) of hydrogen as an ion. The grammilliequivalent weight is 0.04904 gram. A normal solution of sulfuric acid therefore contains 49.04 grams of ILSO4 in a liter of solution, or 0.04904 gram of H 2 S04 in a millimeter of solution. A 1 molar solution of sulfuric acid is 2 normal; a 1 normal soluacid.
The molecular weight
of II 2 SO 4 is 98.08.
H S0
tion of sulfuric acid
is ]/2
molar.
40
Sodium hydroxide is a base with a molecular weight of 40.00. The gram-equivalent weight of NaOH is 40.00 grams, since this amount
is
neutralized
by
1.007
contains 40.00 grams
in
grams of 11+ A normal solution of NaOH a liter of solution and is likewise 1 molar.
.
ACIDS
-
=36.47
These weights are

equivalent to
all
^2^=60.05 g.
-y2-=40.03g.
FIG.
1.
Gram-equivalent weights of some
acids, bases,
and
salts.
The gram-equivalent weight of a simple salt is determined the same way as that of an acid or base, namely by reference
in
to
1.008 grams of 11+ as a standard. In the case of the salt of a metal, the equivalent weight is ordinarily the molecular weight
of the salt divided
by the
total oxidation
number represented by
and
salts are
to the
the atoms of metal in the formula.
The equivalent weights

shown in Fig. same standard,
1.
of a
few
acids, bases,
Since each of these amounts is equivalent they are mutually equivalent to one another.
In each case the specified amount when dissolved in one produce a 1 normal solution.
It follows that 1 liter of 1
41
liter
of solution will
any one-normal any one-normal base. More generally, a certain volume of any acid will neutralize the same volume of any base of the same normality.
NaOH,
base.
or
1 liter of 1
One
liter of 1
N N H2SO4
HC1 will Ba(OH) 2 or 1

,
neutralize
liter of
1 liter
of 1
will also neutralize 1 liter of
Similarly, 1 liter of 1 from 1 liter of 1 NaCl or
N AgNO
1
will precipitate
1
the chloride
latter
liter of
BaCl 2 and the

,
will just precipitate the sulfate
from
1 liter
of
N Na SO4 or 1 liter
2
of
Fe 2 (SO 4 ) 3
We found that when two solutions of equal molarity react, the volumes are in simple ratio to each other. But when two solutions of equal normality react, the volumes of the solution are
equal.
Since volumes of reagents in analytical chemistry are usually measured in milliliters rather than in liters, it is more convenient
to consider a normal solution as containing
milliliter.
I
gram-millicquivalent
weight per weights present in a solution can be found from the simple relationship
:
Hence the number
of gram-milliequivalent
Number
or
of milliliters
X
X
normality
=
of gram-milliequivalent weights of
number
ml.
= number
me.
vvts.
(See footnote, p. 38)
Thus, 2.00 ml. of 0.00

or 12.0
N HOI contain
12.0 millicquivalent weights,
This will 0.438 gram of hydrogen chloride. L,UUU exactly neutralize 12.0 milliequivalents of any base, for example, 4.00 ml. of 3.00 NaOH, or 4.00 ml. of 3.00 Na2 CX) 3 or 80.0 ml.
T-TWWX
I1C1
of0.150NBa(OH) 2
It follows that
etc.
when
solutions
A and B
m\. B
mutually interact to a
complete reaction,
ml.,i
N,i
X N*
the approximate molarity and normality To what volume should of a 13.0 per cent solution of 2 SO 4 ? solution? 100 ml. of the acid be diluted in order to prepare a 1.50
I.
EXAMPLE
What
is
42

From
specific gravity table in the
SOLUTION:
1 liter
Appendix, the
specific gravity of the acid is 1.090.
weighs 1,090 grams
1 liter
1
contains 1,090 X 0.130 mole II 2 SO 4 = 98.08 grams
142 grams
H S0
2
= 142/98.08 = 1.45 M. Ans. 1 gram-equivalent H 2 SO 4 = H 2 SO 4 /2 = 49.04 grams Normality of solution = 142/49.04 = 2.90 N. Ans. 100 ml. contain 290 milliequivalents H 2 SO 4
Molarity of solution
After dilution x ml. of 1.50
contain 290 milliequivalents
1.50
= 290 = x 193
ml.
Ans.
2 3
EXAMPLE
II.
A solution contains 3.30 grams of Na CO

What
is its
.10H 2O
2,
in each 15.0 ml.
normality?
What
is its
2
molarity?
3
With how many
milliliters of 3.10
acetic acid,
HC H O
will
25.0 ml. of the carbonate react according to the equation: C0 8- - 2 O C0 2 ? With how many milliliters of 3.10
H
:
2H+ + N H 2S04
will 25.0 ml. of the
carbonate react?
SOLUTION
Molecular wt.
Na CO 3 .10H 2 O =
2
286
Equivalent wt.
Na2CO 8 .10H2 O = = 0.143 Milliequivalent weight

3 30
JLo.U
=
Zt
143
Solution contains
1
y^ = 0.220 gram per ml.

Q
normal solution would contain 0.143 gram per ml.

'
.
Normality =
Molarity
1.54
N.
Ans.
Ans.
=
x
0.77
M.
3.10
= x = =
25.0
1.54
12.4 ml. 12.4 ml.
HC H O Ans. H SO Ans.
2
2.
4.
EXAMPLE
A12 (S0 4 ) 3
(6)
,
III.
(a)
A
of
would be
0.100 solution of aluminum sulfate, what normality as an aluminum salt?

(c)
normality as a sulfate? of the salt are contained in each
What
How many
(d)
milliequivalents
milliliter?
What volume
of
6.00
43
would be required to react with the aluminum in 35.0 ml. of the salt solution according to the equation: A1+++ + 3NH4 OH -> A1(OH) 8 + 3NH4+ ? (e) What volume of 6.00 N BaCl2.2H 2 O solution would be required to precipitate the sulfate from 35.0 ml. of the solution? (/) How many grams of BaCl 2 .2H 2 O are contained in each milliliter of the above solution? SOLUTION
4
:
N NH OH
(a)
(6)
(c)
mole A1 2 (SO4 ) 3 = 6 equivalents (2 A1+++ o 6H+) 0.100 molar = 0.600 normal as Al salt. Ans. = 0.600 normal as sulfate. Ans.
1
0.600 milliequivalent per milliliter. = ml.* X N* (d) ml.A X N^ = 35.0 X 0.600 x X 6.00
Ans.
(e)
= 3.50 ml. Ans. ml.A X N^ = ml* X N* x X 6.00 = 35.0 X 0.600 x = 3.50 ml. Ans.
x
0.00
(/)
0.732 gram.
Problems
Ans.
71.
What
3
fraction of the molecular weight represents the milliequivalent
weight in the case of each of the following acids, bases,

(fc)
and
salts: (a)
3) 2?
H SiF
2
6,
H As0
Ans.
4,
(c)
HP
4
7,
(d)
(b)
Th02
(e)
(NII 4 ) 2 SO 4
(c)
(/)
Zn3 (AsO
(a)
1/2,000,
1/3,000,
1/4,000,
(d)
1/4,000,
(e)
1/2,000,
(/)
1/6,000.
72.
tion?
How many How many
grams of
millimoles of
K S0 are contained in K SO are present?

2
4
2
50.0 ml. of 0.200
solu-
Ans.
73.
0.872 gram.
solution of
5.00 millimoles.
H SO
2
has a specific gravity of 1.150.
What
is
the
normality of the solution? Ans. 4.90 N.

74.
What
is
the normality of a solution of

4
NH OH having a specific gravity

4 2 4
of 0.900?
15.0 ml.
How many milliliters of 13.0 N H SO would be neutralized by of the NH OH? To what volume should 250 ml. of the 13.0 N H SO
2
4
be diluted to
Aiis.
make a
solution that
is
5.00 molar?
15.0 N.
17.3ml.
325ml.
is its
30 per cent solution of H 3 PO 4 has a specific gravity of 1.180. What normality as an acid assuming partial neutralization to form HPO 4"? What is its molar concentration?
76.
Ans.
7.22 N.
3.61
M.
44
76.

How many
grams
of
SrCk.GHgO are required to prepare 500 ml.
of
0.550
of
N solution? What is the molarity of the solution? How many milliliters 1.00 N AgNOs would be required to precipitate the chloride from 20.0 ml.
36.6 grams.
of the strontium chloride solution?
Ans.
77.
0.275
M.
11.0 ml.
How much
Cr2 (SO4 )3.18H 2 O

0.200
N NH OH
4
water must be added to 50.0 ml. of a 0.400 solution of make it 0.0500 molar? How many milliliters of would be required to precipitate all the chromium as Cr(OH) 3
in order to
from 20.0 ml.

Ans.
of the original undiluted solution?
16.7ml.
40.0ml.
is
piece of aluminum weighing 2.70 grams is treated with 75.0 ml. of 1.18 containing 24.7 per cent After the metal 2 SO 4 by weight). 6H+ > 2A1+++ 3H 2 ) the solution is diluted completely dissolved (2A1
(sp. gr.
to 400 ml.
(a) normality of the resulting solution in free sulfuric of the solution with respect to the aluminum salt it contains, acid, (b) normality total volume of 6.00 4 (c) required to neutralize the acid and precipi-
Calculate
N NH OH
0.750 N,
tate
all
the
(a)
aluminum
0.365 N,
as A1(OH)3 from 50.0 ml. of the solution.

(c)
Ans.
(6)
9.30 ml.
79.
What is the
(a)
gram-equivalent weight of each of the following acids, bases

(6)
and
salts:
II 2 C2O 4 .2H 2O,
H PO
3 2
3,
(c)
CaO,
(d)
Fe2
3,
() SnCU,
(/) (Ca 3 (P0 4 ) 2 ?
of 3.20
How many milliliters of 2.30 M H SO 4 would be neutralized by 15.8 ml. M NaOH? How many milliliters of 4.60 N H2 C2O4 .2H2O solution would be neutralized by 10.0 ml. of 5.10 N NaOH? By 10.0 ml. of 5.10 N Ba(OH) 2 ? How many milliliters of 4.60 N HC 2 H 3O2 would be neutralized by 10.0 ml. of 5. ION NaOH?
80.
to
To what volume must 25.0 ml.of HC1 (sp. gr. 1.100) be diluted in order make a solution of HC1 with a specific gravity of 1.04? How many milliliters of 0.500 N Ba(OH) 2 would be required to neutralize 40.0 ml. of the re81.
sulting diluted solution?

12.0 per cent solution of has a specific gravity of 1.04. 2 C 2O 4 .2H 2 the normality of the solution as an acid? How many milliliters of would be neutralized by 18.0 ml. of the acid? 3.00 molar
82.
What
is
KOH
83.
How many
milliliters of
0.500
BaCl2 solution would be required to
How
precipitate all the sulfate from 10.0 millimoles of FeSO 4 .(NH 4 ) 2 SO 4 .6H 2 O? 3 would be required to precipitate the many milliliters of 0.100
N AgNO
chloride from 8.30 ml. of the

84.
barium chloride solution?
What
3
is
the approximate normality of a solution of nitric acid marked
"HN0
86.
1:4"?
How many
3
milliliters
would theoretically be required to react
with 0.028 F.W. of Fe2O 3 to form
Fe(NO 3) 3?
What is the
A solution of H PO
contains 0.500 millimole per milliliter.
normality of the solution as
a phosphate?
How many
milliliters of 1.20
2
45
KOH would be required to form KH PC>4 with 5.00 ml. of the phosphoric acid?
To what volume must
the solution 1.10
86.
25.0 ml. of the original acid be diluted in order to
make
as a phosphate?
of
How many
grams
chloride solution?
How many
FeCl 3 are contained in 25.0 ml. of 0.520 N ferric millimoles of FeCl 3 .6H 2 O could be obtained by
4 OH evaporating the solution to dryness? How many milliliters of 0.200 are required to react with 25.0 ml. of the ferric chloride solution to precipitate
N NH
Fe(OH) 8 ?
CHAPTER V
EQUILIBRIUM CONSTANTS
26.
action
Law of Mass Action. may be expressed as
In simple terms the law of mass

follows:
The
rate of reaction between

to
two or more interacting substances in a mixture is proportional
the product of the prevailing active concentrations of the substances.
great
many
versible reactions.
of the reactions of analytical chemistry are reThis means that the products of a given reac-
tion interact, at least to some extent, to give the initial substances. and Consider a general reversible reaction between substances
at a given temperature to give substances to the following equation:
and
according
A + B <= C + D
At the
These
start of the reaction, only substances react at a certain rate to give C and
A and B
and B are produced, the concentrations of to the law of mass action, the rate of the reaction between
are present. and, as the latter decrease. According
and
at
trations of
any given A and

Rate
moment
proportional to the prevailing concenat that moment. In symbols this may be

is
expressed as follows:
of reaction
between
and
B=
k'[A][B]
where [A] and [B] are the prevailing molar concentrations of A and B, respectively, and k' is a constant at a given temperature. As the concentrations of substances C and D increase, these substances in turn react at a constantly increasing rate to produce A and B. The rate of this reaction at any moment is proportional to the product of the prevailing concentrations of C and D.
Rate
of reaction
between
and
D=
k"[C][D]
When
equilibrium has been established, these two rates are equal.

[C][D]
[A][B]
Hence,
_ ~
K = k"
B
TC
In the reaction A + 2B <= the rate of reaction between
C+D
(i.e.,
A + B + B^C + D),
and
46
is
proportional to the con-
cent ration of
47 Hence,
A and to the square of the concentration of B.

=
at equilibrium,
[ApP More generally, in the reaction wA + #B +

the equilibrium constant
is
<=*
yC + zD +
expressed as follows:
IAMB?
For the value
centrations
must be
to be approximately a true constant, conrelatively small (see Sec. 32). Furthermore,
although in computations involving chemical equilibria, concentrations are better expressed in terms of the number of moles of substance per kilogram of solvent, for dilute solutions this is practically the same as the number of moles of substance per liter of solution;
and as the
latter is consistent with the definition of a
molar solu-
tion as used in analytical computations, it will be employed here In mass-action in formulating mass-action expressions as well.
expressions molar concentrations will be represented as above by enclosing in brackets the symbol of the element, compound, or radical in question.
In general, if a solid substance is involved in a chemical equilibrium, its concentration is not included in the formulation of
the mass-action constant, since the concentration of the solid is The same is true of water in an itself essentially a constant.
equilibrium involving dilute aqueous solutions. action constant for the dissociation equilibrium
Thus, the mass-
NH OH ^ NH + H O
4 8 2
is
simply
[NH 3 [NH4 OH]

]
K
Water
dissociates slightly
27. Ion Product Constant of Water.
into hydrogen ions
and hydroxyl ions as follows:
<=>
H+ + OH-
1 Experiments indicate that the hydrogen ion is hydrated. It is therefore often expressed as BUG*. This ion is called the hydronium ion and is formed by the union of a proton with a molecule of the solvent. The use of this symbol
complicates equations and offers no particular advantages in analytical
computations.
48

expression for this dissociation
is
The mass-action
simply
[H+][OH-] = Ku,
aqueous is omitted stated as a constant above, and, essentially from mass-action expressions. In any aqueous solution, therefore, the product of the molar hydrogen-ion concentration and the molar hydroxyl-ion concentration is a constant at a given
2
since the concentration of undissociated
in dilute
solutions
is
temperature. This constant is called the ion product constant of water and at 25C. has a value of 1.0 X 1Q- 14
.
[II+][OH-]
Ku,
1.0
(= 1.2
(= 5.8
X X X
10~ 14 (at 25C.) 10~ 15 at 0C.)
10- 13 at 100C.)
In pure water the hydrogen-ion and the hydroxyl-ion concentra7 tions are equal; at 25C. each has a value of 1.0 X 10~ molar.
28.
pH
Value.
It is often convenient to express
concentrations in terms of the
pH
value.
The pH value
hydrogen-ion as used
in analytical chemistry is simply the common logarithm of the reciprocal of the molar hydrogen-ion concentration.
pH =
log
= -
log [H+]
colog [H+]
Similarly the pOH value, although less often used, is the logarithm of the reciprocal of the hydroxyl-ion concentration. The pH value of pure water at 25C. is 7. The pH value of acid solutions
is less
than 7; the
pH
value of alkaline solutions
is
greater
than
7.
In general at 25C.,
pH + pOH =
EXAMPLE
ionization
I.
14
is
What
is
the pll value and what

is
the hydroxyl-
ion concentration of
a solution that
M/
1,000 in
HC1
(effective
100 per cent)?

[H+]
SOLUTION:
0.001 log
X
_3
10- 3
pH =
3.
1Q
Ans.
pOH =
[OH-] =
14
1
- 3 = 11 X 10-". Ans.
EXAMPLE
value?
II.
49
in a certain
is
The hydrogen-ion concentration
dilute solution of sulfuric acid is 2.0
10~ 5
What
the
pH
What
is
the
pOH
value?
SOLUTION:
(5
4 log 10
x
4.70.
+ log 5 = 4 + 0.70 =
=
9.30.
Ana.
pOH =
14
4.70
Ana.
EXAMPLE III. The pH value of a certain solution is 5.92. What is the pOH value, the hydrogen-ion concentration, and the
hydroxyl-ion concentration?
SOLUTION:
pH + pOH = pOH =
= [H+][OH-] = ~ [OH =
[H+]
]
14 14
1.0
i
5.92
=
14
8.08.
08
Ans.
10-6
10-
5 - 92
10+-
X
'
1.20
10-6
Are*.
10-
o
20
= X 10-
8 3
Problems
I
(Temperatures are 25*C.)

(a)
87.
What
is
is
the
pH
concentration X the hydrogen-ion concentration of a solution with a the solution acid or alkaline?
2.8
10~ 3 ?
value of a solution in which the hydrogen-ion Is the solution acid or alkaline? (6) What is
pOH
value of 4.17?
Is
Ans.
88.
(a)
2.55, acid.
is
(6)
1.5
lO" 10 alkaline.
,
What
the
0.30 molar
NaOH
pH value of 0.010 molar IIC1 (100 per cent ionized)? Of (90 per cent effective ionization)? Of a solution of HC1 in
is
which the hydrogen-ion concentration Ans. 2.0. 13.43. - 0.90.

89.
8 molar?
What
is
the hydrogen-ion concentration of a solution in which
pH
0.55?
Ans.
90.
3.6 molar.
(a)
Given
[Oil-]
pH =
.
10.46.
Calculate [H+], [OH~], and
pOH.
,
(6)
Given
5.6
10-2
Calculate [H+], pH, and
pOH.
1.8
Ans.
91.
(a) 3.5
X
is
10-", 2.9
10~4 3.54.
,
(6)
10~ 13 12.75, 1.25.
(a)
What
^s
the
pOH
concentration
5.3
10~4 ?
Is the solution acid or alkaline?
value of a solution in which the hydrogenion (6) What is the
50

pH
value
is
hydroxyl-ion concentration of a solution in which the the solution acid or alkaline?
9.27?
Is
92. What is the pH value of 0.050 molar IINO 3 (100 per cent ionized)? Of 0.80 molar KOH (effective ionization = 85 per cent)? Of a solution of HC1 in which the hydrogen-ion concentration is 5.0 molar?
93.
What
(a)
is
the hydroxyl-ion concentration of a solution in which
pOH =
Given
0.27?
94.
Given
[H]+
pOH =
9
.
5.80.
Calculate [H+], [Oil-], and pH.
(6)
3.1
10~
Calculate IOH~], pll, arid
pOH.
The law of mass action can be applied 29. Ionization Constant. to the equilibrium in dilute solution between the molecules of a weak acid or weak base and its ions. Thus acetic acid, 2 3 O2 ,
HC H
is
partially ionized in solution as follows:
HC H
2
<=>
H+ + C 2 H O 23
2
Therefore,
[H+][C 2
2
H Q ~] [HC H
3 3 2]
_ ~ v Vnc H >*
>
That
a solution containing acetic acid, the total molar concentration of hydrogen ions (from whatever source) multiplied by the total molar concentration of acetate ions (from whatever source) divided by the molar concentration of un-ionized acetic This value is called acid, is a constant at a given temperature.
is,
in
the ionization constant of acetic acid.
Its value at
25C
is
1.86
ioof
5
.
A similar mass-action expression can be set up for the ionization

a solution of ammonia in water. Here ammonium hydroxide molecules are presumably formed which, in turn, dissociate partially into
ammonium
ions
4
and hydroxyl
<=>
4
ions.
NH OH
The
ionization constant
is
NH + + OH-
therefore usually written
[NH4 +][OH-1 _ " KNH OH [NH4 OH]

<
Since
hydroxide molecules (if they exist at all) are in with ammonia and water, the equilibrium is more equilibrium
generally expressed as
ammonium
?=
(NH4 OH)
NH + + OH"
4
and the ionization constant can be written
51
[NH4+][OH-] _
In either case the total concentration of either dissolved as 3 such or combined as NII 4 OH, is used in the denominator of the fraction, so the numerical value of the constant is the same in
,
NH
.
the two cases.
At 25C.
it is
1.75
10~ 5
The
ionization constants of a few
weak
acids
and bases are
given in the Appendix.
EXAMPLE
ionized?
I.
What
is
the ionization constant of acetic acid at

it is 1.3
a certain temperature
if
in tenth-molar solution
per cent
H+ + C H O 2SOLUTION: If 0.10 mole of HC H O were completely ionized, it would give 0.10 mole (or 0.10 gram-ion) of H+ and 0.10 mole (or 0.10 gram-ion) of C H O ~. Being only 1.3 per cent ionized,
HC H
2
2 <=
it
gives 0.10X0.013 = 0.0013 mole of 11+ and 0.0013 mole of C 2 H 3O 2~, leaving 0.0987 mole of undissociated HC 2 H3 2 molecules.
The molar concentrations

[11+]
are therefore as follows:
H [HC H
[C 2
3
2-]
2]
= = =
0.0013 0.0013
0.0987
Substituting these in the above expression for the ionization constant of acetic acid, we get
(0.001 3) (0.0013)
0.0987
K=
EXAMPLE
is
1.7
10- 5
Ans.
II.
5
.
At 25C. the
ionization constant of acetic acid
1.86
10~
What
is
molar solution SOLUTION:

in a 0.20
the molar concentration of hydrogen ions of acetic acid at 25C.?
Let x = molar concentration of
H+
C 2H 30<r
Then
x
= molar
concentration of
and
0.20
x = molar concentration of undissociated
HC H O?
2
52
(0.20
x)
3
Solving,
1.9
10~~
mole per
liter.
Ans.
Numerical values in mass-action expressions need not be expressed to more than two or, at the most, three significant figures. Therefore simplifying assumptions can often be made. In the above fractional equation, the value of x is so small compared with the value 0.20 from which it is subtracted, that it is well
within the limit of precision to write
(*)(*)
0.20
= 1.8GX
10~5
and thus avoid solving a quadratic equation. 1

30.
Common
Ion Effect.
Buffered Solution.
is
Suppose into a
dilute solution of acetic acid

of
sodium acetate,
.
i.e.,
dissolved a considerable quantity a highly ionized salt of acetic acid. The

is
3
total acetate-ion concentration

.
greatly increased, but since the

2
ri equilibrium constant ^-TFT^-TT/A
[H
][C 2
H O -]
==
KHc,H o
3
must be main-
tained, the greater part of the hydrogen ions present must unite with acetate ions to form more of the undissociated acetic acid
molecules.
H+ + C H
2
In other words, the equilibrium reaction HC 2 3 2 <=* ~ must go to the left to a degree sufficient to rees2
tablish the numerical value of the constant.

fore
The
solution there-
becomes much
less acidic,
with a hydrogen-ion concentrais
tion only slightly greater than that of pure water. similar case is one in which an ammonium salt
added to a
",
solution of
ammonium
hydroxide.
3
2
<F
presses the ionization
NH + H O
The common ion, NH44 re(NH4 OH) < NH4+ + OH- to

.
.
a very great extent, for in order to maintain the equilibrium con. , [NH4+][OH-]- = stant i ^" K, the hydroxyl-ion concentration must be
.
^.
In cases where such simplifying assumptions cannot be made, the formula
for solving the general quadratic equation
bx
+c=
0| is
= 2a
greatly decreased. The resulting solution basic than pure water.
is
53
only slightly more
In each of the above two cases the solution is said to be buffered by the common ion added. The acetic acid-sodium acetate combination, for example, has a low hydrogen-ion concentration which is little affected even by the addition of small amounts of a strong acid, for the additional hydrogen ions merely unite with the acetate
present in excess) to give more acetic acid, the ionization of which is repressed by the acetate. Similarly, the basicity
ions
(still
hydroxide solution is not much affected even by the addition of small amounts of a strong base like sodium
of a buffered
ammonium
hydroxide. Buffered solutions are
much used both in qualitative and quanti-
tative analysis to effect certain separations of elements where a carefully controlled hydrogen-ion or hydroxyl-ion concentration
is essential.
Problems covering some of these separations are
in-
cluded in this book.

the hydrogen-ion concentration in 500 ml. of a 0.10 molar solution of acetic acid at 25C. if the solution contains an additional 2.0 grams of acetate ions added in the form
is
EXAMPLE.
What
sodium acetate? SOLUTION

of
:
(KH c H,o =
2
1.86
X JO"
=
5
.)
2 grams
C2H302~~ =
per 500 ml.
0.068 mole per
liter
Let x
concentration of
concentration of
H+ ions
C2H 3 O 2
~
ions
Then
x
+ 0.068 =
0.1
and
x
concentration of un-ionized
Therefore,
or approximately,
W|JP_ 1.86X10-'
(since x is small)
Solving,
2.6
10~ 5 mole per
liter.
Ans.
H C0 H
31. lonization of Polybasic Acids. Polybasic acids like 2 3, 3 P0 4 etc., ionize in steps, and a mass-action expression
,
54
can be written for each step. Thus, 2 S ionizes to form is constant ionization the which case in HS~,
__ T^ _ Kl ~
H
i
H+
and
Q 9>1
v X
in 10-8
The HS~
ions are further ionized into
H+ and
=
,
in
which case
Multiplying the two equations one by the other gives
-[H 2 S]
about 0.10 molar, and [H 2 S] = 0.10. Therefore in cases where metallic elements are precipitated 2 = 1.1 X 10~23 by saturating their solutions with H 2 S, [H+] [S=] It is seen that the primary ionization of 2 S is much greater cannot be ionization than the secondary ionization and that the correctly expressed by the equation H 2 S <=^ 2H+ + S~. The concentration of H+ ions in a solution of H 2 S is not twice that of the
saturated solution of
HS
2
is
S^
ions.
The primary
ionization of
any polybasic acid
is
much
greater than the secondary ionization. EXAMPLE I. What is the approximate hydrogen-ion concen2 S? tration in a solution of hydrogen sulfide which is 0.07 molar in
rTT4-i 2 ra=i
SOLUTION:
1.1
In solving this problem, the expression
10~ 22 cannot be used since neither [H+] nor [S^] is known and there is no simple relation between them. On the other hand,
although 2S is ionized in two steps, the first ionization is so much greater than the second ionization that, for the purpose of obtaining an approximate answer, the latter may be considered negligible. In other words, practically all of the hydrogen ions may be considered to
come from the ionization of H 2 S into H+ and Therefore [H+] and [HS~] are practically equal in value and
[H+KHS-] [H 2S]
or
,
IIS"".
J>1
1Q U
_8
9.1
10-
x = 8 X 10~5 mole per
liter.
Ans.
EXAMPLE
of
II.
55
8
What
is
the concentration of S
ions in 200 ml.
of a solution that is 0.05
molar in
HS
2
and that by the addition
HC1
contains a total of 0.12 equivalent of
H+
ions?
SOLUTION:
Let x
0.05
approx. 0.05 0.12 X 5 = 0.6
= molar concentration of S = ions = concentration of undissociated = concentration of H+ ions
-=
1.5
(0.05)
x
32. Activity
10~ 23 mole per
liter.
Ans.
In analytical chemistry Activity Coefficients. mass-action calculations are usually applied to equilibria involving electrolytes in solution. As solutions of electrolytes are made pro-
and
gressively more concentrated, the quantitative effect erties as conductivity and freezing-point lowering
on such propbecomes pro-
gressively less than that calculated solely from the net change in molar concentration. This is likewise true of mass-action equi-
This phenomenon was formerly explained by assuming that electrolytes are less completely ionized in more concentrated solutions; that the degree of ionization approaches 100 per cent
libria.
more satisfactory explanaonly as dilution approaches infinity. tion is based on the assumption that most salts and the so-called
strong acids and bases are practically completely ionized in all aqueous solutions but that the effective concentration, or activity, of the ions is decreased because of forces of attraction between the positive and negative ions. These forces become less at higher
dilutions since the ions are farther apart.
In mass-action expressions, therefore, activities or effective concentrations, rather than molar concentrations should be used for accurate results. The activity (a) of an ion or molecule can be found by
multiplying
its
molar concentration
(c)
by an
activity coefficient
(/).
a =/c
An
a factor which converts a molar which concentration to a value expresses quantitatively the true
activity coefficient is therefore
effect.
mass-action
is
Thus, the ionization constant of acetic acid
correctly expressed as
/i[H+]X/,[C,H,Qr] =
56

/i,
,
/2 and /3 are the activity coefficients of the hydrogen ion, the acetate ion, and the acetic acid molecule, respectively. The numerical value of an activity coefficient is not always easy to determine, since it depends on many factors such as temperature, the number of charges on the ion, and certain electrical
where
properties of the solution. In the case of relatively dilute solutions (e.g., 0.01 formal or less) and particularly for univalent ions, activity coefficients are not far from unity, and so no great error
is
introduced
tivities.
concentrations are used in place of acSince concentrations in most analytical operations are
when molar
relatively low and since a high degree of precision is seldom required in analytical computations involving mass-action constants,
activity coefficients can be omitted without much error. therefore not included in the calculations in this book.
33. Dissociation Constants of
They
are
Complex
Ions.
complex
ion,
by
definition, is
These a neutral molecule or a negative ion. The mass-action principle can be applied to dilute solutions of such ions. Thus the copper
in equilibrium with its constituents. constituents are ordinarily a simple positive ion and either
one that
is
ammino
(or
copper ammonio) ion,
Cu(NH 3)4"M
",
ionizes slightly
as follows:
Cu(NH
Its dissociation constant
3) 4
++ * Cu++
+ 4NH
xiu
is
therefore expressed thus,

,
[Cu++][NH 3]* _
[Cu(NH 3 )
++ 4
(
]
4.0
u) ;
This means that in a dilute solution containing the complex ion, the total molar concentration of the simple cupric ions present, multiplied by the fourth power of the total molar concentration of ammonia (NH 3 + 4 OH), divided by the molar concentration of the undissociated complex ion, is a constant at a given
NH
temperature.
ions of this type frequently encountered in analytical ++ chemistry are Ag(NH 3 ) 2+, Cu(NH 3 ) 4++, Cd(NH 3 ) 4++, Ni(NH 3 ) 4
Complex
CoCNHah^,
and
Fe(CN) 6 Ag(CN)r, Cd(CN) 4 =, Cu(CN)a- Hg(CN)r, Co(CN) 6 ^, and ~ Ni(CN)4". Halide complexes like SnClr and HgI4 and oxalate
,
s Important cyanide complexes include Fe(CN) 6
Zn(NH 3) 4 ++.
complexes
like
Mg(C 2
4 )<r
are also
commoa
EXAMPLE
I.
57
What
is
the molar concentration of mercuric ions
and of cyanide ions in a tenth-molar solution of = 1Q- 42 .) 4.0 (Dissociation constant of Hg(CN) 4
K2Hg(CN)4?
SOLUTION:
[Hg++][CN-f - 4 oxl [Hg(CN)r] Let x = concentration of Hg++ in the dissociation: = 4CN<=*

-
Hg(CN) 4
4x
Hg++ +
Then
0.10
concentration of
CN~
Hg(CN)4~
0.10 (approximately)
concentration of
=
x 4x
4.0
1.1
10~42
= =
X 4.4 X
is
10~9 molar Hg++. Ans. 10~9 molar CN~. Ans.
if
the dissociation constant of Ag(NHs)2+ a solution of 0.20 formula weights of AgCl, in sufficient excess
EXAMPLE
II.
What
NIÔH
a
total
to give a total
of
ammonia
concentration of 2.0 molar and
volume
:
one
liter,
has a silver-ion concentration of only
0.00037 mg. per
liter?
SOLUTION
[Ag+][NH 3? _
[Ag(NH 3 ) 2+]
[Ag+]
=a
003
1
ny
<
10
~8
3.4
10-9 mole per
liter
[NH,]
2.0
]
[Ag(NH 3) 2+ =
0.20 (approximately)
9 2
(3.4xlO-
)(2.0)
ir
0.20
6.8
10~8
Ans.
Problems
(See
Appendix
for ionization constants
and
dissociation constants.
Tem-
peratures are
96.
25C.
is
unless otherwise specified.)
A certain organic acid has one replaceable hydrogen and in 0.010 molar
0.18 per cent ionized.
aqueous solution the acid?

Ans.
3.2
What
is
the ionization constant of
10-.
58

is
96. Lactic acid
a monobasic acid with an ionization constant of 1.6
10~ 4
What
8.9
is
the lactate-ion concentration in a 0.50 10~3 molar.
N solution of the acid?
Arts.
X
is
97.
What
the molar concentration of each of the three constituents of
acetic acid in 0.050
solution?
Ans.
98.
H+ =
is
0.00096,
C H Or =
2
3
0.00096,
HC H O =
2
0.049.
if it is
What
the concentration of a solution of NII 4OII

0.72 molar.
3.0 per cent
ionized?
If it is 0.50 per cent ionized?
Ans.
99.
0.020 molar.
is
solution.
a monobasic acid that is 3.2 per cent ionized in 0.20 molar the ionization constant of formic acid, and what is its percentage ionization in 0.050 molar solution? Ans. 2.1 X 10~4 6.4 per cent.
Formic acid
What
is
100.
What
is
acetic acid containing sufficient dissolved ion concentration of 0.85 mole per liter?
the hydrogen-ion concentration in a 0.10 normal solution of sodium acetate to give a total acetate-
Ans. 2.2
10-* molar.
101. What is the hydrogen-ion concentration and the molar solution of hypochlorous acid at 25C.? Ana. 2 X 10~5 molar, 9.30. 102.
is
pOH
value of a 0.010
What
is
the
pH
value of a 0.30 normal solution of
NH OII?
4
What
4 O1I containing sufficient dispH value of a 0.30 normal solution of solved NH4C1 to give an ammonium-ion concentration of 1.2 moles per liter?
the
NH
Ans.
103.
11.36.
8.63.
Approximately how
in a liter of 0.10
many grams
of acetate ions should be dissolved
acetic acid in order to cut
down
the hydrogen-ion con-
centration one hundredfold?
Ans.
104.
8 grams.
To what volume
900 ml.
should 100 ml. of any weak 0.30 molar monobasic

its
acid or mono-acidic base be diluted in order to triple
percentage ionization?
<Ans.
/%t)6, What is the approximate concentration of sulfide ions and of hydro mlfide ions (HS") in a 0.070 molar solution of hydrogen sulfide? (Hint: Assume that practically all the hydrogen ions come from the primary ionization,)
Ans.
1.2
10~1B molar, 8
10~6 molar.
106. Calculate the concentration of sulfide ions in a solution
which
is
0.080 molar in
H S and contains sufficient HC1 to give a pH value of 3.40.

2
Ans.
107.
5.5
X
is
10~ 17 molar.
the approximate molar concentration of silver ions and of KAg(CN)2? [Dissociation constant
What
cyanide ions in a tenth-molar solution of of Ag(CN) 2 = 1.0 X 10-21 ].
Ans.
10~8 molar, 6
10~8 molar.
108.
,
,
59
What are the approximate molar concentrations of Na + Cd + CN~, and Cd(CN) 4 in a solution made by dissolving 0.020 F.W. of Na2 Cd(CN) 4 in
water and diluting to one liter? Aru. [Na+] = 0.040 molar, [Cd ++ ] 10~4 molar, [Cd(CN) 4 ~] = 0.020 molar.
6.4
10" 5 molar, [ON"]
2.5
Ag(NH 3
JLns.
109. If 100 milligrams of AgCl are dissolved in excess ammonium hydroxide to give a volume of 500 ml. of solution, and the total concentration of ammonia is 0.30 molar, what is the silver-ioii concentration? Dissociation constant of + = 6.8 X 10~ 8 2
)
.
1.06
X
is
10~ molar.
the concentration of
110.
What
3) 4
Cd++
ions in a solution 0.040 molar in
Cd(NH
Ans.
++ and 1.5 molar in
NH ?
3
2.0
10~ 9 molar.
111.
tion.
A certain organic amine acts A 0.05 molar solution is found

10~B molar.
as a mono-acidic base in aqueous solu-
7.5
What
is
to give a hydroxyl-ion concentration of the ioiiization constant of the base? What is its
pll value?
at
(HC 3 6 O2) is a monobasic acid with an ionization constant 10"4 In a tenth-molar solution how many grains of lactic acid are present in the un-ionized form?
112. Lactic acid
25C.
of 1.6
113.
What
What
is
acid in 0.080 M solution at 25C.?

114.
the molar concentration of the three constituents of benzoic What is the pH value?
\
molarity acetic acid
is
2.0 per cent ionized at
25C.?
115.
like
Ethylamine is a derivative of ammonia and in aqueous solution is basic ammonia. At a certain temperature ethylamine in 0.30 molar solution
2 gives a hydroxyl-ion concentration of 1.3 X 10~ molar. What is the ionization constant of ethylamine at that temperature, and what is its percentage
of ionization in 0.20 molar solution? 116. Calculate the cyanide-ion concentration of a 0.030 molar solution of hydrocyanic acid.
and the percentage ionization
of a solution at 25C. con4 of 1,200 ml. Calculate the acid in a ml. acetic total volume 25 of taining in solution the same after adding 15 grams of concentration hydrogen-ion sodium acetate (assuming the effective ionization of the salt to be 85 per cent).
Xll7. Calculate the hydrogen-ion concentration
What
is
the
pH
value in each case? should 50 ml. of any weak 0.20 molar monobasic
its
118.
To what volume
acid be diluted in order to double

119. In a 0.20
is
percentage ionization?
ammonium hydroxide, what percentage of What is its pH value? 120. Approximately how many grams of NH 4 + ions should be dissolved into a liter of 0.20 M NH 4 OH in order to cut down the concentration of hymolar solution of
the base
un-ionized?
droxyl ions to one-fiftieth
its
previous value?
60
121.
is

What
is
the
pH
value of a 0.25 normal solution of acetic acid?
What
pH value of a 0.25 normal solution of acetic acid containing sufficient dissolved sodium acetate to give an acetate-ion concentration of 2.0 moles per
the
liter?
122. What are the approximate concentrations of HCOs" and of COs*" in a 0.0010 molar solution of carbonic acid? (Hint: Assume that practically all of the hydrogen ions come from the primary ionization of the acid.)
123.
What
What
is
the sulfide-ion concentration of a solution 0.090 molar in
E^S
"
and containing
124.
sufficient
HC1
to give a
pH
value of 4.50?
and
+ are the approximate molar concentrations of Hg++, HgI 4 I" in a solution made by dissolving 0.010 F.W. of in water and 2 HgI 4
,
diluting to one liter?

125.
(Dissociation constant of
HgI
5.0
10~ 31 ).
What
is
the approximate molar concentration of cyanide ion in a
solution 0.010 molar in
K Fe(CN)
4
6?
126. If 50 milligrams of
AgCl
are dissolved in excess

2
2NH OH
4
->
formal in
NH
Ag(NH
3
8) 2
Cl~
+ 2H O)
of
and has a volume

is
NH4OH (AgCl + and the resulting solution is 0.50 500 ml., what is the concentration of Ag +
ions in formula weights per liter?

127.
What
containing 0.020 F.W. of

of
the molar cyanide-ion concentration of an aqueous solution What is the concentration 2 Ni(CN) 4 per 500 ml.?
K
if
Ni++
in such a solution
sufficient additional
KCN is present to give a total
cyanide concentration of 0.10 molar?

If 0.10 F.W. of Hg(NO 3 ) 2 is treated with excess Na2 S solution in the ^SL28. presence of NaOH, the precipitate of IlgS that first forms dissolves to give ~ ~ 10~56 and the sulfideHgS 2 ions. If the dissociation constant of HgS 2 is 2
ion concentration of the solution

of
is
2.0 molar,
what
is
the concentration
Hg++?
34. Solubility Product. very important equilibrium constant applies to a saturated solution of a slightly soluble, completely
ionized salt.
of the precipitates encountered in analytical chemistry belong to this category.
Most
Consider the simple case of a saturated solution of silver chloride

in equilibrium with some of the undissolved salt. What little silver chloride, is in solution is completely ionized, and the equilibrium
can be written
AgCl(solid)
<=>
Ag+
+ Clis
The mass-action
or
equilibrium constant
-]
expressed simply as
KAgCl
more accurately as
where
/i
61
and /2
ions (see Sec. 32). 1.00 in value.
are the respective activity coefficients of the two These coefficients are only slightly less than
it
This constant, applying as

slightly soluble salt,
is
does to a saturated solution of a
called a solubility product
(KS P .).
.
The
numerical value of the solubility product of silver chloride at 25C. is 1.0 X 10" 10 This means that in a solution saturated with silver chloride at this temperature the total molar concen.
tration of silver ions in the solution multiplied by the total molar concentration of chloride ions equals 1.0X10~ 10 Conversely,
.
when the product

this value,
of the total concentration of silver ions
and
the total concentration of chloride ions in any solution exceeds a precipitate of silver chloride is obtained under con-
ditions of stable equilibrium. Lead chloride ionizes as follows:
PbCl 2
Its solubility
Pb++
+ 2C1-
product
is
therefore
[Pb++][Cl-]*
KPbC1
Here the square

used.
of the total chloride-ion concentration must be In terms of activities, the solubility product is
that are warranted

stant
itself.
In most mass-action calculations two significant figures are all by the precision of the data and of the con-
involving the solubilities and solubility products of the more insoluble hydroxides and sulfides. These values are usually known only very
The
precision is
much
less in calculations
approximately, for the composition of a precipitate of this type
may
be quite variable.
I.
the solubility product of Ag3 P04 if the 3 solubility of the salt is 6.5 X 10~ gram per liter? SOLUTION: 6.5 X 10~ 3 gram per liter = (6.5 X 10- 3 )/418.7 =
EXAMPLE
What
is
1 .6
10~~
mole per liter. The salt is 100 per cent ionized as follows
Therefore,
[Ag+]
[PO4
(3
S
]
= =
1.6
10~5
1.6
X
5
)
10~5
1.6
10"
6 3 ) (1.6
10-
1.8
10~ 18
Ans.
62

.
EXAMPLE II. The solubility product of CaF2 is 3.2 X 10~ u How many grams of Ca ++ are present in 500 ml. of a saturated solution of CaF2 ? How many grams of CaCU can be dissolved
500 ml. of a solution containing 9.5 grams of fluoride ions? SOLUTION: Let x = molar concentration of Ca" 4
in
"
"
1
Then
2x
2
(z)(2z)
x
2.0
= molar concentration of F~ = 3.2x 10- u = 2.0 X 10-4 mole per liter

0.0040 gram Ca++ per 500 ml.
1
10-4
9.5
40
X5=
Zi
Ans.
grams F~ per 500 ml. =

2
mole F~ per
liter
(z)(l)
x
3.2
10~ n
111
= 3.2X 10- 11 = 3.2 X 10-" mole Ca++ per liter = 2.9 X 10-9 gram CaCl2 per liter = 1.45 X 10-9 gram CaCl 2 per 500
What
is
ml.
Ans.
the hydroxyl-ion concentration in a solution of sodium hydroxide having a pH value of 11.6? How many grams of magnesium could remain dissolved in 500 ml. of
III.
EXAMPLE
such a solution [solubility product of
Mg(OH) 2 =
or
3.4
10~ u ]?
SOLUTION:
[H+]
= =
10- 11
2.52
i
10 (
14
~ 12 +
4)
= 3 98 X 10~ 3 AnS X10-" pOH = 14 - 11.6 = 2.4 2 4 6 3 3 [OH-] = 10- = 10- X 10~ = 3.98 X 1011 [Mg++][OH-] = 3.4 X 10[OH
]
' '
" =
X 10v 1ft-
12
(since antilog 0.4
2.52)
-
2.52
Ans.
4.
10- 11
^
= 2A X
10
~6
le
per
liter
=
Ans.
2.55
10~ 5 gram per 500 ml.
36. Fractional Precipitation. Ordinarily when a precipitating agent is added slowly to a solution containing two ions capable
agent, the substance with the lesser The point at which the second solubility will precipitate first. substance will precipitate can be determined from the solubility
of being precipitated
by the
products of the two precipitates.
63
Suppose to a solution 0.10 molar in Ba++ and 0.10 molar in is added gradually and in very minute quantities a solution
of
Na SO4.
2 10
Insoluble
BaSO4
(solubility product,
KBaso
1.1
X
:
10~
precipitates
to precipitate.
2.8 X 10~ ) begins first, then SrSO4 (KSrS04 The ratio of the two solubility products is as follows
7
[Ba++][SOrl
[Sr++][SOr]
Therefore,
1.1
X 102.8 X 10~7
10
0J At the point where SrSO4

centration of Sr++
will
is still
rRfl++i
0.00039
just begins to precipitate (and the con-
0.10
M)
the barium-ion concentration
have been reduced to 0.000039 molar, since

[Bar"-]
0.10
= 0.00039
therefore nearly complete at this
Separation of the two cations

point.
is
In qualitative analysis the preparation of a solution of a waterinsoluble salt for the anion tests is usually made by metathesis
of the solid with a solution of
Na C(V The
2
extent of metathesis
solubility product
of the
can be determined, roughly at

of the original salt
least,
from the
and that
of the insoluble
compound
metal formed by the metathesis. EXAMPLE. If lead iodide (PbI 2 )
is
boiled with 2.0
M Na C0
2
solution, the insoluble lead iodide is converted to the more in21" PbC0 3 ). Assuming soluble lead carbonate (PbI 2 COs^
that sufficient PbI 2
present to give equilibrium conditions between the two insoluble substances and that the solubility products of PbI 2 and PbCOs at the temperature of the solution are 2.4 X
is
10~ 14 respectively, what would be the concentration of iodide ion in the resulting solution?
10~ 8 and 5.6
,
SOLUTION:
2.4
5.6
X X
10-*
[I~]
= 930 moles
per
liter.
Ans.
64
This concentration
is of course impossible to attain, not only because of the limited solubility of the Nal formed, but also because the Pbl2 is completely metathesized before the equilibrium condi-
tion
is reached. The result merely shows that PbI 2 and completely metathesized by Na2C03 solution.
is
readily
Problems
(Temperatures are 25C. unless otherwise specified. products is given in the Appendix.)
129.
A
,
table of solubility
saturated solution of barium fluoride,

1.7
BaF2
is
7.5
10~3 molar.
What
is
the solubility product of barium fluoride?
Am.
Wr+.
130. If 0.11
mg. of
10~13
silver
bromide dissolves in one
liter of
water, what
is
the solubility product of silver bromide?
Am.
3.5
how many milligrams will
181. If the solubility product of lead phosphate, Pb 8 (PO 4 )2, is 1.5 10" 32 , dissolve in 500 ml. of water? How many milligrams
of Pb"*~+ can remain dissolved in 500 ml. of a solution that
is
0.20 molar in
PO " ions?
4
Am.
132.
0.070 mg.
7.5
lO" 6 mg.
From
the solubility product of PbI 2 calculate
how many grams
of
lead ions and of iodide ions are contained in each milliliter of a saturated solution of lead iodide?
Am.
133.
3.7
10~4 4.6
,
10~4 gram.
What
are the solubility products of
PbC 2O4 and

1.6
of
Pb(IO 8 ) 2
if
the
solubilities are 1.7
X
,
10~3 gram per
liter
and
10"2 gram per
liter,
respectively?
Am.
3.3
10-11 9.8
10~ 14
134. If the solubility products of AgBrO 3 and of Ag2 Cr2 7 are 5.0 X 10~5 10~ n, respectively, what are the solubilities of the two salts in and 2.7
milligrams per 100 ml.?
Am.
136.
167 mg., 8.2 mg.
milliliter.
2 PtCle contains 11 mg. of the salt in each the solubility product of the salt? How many milligrams of Pt can remain dissolved (as PtCle") in each milliliter of a solution that contains 3.9 grams of K+ per liter?
saturated solution of
What
is
Am.
136.
4.6
10~6
0.90 mg.
Mercurous bromide,
Hg Br
2
2,
dissociates into
liter.
Hg2
"
"h
and
2Br~~.
Its
solubility at
25C.
is
0.039 mg. per
What
is its
solubility product at
that temperature?
Am.
1.4
10-*
137.
65
is
The normality
5.3
What
is
of a saturated solution of the solubility product of A&CO*?
Ag2 COs
2.2
10~4 N.
Ans.
10-12
bility
A moles of AgsP04 dissolve in 500 ml. of water, express the soluproduct of Ag3PO4 in terms of A, and the normality of a saturated solution of Ag3 PO4 in terms of A.
138. If
Ans.
432A 4 6A.
,
139. If the solubility

solubility of normality of
product of Ca8(PO4 ) 2
is
A, express in terms of
Cas(PO4) 2 in moles per liter. Also express in terms of a saturated solution of the salt.
A A
the
the
Ans.
How many milligrams of Mn++ can remain solution of pH 8.6 without precipitating Mn(OH) ?
140.
2
dissolved in 100 ml. of a
Ans.
141.
13.5 mg.
Fe(OH) 8 calculate the weight of Fe+++ in one liter of solution in order to cause be must in milligrams which present when the hydroxyl-ion concentration is 8.0 X precipitation of the hydroxide
From
the solubility product of
10~6 mole per
liter.
Ans.
142.
1.2
10~19 mg.
;
.
In a 2.6 X lO"6 KS.P. CaCOs = 1.7 X 10~8 Given KS.P. MgCO3 + + solution 0.20 molar in Ca+ and 0.20 molar in Mg+ and with a volume of 250 ml., which cation would precipitate first bn the slow addition of Na^COa? How many milligrams of this cation would still remain in solution when the
other cation just starts to precipitate?
Ans.
About
1.3
mg.
143. What are the solubility products of BaF2 and of BaSO4 at a certain temperature if the solubilities at that temperature are 1.3 grams per liter and 2.5 X 10~3 gram per liter, respectively? A solution has a volume of 100 ml. and contains 0.010 mole of Na2 SO4 and 0.020 mole of NaF. If BaCl2 is slowly
added, which anion will precipitate first? How many milligrams of this ion will still remain in solution when the other ion just begins to precipitate?
Ans.
144.
1.6
10-,
1.1
X KT
10
.
Sulfate.
0.027 mg.
,
molar.
146.
saturated solution of magnesium fluoride, MgF2 What is the solubility product of magnesium fluoride?
is
1.2
10" 3
are the solubility products of CaS04 and of CaF 2 if the solubilities are 1.1 mg. per milliliter and 0.016 mg. per milliliter, respectively? How many milligrams of calcium ions can remain in 100 ml. of a solution that
What
is
0.50 molar in fluoride ions?
10~7 146. If the solubility products of BaC 2 4 and of Ba(IO 3 ) 2 are 1.7 and 6.0 10~10, respectively, what is the solubility of each salt in milligrams
per
liter?
66

B^" "* and
1
147. Mercurous iodide, Hg2l2, dissociates into
21"".
Its solu-
product 250 ml.?

bility
is
1.2
10"
28
.
How many
milligrams of the salt dissolve in
148.
5.7
The normality
of a saturated solution of cerous iodate,
Ce(I0 3 )3,
is
10~~ 3 .
What is the solubility product of the salt? How many milligrams
of cerous ions can remain dissolved in 500 ml. of a solution that is 0.30 molar
in iodate ions?
149. If
product of
Ba3 (AsO) 4 )2
grams of Ba 3 (AsO4 ) 2 dissolve in terms of A.
in
500
ml., express the solubility
160. If the solubility product of Ag 2 Cr2 grams of silver will be present in solution
O7
is
2.7
10~u
how many
is
milli-
when
is
excess salt
shaken with
250 ml. of water until equilibrium

151. If a saturated solution of
is
reached?
Pb 3 (PO 4 ) 2
2
normal, what
is
the solubility
product of
Pb3 (PO4 ) 2 ? Ag OrO4 is A, what (in terms of A) is the Ag CrO4 ? How many grams of chromium
2
152. If the solubility product of normality of a saturated solution of
can remain dissolved

silver ions?
(as
CrO4
==
in
500 ml. of a solution that
is
B
>
molar in
++
153.
Mercurous
chloride,
Hg 2 Cl 2
ionizes as follows:
Hg
CI 2
Hg
2C1~.
If its solubility
product
is 1.1
10~
of
18
,
how many
grains of mercurous
mercury can remain dissolved in 2.00 ml.

milliequivalent weight of chloride ions?
154.
a solution that contains one gram-
tion with a
How many grams of FeCl could be present in 200 ml. of an acid solupH value of 3.0 without causing a precipitation of Fe(OH) ?
3
3
155. Show by calculation from the solubility product of Ag2SO4 whether or not this compound would be suitable as a final precipitate in the detection or determination of silver. What would the concentration of sulfate ions theoretically have to be in solution so that not more than 30 mg. of silver would
remain unprecipitated in 500 ml. of solution?

156.
What
is
the ratio of the concentrations of Br~ and Cl~ in a solution in
which
sufficient
AgNO
Solubility products:
AgBr =
has been added to cause precipitation of both halides? 5.0 X lO" 13 AgCl = 1.0 X 10~ 10
;
.
157. Calculate the number of milligrams of CaSO4 converted to CaCO 3 by 20 ml. of 2.0 N Na 2 CO 3 solution under equilibrium conditions at a temperature at which the solubility products are 6.4 X 10~ 5 and 1.6 X 10~ 8 for CaSO4 and
CaCO
3,
respectively.
158. From the appropriate solubility products show which cation would 2 CrO 4 to 500 ml. of a solution 0.10 precipitate first on the slow addition of molar in Sr++ and 0.10 molar in Ba++. How many milligrams of this cation
would
tate?
still
remain in solution when the other cation just starts to precipiare the solubility products of CaSO 4 and of CaF 2 if the solubiligrams per liter and 0.016 gram per liter, respectively? A solution
159.
What
ties are 1.1
67
has a volume of 250 ml. and contains 0.020 mole of Na2SO4 and 0.030 mole of NaP. If CaCl 2 is slowly added, which anion will precipitate first? How many milligrams of this ion will still remain in solution when the other ion just begins
to precipitate?
36. Application of Buffered Solutions in Analytical Chemistry. Buffered solutions are frequently used in both qualitative and
quantitative analysis to effect certain separations of elements. familiar case is one in which a solution is buffered, usually either and the with 4C2 3O 2 2 3O 2 4 C1 or with 4 OII
NH
+ NH
HC H
+ NH
pH value thus brought to such a value that the solubility product of the hydroxide of an element (or the hydroxides of a group of elements) is greatly exceeded but the solubility products of other hydroxides are not reached.
insoluble hydroxides is somewhat " hydrous variable, and they are perhaps more properly called known oxides." Their solubility products are not accurately and
The composition
of
many
numerical values obtained from them should therefore be considered as showing only relative orders of magnitude.
solubility product of Mg(OH) 2 at a certain At 1Q- 36 1Q- 11 ; that of Fe(OH) 3 is 1.1 temperature is 3.4 HHf of and Fe" of how that temperature (a) Mg++ many graips
EXAMPLE.
The
can remain dissolved in 100 ml. of M/10 solution of 4 OH 5 = 1.75 X 10~ ); (6) how many grams of Mg"^ (ionization constant and of Fe^+ can remain dissolved in 100 ml. of M/10 4 OH 4 C1 to make the containing a sufficient amount of dissolved ammonium-ion concentration 2.0 molar?
NH
NH
NH
SOLUTION
(a)
4
NH OH
<=>
NH + + OH4
[NH4+][OH-] [NH4 OH]

Let x
=
x
concentration of OH~~
concentration
Then
0.10
(*)(*)
= =
concentration of undissociated
1.75
NH OH
4
0.10
X
X
10~ 5
=
|ft
1.75
10~5 (since x
is
small compared to 0.10)
68

x=
[Mg++][OH-] =
2
1.3
3.4
3 2 ) 6
X X
=
10~ s mole per
liter
10-"
3.4
[Mg++](1.3
10-
10- 11
[Mg++]
= = =
X 2.0 X 4.9 X
2.0
3
10- mole per liter 10-6 X Ko X 24 -3 10-6 gram per 100 ml. 10- 36
Ans.
[Fe+++][OH-]
[Fe+++](1.3
= 1.1X10- 36 X 10- 3 ) 3 = 1.1 X
2.8
10-27 gram per 100 ml.
Ans.
8.8
10-7
[Mg++](8.8
10-7 ) 2
3.4
10- 11
106 grams per 100 ml.
Ans.
\Fe+++](S.S
X
1-1
10~7 ) 3
=
7 ) 3
1.1
10- 36
X X
10-*
(8.8X10~
_1 X558 10
Ans.
9.0
10~ 18 gram per 100 ml.
The 37. Control of Acidity in Hydrogen Sulfide Precipitations. from acid solution of certain elements by precipitation separation
with
effectively used in analytical chemistry, particularly in qualitative analysis. Probably the most important factor in2
HS
is
fluencing the effectiveness of the separation is the sulfide-ion concentration and its control by the regulation of the hydrogen-ion
concentration.
The concentration of the sulfide ion can be regulated to such a point that the solubility products of certain sulfides are greatly exceeded while the solubility products of other
not reached. The quantitative effect of the presence on the ionization of H 2S and the calculation of the sulfideion concentration have been illustrated in Examples I and II of Sec. 31 and should be reviewed at this time.
sulfides are
of acid
69
Solubility products of sulfides are not known precisely, and hydrolysis effects and rates of precipitation influence the quan-
Therefore, in the following example and problems of a similar nature, the calculated values may not agree well with corresponding values determined experimentally, but they do show relative orders of magnitude
titative aspect of the separation of sulfides.
and are useful only in this connection. EXAMPLE. How many grams of Zn ++ and how many grams of Cd++ can remain dissolved in 200 ml. of the solution of H 2 S + HC1 mentioned in Example II of Sec. 31 (solubility product of
ZnS =
1.2
10~ 23 solubility product of

;
CdS =
3.6
10~ 29 )?
SOLUTION:
[S-]
[Zn++][S=]
= =
=
1.5 1.2
1
X X
10~23 (as calculated) 10-23
[Zn++]
zr 3
0.80
0.80 mole per liter
65
H=
10 grams per 200 ml.
Ans.
[Cd++][S-]
J
3.6 3.6
X X
10~ 29
1.5X10-* = 2.4 X 10~ 6 molc pcr liter = 2.4X 10- 6 X 112 = 5.4 X 10~ 5 gram per 200 ml.
x
X%
Ans.
Certain 38. Separations by Means of Complex-ion Formation. separations in analytical chemistry are effected by making use of
the equilibrium that exists between a complex ion and its constituents. The following cases illustrate the two general ways in which
this is applied.
1.
When
an ammoniacal solution of
silver nitrate containing
carefully controlled excess of ammonia is added to a mixture of iodide and chloride, only silver iodide is precipitated, since most
of the silver in the solution is as the
ammino complex, Ag(NH 3 ) 2 h
"
and the concentration
of
product of AgCl but is product of the more insoluble Agl. 2. When potassium cyanide is added to an ammoniacal solution =s *" of copper and cadmium salts, the two ions Cu(CN)3 and Cd(CN) 4 are formed. When hydrogen sulfide is passed into the solution,
Ag+ too small to exceed the solubility great enough to exceed the solubility
is
70
only

cadmium
sulfide is precipitated, since the degree of dissocia-
tion of the copper
complex
is
much
less
than that of the cadmium
++ is complex. sufficiently high concentration of Cd present to exceed the solubility product of CdS, but the concentration of Cu+ is too low to exceed the solubility product of Cu2S.
EXAMPLE
in
I.
one
liter of
:
NH OH
4
How many
if
bromide will dissolve the resulting solution is 2.0 molar in NH 3 ?
grams
of silver
SOLUTION
[Ag+][Br~]
5.0
10~ 13 (see Appendix)
Let x
moles of AgBr dissolved = [Br~]

5.0
= [Ag(NH 3
,
)2
+
]
X
x
10~
13
(5.0XlO-"/s)(2.0) X
Solving,
5.4
u.o
1U
10~ 3
= X AgBr =
x
5.4
10~ 3 molar
1.0 grain.
Ans.
0.10 molar
EXAMPLE
in
II.
solution 0.10 molar in
Cu++ and
forming
Cd++
is
treated with
NH OH
4
and
KCN,
Cu(CN) 3
===
If
and Cd(CN) 4 ^. The solution is 0.50 molar in excess CN~ ions. H 2S is passed into the solution to give a sulfide-ion concentration of 0.010 molar, will Cu 2 S or CdS precipitate? SOLUTION
:
n J = NJ3
J
10
~ 28
(
see
Appendix)
tCu
l(0.60)
_ ~ =
0.10
5Q
'
X X
1Q 1U
_28
[Cu+]
Therefore,
4.0
10-28
[Cu+] [S=]
= (4.0 X 1(^ = 1.6X10-57
10~50 ) is greater solubility product of Cu2S (= 1.0 value. Hence CuzS will not precipitate. Ans.
The
than this
[Cd++][CN-]*
71
_ ~
* X
2.2
[Cd++](0.50)* 0.10
_ ~
=
= =
[Cd++]
10~ 17
17
Therefore
[Cd++][S~]
(2.2
2.2
X 10X 103.6
)(0.01)
19
The
solubility product of
CdS (=
10~ 29 )
is
less
than
this
value.
Hence CdS
will precipitate.
Ans.
Problems
(See
160.
Appendix
2]
for solubility products
and ionization constants.)

[i.e.,
How many
grams
of
Mg++
could remain dissolved

4
as
Mg(OH)
4
in a liter of 0.2
liter
remain dissolved in a
3.4
M NH OH, and how many grams of Mg+ + could of 0.2 M NH OH containing enough dissolved
4
unprecipitated
NH C1 to make the ammonium-ion concentration 1 molar?

X
1011
.]
[Ks.p.
Mg(OH)->
Ans.
161.
2.4
10~4 gram, 68 grams.
++ + could remain dissolved milligrams of Fe [i.e., unprecipitated as Fe(OII)3] in 100 ml. of a solution 2.0 normal in acetic acid and containing a sufficient amount of sodium acetate to make the acetate-iori con-
How many
centration 0.15 molar?
IK S .P. Fe(OH) 3
1.1
10~ 36 .]
Ans.
0.095 nig.
from appropriate equilibrium constants the number of grams and of cadmium that can remain dissolved in 1,500 ml. of a solution that contains 0.05 mole of dissolved H 2 S and is 0.30 N in hydrogen ions.
162. Calculate
of zinc
Ans.
29.0 grams, 1.5
10"4 gram.
163. By saturating with hydrogen sulfide 350 ml. of a solution that is 0.010 molar in a certain trivalent element and 1.0 molar in hydrogen ions, all but 12 millimoles of the element precipitates as sulfide. What is the approximate = 0.10 (Solubility of H 2 S solubility product of the sulfide of the element?
molar.)
Ans.
164.
1.5
10~72
formula weights of chloride ion must be introduced into a tenth-molar solution of NaAg(CN) 2 in order for AgCl to start to ~~ 21 solubility [Dissociation constant of Ag(CN) 2 = 1.0 X 10~ precipitate?
liter of
;
How many
= 1.0 product of AgCl Ans. 0.0033 F.W.

166.
of
4
lO' 10 .]
How many
formula weights of
3
silver iodide will dissolve in
one
3) 2
liter
NH OII which is 6.0 molar in NH ?
[Dissociation constant of
Ag(NH
72
6.8
10~ 8 solubility product of Agl

;
1.0
10~16 .]
(Hint: In the resulting
solution
[Ag(NH
2.4
8) 2 +}
[I"].)
Ans.
10~4 F.W.
solution 0.080 molar in 3 is treated with Na2 S2O 8 which con166. s If the solution contains verts practically all of the Ag+ into Ag(S 2 Os)2 ~ sufficient excess thiosulfate to make the S 2 O 3 0.20 molar, how many grams of I~ per liter could be present without causing a precipitation of Agl?
AgNO
Ans.
167.
0.16 gram.
What
in
is
the
maximum molar
) 4 Cl2
concentration of sulfide ion in a solution

in
0.20 molar
of
Cd(NH3
and 2.0 molar
NH
without forming a precipitate
cadmium
Ans.
168.
1.2
sulfide?
10-20
0.500 gram of
What must be the maximum pll value of a solution in order that Mg++ in 100 ml. will remain unprecipitated as Mg(OH) 2 ? = 3.4 X lO" 11 How many grams of Fe ++ + [Solubility product Mg(OH) 2
.]
could remain dissolved in such a solution?
++ could remain unprecipitated as milligrams of Mii ++ 4OH, and how many milligrams of Mn(OH) 2 in 500 ml. of 0.10 4 OII containing sufficient could remain dissolved in 500 ml. of 0.10 dissolved 4 C1 to make the ammonium-ion concentration 2.0 molar?
169.
How many
M NH
Mn
M NH
NH
++ could remain unprecipitated as milligrams of Fe+ Fe(OH) 8 in 250 ml. of a solution 1.5 molar in acetic acid buffered by that amount of dissolved sodium acetate that makes the acetate-ion concentration
170.
How many
0.20 molar?
find the weight of 171. If the solubility product of Bi2S 8 is 1.6 X 10~ bismuth ions that must be present in a liter of solution to cause precipitation 4 of Bi2S 8 in a solution which is 0.10 molar in 1X28 and contains 0.010 mole of II
72
,
per
liter.
What is the maximum pH value that 100 ml. of a solution containing 0.0050 gram of PbCl2 can have so that on saturating the solution with II 2 S no = 0.10 molar.) lead sulfide will precipitate? (Saturated solution of 2S
172.
grams of ZnSO 4 .7H 2 O in 500 ml. of dilute acid is resulting solution is found to be 0.10 molar in H 2 S and 0.050 molar in H+ ions. What fraction of the zinc has been precipitated as ZnS? What maximum pll value should the solution have in order for no precipitate to form if the concentrations of zinc salt and H2S are as above?
173.
solution of 1.2
saturated with
H S.
2
The
are 174. If 50 ml. of 0.010 molar AgN0 3 and 50 ml. of 3.0 molar 4 mixed, what is the resulting concentration of Ag+ ions? How many moles of Cl~ would have to be introduced before precipitation of AgCl would take
place? [lonization constant of of AgCl = 1.0 lO"10 .]
NH OH
Ag(NH
3) 2
=
4
6.8
10""8 ; solubility
product
176. If a solution
is
0.050 molar in
K HgI
2
and
calculation whether or not a precipitation of HgS solution is made 1.0 10""15 molar in sulfide ions.
molar in I", show by would be expected if the

1.5
176.
73
0.10 F.W. of
of
How many grams of S"" can be present in a liter of a solution containing Cd(NH 4 Cl and 1.5 mole of NH without forming a precipitate
3) 2
8
CdS?
177. A solution containing 0.10 F.W. of MgCl 2 and 0.20 F.W. of CaCl 2 would require a total of how many milliliters of N/2 H 2 C2 O 2 solution in order to form the complex ion Mg(C 2 C>4) 2 "" and precipitate the calcium as CaC 2 O4
.
H 0?
2
178.
which
10~ 8
;
How many grams of silver bromide will dissolve in one liter of NKUOH + = 6.8 X 1.5 molar in NH ? [Dissociation constant of Ag(NH = 5.0 X 10~ solubility product of AgBr (Hint: In the resulting
is
3
3) 2
13
.]
solution [Ag(NII 3 ) 2 + ]
[Br~].)
39. Distribution Ratio. Occasionally in analytical chemistry the greater part of a solute is removed from aqueous solution by shaking the solution with an organic solvent in which the solute is much more soluble. In qualitative analysis the removal of
liberated bromine
in the test for
and iodine by means of carbon tetrachloride bromide and iodide occurs in many schemes of
analysis. In quantitative analysis ferric chloride is often extracted in greater part from hydrochloric acid solution by means of ethyl
ether or isopropyl ether. This is of value in the analysis of certain constituents in iron alloys where a high concentration of ferric
Certain hydrolytic separations (e.g., titanium from iron) are more readily carried out if a preliminary extraction of the iron is made.
is
ions in the solution
undesirable.
The
distribution law states that
when a
solute
is
in simultaneous
equilibrium with two mutually insoluble solvents the ratio of the concentrations of the solute in the two solvents is a constant at
a given temperature regardless
of the
volumes
of solvents
used
or of the quantity of solute present:
Concentration of x in solvent Concentration of x in solvent
__
The
liquids.
ratio
is
called a distribution ratio
experimentally for each solute
and is determined and each pair of mutually insoluble
The value
is
solutions
and perfectly immiscible
a true constant only in the case of perfect solvents, but it is very nearly
a constant at a given temperature for the dilute solutions ordinarily encountered in analytical chemistry. The law applies only to a particular species of molecule; that is, the solute must be in
the same condition in the two phases.
The law does not
hold,
74

if
for example,
the solute
it is
is
ionized in one solvent
in the other, or if not in the other.
as associated molecules in one solvent
and not ionized and
EXAMPLE.
An
aqueous potassium iodide solution has a volume
of 100 ml. 'and contains 0.120
gram
of dissolved iodine.
Assuming
that the distribution ratio of iodine between carbon tetrachloride
and an aqueous solution of potassium iodide is 85 at 25C., how many grams of iodine will remain in the aqueous phase if the
above solution SOLUTION:
Let x
is
shaken with 25 ml. of carbon tetrachloride?
= grams
iodine remaining in II 2 O phase
Then
0.120
x = grams iodine in CCL* phase
Concentration of iodine in CC14 phase =

Concentration in
~ 120
^=
.Zo
grams per ml.
X KUO phase = y^: grams

(0.120
per ml.
-s)/25
Solving,
0.00539 gram.
Problems
Ans.
of iodine is dissolved in 50 ml. of carbon tetrachloride shaken at a certain temperature with 500 ml. of water, it is found that the aqueous layer contains 0.0592 gram of iodine. Calculate the distribution ratio of iodine at that temperature between the two solvents, in both of which it exists as I 2 molecules.
173. If 0.568
gram
is
and the
solution
Ans.
180.
86.0
At 20C. the
is
and ether
0.400.
A solution of 5.00
distribution ratio of a certain organic acid between water grams of the acid in 100 ml. of water is
shaken successively with three 20-ml. portions of water-saturated ether. Calculate the number of grams of acid left in the water. Also calculate the number of grams of acid that would have been left in the water if the solution had been shaken with a single 60-ml. portion of ether.
Ans.
1.48 grams.
2.00 grains.
an aqueous solution containing 1.00 millimole of bromine ml. of a certain organic solvent, 0.128 gram of the bromine is extracted from the aqueous layer. What is the distribution ratio? What percentage of the bromine would have been extracted by two successive
181. If 90 ml. of
are shaken at
25C. with 30
extractions with 15-ml. portions of the solvent? diatomic molecules in both solvents.
75
to be as
Assume bromine
Ans.
12.0.
88.89 per cent.
182.
The
its
water
is
is
29.0 at
one-half
bromine between carbon tetrachloride and a certain aqueous solution of bromine is shaken with volume of carbon tetrachloride, what percentage of the bromine
distribution ratio of
25C.
If
removed from the aqueous phase?

183. If a 0.0010 molar solution of
its
is shaken with onevolume of solvent B, 78.0 per cent of the bromine remains in A. If at the same temperature a solution of 0.0300 gram of bromine in 50 ml. of
bromine
in solvent
tenth of
solvent
is
remain in B?
molecules in
184.
shaken with 20 ml. of solvent A how many grains of bromine Assume A and B to be immiscible and bromine to be as diatomic both solvents.
}
What
tribution ratio at
explanation can you give to account for the fact that the dis25C. of acetic acid between benzene and water is not even
approximately constant, even at low concentrations of acetic acid?

185. In certain
solution
ether.
removed from hydrochloric acid by repeated extraction with either ordinary ether or with isopropyl If 36 ml. of an aqueous solution of FeCl 3 + HC1 are shaken with 18 ml.
of analysis iron
is
methods
of ether (previously saturated with IIC1), 94 per cent of the iron is removed from the aqueous layer. What is the distribution ratio of iron between the two solvents and what per cent of the iron would have been removed if the initial solution had been extracted with two separate 9-ml. portions of ether?
CHAPTER
VI
40. Relation of the Electric Current to Oxidation-reduction
versely,
Experiment shows that at ordinary concentrations free chlorine or bromine will oxidize ferrous ions (2Fe++ + C12 -> 2Fe+++ + 2C1~), but free iodine will not. Coniodide ions will reduce ferric ions (2Fe+++ + 2I~ *
("Redox") Reactions.
2Fe ++
"
+ 12)
but chloride or bromide
will not.
Hydrogen
ions at
2H+ -> ordinary concentrations will oxidize metallic zinc (Zn Zn*4 H2) but will not oxidize metallic copper. To be able to predict whether or not a given pair of oxidizing and reducing agents will or will not mutually interact to an ap-
of considerable importance, particularly in qualitative analysis, and tables showing relative tendencies for substances to be oxidized or reduced, if used properly, are of great
preciable extent
is
value.
In the light of the modern concept of the structure of atoms, oxidation and reduction may be defined in terms of transfer of electrons. An element is oxidized when it loses electrons; an element is reduced when it gains electrons. Redox reactions can be brought about by the application of an electric current; conversely, an electric current can be obtained from oxidation-reduction processes. The electrolysis of a solution of sodium chloride is an example of the first class. At the anode, negative chloride ions are oxidized to free chlorine gas; at the cathode, positive hydrogen ions from the water are reduced to free hydrogen gas. The voltaic cell is an example of the second class. 41. Specific Electrode Potentials. Suppose we have on the end of a platinum wire a platinum foil covered with platinum black. Suppose further that the foil is immersed in a solution of acid that is one molar in hydrogen ions and that pure hydrogen gas at one atmosphere pressure continually bubbles over the foil. Such a setup is called a normal hydrogen electrode. It may be + represented graphically, thus: H2(l atmosphere), 2H (1 molar)
I
76
Pt.
77
chemically inert, but an equilibrium exists between the hydrogen gas and the hydrogen ions, thus: 2 <=*
is
The platinum
2H+ + 2,
we
the symbol e representing an electron. Suppose now have a strip of metallic zinc immersed in a solution of zinc
sulfate that is one
molar in zinc
thus:
ions.
Equilibrium exists between
Zn <= Zn++ + 2e. If the two elecof a wire and the two solutions means by are connected by means of a capillary tube containing an electrolyte, a current of 0.76 volt will flow through the wire and solution. The "plus to minus " direction of the current in the wire is from the hydrogen electrode to the zinc electrode and in the solution from the zinc electrode to the hydrogen electrode. The
the metal and
its ions,
trodes are connected
flow of electrons in the wire
from the zinc electrode to the hydrogen electrode, and in the solution it is from the hydrogen
is
electrode to the zinc electrode.

is
oxidized
and
represented
fore
by
time, metallic zinc hydrogen ions are reduced, the net reaction being 2H+ > Zn4" " therethe equation Zn 2
At the same
+H
We
have a voltaic cell made up of two half system may be represented thus:
cells,
and the
entire
Zn Zn++(l molar)
In representing
11
H+(l molar),
H (l
2
atmosphere)
Pt
way, a single line represents a junction between an electrode and a solution. A double line denotes a junction between two solutions, and it is assumed that the small potential difference between the solutions has been corrected
cells in this
for in formulating the total e.m.f. of the cell. It should also be noted that oxidation always takes place at
the anode; reduction always takes place at the cathode. The passage of electrons through the wire is from anode to cathode; electrons pass through the solution from cathode to anode.
In similar fashion, a copper electrode dipping in a solution of copper sulfate that is one molar in copper ions can be connected to a normal hydrogen electrode. A current of 0.34 volt will flow
through the wire. The passage of electrons in the wire is from the hydrogen electrode to the copper electrode. If now we connect the above copper half cell with the above zinc half cell, we obtain a voltaic cell that is represented thus:
Cu Cu++(l
I
molar)
II
Zn++(l molar)
Zn
78
It will

be found that a current
of 1.10 volts will
is
be generated. from the zinc to the copper and in the solution from the copper to the zinc. At the same time metallic zinc is oxidized to zinc ions, and the copper ions are reduced to metallic copper, the net reaction being
The passage
of electrons in the wire
Zn
+ Cu++ -> Cu
It is difficult to determine absolute potential differences be-
tween electrodes and solutions; but, since we are usually concerned only with differences of potential, we can refer electrode potentials to some common standard. The normal hydrogen electrode is arbitrarily given the value of zero, and other electrode
The molar electrode potential or potentials are referred to it. of zinc electrode (i.e., the relative potential bespecific potential tween metallic zinc and a one-molar solution of zinc ions) is
volt.
0.76 volt; the specific electrode potential of copper is 0.34 zinc the the and the Giving negative sign potential copper potential the positive sign is again purely arbitrary. It is perhaps
of
more from the point
is primarly interfrom than the cell, point of view of the chemist who is concerned with the changes within the solution. To the physicist, copper is positive to zinc since in the above cell the positive to negative direction of the current in the wire is from the copper to the zinc. Chemists are also adopting this sign convention although many texts and reference books use
view
of the physicist
who
ested in the outer circuit of a
the opposite convention. In this book, specific potentials will be denoted by the symbol E, and a table of such potentials is given in the Appendix. When applied to an active metallic electrode, the numerical value refers to the potential at 25C. between a metal and a one-molar solution of its ions relative to the potential between hydrogen gas at one atmosphere pressure and a one-molar solution of hydrogen
ions.
The e.m.f. its two half

mentioned
1.10 volts.
of
cell is
cells,
cell,
or E E=E l
the difference between the potentials of = EI E2 In the case of the above.
E*
Ecu*
- EZU Q =
+0.34
(-0.76)
Electrode potentials are not limited to those between elements and their ions. They also apply to potentials between ions at
two
states of oxidation.
79
Thus, as shown in the potential table
in the Appendix, the specific potential between ferrous and ferric " ions (Fe++ =* Fe"*"4 4 e) is +0.748 volt, indicating that a current
"
of that voltage
would flow through the following
cell:
Pt
M),
M)
M),
2 (l
atm.)
Pt
Electrons would pass through the solution from the ferrous-ferric half cell to the hydrogen electrode (i.e. from left to right as written
y
above).
They would
enter the solution from the wire at the fer-
rous-ferric half cell.
hydrogen gas would
Ferric ions would be reduced to ferrous ions; be oxidized to hydrogen ions.
Similarly, the specific potential between chromic ions and dichromate ions in the presence of acid (20+++ 7H2O =* CrÔ^
14H+
cell:
+ 6e)
is
+1.30 volt which

Cr+++(l
is
the voltage of the following
Pt
M) M)
"
H+(l M),
2 (l
atm.)
Pt
H+(l
M)
The
e.m.f. of the following cell:
Pt
Pt
would be the algebraic difference between the two half cells com0.55 volt. The negative sign (+1.30) = prising it, or +0.748 indicates that the passage of electrons through the solution is from right to left as written above, and through the wire from left to right. The ferrous ions are therefore oxidized and the dichromate ions reduced during the process. The over-all reaction would be
Cr2 C>7-
14H+
7H2
42. Rules for Writing Equations for Half-cell Reactions. In writing and balancing equations for half-cell reactions the follow-
ing steps should be followed: 1. Write the reduced form of the element that changes its oxidation number on the left-hand side of the equation; write the
oxidized form on the right-hand side. If necessary, balance the number of atoms of the element by inserting the proper coefficients.
80
2.
On the right-hand side
of the equation introduce that
of electrons equal to the total
change in
number oxidation number of the
element.
introduce sufficient hydrogen ions (if the reaction takes place in acid solution) or hydroxyl ions (if the reaction takes place in basic solution) to balance the electrical charges.
3.
If necessary,
Remember that each
electron symbol represents a negative charge. 4. If necessary, introduce water molecules into the equation to
balance the hydrogen and oxygen atoms. EXAMPLE. Write balanced half-cell reactions for the following
changes
(a)
VO++->V0 3~
(c)
(acid solution); (6)
Cr+++ -
=
2
7
(acid solution);
Mn++
MnO
(basic solution).
Following the above four steps, the results in each case are as
follows:
(a)
1.
2.
3.
4.
1.
VO++->VOr VO++ - V0 - + e (change = 5-4=1) VO++ -> V0 - + 4H+ + e VO-*+ + 2H 2 -> V0 3 + 4H+ + e
3 3
(6)
2Cr+++--Cr2
2.
3.
4.
2O+++ -> Cr2O 7 + 6e [change = (6 - 3) X 2O+++ -> Cr2 Or + 14H+ + 6e = 2Cr+++ + 7H 2 O - Cr2 O 7 + 14H+ + 6e
~ -
6]
(c)
1.
2.
3.
4.
Mn++ -+ MnO2 Mn++ -> MnQ 2 + 2e Mn++ + 40H- -> Mn0 2 + 2e Mn-^ + 40H- -> MnO 2 + 2H2 + 2e
tions.
43. Oxidation-reduction Equations in Terms of Half-cell ReacIn order to write an ordinary redox equation in terms of
half-cell reactions the appropriate couples are merely written one below the other and subtracted in algebraic fashion. Since electron
symbols should not appear in the net equation, it is frequently necessary to multiply one or both half-cell equations by a factor " cancel" out. This is illustrated in order that the electrons may
in the following examples.
Obviously the potential of the halfcell reaction is not affected by such multiplication. The oxidation of ferrous ions by chlorine can be written:
Fe++ - FC+++
or
(1) (2)
81
+e
(Ef = +0.747)
2Fe++ = 2Fe^ + 2e 2C1- = C1 2 + 2e 2Fe++
(#2
+1.359)
(l)-(2)
C1 2
= 2Fe+++
+ 2C1~
in the presence of
The
oxidation of ferrous ions
by dichromate
acid can be written:

(1)
(2)
6Fe++ = 6Fe+++ + 6e = 2Cr+++ + 7H 2O = Cr2 7 + 14H+ + 6e

6Fe++
(EJ = +0.747) (E2 = +1.30)
(l)-(2)
+ Cr O - +
2
7
14H+ = 6Fe+++
2Cr+++
+ 7II O
2
oxidation of stannous ions in the presence of acid by permanganate can be written:

(1)
(2)
The
5Sn++ = 5Sn++++ +
2Mn++ + 8H2
We = 2MnOr + 16H+ +
1
4
lOe
2MnO + 16H+ =
If concentrations are all
5Sn++++
= +0.13) = (E +1.52) 2Mn++ + 8H O

(Ei*
2 2
molar, the net potentials of the above three illustrations are the algebraic differences between the specific potentials corresponding to the two half^cell reactions, namely,
E = EJ- E = E = Ef - E = EÊS- E =
z 2 2
(+0.747) (+0.747)
(+0.13)
(+1.359)
(+1.30)
(+1.52)
= -0.612 volt = -0.55 volt = -1.39 volt
In cases like the above, if the algebraic difference between the electrode potentials, as written, is negative, the net reaction can be expected to go as written (i.e., from left to right). If the algebraic difference is positive, the reaction will not go as written but can be
expected to go
from
(1)
right to
left.
Thus,
2Fe++ = 2Fe+++
21-
+ 2e
-
(+0.747) (+0.535)
(2)
(l)-(2)
+ 2e 2Fe-H- + I, =
I2
2Fe+++
+ 2l~
= +0.212
volt]
[(+0.747)
(+0.535)
This reaction at
left
1 molar concentrations will not take place from to right as written, but goes in the opposite direction (2F
21-
2Fe++
+ I ).
2
82

of
The behavior
way.
metals with acids can be treated in the same

1
Metallic zinc dissolves in

(1)
M HCL
+ 2e (-0.758) H = 211+ + 2 (0.00) (2) Zn + 2H+ -* Zn++ + H (l)-(2)

2
Zn = Zn++
Metallic copper does not dissolve in HC1.
Cu = Cu++ + 2e (+0.344) H2 = 2H+ + 26 (0.00) (2) Cu + 2H+ - Cu++ + H 2 (l)-(2)

(1)
_
2
(-0.758)
(+0.344)
Both
zinc
and copper
dissolve in 1
M HNOa.
In this case two
oxidizing agents are present, namely H+ and N0a~, but the nitrate ion has the greater oxidation potential and is the oxidizing agent
in
both
cases.
(1)
(2)
2NO +
3Cu = 3Cu^ + 6e (+0.344) 4H 2 O - 2NO 3- + 8H+ + 6e (+0.94)
(l)-(2)
3Cu
+ 2N0 ~ + 8H+ 3
3Cu++
+ 4H O
2
[(0.344)
(0.94)
= -0.60
volt]
potential table therefore shows relative tendencies for substances to lose or gain electrons. Substances at the top left of
The
the table lose their electrons most readily and gain them least readily. They are therefore the strongest reducing agents. Similarly,
the oxidizing agents at the bottom of the table are the strongest; those at the top are the weakest.
Such predictions as given above must be applied cautiously.

In a few cases reactions that should proceed according to the relative positions in the potential series do so at such a slow rate that
they are almost negligible. More important still, as shown in the next section, the concentration of each component of an oxidation-reduction equilibrium affects the value of the potential. A substance may be present that is capable of forming a complex
ion with one of the components of the half-cell equilibrium and thus reduces the concentration of that component to a point where it no longer reacts. Thus, the potential of the equilibrium Sn++ <=
gn ++++ 4. 2e is greatly affected by the presence of chloride ions which form SnCle" ions with the stannic tin. In a few cases pre-
83
For example, accipitation effects interfere in the same way. to the iodide ions should reduce silver ions to metallic cording table,
silver
(2Ag+
+ 2I~
>
2Ag
+I
2 ).
Actually, a precipitation of silver
Agl) and the concentration of Ag+ in the residual solution is made too small to be affected by excess iodide. In the case of a few metals, passivity effects may occur. Pure aluminum should dissolve readily in nitric acid ~ (Al + NO 3 + 4H+ -> A1+++ + NO + 2H 2 O). Actually it does not
iodide takes place instead (Ag+
>
+ I~
probably because of the formation of a protective coating on the surface of the metal. 44. Relation between Electrode Potential and Concentration. When the prevailing concentrations are not 1 molar, the electrode potentials are no longer molar electrode potentials but can be calculated from them. From considerations of free energy it can be shown that at 25C. electrode potentials can be calculated from the following formula:
so,
do
of oxide
E = EQ H
where
0.0591
log
,_ M
E =
Q
molar electrode potential
n = number of faradays involved in the change = common logarithm log = ratio obtained by dividing the prevailing molar
con-
centrations of the oxidation products of the reaction by the prevailing molar concentrations of the reacting substances, each concentration being raised to a power
equal to the coefficient of the substance in the equation representing the reaction taking place in the half cell.
In expressing
M,
reactions should be written as oxida-
tions, and, as in the case of mass-action expressions, concentrations of water and of solid substances ar
omitted. Gases are expressed in terms of partial pressures (in atmospheres)

in Sec. 41, in some tables of electrode potentials the signs are opposite to those given in this book; that is, the numerical values of those
1
As stated
potentials listed above hydrogen are plus, and those below hydrogen are minus. = If this alternative system is used, the given formula becomes
log
M. The
consistent use of either system leads to correct results.
84
In calculations of electrode potentials, as in the case of calculations of equilibrium constants, activities rather than concentrations should be used for precise results (see Sec. 32). Values for specific electrode potentials should therefore be for unit activity
rather than for molar concentration.
this particular field,
Analytical calculations in
however, do not require a precision greater than one or two significant figures, and the use of activities and activity coefficients (which are not always easily determined) can
be dispensed with.
EXAMPLE
Pt
I.
Find the
e.m.f. at
25O.
of the cell
Cc+++ (0.10 molar) Ce ++++ (0.00010 molar)

:
Fe++(0.010 molar) Fe+++(1.0 molar)
Pt
SOLUTION
(1)
= =
(2)
1.45
1.27
+ 0.0591
log 10-'
Fe++ = Fe+++
+
= =
0.747
+ 0.0591
log 100
0.805
Subtracting
(2)
from
(1)
Fe++
= E -Es= 1.27-0.8G5 = 0.40 volt. Ans.

L
positive sign shows that the passage of electrons in the solution is from left to right. The ferrous ions are, therefore, The reaction Ce 4 4" " oxidized, and the eerie ions are reduced.
" 1
The
Fe+ ++
= Ce
4^"^4"
are reduced, and tions so adjust themselves that
right to left. The eerie ions the ferrous ions are oxidized until the concentra-
FG ++
proceeds from
no current
flows.
In this example the concentrations given are those of the simple cations. These cations may often be in equilibrium with complex
ions,
such as FeOLr, Ce(SO 4 ) 3 ^,

IT.
etc.
cell
2
EXAMPLE
(0.30
What
is
the e.m.f. of the half

Oc?
represented
<=
by the following equilibrium: 2Cr+++(0.20 M)
+ 7II O
Cr 2
M) +
14H+(2.0
M) +
SOLUTION:
85
0.0591
14
,
(0.30) (2.0)
=
EXAMPLE TIL
1.46 volts.
is
Ans.
cell
What
the e.m.f. of the
Cu Cu f+(0.010
SOLUTION:
El
molar)
||
Zn++(1.0
10~6 molar)
Zn?
Ecu"
+Zj
log [Cu++]
= +0.34 +
log (0.010)
+0.28 volt
-0.76
+
Zi
log^l.O
10-6 )
= -0.94 E = h\-E =
2
1.22 volts.
În^.
P]XAMPLB IV.
Calculate the e.m.f. of the following cdl:
Cu Cu ++ (2.0 M)
This type of
C -u
4 "*
cell,
Cu++(0.010
M) Cu
(Cu
made up
of the
same
half-cell equilibrium
+ 2e,
in this case)
but with the ions at two different concell.
centrations, is
known
as a concentration
SOLUTION:
E,
2
0.344
-f
~
z
log 2.0
log 0.010
^ =
0.344
~
=
nwi ^P
o
(log 2.0
log 0.010)
0.068 volt.
Ans.
86

Which an Oxidation-reduction
45. Calculation of the Extent to
Reaction Takes Place.
All reversible reactions proceed in one direction or the other until equilibrium conditions are reached, at
in
which point the two rates of reaction are equal. During the progress of an oxidation-reduction reaction
cell,
the concentrations of the reacting substances are steadily decreasing and those of the products are increasing. The voltage of the
decreases steadily until equilibrium is reached, at which point no current flows. The potentials of the two half cells making up
cell
the
are therefore equal at this point of equilibrium. In order to calculate the extent to which an oxidation-reduction reaction
cell
it is
takes place,
cell
reactions
only necessary to express the reaction as two halfand to express an equality between the two electrode
potentials.
EXAMPLE
solution 0.30
tion of
I.
When
excess metallic
is
aluminum
(2A1
is
added to a
2A1+++ +
M in cupric ions, what
the theoretical concentra-
CU++ after equilibrium is reached
+ 3Cu++ +
is
3Cu)? SOLUTION:
complete.
[A1+++]
Experiment shows that the reaction

0.20
practically
[Cu++]
.
= =
M
,
(3
moles of CU++ give 2 moles of A1+++)

IA9>I>II 0.0591 = +0.344 + =
Zi
-1.70 H
-n
0.0591 , n on log 0.20 5 o

log x
log x
= -69 x = 1 X 10-69
mole.
Ans.
II. A solution is prepared so as to be initially 0.000 + molar in Fe +, 0.10 molar in Cr2 7= and 2.0 molar in II + After the reaction, what would be the approximate concentration of the Fe++ remaining (6 Fe++ + Cr2O 7= + 14H+ <= 6F6+++ + 2Cr-H+ +
EXAMPLE
7H 20)?
SOLUTION:
Experiment shows that the reaction
is
practically
complete. Since, according to the equation, 0.060 mole of Fe++ would react with 0.010 mole of Cr2O 7= and 0.14 mole of H+, the
latter
two
is
are initially present in excess
and the concentration
of
Fe++
[Fe
4
-*-]
the limiting factor.
At
two
[H+]
x; [Cr+++] 0.020; 2.0 - 0.14 = 1.86. The
[Cr2
equilibrium, = 0.10 7 ~]
^6+++] =
0.010
0.060;
0.090;
half-cell equilibria are
87
M) *= 2Cr+++(0.020 M) + 7H O *
6Fe++(z
2
6Fe+++(0.060
M) + 6e
Cr2O7=(0.090 M)
+0.747
,
14H+(1.86
log
M) + 6
log
,
. +1.30 +
.
0.0591 0.060 A _._, +0.747 + log
-p-
10A + 0.0591, = 1.30 log
-g.
; (0.090) (1. 86)
"
Solving,
a:
10~ 17
Ans.
46. Calculation of Equilibrium Constant

tentials.
from Electrode Po-
mass-action constant (Sec. 26) applies to a reaction under conditions of equilibrium. At this point the electrode potentials of the half-cell equilibria are equal
and the
over-all poten-
This gives a method of calculating the numerical value of the mass-action equilibrium constant of an oxidation-reduction
tial is zero.
equation from the respective specific electrode potentials. EXAMPLE. Calculate the numerical value of the equilibrium constant of the reaction 2Fe++ + I 2 2Fe+++ + 2I~ (which at
moderate concentrations proceeds only very

right as written).
slightly
from
left
to
SOLUTION:
(1) (2)
2Fe++
21-
+ +
2Fe+++
I2
2
+ 2e
+ 21-
+ 2e
<=>
(l)-(2)
2Fe++
2
+I
2Fe+++
K-f fFe~
l [I~~l r-n .x-Jorr i 2
(mass-action constant)
[Fe++]
[I 2 ]
EI
= E%
(at equilibrium)
+0.747
f
0.0591
log
/[Fe ++-h]2
0.535
j2 \
<"*
,og
2
0.0591
log
.
"
2
UF^+F
[Fe+++]
2
"~*
DF?/
[I-]
log
log
K- -0.212
K = -7.0 K = 1.0 X
10-7
.
Ans.
88

Problems
(See Table VII, Appendix, for the necessary oxidation potentials. tures are 25C.)
186. Calculate the potentials of the half cells:
(a)
(6)
(c)
Tempera-
(d)
M) + 2 Co Co+++(0.24 M) + 2e ++ Pb (0.050 M) + 2H O ^ PbO2 + 4H + (0.010 M) + H 2 O2 (0.0020 M) Ô2 (2 atm.) +2Ff(1.5 M) + 2e
Hg
=*
Hg++(0.0010
=*
2e
Ans.
volt.
(a)
+0.77
volt.
(6)
-0.94
volt,
(c)
+1.24
volt,
(d)
+0.78
two
187. Balance the following equation half-cell reactions:
and express it as the difference between
+ Br- + 11+ -> Pb+ + Br + H O. Ans. PbO + 2Br- + 4H+ - Pb++ + Br + 211 O; (2Br~ & Br + 2e) + (Pb+ + 2H O <* PbO, + 4H+ + 2e).
PbO 2
2
188. Write the equation showing the net reaction indicated by each of the Show from the respective electrode following pairs of half-cell reactions. potentials in which direction each reaction will go, assuming all ion concen++ + trations to be 1 molar, 2e; (6) 1I 2 O 2 <= (a) A_g?=>Ag e,
+ Cu^Cu + O + 2H-* + 2e, + 2H O ^ MnO + 4H+ + 2e. ++ + Ans. (a) Cu + 2Ag+ -> Cu ++ + 2Ag; (6) MnO + II O + 2H+ - Mn O + 2H O.
2
Mn ++
189. Write complete
and balanced equations
for the half-cell reactions in-
dicated
(6)
by the following changes taking HNO2 - NCV, (c) As -^ UAsO2 (d) BiO+ -* Bi 2 O 4
,
place in acid solution: (a)

,
^b
>
SbO +
(e)
2
Br2 -> BrO,-
Ans.
(a)
3H+
Bi 2O 4
+ 2e, + 411
<
HNO + HO ^ NOr + + H o"^ SbO+ + 2H*- + 3e, 2BiO+ + 2H O ^ As + 2H0 * HAsO, + 311+ + 3e, (c) + 2e, (e) Br + GH O ^ 2BrO.r + 12H+ + 10e.
Sb
2
(ft)
(tt)
190. Write complete and balanced equations for the half-cell reactions indicated by the following changes taking place in basic solution: (a) Zn
>
ZnOT, Ag2 0.
Ans.
(6)
HCHO
(a)
HCO
(c)
IISnO2 -*Sn(OH)r,
(d)
THs -
P, (e)
Ag ->
O + 2e, (6) IICIIO + 3OH- ^> + 4OH- ^ ZnO = + 2H HSnO + 3OII- + II O & Sn(OII).,- + 2e, HCOr + 2II 6 + 2e, (c) (d) PR, + 3011- f P + 3H O + 3e, (e) 2Ag + 2OTI- ^> Ag O + II O + 2e.
Zn
2 2 2 2 2
191.
What
is
the e.m.f. of the following concentration cell?
Ag
In what direction Ans.
is
Ag+(0.40 molar)
Ag' (0.0010 molar)
Ag
the flow of electrons through the solutions as written?

Left to right.
0.10 volt.
192.
89
What
e.m.f.
can be obtained at
25C. from
the following cell?
Zn Zn ++ (0.010 molar)
|
||
Ag+(0.30 molar)
Ag
In what direction
is
equation for the reaction at each electrode
the flow of electrons through the solutions? Write an and for the net reaction. What
for
would the concentration of Ag+ have to be

Ans.
1.585 volts.
no current to flow?
Zn
2Ag'
~>Zii +l
Right to 2Ag. 4.5
left.
-* Zn ++ Zn "
28
2e,
2Ag
2e -> 2Ag,
lO"
molar.
193. Calculate the e.m.f. obtainable from each of the following cells. In each case indicate the positive to negative direction of the current in the wire connecting the electrodes, and write an equation for the net reaction.
(a)
Cd
Cu +l (1.0M On
Hg+*-(0.10
(6)
Hg
M)
II
Hg f + (0.0071 M) Hg
Fe++(0.10 M) Fe + ++(0.30
M)
O Or
2
Cr ++ +(0.010 M)
(0.20)
Pt
H+(1.0M)
Su+ + (0.050 M) Sn+^+(0.020 M)
(0.10
(d)
Pt
Mn ff (0.10M) MnO -(0.060 M)

4
Pt
II+(0.20
M)
Fe +l
Ag Ag+Cl
Ans.
(a)
(sattl.)
Fe+++(0.20
left.
M) Pt M)
0.0340 volt,
(e)
0.742 volt, right to

(d)
(6)
left
to right,
(c)
0.56
volt, right to left,
1.33 volts, left to right,
0.52 volt, right to
left.
194.
What
e.m.f.
can be obtained at
25C. from
the following cell?
Ag Ag+(0.50 molar) Cd f+ (1.0 X

|
10~4 molar)
Cd
||
In what direction do the electrons flow through the solutions as written? Write the equation for the reaction taking place at each electrode and for the + net reaction. What would the concentration of Ag have to be for no current
to flow?
Ans.
195..
1.30 volts.
Left to right.
10~ 23 molar.
What must be
be at equilibrium?
2A1
70
the value of x in order that the following reaction shall 3Cu. 3Cu++(z molar) ^2A1+++(0.10 M)
Ans. 1.6
196.
10~
molar.
What must
25C.?
be the value of x for the following reaction to be at equi-
librium at
Cu
Ans.
6
+
9
2Ag+Cc molar)
:Cu++(0.10 molar)
2Ag
10~ molar.
90

,
"
1
197. If excess metallic iron is placed in a solution 0.010 molar in Cu ++ what concentration of Cu*" will remain when equilibrium is reached? The reaction
is
practically complete as follows:
Fe
Cu ++
>
Fe ++
Cu.
Ans.
198.
10-
29
molar.
is
When
is
excess metallic zinc
added to a solution 0.010 molar in Ag+,
what
is
the theoretical concentration of
Ag+
after equilibrium
is
"
reached? The
reaction
practically complete as follows:
Zn
2Ag+
Zn* 4
2Ag.
Ans.
10~28
199. Equal volumes of a solution 0.10 molar in Fe +f and a solution 0.30 molar in Ce +++ + are mixed. After the reaction is practically complete (Fe++ + Ce++++ > Fe+ + + + Ce+ ++ ) and equilibrium has been attained, what is the concentration of Fe ++ ?
resulting
Ans.
10~ 14 molar.
200. Calculate the equilibrium constant for each of the following:

(a)
(6)
(c)
Cu ++ = Zn++ + Cu A1+++ + 3 Ag =* Al + 3Ag+ Fe+++ + Ag <=> Fe++ + Ag+

Zn
(d)
(e)
2Ce +++
(/)
+ I, 2Ce ++++ + 216F6++ + Cr,07- + 14H+ ^ GFe+++ + 2Ct+++ + 7H O 2Fe + + + + 2Br- ^ 2Fe ++ + Br
<=
Ans.
(/)
(a) 3
10 37
(6)
10' 127
(c)
0.13.
(d)
1.6
10~31
(e)
1056
1.7
10-".
201. Write complete and balanced equations for the half-cell reactions indicated by the following changes taking place in acid solution: (a) P > ++ ++++ -> SbO+ -. Sb 2 O6 (e) Ch -> 2 3 P04 , (6) Mn0 2 -> MnOr, (c) , (d)
UO
HC102
(/)S 2
-->H S0
2
3.
202. Write complete
and balanced equations
for the half-cell reactions in-
dicated
(6)
by the
following changes taking place in basic solution: (a)

(c)
P
4
>
Pb^-^Pba,
S03 -->SO4 -,
(d)
CrO2 -
PO ^,
3
->
CrOr,
(e)
NO
2
-* NO,-,
203. Calculate the potentials of the following half cells:

(a)
(b)
(c)
(d)
AgÂg+(0.010M) + e Co < Co ++ (0.063 M) + 2e Mn^(0.030 M) + 4H 2 O + MnOr(0.020 M) + 8H+(0.10 M) + 5e 2Cr+-H'(0.010 M) + 7II 2 ?=* Cr2 7 (0.020 M) + 14H + (0.030 M) +
,
6e
204. Balance the following equations and express each as the difference between two half-cell reactions: (a) Fe + H+ -> Fe+ + + H 2 (b) Fe ++ -f
MnOr + H+ -* Fe^-^ + Mn++ + H O, (c) Fe + N0 - + H^ -> Fe "^ + NO + H 0, (d) C1 + H O - HOC1 + H + + CJ- (e) PbS + H O2 -> PbS0 + H2O.
42 8
91
H HS2
205. Balance the following equations and express each as the difference ++ H+ -> Fe+++ 2 O, 2 O2 between two half-cell reactions: (a) Fe -> Cr +++ Mn++ O2 11+ 2 O, (c) 2 2 (b) - Cr2O7 I(V 2 O, (e) 2 SO8 Mn++ H+ (d) I2 2 O2 ->H+ 2
MnOr + H O +
+ +H
+H +H
+H
+H
+ MnOr + H +
+ H O.
2
206. Write the following as balanced ionic equations and express each as 2 Cr2 07 the difference between two half-cell reactions: (a) SnSO4
H S04 - SnCSOdt + K2S04 + CftCSO*). + H 2O, H3As04 + NO, (c) Br2 + NHOH -> NH4 Br + N 2 HC1 -* I, + H 2O + KC1.
2
+ + HNO, + H O + H O, (d) KI + KIO, +

(6)
+K
As
2
207. Write an equation showing the net reaction indicated by each of the Show from the respective electrode following pairs of half-cell reactions. should go, assuming all ion conreaction each in direction which potentials
centrations to be
molar,
(a)
Hg <^ Hg^+ +
2e,
Zn *=* Zn++
2
+
2f,
2H+
2e,
Fe++
(d)
Fe++ +
e;
2
(c)
201-
& Cl, + 2e;
2C1~
^ C1 +
+
2c,
Pb++ 2Br~ ?=*
+ 2e; (b) H O + 2II O PbO + 4H+ + Br + 2e.

2
2 <=
<=*
208. Solve the preceding problem with respect to the following half-cell ++++ 7H 2 <= I2 reactions: (a) Sn++ v* Sn 2e; (6) 2O+++ 2e, 2I~ a s 2H ? 2 1411+ Cr2 O7 (c) Fe(CN) 6 e; Fe(CN) 6 6e,
+ + + 4H + 2f, NO - + 411*- + 3e.

MnO,
3
^ +
Fe ++ <^ Fe +++
e;
(d)
O + Hn^ + O + NO + 2H O ? Ag Ag+ +
<=
e,
2
209.
The following reactions take place at ordinary concentrations as written:
+ 2H+ - V +++ + T1+++ + H O Bi + + HjO - BiO+ +.3FC++ + 2H+ Zn + 2Cr+++-> Zn++ + 2Cr++ 6Br~ + Cr O + 14H+ - 3Br + 2Cr+++ + 7II O 3Ti+++ + BiO+ + 2H O - 3TiO ++ + Bi + 4H<~ 2Fe ++ + NO + 3H+ -> 2Fe +++ + HN0 + H ++ Mg + Zn ++ - Mg + Zn ++ C r + V+++ -+ Cr +++ + V++ HNO + Br + H O - NO - + 2Br~ + 3H+
y++
-f
TiO ++
3Fe +++
Convert each of these reactions into two half-cell reactions, placing the reduced form on the left and the oxidized form and electrons on the right. Rearrange the 10 half-cell reactions in tabular form in such a manner that the strongest reducing agent is at the top left and the strongest oxidizing agent From the tabulation predict which of the following do is at the bottom right. not react at ordinary concentrations and write balanced ionic equations for ~ V++ (6) Fe++ + TIO++, (c) Cr ++ + N08 those that do: (a) Zn++ + H+ (d) Bi + Br2 (e) Cr2O7 + TiO+ + H+.
210.
Which
of the following reactions should take place as indicated

1
ion concentrations are
molar?
(a)
,
2C1~
HO
2
Pb ++
- 2Fe(CN) 6 B + O2 + 2H + (c) + 2H2O, (d) 2BJ + 6H+ -> 2Bi +++ 11H2O - 5Cr2O7 - + 6Mn++ + 22H+.
2
-+ C1 2 2I~ PbO 2Fe ++

Ii
when 2Fe(CN)- -f 4H+ -> 2Fe +++ +

(b)
+ 3H
2,
(e)
1QCT+++
+ 6Mn04~ 4-

In each case 211. Calculate the e.m.f. of each of the following cells. indicate the direction of the passage of electrons in the wire connecting the electrodes, and write an equation for the net reaction.
(a)
(6)
Ag
|
Ag+(1.0
f
M)
Cd++(1.0
II
M) Cd
(0.090
Cu Cu
(0.010
M)
M)
Cu
||
'
'
M) Cu M)
Pt
Cr Mt
II +
(0.050
Cr 2 O 7 -(0.10 M)
(2.0
M)
Fe +++ (0.0l5 M)
1
(d)
M) Pt Sii+ ++ +(0.080 M)
Sii++(0.020
(0.050
M)
Pt
MnO -(0.10 M)
4
II
(0.40
M)
Pt
212.
Fc ++ (0.25 M) Fe M (0.050 M)
f
AgCl
(siitd.)
What
is
the
c.ni.f.
of the following concentration cell?
Cu Cu++(1.0 X
|
10~ 5 molar)
||
Cu ++ (0.080
molar)
Cu
In what direction
213.
is
the flow of electrons through the solutions as written?
What
e.m.f.
can be obtained at 25C. from the following

+
(0.50 molar)
||
cell?
Ag Ag
In what direction
is
Cd
'
(1.0
10- molar)
1
Cd
the flow of electrons through the solutions? Write the
equation for the reaction at each electrode and for the net reaction. would the concentration of Ag f have to be for no current to llo\v?
214.
What
25C., and the
What
is
2Ag is practically complete. the concentration of silver ions theoretically remaining in the solution?
'
piece of zinc is reaction
immersed
in
a 0.010 molar solution of silver ions at

>
Zn
2 Ag
Zn
'
215. What must be the value of jc in order that the following reaction shall f Zn + +(1.0 X 10~ 3 molar) + Ag? be at equilibrium: Zn 2Ag (x molar)
216. When excess metallic aluminum is added to a solution 0.10 molar Cu ++ what is the theoretical concentration of Cu ++ after equilibrium reached? The reaction is practically complete as follows: 2AJI + 3Cu f+
,
in
is
2A1+++
217.
3Cu.
+ Equal volumes of a solution 0.40 molar in Fe+ and a solution 0.10 ++ After the reaction is practically complete are mixed. molar in Ce ++ + Ce +++ + > Fe +++ + Ce +++ and equilibrium has been attained, ) (Fe "" what is the resulting concentration of Ce^" "?
!
218. Calculate the equilibrium constant for each of the following:

(a)
(6)
(c)
(d)
(e)
CU++ + 2Ag Cu + 2Ag + ++ 3Cu 3Cu + 2A1 Fe^ + + CG++++ + Fe 2Br- + I 2 + Br2 + 21-+
^
4
101-
+ 2Mn0 ~ +
16II + +
5I 2
+ 2Mn + + + 8H
PART II GRAVIMETRIC ANALYSIS

CHAPTER
VII
THE CHEMICAL BALANCE

Chemical Balance. The determination of the weight or the mass of a body is a fundamental measurement of analytical chemistry and is made with an equal-arm
47. Sensitiveness of the
balance of high degree of precision. An equal-arm balance consists essentially of a rigid beam supported horizontally at its center
on a knife-edge and so constructed that the center of gravity of the swinging portion is below the point of support. The sensitiveness or sensitivity of a chemical balance is the tangent of the angle through which the equilibrium position of the pointer is displaced by a small excess I6ad (usually 1 mg.) on the balance pan. This angle is usually so small that it is sufficiently accurate to define the sensitiveness of a balance as the number of scale divisions through which the equilibrium position of the pointer of the balance is displaced by an excess load of 1 mg. The sensitiveness varies directly with the length of the balance
beam, inversely as the weight of the beam, and inversely as the distance between the center of gravity of the swinging portion and the point of support. That is,
tan
a=
ri k bd
is
where
a=
b
I
= =
the angle through which the pointer the weight of the beam
moved
d
k
= =
the length of the beam the distance between the center of gravity and the
point of support a constant

93
94

The
sensitiveness of a balance decreases slightly with increasing
load.
In most analytical work, it is suffithe method of short swings. ciently accurate to The pointer of the balance is allowed to swing only one or two scale divisions to the right or left of the zero point of the scale, and the reading of the weights is taken when the extreme posi48. of Swings.
Method
make weighings by
tions of the pointer to the right and left of the zero point are equal. The balance is, of course, previously adjusted so that with no load on the pans the extreme positions of the pointer are likewise
equal.
For more accurate work the method
of long swings
is
used.
The
equilibrium position of the pointer is first determined by allowing the beam of the empty balance to swing so that the pointer passes
over six to eight divisions on the scale. Extreme positions of the pointer in an odd number of consecutive swings are recorded;
for example, three readings are taken to the right of the zero point of the scale, and two readings are taken to the left of the zero point. The two sets of readings are averaged, and the
equilibrium position of the pointer is taken as the algebraic mean of the two values. As an illustration, assume that the pointer of
a balance swings as indicated below:

+4.5
^-^
-3.5
\_
-
+4.0
Average: -3.3
Equilibrium position:
+4.1
The weight
the left-hand pan and
an object can then be determined by placing it on (1) adjusting the weights and rider, or weights and chain, so that the equilibrium position is the same
of
as that obtained with the empty balance, or (2) calculating the weight from the sensitiveness of the balance and the equilibrium
95
position corresponding to an approximate weighing of the object.
For example, suppose the equilibrium position of the pointer under zero load is +0.4 as determined above. Suppose that, when an
balanced with 20.1260 grams, the equilibrium position found to be +1.6 and the sensitiveness of the balance under a 20-gram load is 4.0 (i.e., a 1-mg. increment shifts the equilibrium position by 4.0 scale divisions); then the necessary shift of 1.2
object
is
is
divisions to the left to bring the equilibrium position to
+0.4
is
accomplished by increasing the weight on the right-hand side of the balance by 1.2/4.0 = 0.3 mg. The weight of the object is, therefore, 20.1263 grams.
medes
Weight in Vacuo. Archisubstance immersed in a fluid any weighs less by an amount equal to the weight of fluid displaced. Consequently, a substance weighed in the ordinary manner is buoyed up to a slight extent by the surrounding air, and for Weight
7
49. Conversion of
in Air to
principle states that
accurate determinations, especially those involving the weighing
must be
volume, a correction for this buoyant effect method of weighing consists in applied. balancing the substance to be weighed against standard weights, the surrounding air likewise exerts a buoyant effect upon the weights. If the volume occupied by the weights used is equal to
of objects of large
Since the usual
the volume occupied by the substance, the buoyant effects will be equal, and the weight of the substance in vacuo will be the same as its weight in air. If the volume occupied by the substance is greater than the volume occupied by the weights, the substance
will
weigh more in vacuo than in air; and if the weights have the greater volume, the substance will weigh less in vacuo than in air. In any case, the difference between the weight in air and the weight in vacuo will be equal to the difference between the weight of the
air displaced
by the weights used. by the equation
by the substance and the weight The weight in vacuo
of the air displaced

Q
may
be expressed
where
W = the weight of the substance in air

V=
a
V = the volume occupied by the weights used

=
the weight of a unit volume of air
the volume occupied
by the substance
96
Since in practice, the volume occupied by the substance and the volume occupied by the weights are usually unknown, the formula is better written by expressing the values V and V' in terms of weight and density. If d is the density of the substance and d' the density of the weights, the volume occupied by the substance will be W/d, and the volume occupied by the weights used will
be
W/d
f
.
The formula may now be written
Since the value following the plus sign in this expression is small to which it is added and since compared with the value
and
be substituted for the TF in the parenthesis without appreciably affecting the accuracy of the formula. The formula now becomes
are nearly equal,
W W
may
W=W +
or
'
'W
Although the value of a varies slightly with the temperature and barometric pressure, the approximate value of 0.0012 gram for the weight of one milliliter of air may be used except in cases where extreme accuracy is required or whore the atmospheric conditions are highly abnormal. The densities of a few common substances are shown in Table I. A consideration of the precision of the various terms shows that the values of a, d, and d' need be known only approximately and that in most cases the computation may be performed with sufficient accuracy by means of a
slide rule.
TABLE Aluminum
I.
DENSITIES OF A
2.7
8.4
FEW COMMON SUBSTANCES

Mercury
Nickel
13.6 8.7
21 .4
Brass Brass (balance weights)
8.0 8.9
2.6
19.3
Platinum
Porcelain
Copper
Glass
2.4
Quartz
Silver Steel
2.7
10.5
Gold
11.3
7.8

EXAMPLE.
SOLUTION:
Density of platinum Density of brass weights
97
against brass analytical weights.
platinum crucible weighs 25.0142 grams in air What is its weight in vacuo?
Weight
of 1 ml. of air
= = =
21.4
8.0
=d = d' = a
0.0012 gram
Substituting in the above formula,
25.0142
25.0142
= =
0.0024
25.0118 grams.
Ans.
Tn an ordinary quantitative chem50. Calibration of Weights. ical analysis, if the same set of weights is used throughout, it is immaterial whether or not the masses of the weights are exactly
as
marked so long as they are in correct relative proportion. The mass of the 5-gram weight should be exactly one-half that of the 10-gram weight, and the others should be similarly in proportion. In order to establish this relationship and to determine what correction factors must be applied to the individual weights of a given set, the weights must be calibrated. There are several ways of calibrating weights. One of the simplest is to
assume temporarily that one of the smaller weights, say tlurlO-mg. weight, is correct and to determine the value of
In order to allow for the the other weights in relation to it. of the balance may be slightly unequal possible fact that the arms
be made by the method of substitution, which practically eliminates any error from this source. Ordinarily the masses of objects A and B are compared by placing them on opposite pans of a balance, but by the method of substitution, object A is placed on the left-hand pan and is balanced against a tare (which may be a weight from an auxiliary set) on the right-hand pan. A is removed and B is placed on the
in length, weighings should
Tf it exactly balances against the same tare, it left-hand pan. as A. If there is a slight difference, the change mass same has the
in position of the rider or chain necessary to reestablish equilibrium can be taken as a measure of the difference in mass.
98
The relative mass of the other 10-mg. weight (which can be marked 10') in the set is determined by comparing with the 10-mg.
weight; the relative mass of the 20-mg. weight is similarly determined by balancing against the combined 10-mg. and lO'-mg. weights. This process is continued up through the entire set of
weights, the combined values of the smaller weights being used
TABLE
II.
TYPICAL CALIBRATION CORRECTIONS
to establish the values of the larger weights. In this way values similar to those listed in the second column of Table II are ob-
Because of the small standard taken, it will usually be found that the larger weights have large correction factors. It is therefore convenient to convert the values to a larger standard, say one of the 10-gram weights of the set (or an auxiliary 10-gram weight from a set checked by the Bureau of Standards, which has been included in the above series of weighings). In the case cited in the table, the new 10-gram standard has a value of 10.1128
tained.
grams
The 5-gram weight (relative to the original small standard) should have a value of exactly one half of this, or 5.0564 grams.
.
99
Actually its value is 5.0562 grams; hence it is 0.0002 gram too Therefore 0.2 mg. must be subtracted from a weighing in light. which its face value is used.
In weighing a given object, instead of applying a correction for each weight used, it is less tedious to construct a table showing
By means of such a table the total corfound from the sum of the face values of the weights on the pan. In this case it is necessary when weighing an object to adopt the convention of using the smallest number of weights possible, to use an "unprimed" weight (e.g., 0.100 gram) in pref" erence to a primed" weight (e.g., 0.100' gram), and to construct
cumulative corrections.
is
rection
the table accordingly. In the table given, a total weight of 0.18 gram would show a net correction of -0.3 mg., which is the algebraic
sum
of the individual corrections of the weights
face values 100, 50, 20,
and 10 mg.
(i.e.,
+0.1
0.0
having the
0.3
0.1
-0.3).
Problems
addition of a small weight to a certain balance displaces the pointer through an angle of 6. Through what angle would a weight \}<-% times as great displace it?
219.
The
Ans.
220.
57'.
crucible weighing approximately 10 grams is being weighed. The pointer of the empty balance has an equilibrium position at +0.2 on the scale, and the sensitiveness of the balance under a 10-gram load is known to
be 3.6 divisions. With the rider at 4.8 (mg.) on the beam, the equilibrium point of the balance is found to be at +2.7 on the scale. To what point on the beam should the rider be moved to make the correct final reading?
Ans.
221.
5.5.
set in motion,
the pointer of a balance (having a 10-gram load on each pan) is it swings on the scale as follows: right to +7.6; left to 6.4; With an additional 1-mg. weight right to +7.0; left to 5.8; right to +6.2. on the right-hand pan, the pointer swings as follows: right to +1.0; left to
When
-8.2; right to +0.4;

(in scale divisions) of
left to -7.6; right to -0.3. What the balance under a 10-gram load?
is
the sensitiveness
Ans.
222.
crucible
4.2 divisions.
The balance
and
is
zero
when
of the preceding problem is used to weigh a certain adjusted so that the equilibrium position of the pointer is at the balance is empty. With the crucible on the left-hand pan, with
3.0
weights totalling to 10.12 grams on the right-hand pan, and with the rider at mg. on the right-hand beam, the equilibrium position of the pointer is
100

1.7
found to be at
Ans.
223.
on the scale
division.
What
is
the weight of the crucible
to the nearest tenth of a milligram?
10.1226 grains.
sample of an alloy having a volume of 2 ml. is weighed in air with brass weights and is found to weigh 16.0000 grams. What is its weight in vacuo?
Ans.
16.0000 grams.
224. Find the weight in
vacuo
of a piece of gold that weighs 35.0000 grains
in air against brass weights.
Ans. 34.9968 grams.

225.
A substance
weighing 12.3456 grams in
air
density equal to three times that of the weights used.

in
has a volume of 2 ml. and a What does it weigh
vacuo?
Ans.
226.
12.3408 grams.
how many grams

Ans.
227.
quartz crucible weighing 16.0053 grams in air against brass weights?
in
a vacuum would weigh
16.0005 grams.
weights.
What
sample of brass weighs 12.8150 grams is its weight in vacuo?
in
air against
platinum
Ans.
228. If
12.8162 grams.
of gold in vacuo weighs thirty-five times as much as a brass weight in vacuo, what would the brass weigh in air against
a piece
1-gram
Ans.
gold weights?
What would the piece of gold weigh in air against brass weights?
35.0031 grams.
0.99991 gram.
229. In calibrating a given sot of weights the 10-mg. weight is temporarily taken as a standard and assumed to be 0.0100 grain. On this basis the 2-gram weight is found to be 2.0169 grams and a 10-gram weight (certified by the Bureau of Standards to be correct to within less than 0.05 mg.) is found to be 10.0856 grams. What correction should be applied for the 2-gram weight in any weighing in which its face value is taken as its true weight?
Ans.
0.2
mg.
230. A weight of 1 mg. on the right-hand pan of a certain balance displaces the equilibrium position of the pointer by 6.0 mm. The pointer is 24.6 cm. long. What is the tangent of the angle through which the pointer has moved?
beam weighs 32.0 grains and is 16.0 cm. long, what is the distance between the middle knife-edge and the center of gravity of the moving parts?
If the
is
the pointer of a balance (having a 20-gram scale on each pan) 6.1 swings on the scale as follows: right to +6.2; left to to an With additional right to +5.7; left to +5.3. right 5.5; 1-iiig. weight on the right-hand pan, the pointer swings as follows: right to +3.1; left to
231.
set in motion, it
;
When

-9.2; right to +2.6; left to -8.7; right to +2.2. What scale divisions) of the balance under a 20-gram load?
is
101
the sensitiveness (in
232. The balance mentioned in the preceding problem is adjusted so that the equilibrium position of the pointer of the empty balance is at zero and is used to weigh a certain crucible. With the crucible on the left-hand pan, with
8.0 mg.
weights adding to 19.87 grams on the right-hand pan, and with the rider at on the right-hand beam, the equilibrium position of the pointer is 1.2 on the scale division. What is the weight of the crucible found to be at
to the nearest tenth of a milligram?
233.
What would be
it
brass weights
the weight of a piece of gold in vacuo 14.2963 weighs grams?
if
in air against
234. In vacuo, a quartz dish weighs 22.9632 grams.

in air against brass weights.
Calculate the weight
of 6.32
235. In determining an atomic weight, a final product which has a density is weighed in air against gold weights. What percentage error would
failing to
be made by
in vacuo?
convert this weight (10.0583 grams) to the weight
236. Find to the nearest tenth of a milligram the weight in vacuo of a piece of silver which weighs 20.0113 grams in air against brass weights.
237. Find the weights in vacuo of two crucibles, one of gold and one of aluminum, each weighing 15.0000 grams in air against brass weights. What would the gold crucible weigh in air against aluminum weights? 238.
What
is
the density of a solid which weighs approximately 20 grams
in air against brass weights and the weight of which increases by exactly 0.01 per cent in vacuo? What is the density of a similar substance the weight
of
which decreases by 0.01 per cent in vacuo?

239.
From the correction values
lative corrections for weighings ranging
given in Table II construct a table of cumufrom 0.01 to 0.99 gram and construct
another table of cumulative corrections for weighings ranging from 1.00 gram to 99.99 grams. (Hint: To save space use a tabulation similar to that used in
logarithm tables.)
in a given set has a value of 20.2364 weight as a standard, what should be the value of a 500-mg. weight to have a zero correction if the 20-gram weight is taken as the final standard and assumed to be 20.0000 grams? If the 500-mg. weight actually has a value of 0.5063 on the basis of the smaller standard, what
240.
Assuming that the 20-gram weight
grams
in relation to the 10-mg.
correction should be applied for this weight in value is taken as its true weight?
any weighing
in
which
its
face
CHAPTER
VIII

Proportions Applied to Calculations of Gravimetric analysis is based on the law of definite proportions, which states that in any pure compound the proportions by weight of the constituent elements are always the same, and on the law of constancy of composition, which states that masses of the elements taking part in a given chemical change alw ays exhibit a definite and invariable ratio to each other. It
51.
of Definite
Law
Gravimetric Analysis.
consists in determining the proportionate amount of an element, radical, or compound present in a sample by eliminating all interfering substances and converting the desired constituent or component into a weighable compound of definite, known composition.
Having then determined the weight of this pound, the weight of the desired component present
III).
isolated
in the
com-
sample
can be calculated (see also Chap.
EXAMPLE
in water,
I.
sample
of
is
impure sodium chloride
is
dissolved
and the chloride
precipitated with silver nitrate ac-
cording to the following equation.
NaCl
or
+ AgNO
-> AgCl
+ NaNO
What
furnishing 1.000 gram of silver chloride. chlorine in the original sample?
is
the weight of
Since silver chloride always contains silver and chlorine in the respective ratio of their atomic weights, or in the
SOLUTION:
ratio of 107.88:35.46, in every 143.34 (107.88 35.46) grams of In 1.000 gram silver chloride there are 35.46 grams of chlorine.
of silver chloride there
1.000
~
is
is
=
II.
1-000
0.2474 gram of chlorine.
Ans.
inert
EXAMPLE
impurities
The
iron in a sample of
102
FeCOa containing
converted by solution, oxidation, precipitation, and

ignition into Fe2 iron expressed as
3
103
weighing 1.000 gram.

,
What
is
the weight of
FeCO3
SOLUTION:
The
as Fe, and as FeO in the original sample? reactions may be expressed by the following
molecular equations:
FeCO 3 + 2HC1 -> FeCl2 + CO 2 + H2 O 2FeC0 3 + 4HC1 - 2FeCl2 + 2CO2 + 2H2 2FeCl 2 + Br 2 + 2HC1 -> 2FeCl 3 + 2HBr
+ 6NH OH -> 2Fe(OH) + 6NH C1 2Fe(OII) -> Fe O + 3H

2FeCl 3
4
From
these equations
it
is
grams (one mole) of FeC0 3 grams of FeCl 2 or 2 moles of FeCO 3 will furnish 2 moles of FeCl 2 Two moles of FeCl 2 will give 2 moles of FeCl 3 which in turn will precipitate 2 moles of Fe(OH) 3 and this last compound on ignition will give one mole of Fe 2 3 Hence, every 2 moles (231.72 of will FeC0 furnish one mole (159.70) grams 3 grams) eventually of Fe 2 O 3 and it will do so independently of the nature of the process or composition of the reagents used to bring about the conversion. Indeed, the above reactions are better written in
,
.
seen that one molecular weight in will furnish one molecular weight in
the ionic form, thus:
FeCO 3 +
211+ -> Fe++
+ C0 + H O
2 2
Br~
3NH OII -> Fc(OH) + 3NH + 2Fe(OH)s - Fe^ + 3H O

4 3
2
and
for purposes of calculations all the intermediate steps may be omitted and the fundamental change expressed by the hypo-
thetical equation
2FeCO 3 +
-> Fe 2
+ 2CO
In general, it is unnecessary to determine the weights of intermediate products in a reaction that takes place in steps, and for
purposes of calculation only the
initial
and
final
substances need
be considered. Since two moles (231.72 grams) of FeC0 3 will furnish one mole (159.70 grams) of Fe 2 O 3 by simple proportion, 1.0000 gram of
,
9TT*
Fe2
will
be obtained from 1.0000
fÔ 3
'
5.
1.0000
=
159.70
104
1.4510 grams of
FeCO 3
Since each mole of
FeC0 3
contains one
gram-atomic weight (55.85 grams) of Fe and represents the equivalent of one mole (71.85 grams) of FeO(FeCO3 -* FeO 2 ), the
+ C0
corresponding weights of Fe and FeO would be 2 * 5 85 = 0.6994 gram of Fe, r =1.0000 X 1.0000 X ~A
1*6203
and
1.0000
|^ =1.0000 X
III.
9"PVO
V
1
71 '
R^
'.?
0.8998 gram of FeO, respectively.
Ans.
EXAMPLE
of
What
weight of Fe 3 C>4
will furnish
0.5430 gram
Fe 2
3?
SOLUTION: Whatever equations may be written to represent the conversion of the Fe 3 C>4 to the FeaOa it will be found that from
every 2 moles of Fe 3 O4 there are obtained 3 moles of Fe 2 O 3 and the hypothetical equation may be written
,
2Fe 3
Hence,
0.5430
52.
3Fe 2
0.5430
Chemical Factors.
chemical factor
may
be defined as
the weight of desired substance equivalent to a unit weight of given substance. Thus, in the above three examples, the num-
bers obtained from the ratios Cl/AgCl, 2FeCO 3 /Fe 2 O 3 2Fe/Fe 2 O 3 2FeO/Fe 2 O 3 and 2Fe 3 C>4/3Fe 2 O 3 are chemical factors since they represent the respective weights of Cl, FeCO 3 Fe, FeO, and Fe 3 C>4
, , ,
,
equivalent to one unit weight of
AgCl
or of
Fe 2 0s
as the case
may
be.
A weight of one substance is said to be equivalent to that of another substance when the two will mutually enter into direct or indirect reaction in exact respective proportion to those weights.
In the example cited above, 231.72 grams of FeCO 3 produce 159.70 Hence, 231.72 grams of FeC0 3 are equivalent grams of Fe 2 O 3 The equivalent weights of elements to 159.70 grams of Fe 2 O 3
.
and compounds
may be expressed by mutual proportions as in the case just given, or they may be referred to a common standard for which purpose the atomic weight of hydrogen (1.008) is usually taken (see Sec. 24).
105
Notice that in expressing a chemical factor the atomic or molecular weight of the substance sought is placed in the numerator, the atomic or molecular weight of the substance weighed is placed
denominator, arid the coefficients are adjusted in accordance with the reactions involved. When the principal element, or radical desired occurs in both numerator and denominator, usually the number of atomic weights of this element or radical will be the
in the
numerator and denominator, although there are stances when this is not true. For example, in the reaction
same
in both
in-
2CuCl
CuCl 2
+ Cu
the weight of free copper liberated from one gram of cuprous chloride is 1.000 X (Cu '2CuCD = 0.3210 gram, and 0.3210 is the
chemical factor in this particular case. That the principal element does not always occur in both numerator and denominator is shown in the determination of bromine
by
precipitation as silver bromide with a current of chlorine.
and conversion
to silver chloride
2AgBr
Here the weight
.,
.
+ C1
-- 2AgCl
Br 2
of silver
of
bromine represented by one gram

2
AF:r7Q 0.5578 gram.
Br 2
chloride
is
- 2X79.92
53. Calculation of Percentages.
Since the chemical factor rep-
resents the weight of desired element or compound equivalent to one unit weight of the element or compound weighed, from any
weight of the latter the weight of the former can be calculated. The percentage of that substance present in the sample may be
found by dividing by the weight of sample and multiplying by

100.
EXAMPLE
I.
If 2.000
grams
of
impure sodium chloride are
dis-
solved in water and, with an excess of silver nitrate, 4.6280 grams of silver chloride are precipitated, what is the percentage of chlorine
in
the sample? SOLUTION: The chemical factor

1
gram of 4.6280 grams AgCl there are therefore 4.6280 X 0.2474 = 1.145 grams of Cl. Since this amount represents the chlorine present
dicating that
.000
of
AgCl is 0.2474, inAgCl contains 0.2474 gram of Cl. In
of Cl in
106
in 2.000

grams
i
of the material, the percentage weight of chlorine
must be
^^ X 100 =
^.uuu
II.
14^
57.25 per cent.

of
Ans.
is
impure magnetite (Fe3 4 ) converted by chemical reactions to Fe 2 O 3 weighing 0.4110 gram. What is the percentage of FeaO4 in the magnetite?
,
EXAMPLE
A half-gram sample
SOLUTION: The chemical factor of Fe 3 4 from Fe2 O 3 is 2Fe 3 O 4 /3Fe 2 03 = 0.9666 which represents the weight of Fe 3 4 The weight of Fe 3 O4 equivaequivalent to 1.000 gram of Fe 2 O 3 lent to 0.4110 gram of Fe 2 3 must be 0.4110 X 0.9666 = 0.3973 3973 gram, and the percentage of Fe 3 O 4 in the sample must be
.
100
79.46 per cent.
Ans.
Problems
(b)
241. Calculate the chemical factors for converting (a) 2 O, (e) Cb2 6 to Cb, (c) 2 P2 O 7 to MgO, (d) K01O 4 to
BaSO 4
Fe 3 O 4
to
Ba,
.
Mg
to
Fe2O8
Ans.
(a) 0.5885, (b) 0.6990, (c) 0.3621, (d) 0.3399, (e) 1.035.
242. Calculate the chemical factors of the following:
WEIGHED
(a)
(6)
(c)
SOUGHT
(NII 4 ) 2 PtCl6
NH
2
MoS
U0
2
MoO U
PO4 .12Mo0
(c)
8
(d)
(e)
B O3
(NII
(6)
4) 3
Na B 4O
PO
2
6
.10H 2 O
Ans.
243.
(a)
0.07671,
is
0.7492,
0.8480, (d) 2.738,
(e)
0.03783.
What
the weight of sulfur in 5.672 grams of barium sulfate?
Ans.
244.
0.7790 gram.
How many
grams
of
Na2 SO4 .10H O

2
NaCl
required to precipitate
1.896 gram.
AgCl from 2.000 grams
are equivalent to the of 3?
Na
in the
AgNO
Ans.
246.
sample "of impure ferrous ammonium sulfate weighs 0.5013 What is the percentage of gram and furnishes 0.0968 gram of Fe2 O 3 Fe(NH4 ) 2 (S0 4 ) 2 .6H 2 0?
Ans.
246.
of
94.82 per cent.
A
,
Fe 2 O3
sajnple of limestone weighing 1.2456 grams furnishes 0.0228 gram Calculate 2 P2 7 1.3101 grams of CaSO4 , and 0.0551 gram of
Mg
of
the percentage of (a) Fe, (6) CaO, (c) MgO C0 2 could be in combination with the calcium?
in the limestone.
What
weight
Ans.
(a) 1.28
per cent,
(6)
43.32 per cent,
(c)
1.60 per cent.
0.4237 gram.

247.
107
What
been taken for analysis 1.0206 grams? Ans. 0.3850 gram.

248.
lead,
weight of pyrite containing 36.40 per cent of sulfur must have in order to give a precipitate of barium sulfate weighing
What
and zinc
0.4108 gram igniting the zinc
the percentage composition of a brass containing only copper, a half-gram sample furnishes 0.0023 gram of PbSO 4 and of ZnNH 4 PO 4 ? What weight of Zn 2 P2 O 7 could be obtained by
is
if
Ans.
Cu = What
ammonium phosphate? 69.60 per cent, Pb = 0.31
per cent,
Zn =
30.09 per cent.
0.3510 gram.
249.
is
weighing 1.205 grams

Ans.
260.
the percentage of fluorine in a sample of soluble fluoride if it yields a precipitate of CaF 2 weighing 0.4953 gram?
20.01 per cent.
The
4
to
NH HSO
nitrogen in a half-gram sample of organic material by digestion with concentrated 2 SO4 If the
is
4
converted
ions are
NH +
precipitated as (NH 4 ) 2 PtCl 6 and the precipitate is ignited to Pt, what is the percentage of nitrogen in the sample if the metallic platinum weighs 0.1756
gram?
Ans.
261.
5.044 per cent.
A sample of pyrite, FeS
and weighs 0.5080 gram. precipitate of 1.561 gram

cipitated as
2 contains only silica and other inert impurities After decomposing and dissolving the sample, a of BaSO4 is subsequently obtained. Calculate the
,
percentage of sulfur in the sample.
If
the iron in the solution had been pre,
Fe(OH) 3 and
ignited to
Fe2O3 what weight
of ignited precipitate
would have been obtained?

Ans.
262.
42.20 per cent.
0.2671 gram.
purities weighs 1.421 grams.

,
2 4 containing only inert ima precipitate of A1(OH) 8 which, after ignition to A1 2 O 3 weighs 0.1410 gram. What is the percentage of S in the alum? What is the percentage purity of the alum?
sample of alum,
K SO .A1 SO .24H O,
2
It gives
Ans.
6.246 per cent.
92.43 per cent.
263. Calculate
the
;
chemical factors for converting

3 2 2 3 ) 2
)
(a)
Fe2 O3
wt.
.
to
Fe;
AgCl to As 2 3
(b)
;
to
(d)
KC1O4 (c) Cu3(AsO )2.2As O3.Cu(C H O2 2 (mol. BaSO to HSCN; (e) K2 A1 (SO 4 4 .24H 2 O to H SO4
4 2
1,014)
264. Calculate the chemical factors of the following:
WEIGHED
(a)
(6)
(c)
SOUGHT
K PtCl
2
Mg P
2
7 6
P KC1
(d)
(e)
Mn3O4 Cu 2 (SCN) 2
KBF
Mn O HSCN Na B O
2 3
.10H2O
108
255.

What
7?
weight of
AgBr
of
could be obtained from 4.7527 grams of
Ag2 Cr 2
256.
How many
4) 2?
pounds
phosphorus are contained
in
1.000 ton of
Ca 3 (P0
257. A manufacturer using potassium cyanide in a process involving its use as cyanide only, substituted sodium cyanide at 45 cents a pound for a chemically equivalent quantity of potassium cyanide at $2 a pound. How much did he save per pound of KCN? 268.
An ammonium
salt is
converted into
(NH 4 )
PtCL> and the latter
If the residue weighs ignited until only the Ft remains in the crucible. 0.1000 gram, what weight of Nils was present in the original salt?
259.
What
grams
of
(r)
of datolite
weight of water could be obtained by strongly igniting 2.000 [CaB(CII)SiO 4 (mol. wt. - 160.0)?
]
260. Find the percentage composition of the following in terms of the oxides the metallic elements: (a) FeSO 4 .7H 2 O, (ft) 2 SO 4 .A1 2 (S0 4 ) 3 .24II 2 O,
3Ca3 (PO4 ) 2 .CaCO3

261.
(mol. wt.
of the
503.7).
An
alloy
is
Pb =
0.24 per cent;
Fe =
following composition: Cu = 65.40 per 0.56 per cent; Zn = 33.80 per cent.
cent;
A sample weighing 0.8060 gram is dissolved in HNO3 and electrolysed. Copper is deposited on the cathode; PbO 2 is deposited on the anode. When NH4 OH is added to the residual solution, Fe(OTI) 3 is precipitated and the The zinc in the filtrate is precipitated as precipitate is ignited to Fe 2 Oa. ZnNH 4 PO4 and ignited to Zn 2 P2 7 What weights of Cu, PbO2 Fe 2 O 3 and Zn 2 P 2 O 7 were obtained?
.
262. How many grams of 3 are equivalent to the potassium iri that 3 PO4 which contains the same amount of combined P 2 O& that is weight of contained in 1.100 grams of Ca3 (PO 4 ) 2 ?
KNO
The antimony in a sample of alloy weighing 0.2500 gram is converted Sb 2 O 6 arid this substance is ignited to Sb 2 O4 If the latter weighs 0.1305 gram, what is the percentage of Sb in the alloy?
263.
to
.
sample of Pb 3 O4 containing only inert matter, weighs 0.1753 gram and, after dissolving, subsequently yields a precipitate of PbSO 4 weighing 0.2121 gram. What is the purity of the sample expressed in terms of percentage of Pb? In terms of percentage of Pb 3 O 4 ?
264.
,
containing only inert impurities After dissolving, oxidizing, and precipitating the iron, the Fe(OH) 3 ignites to Fe 2 O 3 and weighs 0.3174 gram. Calculate the percentage of sulfur in the sample. What is the percentage of impurities in the
266. A sample of weighs 1.658 grains.
FeS0 4 .(NII 4 ) 2 S0 4 .6H 2 O
sample?
266. 2 O 3 is dissolved, and the manganese subsequently sample of If the latter weighs 0.1230 gram, 2 and ignited to 3O4 precipitated as calculate the weight of 2 3 shown to be present in the original sample.
Mn
MnO
Mn
Mn

64. Calculation of
109
Atomic Weights.
Determinations of atomic-
weight values at the present time are chiefly revisions of those already established, in order that their accuracy may be in keeping with improved apparatus and methods. In such cases, the
formulas of the compounds involved are well established and the
required calculations are thereby made very simple. The experimental procedure usually followed is to prepare from the element
known compound
weighed, and
of high degree of purity. This compound is the percentages of its constituents are determined
gravimetric-ally.
The mathematical computations involved
are
exactly similar to those of an ordinary gravimetric analysis, except that the atomic weight of the desired element is the only unknown
factor.
EXAMPLE.
grams
Carefully purified sodium chloride weighing 2.56823 furnishes 6.2971 grams of silver chloride. Assuming the
silver to
atomic weights of the chlorine and

35.457 and 107.880,
be established as
respectively, calculate the atomic weight of
sodium.
SOLUTION
Weight
of
NaCl = weight
of
AgCl X
2.50823
= =
G.2971
X X
NaC1 AgCl
2.50823
Solving,
0.2971
Na + 35.457
107.880
+ 35.457
Na =
23.003.
Ans.
Problems
267. Tf silver phosphate is found by careful analysis to contain 77.300 per what is the calculated atomic weight of phosphorus (Ag = 107.88)?
cent silver,
Ans.
31.04.
268. From an average of 13 experiments, Baxter finds the ratio of silver bromide to silver chloride to be 1.310171. If the atomic weight of silver is taken as 107.880 and that of chlorine as 35.457, what is the atomic weight of bromine?
Ans.
79.915.
269. In determining the atomic weight of manganese, Berzelius in 1828 obtained 0.7225 gram of Mn 2 O 3 from 0.5075 gram of Mn. Von Hauer in 1857 obtained 13.719 grams of Mn 3 O 4 from 12.7608 grams of MnO. In 1906
110
Baxter and Hines obtained an average of 11.43300 grams of AgBr from What are the three values as determined? (Br = 6.53738 grams of MnBr 2
.
79.916).
Ans. 56.66, 55.024, 54.932.

270. In determining the atomic weight of arsenic, Baxter and Coffin converted several samples of Ag3 As04 into AgCl and found the average value for the factor 3AgCl/Ag3 AsO 4 to be 0.929550. Using the factor Ag/AgCl as found by Richards and Wells to be 0.752632, calculate the perTaking the atomic weight of silver as 107.880, centage of Ag in Ag 3 AsO 4 calculate to five figures the atomic weight of arsenic.
.
Ans.
69.9609 per cent.
74.961.
271. In determining the atomic weight of aluminum, Richards and Krepelka prepared pure samples of AlBrs and experimentally determined the weight of silver required to precipitate the halogen. Results of four experiments were
as follows:
WT. ALBRJ
WT. AG
6.11324
6.55955 4.14786 2.40285
Sample Sample 2 Sample 3 Sample 4
5.03798 5.40576
3.41815
1.98012
If the atomic weight of silver is taken as 107.880 and that of bromine is taken as 79.916, what is the mean value obtained for the atomic weight of
aluminum?
272.
The
ratio of the weight of silicon tetrachloride to the weight of
an
equivalent amount of silver has been found to be 0.393802 db 0.000008. Assuming Cl = 35.457 and Ag = 107.880, calculate the atomic weight of
silicon.
273. Classen and Strauch have determined the weights of bismuth oxide In one such obtainable from several samples of pure bismuth triphenyl. determination, 5.34160 grams of Bi(C c 6 )3 gave 2.82761 grams of Bi 2 O 3
Calculate the atomic weight of bismuth as shown from these figures.

12.010; 274.
C =
1.0080.
is
What
by the reduction
276.
the atomic weight of copper of 1.2518 grams of CuO?

3
if
1.0000
gram
of
Cu
is
obtained
From the ratios NaNO /NaCl = 1.45422, AgCl/Ag = 1.328668, and NaCl/Ag = 0.541854 and assuming N = 14.008, calculate the atomic
weights of
silver,
sodium, and chlorine.
55. Calculations Involving a Factor Weight Sample. It is sometimes desirable in industrial work, where large numbers of samples of similar material are analyzed, to regulate the weight of sample so that the weight of the final product obtained multiplied by a simple factor will exactly equal the percentage of the

desired constituent.
111
This makes
it
possible to
have the sample
weighed out directly against a tare, perhaps by someone inexperienced in exact weighing, and at the same time to eliminate both the tedious calculations necessary for each analysis and the possibility of
mathematical errors. The calculation of a desired constituent in a chemical analysis involving a direct gravimetric determination is carried out by
of the following formula: of - product
means
Grams
X
j
chemical factor
;
Grams
^ X
1AA 100
ot
sample
per cent
Since for a specific determination the chemical factor is a constant, the expression contains only three variable factors, viz., the weight of product, the weight of sample', and the percentage of
desired constituent.
If
any two are known, the
third can be cal-
culated; or, since the expression involves only multiplication

if
and
the numerical ratio between the weight of product and division, the weight of sample, or between the weight of product and the percentage of desired constituent, is known, the remaining term
can be determined.
Thus,
if
the weight of product
is
numerically
equal to the percentage of desired constituent, these values cancel, and the weight of sample becomes equal to one hundred times
the weight of product is numerically equal to the weight of sample, these values cancel, and the percentage of desired constituent becomes equal to one hundred times the the chemical factor.
If
Other ratios may be inserted in the expression, and the calculation made in a similar way.
chemical factor.
EXAMPLE.
It is
factor of a certain analysis is 0.3427. desired to regulate the weight of sample taken so that (a) each
The chemical
centigram of the precipitate obtained will represent 1 per cent of the desired constituent; (6) every 2 centigrams of precipitate will represent 1 per cent of the desired constituent; (c) the percentage will be twice the number of centigrams of precipitate; (rf) threefourths of the weight in grams of precipitate will be one-fiftieth
of the percentage of desired constituent. should be taken in each case?
What
weight of sample
SOLUTION: (a) The relation between the weight of precipitate and the percentage of constituent is such that 0.01 gram =s= 1 per
cent.
Hence,
112

0.01
X 0.3427
X
0.3427 gram.
A ns.
OJ2X 0.3427 X100 _, X

x
0.01
(c)
O.G854 gram.
Ans.
X0.3427
1QO
# = 0.1714 gram.
a;
0.9135 gram.
Ans.
Problems
276. In the analysis of a sample of feldspar for silica, the sample is fused, dissolved in HC1, and the solution is evaporated to dryness, heated, and treated with acid. The residue is filtered off and weighed as SiO 2 What
.
sample should he taken for analysis so that (a) each centigram of residue will represent 1 per cent SiO 2 (b) the number of centigrams will represent directly the percentage SiO 2 (r) every 2 centigrams of residue will
weight of
, ,
represent
per cent
SiO-2,
(d)
twice the
number
(r)
of centigrams will equal the
percentage of Si02?
Ans.
277.
(a) 1.000
gram,
(fe)
1.000 gram,
2.000 grams,
(d)
0.5000 gram.
What weight of cast iron should be taken for analysis so that the of ignited SiO in centigrams will be equal to one-third of the perweight Si in the cast iron? of centage
A?is.
0.156 gram.
278. Calculate the weight of limestone to be taken so that the number of centigrams of CaO obtained and the percentage of Ca in the sample will be
in the respective ratio of 7:5.
Ans.
1.001 grams.
is determined as be taken for should sample analysis such that the obtained will grams represent (a) one-thirtieth the
279. In the analysis of a sample of lead salt, the lead
weight of lead sulfate in of weight in the of lead percentage

.
PbSO4
What
sample expressed as Pb,
centage of lead expressed as

expressed as
PbO
2,
(c)
(b) one-thirtieth the perone-thirtieth the percentage of lead
PbCrO 4 ?
2.277 grams,
(6)
Ans.
280.
(a)
2.629 grams,
(r)
3.553 grams.
sample of
nium
radical as
ammonium salt is analyzed by precipitating the ammo(NH^Ptdfl and igniting the precipitate to metallic platinum.
(a)
Calculate the weight of sample to be taken for analysis
so that the weight

of ignited precipitate in
will give
113
grams multiplied by the atomic weight
(b) so that the weight of ignited in will milligrams multiplied by îoo precipitate equal four-thirds of the perin of the 3 sample. centage
the percentage of
of platinum
in
the sample,
NH
Ans.
(a)
0.07357 gram,
(b)
0.7753 gram.
281.
What
so that each milligram of in the sample?
weight of impure ferrous sulfate should be taken for analysis Fe 2 O 3 obtained will correspond to 0.120 per cent FeO
282. What weight of dolomite should be taken for analysis so that, in the determination of magnesium, the number of centigrams of Mg 2 P2O 7 obtained will be twice the percentage of Mg in the mineral? 283. In the analysis of potassium in a silicate, the mineral is decomposed and the potassium subsequently weighed as KCKXj. What weight of sample was taken if it was found that the percentage of K 2 O in the mineral could
be found by dividing the number of milligrams of

284.
What
,
weight
of
KC1O 4 obtained by 12? Fe O 4 ) should be taken a magnetite (impure
for
analysis so that after decomposition of the sample, precipitation of the iron as Fe(OTT) 3 and ignition to Fe 2 Oj (n) the number of centigrams of FcoO,*
be equal to the percentage of Fe.s() 4 in the sample, (/>) the number Fc 2 O 3 obtained will be live times the percentage of Fe 3 O 4 the (r) percentage of Fc in the sample and the number of centigrams of Fe 2 O 3 obtained will be in the ratio of 3:2?
obtained
will
of milligrams of
Given Reaction.
Volume of a Reagent Required for a The volume of a solution required to carry out
a given reaction can be calculated if the concentration of the solution is known. If the concentration is expressed in terms of normality, the calculation
analysis,
i.e.,
is
best
made by
the methods of volumetric

(see Sec. 21);
if
in
terms of milliequivalents
the con-
expressed as grams of solute per unit volume of solution or in terms of specific gravity and percentage composition, the calculation is usually easiest made by the use of the chemical
cent-ration
is
factor.
EXAMPLE
I.
How many
milliliters of
barium chloride solution
per liter are required containing 90.0 grams of liuCl 2 .2H 2 from 10.0 grams of pure to precipitate the sulfate as BaSO 4
Na $CVH)H 0?
2
SOLUTION: The weight of BaCl 2 .2H 2 O for the precipitation found by means of the chemical factor, thus:
10.0
is
X J^HrfiT^ JNa2olJ4.1vUl2vJ
10
-Q99 o^
7 58 8rams of
-
BaCl 2 .2H2
114
Since each milliliter of reagent contains 0.0900 gram of BaCl2.2H 2 O, the volume of solution required is
7.58
84.2 ml.
Ans.
0.0900
the concentration of the required reagent is expressed in terms of the percentage by weight of the solute, the specific
When
must also be known in order to determine As stated in Sec. 21, there is no exact mathematical relationship between these two factors, but tables are given in all standard chemical handbooks showing this relagravity of the solution the volume required.
tionship for solutions of common substances experimentally determined at many different concentrations. Consequently, when a
problem includes only one
of these factors, tables
must be con-
sulted in order to determine the other.
In the Appendix, specific-
gravity-percentage tables are given for a few common acids and bases. These tables apply to weighings in vacuo at definite temperatures, but since three-significant figure accuracy is all that is needed in most calculations involving specific gravity of solutions, it is usually not necessary to make corrections for temperature
and buoyancy
differences.
EXAMPLE II.
How many milliliters of ammonia water of specific
3 by weight) are gravity 0.950 (containing 12.72 per cent of 0.800 iron from to the gram of pure ferrous required precipitate ammonium sulfate, FeSO4.(NH4 ) 2S04.6H20, after oxidation of the
NH
iron to the ferric state?
SOLUTION: Since 3 molecules cipitate one atom of ferric iron
of
ammonia
are required to pre-
Fe+++
it
+ 3NII + 3H O -> Fe(OH) + 3NH +

3
follows that the weight of iron from 0.800 gram of ferrous
NH
"
necessary to precipitate the

sulfate will be
-
ammonium
'
3NH
51 10
392.1
"
gram
of
FeS0 4 .(NH4) 2 S0 4 .6H 2

Since the
0. 1043
NH*
tains 12.74 per cent of tion weighs 0.950 gram of
ammonia water has a NH 3 by
specific gravity of 0.950
and conthe soluis
weight, one
milliliter of
which 12.74 per cent by weight
NH

and 87.26 per cent by weight
in
is
115
water.
The
actual weight of
NH
one
milliliter of solution is therefore
0.950X0.1274 = 0.121
gram." Since 0.1043 gram of

iron
of
and
3,
NH
3 is required to precipitate the since each milliliter of the solution contains 0.121 gram
NH
it
follows that the
volume
of solution required is
0.1043
0.121
0.862 ml.
Ans.
As explained
in Sec. 51 in calculations of this type, the
com-
putations should not be carried through unnecessary steps. In the example above, it is not necessary to compute the weight of iron contained in the ferrous ammonium sulfate, the weight of
ammonium
weight of
droxide.
hydroxide required to precipitate the iron, and the anhydrous ammonia contained in the ammonium hyexpressing the whole, the
On
common
factors cancel.
0800 UU
FeSO4.(NH4 )2SO4.6H 2
QXTTT3NH
3
(3NII40II)
0.1043
0.121
_= 0.1043 gram of
NHs
0.862 ml.
In general, with problems of this type, time will be saved if the and divisions are not made until all the factors are combined and expressed as a whole. In the above example the only essential factors are
final multiplications
0.800X51.10 QA o ml. = ,, 0.862 392.1X0.950X0.1274

i
A Ans.
similar type of problem is one in which it is required to calculate the volume of a solution of given percentage composi-
A very
tion required to react with a certain

of given percentage composition. reacting component in the given
volume
of another solution
By computing
volume
the weight of
of the latter solution,
the problem becomes exactly like the one discussed above. EXAMPLE III. How many milliliters of sulfuric acid (sp. gr. 1.135, containing 18.96 per cent H^SOi by weight) are required to neutralize 75.0 ml. of ammonium hydroxide (sp. gr. 0.960, containing 9.91 per cent
NH
by weight)?
116

In 75.0 ml. of the
75.0
SOLUTION:
ammonia
solution there are
0.960
0.0991 grams of
NH
The
75.0
required weight of
HC1
2
for this
NH
is
0.960
0.0991
X 2NH4 3
QQ no
75.0
H S0
0.960
0.0991
grams
Since each milliliter of the acid contains 1.140
0.2766 gram of
HC1, the volume of acid required

75.0
is
0.960
0.0991
98.08
1.135
0.1896
= OK 95
'
34.06
ml An8
,
'
Problems
285. What volume of ammonium oxalate solution [35.1 grams of (NH4) 2 C 2 O4.Il2O per liter] will be required to precipitate the calcium as CaC 2 O4 from 0.124 gram of 3Ca3 (PO4 )2.CaCl 2 ? What volume of "magnesia mixture" containing 1 F.W. of MgCl 2 per liter will be necessary to precipitate the phosphate as MgNH 4 PO 4 from the filtrate from the calcium determination?
Ans.
286.
4.82 ml.
0.71 ml.
How many milliliters of silver nitrate solution containing 20.00 grams of AgNO per 100 ml. are required to precipitate all the chloride as AgCl from a solution containing 2.012 grams of dissolved BaCl .2H O? How many milli3 2 2
liters of
H S()
2
(sp. gr. 1.105)
are required to precipitate the barium as
BaSO4
from the same solution?

Ans.
14.00ml.
4.86ml.
287. In the precipitation of arsenic as 4 AsO 4 from a solution of 0.4000 gram of pure As 2 Oa that has been oxidized to arsenic acid, it is desired to add sufficient magnesium chloride reagent (64.00 grams MgCl 2 per liter) to precipitate the arsenic and also have 200 mg. of Mg remaining in solution.
MgNH
What volume
Ans.
is
required?
18.26 ml.
chlorides of sodium, potassium,
288. Chloride samples are to be prepared for student analysis by using the and ammonium, alone or mixed in various
proportions. gravity 1.041
How many
milliliters of 5.00
must be added to a 0.300-gram sample
per cent silver nitrate of specific in order to ensure com-
plete precipitation in every possible case?
Ans.
18.3 ml.

289.
117
How many
milliliters of
quired to precipitate the iron as
aqueous ammonia (sp. gr. 0.900) are reFe(OH) 8 from a half-gram sample of pure
Fe2 (S04 ) 3 .9II2 O?

Ans.
0.36 ml.
290. Calculate the volume of hydrochloric acid (sp. gr. 1.050, containing 10.17 per cent HC1 by weight) to neutralize (a) 48.6 ml. of a solution of
(sp. gr. 1.100,
KOH
containing 12.0 per cent

(sp. gr. 1.327), (c)
KOH H
by weight),
(6)
152.1 ml.
a solution containing 10.0 grams of (96.6 per pure KOH, (d) a solution containing 10.0 grams of impure 1.2 per cent cent KOH, 2.2 per cent 2 CO 3 2 O), (e) 25.3 ml. of ammonia water containing 15.04 per cent by weight of 3 Ans. (a) 39.0 ml., (6) 508 ml, (c) 60.9 ml., (d) 59.8 ml., (e) 72.0 ml.
of a solution of
NaOH
KOH
NH
3 2.21 ml. following are added to water: 1.60 grams of pure Na2 solution (sp. gr. 1.700), and 16.0 ml. of solution (56.0 grams of This solution is to be brought to the exact neutral point. solid per liter). The solutions available for this purpose are hydrochloric acid (sp. gr. 1.141)
291.
2
The
4
CO
of
H SO
KOH
and ammonia water

required?
(sp. gr. 0.930).
Which should be used? What volume
is
Ans.
1.26 ml. of
ammonia
water.
292. In the reaction 2NaCl + H 2 SO 4 -> Na 2 SO 4 + 2HC1, it is desired to add sufficient sulfuric acid (sp. gr. 1.835) to liberate that amount of HC1 which when absorbed in water will furnish 250 ml. of solution of specific gravity 1.040. Calculate the volume necessary.
Ans.
293.
16.7 ml.
solution of ferrous
2.200 grams of pure 15.0 ml. 2 SO 4 (sp. gr. 1.135, containing 18.96 per cent The iron is then oxidized by bromine water (2Fe+ + Br2
ammonium sulfate is prepared by dissolving FeSO 4 .(NII 4 ) 2 SO 4 .6H 2 O in 500 ml. of water containing
H S()
>
What
total
is
weight)
volume of 4 OII (sp. gr. 0.950, containing 12.74 per cent 3 by required to neutralize the acid and just precipitate all of the iron as
NH
2 4 by weight). 2Fe+++ + 2Br~).
NH
Fe(OH) 3 ?
Ans.
11.6 ml.
294. How many milliliters of barium chloride solution containing 21.05 grams BaCl 2 .2H 2 O per liter are required to precipitate all the sulfate as BaSO4 from a solution containing 1.500 grams of dissolved Fe 2 (SO4 ) 8 .9H 2 O? How many
of
milliliters of
NaOH
iron as
Fe(OH) 3 from the same
solution (sp. gr. 1.200) are required to precipitate all the solution?
sample of MgCO3 contaminated with SiO2 weighs 0.5000 gram and gram on ignition to MgO. What volume of disodium phosphate solution (90.0 grams Na2 HPO4 .12H 2 O per liter) will be required to precipitate
295.
loses 0.1002
the magnesium as
296.
MgNH PO ?
4 4
How many
Cr2O3
milliliters of
ing 26.30 grams of
K Cr O
2 2
a solution of potassium dichromate containmust be taken in order to yield 0.6033 per

liter
gram
of
after reduction, precipitation,
and
ignition of the
chromium?
118
297.
acid,

The
is
and
per
arsenic in a half-gram sample of As2Sa is oxidized to arsenic " precipitated with a solution of magnesia mixture" (MgCU
NI^Cl).
If exactly 12.6 ml. of the

liter
mixture are required,
MgCl2
MgNH4AsO4 + 298. How many

of
does the solution contain? 2NH4 C1 3H 2O.)
(H 3AsO4
how many grams MgCl2 + 3NH4OH
of
>
grams of
silver chloride will
be formed by the addition
an excess of
silver nitrate to 10.00 ml. of hydrochloric acid (sp. gr. 1.160,
HC1 by
weight)?
299. Sulfuric acid of specific gravity 1.800 is to be used to precipitate the barium as barium sulfate from 1.242 grams of pure BaCl 2 .2H 2 O. Calculate
the volume of acid necessary for precipitation.

300.
How many
milliliters
of
ammonia
(sp.
gr.
0.940)
will
neutralize
40.00 ml. of
H SO
2
solution (sp. gr. 1.240)?
301. According to the following equation what volume of HNOs (sp. gr. in the 1.050) is required to oxidize the iron in 1.000 gram of FeS04 .7II 2 --> of sulfuric 2IINO acid? 3H SO 3Fe 3 4 2 4 2 (SO 4 ) 3 [6FeSO presence
2NO +
302.
4TI 2 O.]
How many
per cent of
A1(OH) 3 and 100 ml.

303.
ammonia (sp. gr. 0.960 containing 9.91 be required to precipitate the aluminum as from a solution containing 500 grams of alum [KA1(SO4 )2.12II 2 O)
milliliters
of
NH
of
by weight)
will
HC1
(sp. gr. 1.120,

is
HC1 by
weight)?
Alum, KA1(SO4 ) 2 .12H 2 O, weighing 0.6000 gram

(sp. gr. 1.120,
dissolved in water
and 10.0 ml. of hydrochloric; acid by weight) are added. It takes

cent
5.11 ml. of
ammonia
8 by weight) to neutralize the acid and precipitate the aluminum as A1(OH)3. Find the specific gravity of the ammonia, the normality of the acid, and the ratio of the base to the acid.
NH
containing 23.82 per cent HC1 (containing 28.33 per
304.
To
a suspension of 0.310 gram of A1(OH) 3 in water are added 13.0 ml.
of aqueous
ammonia
(sp. gr. 0.900).
How many
milliliters of sulfuric acid
(sp. gr. 1.18)
must be added to the mixture
in order to bring the
aluminum
into solution?
differ
Problems relating to indirect analyses of direct analyses in much the same way that algebraic equations involving two or more unknown quantities dif57. Indirect Analyses.
from those
fer
from those involving only one unknown quantity. Indeed, such indirect problems are often solved by algebraic methods. The simplest type of indirect problem is that in which two pure chemical substances are isolated and weighed together. Then
either
by
further chemical action on the substances or
by chemi-
a new sample of the same material, additional data are derived by which one of the components is determined. The
cal analysis of
other component
is
then found by difference.
119
In any case, results of analyses of this type are usually less precise than results of analyses in which a single component is determined by a direct method. In solving simultaneous algebraic equations, for example, there is often a decrease in the number of significant figures that may properly be retained. For
example, in solving the following simultaneous equations:

0.2395z
+ 0.2689y = 0.2067X + 0.2689y =

= x =
1.937
1.222
0.0328z
0.715
2.18
there
is
a decrease from four-significant- to three-significant-figure

I.
precision.
EXAMPLE
In the analysis of a two-gram sample of lime-
stone, the weight of combined oxides of iron and aluminum (Fe 2 O 3 + A1 2 O3 ) is found to be 0.0812 gram. By volumetric the of total iron as calculated FeO is found methods, percentage
to be 1.50 per cent.
What
is
the percentage of A1 2
in the
sample?
SOLUTION
Weight Weight
of
FeO =
2.00
-~ = 0.0300 gram
rjn
of
of
Fe 2 O 3 = 0.0300
A1 2 O 3
X
-
~~ =
0.0333
0.0333 gram
0.0479 gram
Weight
0.0812
Percentage of A1 2 O 3
0479 nn ^.uu
'
100
2.40 per cent.
Ans.
second general type of indirect analysis is that in which two chemical substances are isolated and weighed together. Then another measure of the two substances is obtained either by con-
compounds and again finding the combined weights or by determining the amount of reagent In this way, by the use of required to effect such conversion. to the unknown algebraic symbols represent quantities, two independent equations can be formulated, and from them the values of the unknowns can be determined. It is evident that this type of problem may be extended to any number of unknown quantities,
verting
different
them to two
120
provided sufficient data are given to allow the formulation of as many independent algebraic equations as there are unknowns. EXAMPLE II. In the analysis of a 0.5000-gram sample of feldspar, a mixture of the chlorides of sodium and potassium is obtained which weighs 0.1180 gram. Subsequent treatment with
silver nitrate furnishes 0.2451
gram
2
of silver chloride.
What
is
the percentage of
Na O and
2
KO
in the
sample?
SOLUTION:
Let x = weight of KC1 y = weight of NaCl Z + i/ = 0.1 180
(1)
Number
of
grams
of
AgCl obtainable from x grams
of
KC1
Number
of
grams
of
AgCl obtainable from y grams
of
NaCl
=
Therefore,
(2)
2.452ty
1.923*
+ 2.452?y = 0.2451
KC1 NaCl
100
Solving
(1)
and
(2)
simultaneously,
= y =
0.0837 gram of 0.0343 gram of

2 = /K (s
, fT-n Percentage of 2 T>
\00837X
T
)
^rSnn
=
'
lftr G 10
,
yd
-MO
P Percentage
4.
fAi of NazO
o = i'NaO\0.0343X OM^T) Q^QQ

{
100
~ . 3 f 64
-
for determining sodium an example of an indirect analysis of this type. By this method the sample is decomposed and the These alkalies are isolated and weighed as combined chlorides. are dissolved and the potassium alone is precipitated from wateralcohol solution as K^PtCle (or as KC1O4) and weighed as such. The K 2 PtCl6 can also be ignited and weighed as 2KC1 + Pt, or
The standard J. Lawrence Smith method

in a silicate is
and potassium
(after
washing) as metallic platinum (see also Part VI).

EXAMPLE
III.
121
In the analysis of a sample of feldspar weighing of KC1 + NaCl is obtained weighing 0.0715 a mixture 0.4150 gram, gram. From these chlorides 0.1548 gram of 2 PtCl6 is obtained.
Calculate the percentage of
Na2 O
in the feldspar.
SOLUTION: Let x
weight of NaCl in combined chlorides

0.0715
Then
x = weight of KC1
(0.0715
Solving,
x)
x
/IVL/l
0.1548
0.0415
- 2 *
'
0.0415 gram
X (Na O/2NaCl) - vx X n\
0.4150
1
inn 100
5.30 per cent
OA
XT
Na O.
2
Ans.
Problems
306.
mixture of 0.2600 gram of

is
num
oxide
ignited in
metallic iron.
What
is
ferric oxide and 0.4500 gram of alumiferric oxide alone being reduced to the hydrogen, the final weight?
Ans.
306.
0.6318 gram.
weighing 0.6000 gram yields a mixture of pure NaCl and pure KOI weighing 0.1800 gram. In this residue the KC1 is converted to Find the percentage of 2 O and the percentage 2 PtCl 6 weighing 0.2700 gram. of Na2 O in the silicate.
silicate
A ns.
8.72 per cent
K O,
2
8.60 per cent
Na2O.
of Na 2 O and K 2 O in the feldspar. What weight of been obtained if perchloric acid had been used as the have would precipitate had been dried and weighed without the and precipitate precipitating agent
307. In the analysis of a sample of feldspar weighing 0.7500 gram there is KC1. These chlorides are dissolved in obtained 0.2200 gram of NaCl water-alcohol mixture and treated with chloroplatinic acid. The precipitate in hydrogen. of 2 PtCl 6 is filtered on a Gooch crucible, dried, arid ignited After washing with hot water, the residual platinum then weighs 0.0950 gram.
Compute the percentages
ignition?
Ans.
308.
10.42 per cent
Na 0,
2
6.11 per cent
K O.
2
0.1349 gram.
is
mixture of
silver chloride
and
silver
bromide
found to contain
66.35 per cent of silver.
What
is
the percentage of bromine?
Ans.
309.
21.3 per cent.
A sample
of carbonate rock weighing 1.250
of the hydrated oxides of iron
The combined
oxides
Fe 2
grams yields a precipitate and aluminum. These are filtered off and ignited. + A12 3 are found to weigh 0.1175 gram. Iron is
122
determined by a volumetric method on a separate sample of the rock and the results show 3.22 per cent Fe. Calculate the percentage of Al in the rock.
Ans.
2.54 per cent.
310. An alloy weighing 0.2500 gram when treated with 3 gives a residue of the hydrated oxides of tin and antimony. These on ignition yield 0.1260 Sb 2 C>4. This residue is brought into gram of the combined oxides SnO 2
HNO
found by a volumetric method to contain 32.56 per cent Sn. Calculate the percentage of antimony in the original alloy. Ans. 23 A per cent.
solution
and
is
mixture of silver chloride and silver bromide weighs 0.5267 gram. By treatment with chlorine, the silver bromide is converted into silver chloride, and the total weight of silver chloride becomes 0.4269 gram. What is the weight of bromine in the original mixture?
311.
Ans.
312.
0.179 gram.
mixture of pure
CaO and
pure
BaO
weighing 0.6411 gram yields

of
1.1201 grams of pure mixed sulfates. Ca in the original mixture.
Find the percentages of Ba and
Ans.
17.6 per cent Ca, 67.4 per cent Ba.
313. A sample of silicate weighing 0.6000 gram yields 0.1803 gram of a mixture of pure NaCl and pure KC1. When these are dissolved and treated with AgNO3 the resulting precipitate of AgCl is found to weigh 0.3904 gram.
,
Calculate the percentages of
Na O and
2
K O.
2
Ans.
7.32 per cent
Na
0, 10.27 per cent
K O.
2
314. From a sample of feldspar a mixture of KC1 and NaCl is obtained that weighs 0.1506 gram and contains 55.00 per cent chlorine. What weight of 2 PtCl 6 could be obtained from the KC1?
Ans.
315.
0.212 gram.
silver nitrate solution yields 1.440
mixture of BaCl 2 .2II 2 O and LiCl weighs 0.6000 gram and with grams AgCl. Calculate the percentage of
Ba
in the original mixture.
Ans.
316.
25.0 per cent.
with
A mixture of pure NaCl and pure Nal weighs 0.4000 gram and yields AgNO a precipitate of AgCl and Agl that weighs 0.8981 gram. Find
3
the percentage of iodine present in the original mixture.
Ans.
19.8 per cent.
317. What percentage of MgCO 3 is present with pure BaCO 8 so that the mixture contains the same CO2 content as if it were pure CaCO 3 ?
Ans.
72.5 per cent.
318.
ignited.
The weight
1.0045-gram sample containing only CaCO3 and MgCO 3 is strongly of the ignited product (CaO and MgO) is 0.5184 gram.

Calculate the percentages of
ignited sample.
123
Ca and
of
Mg in
the original sample and in the
319.
sulfuric acid
amount.
mixture of BaO and CaO weighing 1.792 grams, when treated with and transformed to mixed sulfates, weighs twice the original What is the percentage of BaO in the mixture?
320. Iron and aluminum are precipitated from a sample of a mineral weighFe2O 3 are found to weigh ing 0.9505 gram and the combined oxides A1 2 O 3 0.1083 gram. By a volumetric method this oxide residue is found to contain
10.50 per cent Fe.

321.
What
is
the percentage of Al in the original mineral?
alloy weighing 0.5180 gram yields a residue of the hydrated oxides of tin and antimony which on ignition produces 0.1661 gram of the combined oxides SnC>2 Sb2O4. By a titration method a separate sample of the alloy shows the presence of 10.12 per cent Sb. Calculate the percentage of Sri in
An
the alloy.
322. A silicate rock weighing 0.7410 gram is analyzed by the J. L. Smith method, and a mixture of the chlorides of sodium and potassium weighing 0.2172 gram is obtained. These chlorides are dissolved in a mixture of alcohol and water and treated with I1C1O 4 The dried precipitate of KC1O4 weighs
.
0.3330 gram.
What is the percentage of Na2O in
the silicate?
If
the potassium
had been precipitated as K 2 PtCl6 and the precipitate converted to metallic platinum, what weight of platinum would have been obtained? 323. How many grams of BaCO 3 must be added to 2.40 grams of MgCOs so that the mixture will contain the same percentage of CO 2 as CaCO 3 does?
324.
mixture of NaBr, Nal, and NaNO3 weighs 0.6500 gram. With a precipitate of the halides of silver is obtained and is found to weigh 0.9390 gram. When heated in a current of chlorine gas the precipitate is converted entirely into AgCl weighing 0.6566 gram. What is the percentage composition of the original sample?
silver nitrate,
325.
precipitate of
AgOl
a current of chlorine, the AgBr

0.1450 gram in weight.
precipitate?
326.
4
What
0.8132 gram. On heating in converted into AgCl, the mixture losing was the percentage of chlorine in the original
AgBr weighs
is
NH C1 is
One
its
one-gram sample consisting of a mixture of LiCl, KC1, NaCl, and dissolved in water and the solution is divided into two equal parts.
portion gives with chloroplatinic acid in the presence of alcohol a precipitate of K^PtCle that weighs 0.9500 gram and that loses 35.00 per cent of
weight on ignition. weighing 1.2500 grams. mixture?

327.
The other portion gives a precipitate with AgNO3 What is the percentage of each constituent in the
With chloromixture of 4 C1 and KC1 weighs 0.5000 gram. is when 1.0400 a obtained grams. that, precipitate ignited, weighs platinic acid If the ignited precipitate were What is the percentage of 3 in the mixture? washed with water and reignited, what would be the weight obtained?
NH
NH
mixture of AgCl and AgBr contains chlorine and bromine in the proportion by weight of Cl:Br = 1:2. What is the percentage of silver in
328.
124

If
one gram of the sample were heated in a current of chlorine, thereby converting the AgBr into AgCl, what would be the weight of the resulting mixture?
the mixture?
sample of an impure mixture of NaCl, NaBr, and Nal weighing 1.5000 grams is dissolved in water, arid the solution is divided into two equal One portion gives a precipitate of Pdl2 weighing 0.1103 gram. portions.
329.
The
other portion gives a precipitate of AgCl AgBr Agl weighing 1.2312 grams; and when these salts are heated in a current of chlorine they are all converted into AgCl weighing 1.0500 grams. What are the percentages
NaCl, NaBr, and Nal in the original sample? 330. A mixture of silver bromide and silver iodide weighs x grams. After the mixture has been heated in a current of chlorine, the resulting silver chloride is found to weigh y grams. Derive an expression for the percentages of bromine and of iodine in the original mixture.
of
mixture of silver chloride and silver iodide on being heated in a current of chlorine is converted entirely into silver chloride and is found to have lost 6.00 per cent of its weight. What is the percentage of chlorine in the
331.
original mixture?
CHAPTER IX
The decomposition potential of an electrolyte is the lowest e.m.f. that must be applied in order to bring about continuous decomposition of cation and anion at
68.
Decomposition Potential.
the electrodes.
If a nitric or sulfuric acid solution of copper is electrolyzed between platinum electrodes, the copper plates out on the cathode.
CU++
Water
is
+ 2e -> Cu
decomposed at the anode.
As a
result there
is
produced a voltaic
cell of
the type
Cu Cu++ 2H+
This
Pt
cell exerts a "back e.m.f." which opposes the applied voltage and which can be calculated from the formula
log [Cu+
#H o
2
log [H+]
[press.
this
In order to continue the electrolysis, a voltage at least equal to must be applied. In addition, enough voltage to overcome
the simple ohmic resistance of the solution (E
= IK)
is
necessary,
and, in cases where polarization effects occur, the required e.m.f. must be still further increased.
Decomposition potential
= back
e.m.f.
+ IR + overvoltage
The extent of overvoltage depends on several factors, such as current density (amperes per square centimeter of electrode surface), concentration, temperature, nature of the substances liberated,
and the character
of the electrodes.
125
126
During an electrolysis, those ions in solution will first be discharged which have the lowest decomposition potentials. So long as these ions are present around the electrode in considerable concentration, they, almost alone, are discharged; but, as their concentration diminishes, other ions whose deposition potentials are
higher but still within that of the current applied will also begin to be discharged.
69. Analysis
by
Electrolysis.
of electrochemical
methods
is
Quantitative analysis by means usually restricted to the determinasalt of
tion of metals.
ditions,
itself is
An
electric current is passed,
through a solution of the
under suitable cona metal, and the metal
gradually deposited, usually in the elementary condition, upon one of the electrodes. The calculation of the amount of metal which will be deposited at the end of a given time is founded
on Faraday's laws which may be stated as follows: 1. The mass of any substance deposited at an electrode
is
propor-
tional to the quantity of electricity which passes through the solution. 2. The amounts of different substances liberated at the electrodes
by
the passage of the
same quantity of
is
electricity are
proportional
to
the equivalent weights of the substances.
expressed in terms of the ampere, which is defined as that strength of current which, when passed through a solution of silver nitrate under certain standard conditions, will deposit silver at the rate of 0.001118 gram per second.
Current strength
Quantities of electricity are expressed in terms of the coulomb, which is defined as that quantity of electricity which passes through a conductor in 1 second when the current is 1 ampere. That is,
Q=
where
It
Q=
/
t
quantity of electricity, coulombs

current strength, amperes time, seconds
first
= =
law, it follows that the weight of a substance liberated from solution by electrolysis during a given time
From
Faraday's
be directly proportional to the current strength and under a given amperage will be directly proportional to the time. Faraday's second law states that the weights of different substances liberated at the electrodes by a given quantity of elecwill
tricity are proportional to the respective equivalent weights.
The
127
equivalent weight of a substance in this case is the atomic or molecular weight divided by the total change in oxidation number. It is found by experiment that 90,500 coulombs are required tc
a gram-equivalent weight (equivalent weight in grams) of any substance. Thus, 96,500 coulombs of electricity are capable
liberate
of depositing at the cathode:
Ag =
107.88 grams of silver from a solution of a silver salt

of iron
Fe = 27.92 grams -75Zi
from a solution
from a solution
is
of
a ferrous
salt
Fe = -5o
18.61
grams
of iron
of
ferric salt
therefore a unit of quantity in electrochemical measurements, and in that capacity it is called
The value 96,500 coulombs
a faraday.
seconds
The
26.81 ampere-hours. above reactions may be expressed

(a)
One faraday = 96,500 coulombs = 96,500 ampereby equations,

as follows:
Ag+
+ 6->Ag
(c)
where the symbol

electricity.
If
represents the electron, or unit of negative the equations are considered as representing gramratios,
then the symbol represents the faraday. That is, 1, 2, and 3 faradays are required to deposit a gram-atomic weight of metal from a solution of silver salt, ferrous
atomic or gram-molecular
salt,
and
ferric salt, respectively.

I.
3.00 hours
How many grams of copper will be deposited in a by current of 4.00 amperes, on the assumption that no other reactions take place at the cathode?
EXAMPLE
SOLUTION:
t
Number
1
of
= 10,800 seconds coulombs = It = 4.00 X 10,800 =

3.00
3,600
43,200
faraday would deposit
~ &
=
onrj
31.8 grams of copper
40
43,200 coulombs would deposit
31.8
=
grams Cu.
Ans.
14.2
128
Faraday's laws apply to each electrode. A current of 1 ampere flowing for 96,500 seconds through a copper sulfate solution is not only capable of depositing Cu/2 = 31.79 grams of copper at the cathode, but at the same time will liberate O/2 = 8.000 grams
of
oxygen at the anode.
Cu++
H
The passage
of
->
+ 2* -> Cu 2H+ + HO + 2e
2
(cathode)
(anode)
2 faradays therefore deposits one gram-atomic mole, or 16 grams, weight of copper (63.57 grams) and liberates of oxygen gas, occupying 1L.2 liters under standard conditions. As seen from the equation, the acidity of the solution increases == 1 ôle H 2SO 4 etc.) by one gram equivalent (=0= 1 mole HNO 3 per faraday passed. This gain in acidity may be expressed in terms of acid normality (see Sees. 24 and 68). It is possible to prepare a solution suitable as a standard in acidimetry by electrolyzing a neutral solution of copper sulfate and determining the acid concentration of the resulting solution from the weight of
copper deposited.
The
electrolysis of a dilute sulf uric acid solution causes the fol:
lowing reactions to take place
2H+ +
2e ->
(cathode)
2
H
The passage
->
2H+
+ H0 +
(anode)
faraday liberates Yz mole of hydrogen (1.008 mole of grams; 11.2 liters under standard conditions) and oxygen (8.000 grams; 5.6 liters under standard conditions). The mole total amount of gas evolved per faraday is therefore (16.8 liters). In this electrolysis, there is no net change in acidity if the volume of the solution is kept constant, for the loss in acidity at the cathode is balanced by the gain in acidity at the anode. The electrolysis of a dilute nitric acid solution of lead causes the deposition of lead dioxide on the anode:
of 1
Pb++
+ 2H
2H+ +2e
One faraday
- PbO + 4H+ + 2e -+H

2
(anode)
(cathode)
,
119.6 grams of PbO 2 the acidity by 1 gramincreases and liberates Yi mole of hydrogen, equivalent weight (1.008 grams) of hydrogen ion.
therefore deposits
PbO 2 /2 =
129
EXAMPLE
copper
is
neutral solution containing 0.4000 gram of electrolyzed until all the copper is plated out, and the
II.
electrolysis is continued 7
solution
minutes longer. The volume of the at 100 and the current strength is maintained kept ml., at an average of 1.20 amperes. On the basis of 100 per cent curis
rent efficiency (a)

(6)
how
long did
it
take for the copper to deposit,
what
total
trolysis, (c)
volume of gas was evolved during the entire elecwhat was the acidity of the solution at the end of the
electrolysis?
SOLUTION:
1
faraday deposits -^z
31.8 grams
Cu
f\ Af\f\f\
Number
m.
of faradays to deposit 0.4000
Time
required
= = 0.0126X96,500 T~w\
-.
gram Cu = HpTo"" ul.o
==
0.0126
1*012 seconds
mo
=
Ans.
16.9 minutes.
During deposition of Cu, each faraday corresponds to J^ mole O 2
(i.e.,
each
^ mole Cu)
Moles
After
O2
evolved
0.0126
M = 0.00315
Cu
deposited,
number faradays passed =
60
1.2
96,500
Each faraday evolves

Moles
H +O
2
Total gas evolved
% mole O evolved - 0.00522 X % = 0.00392

J/
mole
and
0.00315
+ 0.00392 =
0.00707 mole.
Ans.
of
During Cu deposition each faraday corresponds to a gain

1
gram atom
After
of
H+
Cu
deposition, acidity does not change
Gain
in acidity
=
is
0.0126 gram-equivalent of H+.

10
Ans.
(Resulting solution
0.01258
0.1258 normal as an acid.)
In the above calculations involving Faraday's second law, it has been assumed that all the current serves for the decomposition of the substance in question; i.e., 100 per cent current effi-
130
ciency has been assumed. In actual analyses, this is not usually the case. The electrolysis of an acid solution of a copper salt will
not only cause the deposition of copper at the cathode, but small amounts of hydrogen will usually be given off at the same electrode before the copper has all plated out. In such cases, the sum
of the weights of the products discharged at
each electrode exactly
is, in the copper electrolysis, for each faraday of electricity passed, the number of gram-equivalent
corresponds to the law.
That
lent weights of
weights of copper deposited added to the number of gram-equivahydrogen liberated will be unity. In problems of
electroanalyses, unless otherwise specified, 100 per cent current

efficiency
may be assumed. Other electrical units which are frequently used in electrochemical computations are as follows
:
The ohm, R,
is
the unit of resistance.
It is the resistance offered
to a constant current of electricity at 0C. by a column of mercury 1 sq. mm. in cross section and 106.3 cm. long.
The
sure.
the unit of electromotive force or electrical presIts relation to the ampere and ohm is expressed by Ohm's
voltj
E,
is
law.
The joule,
expended of 1 ohm.
J, is the unit of work. It is represented by the energy in 1 second by a current of 1 ampere against a resistance
J = Elt - EQ The
watt,
107 ergs
is
W,
is
done at the rate of
the unit of power. It 1 joule per second.
represented
by the work
J=
Problems
100-watt 110- volt incandescent lamp is connected in series with an electrolytic cell. What weight of cadmium could be deposited from solution by the current in 30 minutes?
332.
Ans.
0.953 gram.
333. How many minutes will it take for a current of 0.500 ampere to cause the deposition of 500 mg. of silver from nitric acid solution on the basis of 80 per cent current efficiency?
Ans.
18.6 minutes.
334.
131
coulombs of electricity are required to deposit 0.1000 from a solution of cobaltous salt? How many amperes would gram be required to deposit that amount in 20 minutes 20 seconds? How many grams of nickel would be deposited under identical conditions?
of cobalt
How many
Ans.
336.
327.3 coulombs.
0.2682 ampere.
0.09951 gram.
With a current
at 8.00 volts,
required to deposit (a) 0.100 solutions containing these metals in the higher state of oxidation?
how much electrical energy is theoretically gram of gold, (6) 0.100 gram of mercury from
joules.
Ans.
336.
(a)
1,180 joules,
(6)
770
of PbO2 will be deposited in separate 100 per cent current yield by a current electrolytic cells, on the assumption of of 0.0800 ampere flowing for 30 hours?
What
weights of Cu, of Zn,
and
Ans.
2.85 grams Cu, 2.93 grams Zn, 10.7 grams
PbO2
337. Using a rotating electrode, Sand obtained 0.240 gram of copper from current of 10.0 amperes a nitric acid solution of copper sulfate in 6 minutes.
under 2.80 volts was used.
What
electrical
energy was expended and what
was the current

Ans.
efficiency?
10,080 joules, 20.2 per cent.
17.0
338. Using a rotating electrode, Langness found that with a current of amperes and a potential of 10.0 volts, 0.200 gram of platinum could be
deposited in 5 minutes from a solution of potassium chloroplatinate. How electrical energy was expended per second? What quantity of electricity was used? What was the current efficiency?
much
Ans.
339.
170 joules.
5,100 coulombs.
7.75 per cent.
quantity of electricity is required for (a) the electrolytic deposigrams of PbO2 (6) the liberation of 0.800 gram of oxygen gas, of 30.0 ml. of chlorine when measured under standard condiliberation the (c) tions (one molecular weight in grams occupies 22.4 liters)?
tion of 1.196
,
What
Aris.
(a)
965 coulombs,
(6)
9,650 coulombs,
(c)
259 coulombs.
For how long a time must a current of 1.00 ampere be passed through a dilute solution of sulfuric acid in order to liberate a total volume of 600 ml. of gas when measured dry and under standard conditions?
340.
Ans.
341.
57 A minutes.
in 1
With a current of 1.00 ampere, what weight of silver would be deposited minute in a silver coulometer? What volume of gas (under standard conditions) would be evolved in 60 seconds in a water coulometer?
Ans.
0.06708 gram.
10.44 ml.
is
342. Pure crystals of copper sulfate are dissolved in water, and the solution electrolyzed until the solution is colorless. The cathode gains 0.4280 gram.
is
What
the acidity of the solution in terms of moles of

0.006731 mole.
H SO ?
2 4
Ans.
132
343.

What would be
the net gain or loss in gram-equivalents of H+ per a solution of HNOs in which 80 per cent of the
faraday in the electrolysis of
current goes to the simple decomposition of water and 20 per cent goes to the reaction involving the reduction of nitrate to free nitrogen at the cathode and liberation of oxygen at the anode?
Ans.
344.
0.040 gram-equivalent
lost.
alloy consists of 20.72 per cent lead and 79.30 per cent zinc. 1-gram sample is dissolved in acid and the solution diluted to exactly one liter. and requires 30.00 ml. to 100-ml. pipetful is titrated with 0.1000
An
N NaOH
many
(ft)
The remaining 900 ml. are electrolyzed under neutralize the acid present. 2.00 amperes for exactly 5 minutes (100 per cent current efficiency) with the
(a) How deposition of the lead as PbO 2 time? evolved this are conditions) during
.
milliliters of
gas (standard
after electrolysis
is
brought again to 900 ml.,

0.034 N.
volume of the solution what would be the acid normality

If the
of the solution.
Ans.
346.
(a)
94.4 ml.
(6)
average current of 0.5000 ampere is passed through a dilute acid alloy containing 0.5000 gram of copper, 0.2000 gram of zinc, and 0.1000 gram of lead. Assuming 100 per cent efficiency, compute the total gain in acidity in terms of moles of 2 SO4 (a) at the end of the PbO 2 deposition at the anode, (6) at the end of the Cu deposition at the cathode, (c) after the cursolution of
An
an
rent has been continued 5 minutes longer.
What volume
(c)
of gas (standard
conditions) has been evolved during the entire process?
Ans.
(a)
0.0009652 mole,
(h)
0.008347 mole,
0.008347 mole.
108.8 ml.
346. How many milligrams of silver can be deposited from solution in 23 minutes by a current of 0.700 ampere at 100 per cent efficiency? How long would it take the same current to deposit the same weight of nickel?
tion
ampere is passed through a copper sulfate soluand a 90 per cent current yield is obtained, compute (a) the weight of copper which can be deposited in one hour, (6) the gain in acidity in moles of
347. If a current of 0.250
sulfuric acid during that time.
348. If 6.30
amperes
will deposit 0.532
gram
of tin in 20
minutes from a
solution of stannous salt,

349.
what
is
the current efficiency?
pure alloy of copper and zinc is dissolved in acid and electrolysed under 0.500 ampere (100 per cent efficiency). It is found that just 40 minutes are required to deposit all the copper. From the filtrate the zinc is precipitated and ignited to 0.245
gram
of
Zn 2 P2O 7
Calculate (a) grams of copper
deposited, (b) percentage of copper in the alloy, (c) volume of gas liberated, (d) gain in acid normality of the solution assuming the volume at the end
of the electrolysis to be 500 ml.
find the
Assuming the volume of an electrolytic cell to be kept at 125 ml., normal acid concentration of a solution containing 0.42 gram of 0.20 gram of lead, and 0.26 gram of zinc and 144 milliequivalents copper,
350.
all
133
of acid at the start (a) after just enough current has been passed to deposit the lead as PbO2 and assuming no other reaction takes place at the anode
(c)
of 1.8
during that time, (6) after all the copper has deposited, amperes has been continued 30 minutes longer.
of gas evolved during the entire electrolysis,
when the current Compute the total
volume
measured under standard
conditions.
351. On the basis of 30 per cent current yield, compute the cost of the power required to produce 1 pound of NaMnO4 from a manganese anode and 0.3 N Na 2 CO3 solution. E.m.f. = 8 volts. Cost of current = 3 cents per
kilowatt-hour.
following represents the net reaction for the discharge of an 2H+ PbO2 2HSO4 - - 2PbSO4 ordinary lead storage battery: Pb 2H 2 O. Write the two half-cell reactions involved. If the charged battery contains two liters of sulfuric acid of specific gravity 1.28 (36.9 per cent 2 SO4 by weight) and in 1 hour the cell is discharged to the point where the specific gravity of the acid is 1.11 (15.7 per cent 2 SO4 by weight), what is the average
352.
The
amperage produced?
353.
Assume no change
is
in
volume
of the electrolyte.
current of one ampere
passed for one hour through a saturated
solution of sodium chloride connected in series with a copper coulometer conWrite sisting of copper electrodes dipping in a solution of cupric sulfate.
equations for the anode and cathode reactions that take place in the NaCl cell and in the CuSO4 cell. Assuming 100 per cent current efficiency, calculate
(a)
grams of copper deposited on the cathode
liters of
N/10
of the coulometer, (6) number of C1 2 gas evolved (standard conditions), (c) number of milliliters of HC1 required to titrate one-tenth of the cathode portion of the NaCl cell.
354. copper coulometer, consisting of copper electrodes dipping in a solution of cupric sulfate, is connected in series with a cell containing a concentrated solution of sodium chloride. After a direct current is passed through
both the
cell
and the coulometer
for exactly
gram
of copper has been dissolved
50 minutes, it is found that 0.636 from the coulometer anode, (a) What is
cent efficiency,
the average amperage used during the electrolysis? (6) Assuming 100 per how many grams of NaClO3 could be produced from the C12 and NaOII formed during the electrolysis (3C1 2 6OH~ -> C1O3 - 5C1-
3H
0)?
weight of CuSO4 .5H2 O must be dissolved in water so that after complete deposition of the copper by electrolysis, a solution will be obtained which is equivalent to 100 ml. of 0.100 N acid?
355.
What
356. Pure crystals of CuSO4 .5H 2 weighing 1.0000 gram are dissolved in an average current of 1.30 amperes and the is with solution water, electrolyzed
20 minutes. What weight of copper has been deposited? What volume measured dry and under standard conditions has been liberated? If the resulting solution is made up to 100 ml. with water, what is its normality as an acid?
for
of gas
is
CuSO4 .5H 2 O are dissolved in water, and the solution with an electrolyzed average current of 0.600 ampere. The electrolysis is
357. Pure crystals of
134

all
the copper has been deposited, and it is found that a total volume of 62.5 ml. of gas measured dry at 18C. and 745 mm. pressure has been evolved. What weight of crystals was taken for
continued for 5 minutes after
electrolysis?
(Assume
all
the copper
is
deposited before hydrogen
is
evolved.)
How many milliliters of 0.100 N NaOH will the resulting solution neutralize? 368. A solution of brass in nitric acid contains 1.10 grams of copper and
0.50
gram
of zinc
is
and
is
2.00
N in acid.
is
the volume
kept at 100 ml.
What is the acid normality of the solution if the continued 20 minutes longer and 40 per cent of it goes to the reduc8 10H+ = tion of nitrate ions to ammonium ions: (cathode) NOa" + 3H 2 0; (anode) 4II 2 O - 8 = 8H+ 202 How long before the acid 4 would be entirely destroyed?
current
is
copper at the cathode, what copper has just deposited?
It is electrolyzed at 1.50 amperes, and the current goes to the deposition of the acid normality of the solution when all the
If all
NH +
359.
Assuming 100 per cent current

is
efficiency
and assuming that the
elec-
discontinued as soon as the copper is deposited, compute the time trolysis required, the volume of gas evolved, and the gain in acidity in terms of millimoles of hydrogen ions when 0.8000 gram of brass in dilute HNOs
is
electrolyzed.
Cathode gains 0.6365 gram; anode gains 0.0240 gram.
Current
brass.
0.900 ampere.
Compute
also the percentage composition of the
CHAPTER X CALCULATIONS FROM REPORTED PERCENTAGES

a
60. Calculations Involving the Elimination or Introduction of Constituent. It is occasionally necessary to eliminate from or
and
introduce into a report of an analysis one or more constituents, calculate the results to a new basis. Thus, a mineral may contain hygroscopic water which is not an integral part of the
molecular structure. After complete analysis, it may be desirable to calculate the results to a dry basis as being more representative of the mineral under normal conditions. On the other
hand, a material may contain a very large amount of water, and because of the difficulty of proper sampling, a small sample may be taken for the determination of the water while the bulk of the material is dried, sampled, and analyzed. It may then be desirable to convert the results thus obtained to the basis of the original wet sample. This applies equally well to constituents other than
water, and, in any case, the method by which these calculations are made is based upon the fact that the constituents other than the ones eliminated or introduced are all changed in the same
proportion,
and the
I.
total percentage
must remain the same.
EXAMPLE
A sample
of lime
gave the following analysis:
CaO
MgO
Fe 2 O 3
SiO 2
2
+ A1 O
2
2
H O + CO
What
is
(by loss on ignition)
= = = = =

1.03 per cent
100.03 per cent
the percentage composition of the ignited sample on the assumption that the volatile constituents are completely expelled?
In the sample as given, total percentage of all constituents is 100.03. The slight variation from the theoretical 100 per cent is due to experimental errors in the analysis. The
SOLUTION:
135
136
2.16 = total percentage of nonvolatile constituents is 100.03 97.87 per cent. Ignition of the sample would therefore increase
the percentage of each of the nonvolatile constituents in the ratio of 100.03:97.87, and the percentage composition of the ignited
sample would be
CaO
= = =
90.15
6.14
X X X
X
100.03
97.87
92.14 per cent

6.28 per cent
MgO
100.03
97.87
100.03
97.87
100.03
Ans.
1.05 per cent
1.03
SiO 2
0.55
97.87
0.56 per cent
100.03 per cent
the original sample of lime mentioned in the were heated only sufficiently to reduce the preceding problem percentage of volatile constituents from 2.16 to 0.50 per cent, what would be the percentage composition of the product? SOLUTION: In the original sample, total percentage of nonIn the volatile constituents is 100.03 - 2.16 = 97.87 per cent. total of residual constituents would the percentage ignited sample, 0.50 = 99.53 per cent. The loss of volatile matter be 100.03 would therefore have caused the percentage of the various conII.
EXAMPLE
If
stituents to increase in the ratio of 99.53 to 97.87.
Hence, the
percentage composition would be
CaO
= =
90.15
6.14
X X
=
97.87 99.53
97.87
91.68 per cent

6.24 per cent
1.05 per cent
MgO
Fe2O3
SiO 2
Volatile matter
+ Al
=
=
Ans.
1.03XJ~|=
0.55
99 53 X T^T^ = 97.87
0.56 per cent 0.50 per cent 100.03 per cent
61. Cases Where Simultaneous Volatilization and Oxidation or Reduction Occur. Occasionally a material on ignition may not
CALCULATIONS FROM REPORTED PERCENTAGES

only lose volatile constituents but
137
also undergo changes due In such cases the percentages of the constituents after ignition can best be calculated by assuming that oxidation or reduction occurs first, and loss of volatile material afterward. In other words, it is easiest to solve the prob-
may
to oxidation or reduction effects.
lem in two separate
steps.
EXAMPLE.
mineral analyzes as follows:
CaO = MgO = FeO = SiO2 = CO2 = H2 O =


100.00 per cent
of
After heating in oxygen the ignited material shows the presence The iron is all oxidized to no water and 3.30 per cent CO 2
.
the ferric state.
CaO and
of
Fe 2 O 3
in
the ignited material.
SOLUTION: Assume first that 100 grams of the original mineral are taken and that the only change is that of oxidation of FeO to Fe 2 O 3 Here 4.00 grams of FeO would form 4.00 X Fe 2 3 /2FeO = 4.44 grams of Fe 2 3 and the resulting material would gain in weight by 0.44 gram due to this change alone. The material now weighs 100.44 grams and the percentages of the constituents (other than Fe 2 O3 ) are decreased in the ratio of 100/100.44. The per.
centages are
now
45.18
CaO = MgO = FeO = SiO 2 = CO2 = H2 =
X 8.10 X 4.44 X 6.02 X 34.67 X 2.03 X
100/100.44
100/100.44
100/100.44
100/100.44
100/100.44
100/100.44
= = = = = =


100.00 per cent
Assume now that the second change takes

all
the water
is
is lost
and
that the percentage of
place, namely, that 2 in the ignited
C0
material
brought down to 3.30 per cent due to
loss of
most
of
138

The
calculation then
the C02.
becomes similar to that
of the
preceding example:
Percentage of
CaO =
=
44.98
100 00
3 30
mo(
0()
_'
(34.52
+ 2 .02)
60.97 per cent.

A 4.44 , X
Ans.
f ** Percentage of Fe2 O 3
=
=
100.00-3.30
100
.
(34 .52
+ 2.02)
6.61 per cent.
Ans.
Problems
360.
The percentage
of copper in a
is
sample of copper ore with a moisture

Calculate the percentage
content of 8.27 per cent
found to be 36.47 per cent.
on a dry sample.
Ans.
361.
39.76 per cent.
An
sample of coal as taken from the mine contains 8.32 per cent ash. sample of the same coal contains 10.03 per cent ash and 0.53 per cent moisture. Calculate the percentage of moisture in the original sample.
air-dried
Ans.
17.50 per cent.
362. powder consisting of a mixture of pure BaCl 2 .2H 2 and silica contains 20.50 per cent Cl. What would be the percentage of Ba in the material after all the water of crystallization is expelled by ignition?
Ans.
363.
44.34 per cent.
sample of lime gives the following analysis:
CaO = MgO = Si02 = Fe2 O3 =

2.16 per cent 3 JL4 per cent
CO = HO =
2
2
99.96 per cent
What
the
the percentage of each constituent after superficial heating in which content has been reduced to 1.08 per cent and the water content to 1.00 per cent?
is
CO
=
Ans.
CaO =
1.00.
77.66,
HO
2
MgO =
16.35,
SiO2
2.21,
Fe 2 O3 =
1.66,
CO =
2
1.08,
364. Lime is to be manufactured by the ignition of a sample of The only data as to the composition of the dolomite are as follows:
dolomite.
96.46 per cent CaC0 3 2.21 per cent SiO 2

+ MgCO
MgO

The
analysis of the lime shows no water
139
dioxide.
Calculate the percentages of CaO,
Ans.
CaO =
76.14,
MgO =
and 1.37 per cent carbon and SiC>2 in the lime. MgO, = = 1.37. 18.52, SiO2 4.00, CO2
366. The oil in a sample of paint is extracted, and the residual pigment is found to be 66.66 per cent of the original weight. An analysis of the pigment
gives
Zinc oxide
Lithopone Barium chromate
= = =

Calculate the percentage composition of the original paint.
Ans.
oil
Zinc
oxide
16.6,
lithopone
34.4,
barium
chromate
15.7,
33.3.
366.
The same sample
of iron ore
is
other constituents, Chemist

cent.
Chemist 2 reports: per cent. Calculate the percentage of iron in both cases on a dry sample. Analysis of a dry sample shows A to be correct. What are the error and percentage error
in the constituent iron in
A reports: H O = 1.62 per cent, H O = 0.96 per cent, Fe = 44.36

2
analyzed by two chemists.
Fe = 43.92 per
Among
B's analysis as reported?
Ans.
367.
A =
44.64 per cent,
B =
is
44.79 per cent.
0.15 per cent, 0.34 percent.
properly sampled and the loss in weight at The dried sample is used for the of other as follows: analysis constituents, cargo of wet coal
105C.
is
determined as 10.60 per cent.
Volatile combustible matter
21.60 per cent
Coke = 60.04 per cent Ash = 18.36 per cent
The
air-dried coal (moisture content
1.35 per cent) costs $8.80 a ton at
percentage of ash? Neglecting other factors except water content, calculate the value of the wet coal.
is its
the mine.
What
Ans.
18.11 per cent.
$7.98 a ton.
368. The moisture content of a sample of A1 2 (SO4)3.18H 2 O is reduced from the theoretical to 7.36 per cent. Calculate the analysis of the partly dried The original salt material reporting percentage of Al 2 Os, SOs, and JHÔ. costs $0.0262 per pound. Calculate the cost of the dried material, considering
only the
loss in
water content.
27.64 per cent,
Ans.
$0.0473.
A1 2
O3 =
SO3 =
64.98 per cent,
HO
2
7.36 per cent.
369. In the paper industry "air-dry" paper pulp is considered as containing 10 per cent of water. A sample of wet pulp weighs 737.1 grams and when heated to "bone dryness" weighs 373.6 grams. What is tne percentage of
air-dry pulp in the original sample?
Ans.
56.30 per cent.
140
A 3 04. 370. Ignition in air of MnOa converts it quantitatively into = 80.0 is of the MnO2 of cent; per following composition: pyrolusite sample SiO2 and other inert constituents = 15.0 per cent; 2 = 5.0 per cent. The
Mn
HO
sample
Ans.
371.
is
ignited in air to constant weight.
Mn
in the ignited sample.
59.4 per cent.
A salt mixture is found to contain 60.10 per cent UO3 (essentially form of ammonium diuranate). It is also found that 10.00 per cent of the mixture is combined and uncombined volatile matter (essentially NH 3 and H 2 O) and 29.90 per cent is nonvolatile inert matter. What is the percentage of the clement uranium in the material after ignition if the volatile matter is all lost and the uranium is converted to the oxide U3 O8 ?
in the
Ans.
56.27 per cent.
372. A sample of a mineral containing water as its only volatile constituent contains 26.40 per cent SiO2 and 8.86 per cent water. What would be the percentage of SiO 2 in the material after heating sufficiently to drive off all the water, assuming that no chemical changes occur? What would be the percentage of SiO 2 if the ignited material still showed the presence of 1.10 per cent water?
a mixture of pure CuS04 .5H 2 O and silica contains 18.10 per cent Cu. What would be the percentage of combined sulfur in the material after the water of crystallization is all driven off by ignition?
373.
powder consisting
of
374. One pound of an ore lost 0.500 ounce of water by drying at 110C. to constant weight. The dried ore upon strong ignition with a flux lost 1.50 per cent of its weight as moisture and was also found to contain 20.10 per Find the percentage of water and of silica in the ore as received. cent SiO2
.
ment was purchased
sample of crude copperas (FeSO4 .7H 2 O) representing a large shipat 1.25 cents per pound. An analysis for iron content gave 20.21 per cent Fe. The shipment was stored for a considerable period during which time water of crystallization was lost. To fix the price at which the copperas was to be sold, it was found that an increase of 0.023 cent per pound would be necessary, due entirely to the change in the percentage of
376.
iron.
Calculate the percentage of iron in the sample after storage. the increase to be due wholly to loss of water.
376.
Assume
sample of dolomite analyzes as follows:
SiO2
A1 2 O3
Fe 2O 3
MgO
CaO
CO
The dolomite
is
= = = = = =
47.55 per cent

of the ignited material
ignited,
and a 5.00-gram sample
shows
the presence of 0.80 per cent
CO
2.
What
weight of
Mg P2O7
2
could be obtained
from a 0.500-gram sample of the ignited material?

377.
tains a
fat
141
shipment of meat scrap
is
minimum
of 55.00 per cent protein
sold with the specification that it conand a maximum of 10.00 per cent
calculated to a dry basis. The analyst for the sender reports 53.20 cent per protein, 9.59 per cent fat, and 3.60 per cent moisture. The material takes on moisture during shipment and the analyst for the receiver reports 50.91 per cent protein, 9.31 per cent fat, and 7.50 per cent moisture. Do either
when
or both of the analyses
On
the dry basis, what values and between the

378.
of the material to specifications? the percentage variation between the two protein two fat values as reported by the analysts?
is
show conformity
sample of limestone analyzes as follows:
CaCO =
3
MgCO =
3
Fe2 O 3 =
A1 2 O 3
86.98 per cent 3.18 per cent 3. 10 per cent

= = H2O =
SiO 2
Analysis of the ignited material shows no moisture and only 1.30 per cent CO2. What is the percentage of Fe in the ignited material?
379. A sample of pyrolusite analyzes as follows: MnO 2 = 69.80 per cent; SiO2 and other inert constituents = 26.12 per cent; CO 2 = 1.96 per cent; H 2 O = 2.15 per cent. On ignition in air all the H2O and CO2 are lost arid the
MnO
2 is
converted to
Mn O
3
4.
Mn O
3
in the ignited
material.
carbonate rock analyzes as follows: CaO = 43.18 per cent; MgO = 8.82 per cent; FeO = 3.10 per cent; Fe 2 O3 = 1.90 per cent; SiO 2 = 7.30 per = 2.00 per cent. A portion of this rock is cent; CO 2 = 33.69 per cent; H 2 ignited and a sample of the ignited material on analysis shows 2.00 per cent CO2 and no water. It also shows that the ferrous iron has been completely oxidized. Calculate the percentage of total Fe 2 Os and of CaO in the ignited
380.
material.
Molecular Formulas from Chemical AnalyGiven a compound of unknown composition, a chemical analysis will determine the proportion in which the constituents of the compound exist. The results of such an analysis may then be used to calculate the empirical formula of the compound.
62. Calculation of
ses.
Thus, the analysis of a certain

Zinc
salt gives
the following results:
Chlorine
= =
lOOOO per cent

Dividing the percentage of each constituent by
will give the
its
atomic weight
number
of
gram-atoms
of that constituent in 100
142

of the
grams
In 100 grams of the above salt there are = 0.7335 gram-atom of zinc and 52.04/35.46 = present 47.96/65.38 1.4674 gram-atoms of chlorine. These numbers are seen to be in the ratio of 1 to 2. The empirical formula of the salt is there-
compound.
fore ZnCl'2, although, as far as the
actual formula might be Zn2 Cl4, Tn general, the determination of tiple of the empirical formula. a of the molecular weight compound is necessary in order to deter-
above analysis is concerned, the ZnaCle, or any other whole mul-
mine which multiple

formula.
of
of the empirical
formula
will give the actual
The usual methods
of establishing
molecular weights
vapor density, freezing-point lowering, boiling-point by means other and physicochemical phenomena should already be raising,
familiar to the student but the following will serve as a brief review. Equal volumes of gases under identical conditions of tempera-
ture and pressure contain the same number of molecules (Avogadro). Therefore the molecular weights of gases are proportional
to their densities.
Since under standard conditions of tempera-
ture and pressure (0C., 760 mm.) a gram-molecular weight of a 2 ) occupies 22.4 liters, gas (e.g., 32 grams of O 2 28.016 grams of
;
an experimental method of determining the molecular weight of a gas is to measure its density under known conditions of temperature and pressure and calculate the weight of 22.4 liters of
under standard conditions (see Sec. 109). The molecular weight of a solid or liquid can also be determined in this way if the substance can be converted to a gas without decomposition or change
it
in degree of molecular association.
soluble substance lowers the freezing point and raises the boiling point of a definite weight of a solvent in proportion to
the
of a
number
of molecules or ions of solute present.
In the case
nonpolar (un-ionized) solute dissolved in water, one grammolecular weight of the solute dissolved in 1,000 grams of water raises the boiling point of the water by 0.52C. (i.e., to 100.52C.) and lowers the freezing point of the water by 1.86 (i.e., to
1.86C.).
In general, for aqueous solutions of nonpolar solutes.
X
Grams
of solute
of solute
.
.
0.52
1.86
raising of
1,000
boiling point
Mol. wt.
grams
of
water
lowering of
freezing point
143
Ionized solutes change the boiling point or freezing point of a solvent to a greater degree owing to the greater number of particles present. Thus, NaCl at ordinary concentrations depresses
twice as
give an
solute.
the freezing point of water and raises the boiling point by about much as calculated from the above formula, owing to
ionization into
effect
Na+ and Cl~ ions. Similarly, CaCl2 and Na2SO4 about three times as great as that of a nonpolar
Solutes dissolved in solvents other than water show analogous behavior in that the changes in freezing point and boiling point brought about by a mole of solute in 1,000 grams of solvent are fixed values (but of course different from those values given by
water as the solvent). The determination of the molecular weight of a soluble substance can therefore be made by preparing a solution of a known weight of it in a known weight of solvent (preferably water) and measuring the point at which the solution begins to freeze or boil.
found by analysis to contain 40.00 per cent carbon, 6.71 per cent hydrogen, and the rest oxygen. When converted to a gas it has a density 2.81 times that of oxygen at the same temperature and pressure. What is the formula of the compound? SOLUTION: In 100 grams of substance there are 40.00 grams of C, 6.71 grams of H, and 53.29 grams of O. This corresponds to
1.
EXAMPLE
certain organic
compound
is
40.00
12.01
6.71
=
=
. 00 3.33 gram-atoms of
,
1.008
6.66 gram-atoms of
53.29
16.00
3.33 gram-atoms of
These are
in the ratio of 1:2:1
Empirical formula = CH 2 O Formula weight of CH 2 = 30 (approx.) Molecular weight of compound = 2.81 X 32

Therefore,
= 90
(approx.)
Formula
of
compound = CaHeOa.
Ans.
144
II. Butandione is a yellow liquid containing 55.8 7.00 cent carbon, per cent hydrogen, and 37.2 per cent oxygen. per It is soluble in water, and the solution does not conduct electricity.
EXAMPLE
water solution containing 10.0 grams of the compound in 100 2.16C. What is the formula of grams of water freezes at butandione? SOLUTION:
rr
Gram-atoms per 100 grams =
= 4.65 of C r^ Z.U
J
-^-7.00 ofH
These are
f?_ 2.32 of O
in the approx. ratio of 2:3: 1
Empirical formula
Formula weight
10
Solving,
'
= C^HaO of C 2 H 3 O =
43
Mol. wt.
X 1^X1.80 = 100
Mol. wt.
2.16
= 86
Ans.
Therefore,
Actual formula = C^Hf^.
63. Calculation of Empirical Formula of a Mineral. The calculation of molecular formulas plays an important part in the
analysis of natural minerals.
A careful analysis furnishes a means
of establishing the empirical formula of a mineral of high degree of purity, although its actual formula is usually impossible to
determine by ordinary physicochemical methods since minerals cannot be vaporized or dissolved unchanged. The method of calculation is similar to that of the preceding examples, except that the basic constituents of a mineral are usually expressed in terms of their oxides. If the percentage of each constituent is divided by its molecular weight, the number of moles (grammolecular weights) of that constituent in 100 grams of the mineral From the ratios of the number of moles of the various is obtained.
constituents thus obtained, the formula of the mineral may be determined. It should be remembered, however, that analytical

methods are subject to
fore,
145
errors.
that the
number
It can hardly be expected, thereof moles of the various constituents as
determined analytically will be exactly in the ratio of small whole numbers, although in the actual molecule (except in cases involving isomorphism, discussed below) the molar ratios are small whole numbers. In a few cases, some judgment must be exercised in order to determine from the analysis the true molar ratios of the
constituents in the molecule.
slide rule will
be found to be
almost indispensable for this purpose, since, with two settings of the rule, all possible ratios are visible. EXAMPLE. The analysis of a certain mineral gives the following results
:
KO
2
A1 2 O3 - 38.07 per cent
= 17.70 CaO = 10.46 SiO 2 = 3370
per cent per cent
per cent 99.93 per cent
What
the empirical formula of the mineral? SOLUTION: In 100 grams of the mineral there are present
is
38.07
38.07
102.0 17.70
A1 2 O 3
17.70
= =
0.3733 mole of A1 2
KO
2
94.20
0.1879 mole of
KO
2
10.46
CaO
33.70
"SiO 2
~ = "
10.46
56.07
-0.1865 mole
of
CaO
33.70
60.3
0.559 mole of SiO 2
moles of these constituents are near enough in the ratio of 2:1:1:3 to be within the limits of experimental error. The molecule is therefore made up of 2A1 2 O 3 .K2 0. Ca0.3SiO 2 and may be written 2 CaAl 4 Si 3 Oi4. 64. Calculation of Formulas of Minerals Exhibiting Isomorphic
It is seen that the
Complications arise in the calculation of formulas in the cases of minerals exhibiting isomorphic replacement, i.e., the partial replacement of one constituent by one or more other
Replacement.
It therefore constituents having the same general properties. happens that, owing to different degrees of replacement, samples
146
of the
same kind of mineral obtained from different localities often on analysis numerical results which apparently bear little give resemblance to one another. As a general rule, a constituent may be replaced only by another of the same type and valence. Thus, Fe 2 3 is often partially or wholly replaced by A1 2 O 3 and vice versa. CaO may be replaced by MgO, MnO, FeO, etc. Exceptions are sometimes met with,
,
but, for purposes of calculation, this assumption may be safely made. Since the isomorphic replacement occurs in no definite
proportion, it follows that the molar amounts of the constituents in such minerals do not necessarily bear any simple relation to one another. On the other hand, if constituent B partially replaces constituent A, since the valences are the same, the sum of the molar amounts of A and B would be the same as the molar
amount of A if it had not been replaced. Consequently, when the molar quantities of the constituents of a mineral in themselves bear no simple ratio to one another, the quantities of constituents of the
same type should be combined
in
an
effort to
obtain sums that do exist in ratios of simple whole numbers. EXAMPLE. A certain mineral gives the following analysis:
A1 2
= = Fe2 O 3 CaO = Si0 2 =

3
20.65 per cent 7.03 per cent 27.65 per cent 44.55 per cent
99J88 per cent
What
grams
is
the empirical formula?
SOLUTION:
The number
of the mineral is
of moles of each constituent in 100 found to be
0.2025 mole of A12O 3

(
,=
0.2465 mole
4rr reaUa
27.65
=
= =
0.0440 mole of Fe2
CaO
44.55
0.4932 mole of
CaO
Si0 2
0.7389 mole of Si0 2

Only when the molar quantities of the all the above numerical
first
147
two constituents
found to be in
are combined are
results
simple ratio to one another, these being approximately as 1:2:3. This shows isomorphic replacement between Fe20 3 and AhOa, and the formula of the mineral may therefore be written
(Al,Fe) 2 O 3 .2CaO.3Si0 2
or
Ca2 (Al,Fe) 2 Si3 Oii.

Problems
381.
its
Ans.
From
empirical formula:
the following percentage composition of ethylamine, calculate = 31.08 = 15.65 per cent, C = 53.27 per cent,
per cent.
Ans.
H N.
7
382. Calculate the empirical formula of the compound having the following = 2.37 per cent, P = 36.49 per cent, composition: Ca = 23.53 per cent, = 37.61 per cent.
Ans.
Ca(H P0 2 ) 2
2
following composition:
cent.
383. Calculate the empirical formula of an organic compound having the == 4.96 = 26.21 per C = 68.83 per cent, per cent,
Ans.
384.
CylleOjN
that the following analysis of diethylhydrazine agrees with the formula (C 2 6 ) 2 :N.NH 2
Show
Carbon
Nitrogen
Hydrogen =
386. Calculate the molecular formula of a compound that has a molecular weight of approximately 90 and has the following composition: C = 26.67 per = 2.24 per cent, O = 71.09 per cent. cent,
Ans.
HCO
2
4.
386. A certain compound of carbon and oxygen has an approximate molecular weight of 290 and by analysis is found to contain 50 per cent by weight of each constituent. What is the molecular formula of the compound?
Ans.
Ci 2 Og.
387. What is the molecular weight of a substance, 0.0850 dissolved in 10.0 grams of water gives a solution freezing at
gram
of which 0.465C. and
not conducting electricity? What is the molecular formula of the substance if it contains 5.94 per cent hydrogen and 94.06 per cent oxygen?
Ans.
34.0.
2.
148
388.
A certain organic compound contains 48.64 per cent carbon, 43.19 cent oxygen, and the rest hydrogen. A solution of 7.408 grams of the solid per in 100 grams of water boils at 100.52C. and does not conduct electricity. What is the molecular formula of the compound?
Ans.
C,H 6O2
389. A certain gaseous compound is found by analysis to consist of 87.44 per cent nitrogen and 12.56 per cent hydrogen. If 500 ml. of the compound has almost exactly the same weight as that of 500 ml. of oxygen at the same
temperature and pressure, what
is
the molecular formula of the
compound?
Ans.
390.
N
A
2 II 4 .
certain organic compound contains almost exactly 60 per cent 5 carbon, per cent hydrogen, and 35 per cent nitrogen. A solution of 20.0 of the grams compound in 300 grams of water does not conduct electricity
and
freezes
at
1.55C.
What
is
the molecular formula of the com-
pound?
Ans.
391. A certain sugar is a compound of carbon, hydrogen, and oxygen. Combustion in oxygen of a sample weighing 1.200 grams yields 1.759 grams of C02 and 0.720 gram of H 2 O. A solution of 8.10 grams of the substance in 150 grams of water boils at 100.156C. What is the molecular formula of the sugar? At what temperature should the above solution freeze?
Ans.
392.
C 6H 12 O
6.
-0.558C.
At a certain temperature and pressure 250 ml. of a certain gas consisting of 90.28 per cent silicon and 9.72 per cent hydrogen has a weight equal to that of 555 ml. of nitrogen at the same temperature and pressure. What
is
the molecular formula of the gas?
Ans.
393.
Si 2
6.
When
0.500
gram
of a certain hydrocarbon
is
completely burned in
When a 2 O and 1.717 grams of CO 2 are formed. oxygen, 0.281 gram of certain weight of this compound is vaporized, it is found to have a volume almost exactly one-quarter that of the same weight of oxygen under the same
conditions of temperature
and
pressure.
Calculate the molecular formula of
the compound.
Ans.
394.
cent,
dolis.
An analysis of a mineral gave the following results: H 2 = 4.35 per CaO = 27.15 per cent, A1 2O3 = 24.85 per cent, SiO2 = 43.74 per cent.
Calculate the empirical formula of the mineral.
Ans.
395.
cent,
H Ca Al Si Oi
2
2.
Dana gives the composition of FeO = 43.0 per cent, H2 = 28.7
vivianite as follows:
per cent.
Show
P2 Os 28.3 per that this conforms to
the formula
149
= 396. The percentage composition of a certain silicate is as follows: 2O 21.53 per cent, A12 O3 = 23.35 per cent, Si02 = 55.12 per cent. Calculate the empirical formula of the silicate.
Ans.
397.
KAlSi 2 O6
compound contains only the following constituents: CaO, The percentages of these constituents are in the respective approximate ratios of 9:10:26. What is the empirical formula of the comcertain
.
Na2 O, SO8
pound?
Ans.
398.
Na2 CaS2
What
is
8.
the empirical formula of a simple basic cupric carbonate 2 O? which, according to Rogers, contains 57.4 per cent Cu and 8.1 per cent
Ans.
399.
Cu 2 (OH) 2 CO3
The composition
of bismutite
is
given
2
by
Ramm
as follows:
CO =
2
6.38 per cent, Bi 2 O3 empirical formula.
89.75 per cent,
HO=
3.87 per cent.
Calculate the
Ans.
400.
2Bi8 C 3 Oi 8 .9H2 O.
What
is
the empirical formula of a silicate which gives the following
analysis:
CaO = MgO = FeO = SiO2 =

Ans.
401.
24.72 per cent 11. 93 per cent

Ca(Mg,Fe)(SiO3 ) 2
silicate gives
exists as water of crystallization,
the following analysis. Tf two-thirds of the water what is the empirical formula?
HO
2
CaO
Na*O
A1 2 O3
SiO2
Ans.
= = = = =
99.93 per cent
4 (Ca,Na 2 )Al 2 (Si03 ) 6 .4H 2 0.
402. Calculate the empirical formula of a mineral that analyzes as follows:
MnO =
CaO = Si02 =
Ans.
403.
(Mn,Ca)SiO8
The analysis of samples of microcline and of albite are given below. that these minerals are of the same type. Give the general empirical formula. Assume the percentages of silica and alumina to be the most reliable.
Show
150

MICROCLINE
ALBITB
Na2 O = K2 O = A1 2 O3 = SiO2 =
1.61 per cent
Na2O
KO
2
CaO
A12 O3

8
SiO2
= = = = =
0.38 per cent 19.29 per cent 68.81 per cent 100.10 per cent
Ans.
(K,Na)AlSi O
3
404. Calculate the empirical formula of axinite from the following analysis:
H2 O = CaO = FeO = MnO = A1 2 O3 = B 2 O3 = SiO 2 =

Ans.
406.
2
2 4

HCa (Fe,Mn)Al B(SiO )4. A sample of the mineral biotite
gave the following analysis:
HO
2
FeO =
A1 2 O3
= = MgO = SiO2 =
KO
2
What
is
the empirical formula of the mineral?
Ans.
(H,K) 2 (Mg,Fe) 2 Al 2 Si 3
12 .
406.
tion:
What is the empirical formula of a compound of the following composi= 38.68 per cent, H = 0.50 per cent, As = 37.08 per cent, O = 23.74
:
per cent?
407. Analysis of anorganic compound gave the folio wing results C = 60.86 = 4.38 per cent, = 34.76 per cent. Calculate the empirical per cent,
formula of the compound.

408. An organic acid is found to have a molecular weight of approximately 160 and to give the following analysis: carbon = 57.82 per cent, hydrogen = 3.64 per cent, oxygen (by difference) = 38.54 per cent. Calculate the molecular formula of the acid. 409. Calculate the empirical formula of the compound of the following = 6.60 per cent, Cl = 43.85 per cent. composition: Sb = 49.55 per cent,
Metaformaldehyde contains 40.00 per cent carbon, 6.67 per cent hydroand 53.33 per cent oxygen. A solution of 10.01 grams of the compound gen,
410.

in
151
250 grams of water freezes at 0.827C. and does not conduct electricity. is the molecular formula of metaformaldehyde? 411. A certain derivative of benzene contains only carbon, hydrogen, and nitrogen, and is not ionized in aqueous solution. Analysis of the compound shows 58.51 per cent carbon and 7.37 per cent hydrogen. A solution of 30.0 3.02C. What is grains of the compound in 150 grams of water freezes at the molecular formula of the compound?
What
is the molecular weight of a substance 4.50 grams of which, dissolved in 50.0 grams of water, gives a solution freezing at 0.93C. but not conducting electricity? What is its molecular formula if it contains 40.00 per cent carbon, 6.67 per cent hydrogen, and 53.33 per cent oxygen?
412. Wliat
when
At what temperature would the

413.
solution boil?
certain hydrocarbon contains 79.89 per cent carbon and has a times that of 2 at the same temperature and pressure. What is 1.07 density the molecular formula of the hydrocarbon?
414. A sample of a certain compound of carbon, hydrogen, and oxygen weighing 2.000 grains yields on combustion in oxygen 2.837 grams of CO 2 and A solution of 2.150 grams of the compound in 50.0 grams 1.742 grams of 2 O. of water is nonconducting and freezes at 1.288C. What is the molecular formula of the compound?
Under standard conditions a liter of a certain gaseous compound of and boron hydrogen weighs 2.38 grains. When 1.00 gram of this compound is heated, it is completely decomposed into boron and hydrogen, and the latter has a volume of 2.10 liters under standard conditions. Calculate the molecular formula of the boron hydride.
416.
416.
certain gas
is
composed
of 46.16 per cent carbon
nitrogen.
pressure.
Its density is 1.80 times that of air at the
and the remainder same temperature and
What is the molecular formula of the gas? (Calculate the apparent molecular weight of air by considering it four-fifths nitrogen and one-fifth oxygen.) 417. Calculate the formula of a compound of carbon, hydrogen, nitrogen,
and oxygen from the following data. Approximate mol. wt.
140. Decomposition of a 0.2-gram sample gives 32.45 ml. of nitrogen when measured dry under standard conditions. The same weight of sample on combustion in oxygen yields 0.3824 gram of 2 and 0.0783 gram of I1 2 O.
CO
the empirical formula of a mineral containing 3.37 per cent 19.10 per cent aluminum oxide, 21.00 per cent calcium oxide, and water, 56.53 per cent silica?
418.
is
What
419. Zircon
What
is its
a pure silicate of zirconium containing 33.0 per cent of empirical formula?

is
silica.
420.
FeO =
9.5 per cent,

is
= 76.5 per cent, tungstate has the following composition: 3 = 14.0 per cent. Calculate the empirical formula.
WO
MnO
421. Calamine
a basic zinc
silicate of
67.5 per cent, pirical formula.
HO =
2
7.5 per cent,
SiO 2
the following composition: 25.0 per cent. Calculate
ZnO =
its
em-
152
422.
A silicate of the
composition given below
is
found to have 85 per cent
of its water in the form of water of crystallization.
What
is
the empirical
formula?
= = CaO = SiO2 =
KO
7.7 per cent
silicate
sample of a certain hydrogen-potassium-magnesium-aluminum weighing 1.2000 grams yields the following products: 0.0516 gram of water, 0.4000 gram of KC10 4 0.9550 gram of Mg2 P2 O 7 and 0.1461 gram of alumina. What is the empirical formula of the mineral?
423.
,
,
424. From the following data obtained from the analysis of a feldspar, calculate the percentage composition of the sample and determine the empirical formula of the mineral, omitting the calcium from the formula and
assuming the percentages of
silica
and alumina to be the most
reliable.
Sample taken
Silica obtained
Alumina obtained Calcium oxide obtained
KC1
2
NaCl obtained
6
K PtCl
obtained
= = = = = =
.2000 grams
0.7751
gram
0.2255 gram 0.0060 gram 0.3193 gram 0.7240 grain
PART III VOLUMETRIC ANALYSIS

CHAPTER XI CALIBRATION OF MEASURING INSTRUMENTS
Measuring Instruments in Volumetric Analysis. The principle of volumetric analysis differs from that of gravimetric analysis in that, instead of isolating and weighing a product of a reaction directly or indirectly involving the desired substance, the volume of a reagent required to bring about a direct or indirect reaction with that substance is measured. From the volume of the reagent and its concentration, the weight of the substance is calculated. Since volumetric analysis makes use of exact volume relationships, it is essential first to adopt a definite standard for a unit volume and then to calibrate all measuring instruments to conform to this standard. The measuring instruments most often used are burets, pipets, and measuring flasks, and the experimental methods of calibrating them may be found in any standard reference book on quantitative analysis. A liter is the volume occupied 66. Calculation of True Volume.
65.
kilogram of water at the temperature of its maximum denA milliliter (ml.} is 1/1,000 liter. A sity (approximately 4C.). cubic centimeter (cc.) is the volume occupied by a cube 1 cm. on cc. a side. One liter contains 1000.027 In calibrating a vessel, since the cubical content of the vessel holding the water to be weighed varies with the temperature, it is evident that the tem-
by
perature of the container must be included in the specifications. Instead of taking the corresponding temperature of 4C., the temperature of 20C. has been accepted as the normal temperature by the Bureau of Standards at Washington.
To 20C.
contain a true
then, a flask must be so marked that at its capacity will be equal to the volume of water which
liter
153
154
at
weighs 1 kilogram in vacuo. From the density of water at different temperatures (Table IV, Appendix), the coefficient of cubical expansion of glass (0.000026), and the relationship existing between the weight of a substance in air and the weight
4C.
in
vacuo
(Sec. 49), it is possible to calculate the

it
amount
of water
to be weighed into a container in order that liter at any given temperature.
shall
occupy a true
should be weighed in air with brass weights so that when placed in a flask at the same temperature and under normal barometric pressure it will occupy
EXAMPLE.
How much
water at
25C.
true liter at
20C.?
SOLUTION: Density of water at 25C. = 0.99707 (Table TV). At 4C. and in vacuo, 1,000 grams of water will occupy 1 true liter. At 25C. and in vacuo, 1,000 X 0.99707 grams of water will
occupy
true
liter.
At 25C. and
in the formula
in air, the weight of
water
is
found by substituting
W\
and solving
Thus,
for
W (see Sec. 49).
(W ?-?>
Since the term to the right of the plus sign is required to only two significant figures, it is sufficiently accurate to write
997.07
W W = 996.02 grams
liter,
whence
Theoretically, to contain a true
the flask must be at
20C.
and yet contain

cubical content
this
perature of the flask is also

is
weight of water at 25C. Actually, the tem25C. It has therefore expanded, the
The
greater, and the true-liter volume is also greater. of cubical expansion of glass is 0.000026, and the coefficient
increase in
0.13 ml.
volume from 20 to 25C. is 1,000 X 0.000026(25 - 20) = This volume is represented by 0.13 X 0.99707 = 0.13
gram
of water.
The
required weight of water
is
therefore
996.02
+ 0.13 =
996.15 grams.
Ans.
CALIBRATION OF MEASURING INSTRUMENTS
155
A general formula may now be written for calculating the weight

of
water required for a true
liter.
W=
where
1>00
1 4T"
1
~j
d a J7 d
+ [1,000 X d X c(t 1
20)]
W = grams of water required for

t
true
liter
= temperature of water and flask d = density of water at t a = weight of 1 ml. of air under given conditions d' = density of balance weights c = coefficient of cubical expansion of the container
(The values of these
last three
terms are usually 0.0012,
8.0,
and
0.000020, respectively.) The correction for the expansion or contraction of the container is in each case small compared with the quantity to which it is
Consequently, only an approximate value containing two or three significant figures need be used. Indeed, in the case of instruments of 50-ml. content or less and for small differences in
temperature, this correction may ordinarily be neglected. By using the third column of Table IV, calculations like the above can be simplified. This column gives the weight of 1 ml.
of
air against brass weights
added.
water at a given temperature when the weighing is made in and the water is in a glass container.
In other words, corrections for expansion of glass and for conversion to vacuo are incorporated in the values given. It is seen, for example, that the answer to the above problem is found directly
by multiplying by
0.99615
1,000 the weight of
ml. of water at
25C. under
the conditions specified.
1,000
996.15 grams.
Ans.
Problems
426. Calculate accurately the
into a tared flask at
order that the flask
amount of water which should be weighed 18C. and 770 mm. pressure against brass weights in may be marked to contain exactly 250 true milliliters.
with
Ans.
249.37 grams.
is filled
426. A flask which has been marked to contain 1 true liter water at 15C. to the mark, and the temperature of the water
is
allowed to
156
rise

to
25C.
10.2
How many
mm.
millimeters above the
stand (inner diameter of the neck of the flask
15.0
mark does the water now mm.)?
Ans.
427. In calibrating a flask to contain 3^ true liter, if the water is weighed 26C. against brass weights, what percentage error would be introduced in the weight of water necessary if the expansion of glass were neglected?
at
What
weight of water should be taken?

0.016 per cent.
Ans.
428.
498.07 grams.
746.24 grams of
What is the true volume of a flask that contains water at 30C. when weighed in air against brass weights?
Ans.
750.06 ml.
429. A flask is accurately marked to contain 1 true liter, and the inner diameter of the neck of the flask is 16.0 mm. If 996.00 grams of water are weighed out in air against brass weights at 20C. and placed in the flask at this temperature, how far above or below the true-liter mark does the meniscus
of the
water
5.9
lie?
Ans.
mm.
below.
430.
To
at 31 C.
calibrate a flask to contain a true liter at 20C., how much water and 760 mm. pressure must be weighed into the flask in air against
brass weights?
431. In calibrating a flask to contain J^ true liter using water at 30C., error would be introduced by neglecting the expansion of of the weight of water required? calculation in the glass
what percentage
432.
at
What is the true volume of a flask that contains 398.70 grams of water 26C. when weighed in air against brass weights?
433.
pipet
It is
standard.
in air
marked to contain 100 ml. according to the true-liter How much would the water weigh filled with water at 12C.
is
under normal barometric pressure against gold weights?
434.
The
inner diameter of the neck of a flask
is
14 mm., and the flask
contains 498.00 grams of water at 28C. weighed in air against brass weights. How far above or below the meniscus of the water should a mark be placed
in order to represent
a volume of 500 ml.
according
to
the
true-liter
standard?
436.
A 50-ml.
buret
is
calibrated
by weighing
in
ah (against brass weights)

1
the water delivered between 10-ml. intervals in the graduations. Calculate from the following data the true volume of solution that the buret will deliver
between each 10-ml. interval, calculate the true total volume delivered between the 0- and the 50-ml. mark, and make a graph showing the correction that must be applied to the buret reading to obtain the true volume in any titration where the buret is initially filled to the zero mark (temperature of the water = 25C.).
CALIBRATION OF MEASURING INSTRUMENTS

IKTEKVALS, Mr,.
157
0.03-10.07
10.04
10.07-19.93
19.93-29.97
9.84
10.07
29.97-40.03 40.03-49.96
If this
10.13
10.05
initial
buret
is
used in a titration and the
and
final
readings are 0.11
and 46.38,
respectively,
what volume
of solution has actually been delivered?
CHAPTER
XII
NEUTRALIZATION METHODS (ACIDIMETRY AND ALKALIMETRY)

It is customary to di67. Divisions of Volumetric Analysis. vide the reactions of volumetric analysis into four groups, viz.,
1.
2.
Acidimetry and alkalimetry Oxidation and reduction ("redox") methods

Precipitation methods
3.
4.
Complex formation methods In Sees. 24 and 25 the principles underlying the use of equivain a lents, milliequivalents, and normal solutions were taken up general way. In this and succeeding chapters these principles are reviewed, developed, and applied to the above four types of volumetric analysis.
68. Equivalent
Weights Applied
to Neutralization
Methods.
is
The fundamental
follows
:
reaction of acidimetry
and alkalimetry
as
H+ +
i.e.,
Oil-
- HO
2
the neutralization of an acid by a base, or the neutralization of a base by an acid. The gram-equivalent weight of a substance acting as an acid is
that weight of it which is equivalent in total neutralizing power to one gram-atom (1.008 grams) of hydrogen as hydrogen ion. The gram-equivalent weight of a substance acting as a base is that weight of it which will neutralize one gram-atom of hydrogen
ion.
A normal solution
Sec. 24).
of
an acid or base contains one gram-equiva-
lent weight of the acid or base in one liter of solution, or one gram-milliequivalent weight in one milliliter of solution (see also
hydrochloric acid reacts as an acid, the gram-molecular weight (36.47 grams) of hydrogen chloride furnishes for the neutralization of any base one gram-atom (1.008 grams) of reacting
158
When
NEUTRALIZATION METHODS
hydrogen.
159
According to the definition, the value 36.47 grams constitutes the gram-equivalent weight of hydrogen chloride, and a liter of solution containing this amount is a normal solution of the
In this case, the normal solution and the molar solution are identical. On the other hand, the amount of hydrogen sulfate
acid.
is
required to furnish in reaction one gram-atomic weight of hydrogen = 49.04 2 S0 4 /2 only one-half the gram-molecular weight, or
grams, and a normal solution of sulfuric acid would contain 49.04 grams of hydrogen sulfate per liter of solution. A molar solution of sulfuric acid is therefore 2 normal and contains 2 gram-equivalent weights per
liter.
liter,
or 2 gram-milliequivalent weights per milli-
contains 4 hydrogen atoms in its molecule; but, when the compound acts as an acid, only one of these hydrogens is involved in active reaction, thus:
Acetic acid,
HC2H
2,
acid consti2 2 3 Consequently, tute the gram-equivalent weight, and the normal solution contains this weight of acid in a liter, or 0.06005 gram of acetic acid
HC H O + OH- -> C H - + H O H0 II /1 = 60.05 grams of acetic

2
3
per
milliliter.
is
Sodium hydroxide
neutralized as follows
(Na+)OH-
+ H+ -> H
(+ Na+)
NaOH/1,
or 40.00 grams, of sodium hydroxide constitutes one
gram-equivalent weight of the alkali, not because the molecule contains one atom of hydrogen, but because it involves in reaction
one atomic weight of hydrogen ion, as shown in the above equation. Therefore, a weight of 40.00 grams of sodium hydroxide in a liter of solution represents the normal solution. When calcium
oxide
used as a base, each gram-molecule reacts with two gramatoms of hydrogen, thus: CaO + 211+ -* Ca++ + 2
is
or
28.04 grams of calcium oxide are needed to involve in reaction one gram-atom of hydrogen. Therefore, 28.04 grams
CaO/2 =
calcium oxide constitute the gram-equivalent weight in this case, although calcium oxide in itself contains no hydrogen whatever.
of
Total neutralizing power should not be confused with degree of

ionization.
Equal volumes
of
normal solutions of hydrochloric
160
acid

and
acetic acid
but In other words, equivalent weight is based on neutralizing power and not on rela" tive strength" or degree of ionization.
total neutralizing power,
have the same
the acids have very different degrees of ionization.
Problems
436.
What
is
the equivalent weight of zinc oxide as a base?

136.2
Of
KHSO
as an acid?
An*.
40.69.
437. What is the milliequivalent weight in grams of each of the following acids or bases, assuming complete neutralization in each case: (a) NaaCOj,
(6)
K O,
2
(c)
NH OH,
4
(d)
HBr,
(e)
H SO
2
3,
(/)
H,PO
(c)
4?
Ans.
gram,
438.
(e)
(a) 0.05300 gram, (6) 0.04710 gram, 0.04103 gram, (/) 0.03267 gram.
0.03505 gram,
(d)
0.08093
What is the equivalent weight of the following acids or

(a)
bases,
(c)
assuming
Ba(OII)2,
complete neutralization in each case:

(d)
NO
2
5,
(6)
(NH 4 )
O,
N1I3
(e)
S0 2 ?
() 32.03.
Ans.
439.
2
(a) 54.01, (6) 26.05, (c) 85.69, (d) 17.03,
What
is
K CO + HC1 -> KHCOs + KC1? What the gram-equivalent H PO in the reaction H PO + 2NaOH -> Na HPO + 2H O?
3
the gram-milliequivalent weight of

is
8 4 2
KsCOs
2
in the reaction
weight of
Ans.
440.
0.1382 gram.
49.00 grams.
of oxalic acid,
(b)
How many
grams
H C O .2H O,
2
are required to
(c)
make
(d) a liter of molar solution, half-normal solution?
liter of
normal solution,
12.61 grams.
400 ml. of
A?is.
(a)
126.1 grams,
(b)
63.00 grams,
(c)
Formic acid (HCHO2 ) is a monobasic acid that is 3.2 per cent ionized normal solution. What weight of the pure acid should be dissolved in 250.0 ml. in order to prepare a 0.2000 normal solution?
441.
in 0.20
Ans.
442.
2.301 grams.
What
(a)
weight of
CaO
is
of a one-hundredth molar solution of
necessary to prepare the following: (a) 500 ml. Ca(OH) 2 (6) 30.63 ml. of N/100 Ca(OH) 2 ?
,
Ans.
443.
0.2804 gram,
is
(b)
0.008588 gram.
What
the normality of a sulfurous acid solution containing 6.32
grams of S0 2 per liter? Of an ammonium hydroxide solution containing 17.5 grams of NH3 in 480 ml. of solution? Ans. 0.197 N. 2.14 N.
444. A solution of hydrochloric acid has a specific gravity of 1.200 and contains 39.11 per cent HC1 by weight. Calculate (a) the molar concentra-
tion of the solution, (b) the normality of the solution, (c) the equivalent weights of HC1 in every 750 ml. of solution.
161
number
of
gram-
Ans.
446.
(a) 12.87
molar,
(6)
12.87 N,
(c)
9.65.
A solution of sulfuric
15.71 per cent
Ans.
446.
H2SO4 by weight. 3.524 N.
acid has a specific gravity of 1.100 and contains What is the normality of the solution?
Assuming complete neutralization

(b)
in each case,
alent weights of the following substances

(a)
when
2,
LiOH,
H SO
2
4, (r)
Fe2 O3
(</)
HC H O
2
3
(e)
what are the equivacting as acids and bases? cream of tartar (KHC 4 H4O6 ).
447.
How many How many How many

and
grams
of II 2 SO4 does a liter of 0.1000
sulfuric acid
solution contain?
448.
milliliters of
HC1 by
water?
449.
weight) are required to
HC1 (sp. gr. 1.200, containing 39.11 per cent make a liter of N/10 solution by dilution with
oxalic acid
grams of hydrated
(H 2 C 2 O4 .2H 2 0) must be
0.1230
dissolved
diluted to exactly one liter to
make a
N solution for use
as an acid?
= 94.50), is a monobasic 460. Chloracetic acid, 2 C1.COOH (mol. wt. 3 How many grams of the acid acid with an ionization constant of 1.6 X 10~ should be dissolved in 300.0 ml. of solution in order to prepare a half-normal
CH
solution?
2 4 .H 2 C 2 O 4 .2H 2 O) water and diluted to exactly 780 ml. to make a 0.05100 solution for use as an acid?
451.
How many grams of pure potassium tetroxalate (KHC O

in
must be dissolved
452.
How many
milliliters of sulfuric acid (sp. gr. 1.200,
per cent
453.
H SO
2
by
weight) are required to
make one
liter of
containing 27.32 solution 0.4980
by dilution with water?
What
is
gravity of 1.839
the normality of a sulfuric acid solution that has a and contains 95.0 per cent H2 SO4 by weight?
specific
454. If 75.0 milliliters of hydrochloric acid (sp. gr. 1.100, containing 20.01 per cent hydrochloric acid by weight) have been diluted to 900 ml., what is the normality of the acid?
milliliter
could a solution of HC1 be prepared of such normality that each would represent 0.01000 gram of NaNO2 when the latter is determined by reducing to an ammonium salt, distilling the NH3 with excess caustic alkali, and titrating the NH 3 with the standard HC1?
455.
456.
How
0.2000 N solution of barium hydroxide is to be prepared from pure .8H 2 O crystals that have lost part of their water of crystallization. Ba(OH) How may the solution be made if no standardized reagents are available? State specifically the treatment given and the weight and volume used.
A
2
69.
Normality of a Solution
Made by Mixing
Similar
Comdis-
ponents.
When
several similar
components are mixed and
162
solved in water, the normality of the resulting solution is determined by calculating the total number of equivalent weights
present in a
liter of solution.
EXAMPLE.
NaOH
3.00 grams of solid and 5.00 grams of solid are mixed, dissolved in water, and the solution made up
If
is
KOH
to 1,500 ml., what
the normality of the solution as a base?

of equivalent weights of
,
SOLUTION:
The number
KOH in 1,500
is
mL
i
3.00
1S
KOH
3.00
5630"
,, T , r In l hter thcre 1S
.
3.00
500
1,000
equivalent weight of
also
of
KOH.
-
In a
liter of
the solution there
^^\ x r?S = 0833 equivalent weight of NaOH. A total 0.0356 + 0.0833 = 0.1189 equivalent weight of base in a liter
of the solution as a base 0.1189
y
makes the normality

What
N.
Ans.
Problems
467.
is
the normality of an alkali solution
grams of NaOH (99.5 per cent NaOH, 0.5 per cent H 2 O) pure Ba(OII)2.8H2O in water and diluting to 850 ml.? Ans. 0.267 N.
made by
arid 9.42
dissolving 6.73 grams of
of
468. If 50.00 ml. of sulfuric acid (sp. gr. 1.420, containing 52.15 per cent 2 SO4 by weight) and 50.00 ml. of sulfuric acid (sp. gr. 1.840, containing
95.60 per cent 2 SO4 by weight) are mixed and diluted to 1,500 ml., what the normality of the solution as an acid?
is
Ans.
1.699 N.
459. If 50.00 ml. of a solution containing 5.000 grams of 50.00 ml. of a solution containing 5.000 grains of KOH, what
of the mixture before and after dilution to 116.3 ml.?
Arts.
NaOH are added to

is
the normality
2.141 N, 1.841 N.
contains 2.00 per cent by weight of Na 2 460. If a sample of 3 of and if 40.0 grams are dissolved in water cent 6.00 and 2 by weight per
NaOH
CO
HO
and diluted to a liter, what is the normality base? Assume complete neutralization.
Ans.
0.935 N.
of the resulting solution as a
461. If 50.00
grams
of a solid dibasic acid (mol. wt. 126.0) are
mixed with
25.00 grams of a solid monobasic acid (mol. wt. 122.0) and the mixture is dissolved and diluted to 2,500 ml., what is the normality of the solution as
an acid?
Ans.
462.
0.3995 N.
What
is
the normality as an acid of a solution

in
following
components? Assume no change
made by mixing the volume due to chemical effects.
(a)
163
,
160 ml. of 0.3050
HC1,
(6)
containing 1.621 grams of IIC1,
(d)
300 ml. of half-molar H 2 SO 4 (c) 140 ml. 200 ml. containing 1.010 grams of II 2 SO 4
.
Ans. 0.517 N.
463. In preparing an alkaline solution for use in volumetric work, a student mixed exactly 46.32 grams of pure KOH and 27.64 grams of pure NaOH and, after dissolving in water, diluted the solution to exactly one liter. How many
milliliters of 1.022
HC1
are necessary to neutralize 50.00 ml. of the basic
solution?
464. One gram of a mixture of 50.00 per cent anhydrous sodium carbonate and 50.00 per cent anhydrous potassium carbonate is dissolved in water and
17.36 ml. of 1.075
How many
465.
milliliters of 1.075
N acrid are added. Is the resulting solution acid or alkaline? N acid or base will have to be added to make
the solution exactly neutral?
What would be
by mixing the following amounts
solution, (6)
the approximate normality of an acid solution made of II 2 SO 4 solutions? (a) 160 ml. of 0.3050 300 ml. of 0.4163 molar solution, (c) 175 ml. of solution con-
taining 22.10 grams 17.01 per cent 2 SO 4
H SO
2
4,
(d)
250 ml. of solution
(sp. gr. 1.120,
containing
by weight).
466. What is the normality of an alkali solution made by mixing 50.0 ml. of a solution containing 5.00 grains of with 100 ml. of a solution containing 2.90 grams of Ba(OH) 2 .8II 2 and diluting with water to 250 ml.?
NaOH
70. Volume-normality-milliequivalent Relationship. normal solution contains one gram-equivalent of solute per liter of solution, or one gram-milliequivalent weight per milliliter of solution.
It follows that the product of the
number
of milliliters of a given
solution
and the normality
of the solution
must give the number
of milliequivalents of solute present, or
ml.
X N = number
of milliequivalents
where ml.
= =
volume, milliliters normality
This simple relationship is the basis of most calculations involving simple volume relationships between solutions and is illustrated
in the following sections. 71. Adjusting Solution to a Desired Normality. solution with a given normality is often found to be too concentrated or
too dilute for the purpose for which it is to be used. In order to decrease its concentration, water is usually added; and in order to increase its concentration, a solution is added which contains the solute in greater concentration than the one given. The
164

in each case
amounts required
calculation.
may
be determined by simple
EXAMPLE
solution
To what volume must 750.0 ml. of a 2.400 normal be diluted in order to make it 1.760 normal?
I.
:
SOLUTION
Before diluting,
number
of gram-milliequivalents
=
After diluting to x ml., these would be
750.0
2.400
1,800
1,800 gm.-milliequivalents in x ml.
x
Solving,
= normality =
x = 1,023 ml.
1.760
Ans.
EXAMPLE
II.
How much
0.600 normal base must be added
to 750 ml. of a 0.200 normal base in order that the resulting solution shall be 0.300 normal?
SOLUTION
Let x =
milliliters of
0.600
N base added
= 750
Total volume after dilution Total number
+x
=
0.200)
of gram-milliequivalents present
Resulting normality (number of gram-milliequivalents per
(750
0.200) -
frA 750
fr
+x
i
is
(750
(O.GOOr)
milliliter)
U.
0.300
+ O.GOOx _ -
= 250
Problems
ml.
Ans.
467. Each milliliter of a solution of sodium carbonate contains exactly To what volume must 100 ml. of the solution 0.0109 gram of pure Na2 CO 3 be diluted to make it exactly N/100?
.
Ans.
468.
to
2,056 ml.
What volumes
liter of
of 3.00
N and 6.00 N hydrochloric acid must be mixed
make a
Ans.
469.
5.00
N acid?
standardized gravimetrically, and
.
667 ml. 6 N, 333 ml. 3 N.
solution of sulfuric acid
it is
found that 25.00 ml. will precipitate 0.3059 gram of BaSO 4 To what volume must a liter of the acid be diluted in order to be exactly N/10?
Ans.
1,047 ml.
470.
165
solution of sodium hydroxide is found on analysis to be 0.5374 normal, and a liter of it is available. How many milliliters of 1.000 solution must be added in order to make the resulting solution 0.6000 normal?
N NaOH
Ans.
471.
156.5 ml.
barium water must be added to 760 ml. of 0.2500 hydroxide solution in order to prepare a tenth-normal solution? How many grams of Ba(OH)2.8H 2 O must be dissolved and diluted to 400 ml. to prepare a twelfth-normal solution? How many moles per liter, and how many gramequivalent weights per liter does this last solution contain?
How much
Ans.
weight.
3,040 ml.
5.26 grams.
0.04167 mole, 0.08333 gram-equivalent
2 S0 4 (sp. gr. 1.80, containing the equivalent of 472. A 10-ml. pipetful of 80.0 per cent SO 3 by weight) is diluted to 500 ml. What is the normality of 3 PO 4 should be the solution as an acid? How many milliliters of 4.00 molar added to this solution so that the resulting mixture will be 1.00 normal as an 4 takes place? acid in reactions where neutralization to Na 2 SO 4 and Na2
HPO
Ans.
473.
0.719 N.
20.1ml.
of 0.2063
What volume
N KOH
must be added to 150.0 ml.
of
in order that the resulting solution shall have the same basic 0.1320 which contains 15.50 grams of Ba(OII) 2 per liter? solution a as strength
N KOH
Ans.
288.6 ml.
474.
liters of
What volumes
0.200
of 0.500
and 0.100
HC1 must be mixed

liter of
to give
acid?
milliliters of
it
2
476.
How many
sulfuric acid to
make
water must be added to a exactly 0.1000 N?

4
0.1672
containing the equivalent of 48.7 per cent of combined SOs by weight) are diluted to 400 ml., what is the normality of the solution as an acid? What volume of 6.00 molar IT 2 SO 4 should be added
476. If 10.0 ml. of
(sp. gr. 1.50
H SO
to this in order to
make
the resulting mixture 1.00 normal as an acid?

2
solution (sp. gr. 1.080, containing 8.00 per cent Na 2 3 by weight) are diluted to 50.0 ml, what is the normality of the result2 3 solution should be ing solution as a base? What volume of 4.00 molar 1.00 normal? mixture will be added to this solution so that the resulting
477. If 10.0 ml. of
3
Na CO
CO
K C0
sulfuric acid. graduated flask contains 150.0 ml. of 0.2000 is the solution sulfuric brought up to acid, By addition of more concentrated was the What be N. 0.3000 to the mark and after mixing is found exactly normality of the acid added?
478.
A 500-ml.
2 SO 4 per of sulfuric acid (containing 0.150 gram of of sulfuric acid ml. 250 (sp. gr. 1.035, conmilliliter) should be added to in order that the 2 S0 4 by weight) resulting solution taining 5.23 per cent
479.
What volume
shall be one-molar?
166
480.
chemist desires to prepare approximately 14.00 liters of exactly How many grams of the solid should be weighed out? After preparing 14.00 liters of the solution, the analyst standardizes it and What volume of 6.00 N NaOH should be finds it to be actually 0.4895 N. added to bring the solution up to half normal? After adding approximately this amount, the analyst standardizes the solution and finds it to be 0.5010 N.
0.5000
NaOII.
How much
72.
water should
now be added?
Volume and Normality Relationships between Reacting
Since a gram-milliequivalent weight of an acid will just neutralize a gram-mil liequivalent weight of a base and since the number of milliequivalents in each case is found by multiplySolutions.
ing the number of millilitcrs of solution by its normality, we have the following simple relationship between two reacting solutions:
ml.,i
X N^ =
ml.B
X N#
by determining what with a definite volume of another solution the normality of which is already known. The normalities of the two solutions will then be in inverse ratio to the respecsolution can therefore be standardized
of
it
volume
will exactly react
Thus 50 ml. of any half-normal acid will neutralize 50 ml. of any half-normal base, or 100 ml. of quarternormal base, since the solutions contain the same number of
tive
volumes used.
equivalent weights of reacting substance (i.e., 25 gram-milliequivaalkali solution (30 milliTo neutralize 60 ml. of 0.5 lents).
(30 milliequivalents) will be required regardless of the chemical composition of the acid or alkali used. The chemical compositions of the reacting substances
equivalents), 15 ml. of 2
acid
are taken into account in preparing their standard solutions. EXAMPLE. What is the normality of a solution of 2 SO 4
if
27.80 ml. are required to neutralize a 25-ml. pipetful of 0.4820
N alkali?
SOLUTION:
27.80
x x
= =
25.00
0.4820
0.4334 N.
Ans.
Problems
481.
How many
milliliters
of
required to neutralize 5 ml. of (a)

(d)
normal sodium hydroxide solution are N HC1, (6) N/2 IIC1, (c) N/5 H2SO4
,
N/5 HC1?
(a)
Ans.
ml,
(6) 2.5 ml., (c) 1 ml., (d) 1
ml.
482.
167
solution of
HC1
How many
Ans.
483.
milliliters of
half-normal
contains 0.1243 gram-equivalent of HC1 per liter. solution are necessary to neutralize
KOH
10.00 ml. of the acid?
2.486 ml.
normal
Ans.
A solution of H SO is 0.1372 normal. How many milliliters of 0.1421 KOH solution are required to neutralize 13.72 ml. of the acid?
2
13.24 ml.
484. Convert 42.95 ml. of 0.1372 normal hydrochloric acid to the equivalent
volume
Ans.
of
normal solution.
5.892 ml.
HC1 from 42.00 ml. of 0.2000 N HC1 by volumes of normal acid. Express the the to both values equivalent converting answer in terms of (a) milliliters of 1.000 N HC1, (6) number of milliequivalents of IIC1, (c) number of milliliters of 0.5000 N NaOII.
486. Subtract 34.37 ml. of 0.1972
Ans.
486.
(a)
1.622
ml,
(6) 1.622, (c)
3.244 ml.
To
KOH were required.

Ans.
487.
neutralize 10.00 ml. of dilute acetic acid, 13.12 ml. of 0.1078 What was the normality of the acid?
0.1415 N.
A solution containing 31.21
ml. of 0.1000
,
2 SO 4 and containing 98.53 ml. of 0.5000 added. Is the resulting solution acid or alkaline?
NH
it
N HC1 is added to a solution 50.00 ml. of 1.002 N KOH are

How many
milliliters of
0.3333
acid or alkali will
make
exactly neutral?
Ans.
Acid.
6.85 ml. of alkali.
488. If 50.00 ml. of 1.087 normal

of a solid substance having
HC1
are added to 28.00 ml. of a solution

alkali is
an alkaline reaction, the
more than neu-
alkali to make the solution It then requires 10.00 ml. of 0.1021 tralized. of base per milliliter did the exactly neutral. How many milliequivalents what was its normality as an original solution of solid substance contain, and
alkali?
Ans.
1.904, 1.904
N.
489. Given: Standard sulfuric acid
How many
0.1096 Standard sodium hydroxide milliliters of the sodium hydroxide solution are equivalent to
= =
0.1072
N N
26.42 ml. of the sulfuric acid solution?

490. If 50.0 ml. of 6.00
ammonium
is
hydrochloric acid are mixed, what ammonium chloride solution?

491.
hydroxide and 50.0 ml. of 6.00 the approximate normality of the resulting
How many milliliters of 0.300 N II
SO4 will be required to

3
(a) neutralize
2,
30.0 ml. of 0.500
N KOH,
(b)
neutralize 30.0 ml. of 0.500
tralize 20.0 ml. of

(d)
a solution containing 10.02 grams of a precipitate of BaSO4 weighing 0.4320 gram? give
N Ba(OH) KHCO per
(c)
neu-
100 ml.,
168
492.

1.000 ml.
NaOH o
HC1 =
1.012 ml.
HC1
0.4767
If 100.0 ml. of
preparing an exactly
the alkali have been diluted to 500.0 ml. with the idea of N/10 solution, how much too large is the volume?
73. Determination of the Normality of a Solution.
solution
be standardized (i.e., its normality may be determined) in a variety of ways. In a few specific cases, it is possible to prepare a standard solution by accurately weighing out the solute, This method is dissolving, and diluting to a definite volume. of such can be weighed to solutions substances as applicable only out accurately and the composition and purity of which are definitely known. In some cases, it is possible to determine the normality of a given solution by gravimetric methods, i.e., by taking a definite
may
volume of solution and precipitating the principal constituent in the form of a weighable compound of known composition. From
the weight of this
compound the weight

is
ume
of solution
taken
calculated.
of the solute in the volThis gives a direct measure
For example, if a certain volume of hydrochloric acid is treated with an excess of silver nitrate, the weight of the precipitated silver chloride is a measure of the weight of hydrogen chloride in a liter of the acid. Since a liter of normal hydrochloric
of the normality.
acid contains 36.47 grams of HC1, the normality of the solution

is
found by direct proportion.
A solution is most
the exact volume
often standardized, however, by determining of required to react with a known weight of

it
substance of
cent pure). contains one gram-equivalent weight of that acid and therefore must just neutralize one gram-equivalent weight of any base, or
known purity (usually, but not necessarily, 100 per One liter of a normal solution of an acid, for example,
one
milliliter (a
more convenient unit

milliliter
work)
of the acid will neutralize
of *any base.
One
for ordinary experimental one gram-milliequivalent weight of normal acid will just neutralize
one milliequivalent weight in grams of any base.

it will
3 /2,000 = 0.06910 gram of pure potassium carcarbonate, K2CO3/2,000 = 0.04000 gram of pure sodium hydroxide. bonate, or NaOH/ 1,000 2
neutralize
Na C0
= 0.05300 gram
of pure
For example, sodium
If 1 ml. of
an acid solution were found to neutralize 0.1060 gram
(i.e.,
169
2 gram-milliequivalents) of pure sodium carbonate, the acid would be two-normal. If 1 ml. of an acid solution were found to
gram (}^ gram-milliequivalent) of pure sodium acid would be one-half normal. The same reasonthe hydroxide, ing holds true for the standardization of alkali solutions against acids and, as will be seen later, for the standardization of solutions of oxidizing, reducing, and precipitating agents. In calculating the normality of a solution standardized in this way, the
neutralize 0.02000
number
of
grams
of pure standardizing agent divided
by
its milli-
equivalent weight gives the number of gram-milliequivalents present. This must be the same as the number of gram-milliequivalents
of substance in the solution used.
Since this equals the
number
of milliliters times the normality,
ml. 8
or
X N. =
__
3
grams*
ml.,
ex
where
is
e x is
the milliequivalent weight of pure substance x which

s.
titrated with solution
sample of pure oxalic acid (H2C 2 O4.2H 2 O) weighs 0.2000 gram and requires exactly 30.12 ml. of potassium hydroxide solution for complete neutralization. What is the normality of
the
EXAMPLE.
KOH solution?
:
SOLUTION
The
milliequivalent weight of oxalic acid
is
200
The number
of
milliequivalents
of
oxalic
acid
present
is
The 0.2000/0.06303. N. is 30.12 X quired

'
number
of
milliequivalents of
KOH
re-
OA1x, XT 30 12XN==
0.2000
006303
0.1053.
N
74. Conversion of
Ans.
In general, the
initial
Data
to Milliequivalents.
student
will usually find that the
most satisfactory
step in
of
solving problems
in analytical chemistry is to convert
amounts
170
lents of these substances.
reacting substances to the corresponding number of milliequivaSince the number of milliequivalents
of reacting substances are the same, such problems resolve themThe folselves into the simplest types of algebraic equations.
lowing three formulas are of general applicability. 1. Solution s of given normality:

ml.,
2.
X N, =
no. of me.-wts. of solute
Solution s of given specific gravity and percentage composi-
tion:
ml. 8
sp. gr. s
percentage x in solution
j-QQ
no. of me.-wts. of solute
ex
3.
Solid x
=
ex
no. of me.-wts. of solid
where
ex
gram-milliequivalent weight of solid or solute
in gravimetric analysis, the chemical factor (Sec. 52) expresses nothing more than a ratio between two equivalent or milliequivalent weights. For example, the chemical factor 2Fe/Fe2O 3
Even
represents the weight of iron equivalent to a unit weight of ferric
^ L r,n ^> which 6203/2,000 ratio of the milliequivalent weights of the two substances.
oxide.
It is identical to the fraction
,..
is
the
Jp
Problems
hydrochloric acid solution is of such strength that 45.62 ml. are equivalent to 1.600 grams of pure Na 2 CO 3 Calculate: (a) the number of gramequivalents of Na 2 CO 3 neutralized by 1.000 liter of the acid, (6) the number
493.
.
of gram-milliequivalents of (c) the normality of the acid.
Na CO
2
neutralized
by 1.000
ml. of the acid,
Ans.
494.
(a) 0.6616, (6) 0.6616, (c)
0.6616
1ST.
What is
neutralize the
NH
the normality of a solution of HC1 if 20.00 ml. are required to 3 that can be liberated from 4 millimoles of (NH 4 ) 2 SO 4 ?
Ans.
496.
0.4000 N.
How many milliliters of 3.100 N NaOH will be neutralized by

(6)
(a)
105.0
ml. of II 2 SO 4 (sp. gr. 1.050),
10.50 grams of
SO
3?
Ans.
53.44 ml., 84.61 ml.
496. Three millimoles of pure thiourea,
CS(NH2
) 2,
are digested with conbisulfate.
centrated
H SO
2
and the nitrogen thereby converted to ammonium
Excess
171
NaOH
-
is
added and the liberated NII 3
is
2
(1.00 ml.
2.00 ml.
NaOH ^
caught in 25.0 ml. of

2
H SO4
2
0.0315 gram
H C O .2H O).
4
2
The
excess acid
then requires 20.0 ml. of KOH. How many millimoles of P2 O 6 would each be equivalent to in the neutralization of milliliter of the 3 PO 4 to the of 2 HPO4? forming point
KOH K
Ans. 0.0813 millimoles.

10-ml. pipetful of dilute sulfurie acid was standardized gravimetrically by adding an excess of BaCl 2 filtering, igniting, and weighing the Calculate resulting precipitate. The weight was found to be 0.2762 gram.
497.
the normality of the acid.
Ans.
498.
0.236G N.
The normality
of a sulfuric acid solution
is
0.5278.
If 38.61
ml.
of the acid are equivalent to 31.27 ml. of a solution of NaOH, calculate the normality of the NaOH. If 38.61 ml. of the acid are equivalent to 62.54 ml. of a solution of Ba(OII) 2
,
what
is
the normality of the
Ba(OH) 2 ?
Ans.
0.6516 N.
0.3258 N.
a.
499. Calculate the normality of
solution of hydrochloric acid
and
of
sodium hydroxide from the following data:

1.000 ml. of
39.81 ml. of
H(a ~ HC1 o
0.9492 ml. of
NaOH
0.6293 gram of AgCl

0.1162 N.
Ans.
600.
IIC1
0.1105 N,
NaOH =
weighs 1.0000 gram and requires 40.10 ml. of a solution of HC1 for neutralization. What is the normality of the acid? What volume of sulfuric acid of the same normality would be required for the
sample of pure
CaC0 3
same weight
of the acid?
of
CaCO
3?
What volume
of
2 4
will neutralize 1.420
grams
of KOH solution of which 20.00 ml. KHC O .H O would be neutralized by 50.32 ml.
2
Ans.
601.
0.4985 N.
40.10ml.
51.59ml.
a sample of sodium carbonate (99.20 per cent pure Na2 C0 3 ) 1.0500 grams are added 48.24 ml. of a solution of acid. This is in weighing The resulting excess of the amount required for complete neutralization. solution is brought back to the neutral point with exactly 1.31 ml. of sodium hydroxide solution of which 1.000 ml. is equivalent to 1.010 ml. of the acid. Calculate the normality of the acid.
To
Ans. 0.4189 N.
602. In standardizing
lent weight
an
alkali against 0.1200
gram
114.7), 38.92
ml
of the alkali are
added before
of a solid acid (equivait is realized
that the end point has been overstepped. By introducing 0.0050 gram of 2 C 2 04.2H 2 O into the solution, it is found that 0.58 ml. of the alkali is pure required to make the solution neutral. What is the normality of the alkali?
Ans.
0.02850 N.
172
603.
A solution of sulfuric acid was standardized against calcium carbonate
containing 91.90 per cent CaCOs and no other basic material. The sample weighing 0.7242 gram was titrated by adding an excess of acid (29.97 ml.), and the excess was titrated with 10.27 ml. of NaOH solution (1.000 ml. of the
acid
1.024 ml. of the
NaOH).
Calculate the normality of each solution.
Ans.
604.
8
H SO =
2
0.6664 N.
NaOH =
0.6507 N.
A
4
KHC H O4)
One
6.00
sample of pure potassium acid phthalate (a monobasic acid, weighing 4.070 grams is titrated with NaOH solution and back2
titrated with
HCL NaOH required = 46.40 ml.; HC1 required = 5.35 ml. HC1 ^ 0.01600 gram Na O. How much water or how much N NaOH must be added to 500 ml. of the NaOH to bring it to 0.5000 N?
milliliter
Ans.
0.96 ml. of 6
NaOH.
0.0930 II 2 C 2 O4 .2H 2 0.850 ml. HOI.
606. 10.0 ml.
1.00 ml.
NaOH o NaOH o
606.
if
What is the normality of the II Cl solution? What would be the normality of a solution of
(a)
HC1 and
(6)
H SO
2
4,
40.0 ml. of the acid are required to neutralize 0.500 2 CO 3 ? taining 95.0 per cent total alkali calculated as
gram
of pearl ash con-
trated
Three millimoles of pure urea, CO(NH 2 ) 2 are digested with concen2 4 and the nitrogen is thereby converted to ammonium bisulfate. Excess NaOH is added and the liberated NH 3 is caught in a 25-ml. pipetful of
607.
,
H S0
2
0.5200
N II SO
4.
2
How many milliliters of NaOH

2
4 2
(each milliliter will neutralize
0.01640 gram
be required to neutralize the excess acid? How many millimoles of hydrated Al 2Oa will each milliliter of the above II 2 SO4 be capable of reacting with to form A1 2 (SO4) 8 ?
will
H C O .2H O)
is
KHC
prepared by dissolving 19.264 grams of pure and diluting to exactly 900 ml. Fifty milliliters of this solution are neutralized by 35.00 ml. of solution. What is the normality of each solution?
2
608.
An
acid solution
2
.H 2
CO
.2H 2
in water
KOH
609. 1.000 ml.
1.000 ml.
NaOH o 0.0302 gram H C O HC1 o 0.1123 gram BaC0

2 2
.2H 2O
the ratio by volume of HC1 to NaOH? How much solid NaOH must be added to 800 ml. of the alkali solution so that when the resulting
What
is
is diluted to 1,000 ml. it will be 0.5000 N? How much water must be added to 1,000 ml. of the HC1 to make it 0.5000 N? What is the value of 1.000 ml. of the original NaOH in terms of grams of benzoic acid (HC 7 H 6 O 2 )?
solution
610.
neutralize (a) 32.35 ml. of
What is the normality of a solution of KOH if 20.60 ml. are required to H2 SO4 (sp. gr. 1.160), (b) 1.000 gram of P2O5 (forming
K HPO )?
2
611.
(a)
How many
milliliters of
H SO
2
(sp. gr. 1.105) will
20.00 ml. of 2.680

612. 1.000 ml.
be neutralized by
NaOH,
=0=
(6)
5.100 grams of
Fe2O3 ?
1.000 ml.
NaOH HC1 o
1.342 ml.
HC1
0.0225
gram CaC0 3
How much
solution to
173
water must be added to 1,000 ml. of the sodium hydroxide it half normal? How much hydrochloric acid (sp. gr. 1.190, containing 37.23 per cent HC1 by weight) must be added to 1,000 ml. of the arid solution to make it half normal?
make
613. Pure dry
50.00 ml. of 0.1024
sodium carbonate weighing 0.1042 gram is dissolved in N sulfuric acid and the solution heated to boiling to expel
the carbon dioxide liberated by the reaction. The solution is then titrated with 0.1120 sodium hydroxide. What volume of the base is necessary to
neutralize the solution?

614. Calculate the normality of a solution of
NaOH
from the following
data:
Weight
of
potassium acid phthalate (KHC 8H404) = 4.119 grams. NaOH used = 42.18 ml. HC1 used - 3.10 ml. 1.000 ml. HC1 =0= 0.02577 gram 2O
What volume
the
of 2.000
N NaOH
or of water should be added to 750 ml. of
NaOH
in order to bring it to 0.5000
N?
76. Calculation of Percentage Purity from Titration Values. Just as the normality of a solution can be found from the volume required to react with a definite weight of substance of known
purity, the percentage purity of a substance can be determined from the volume of a solution of known normality required to
milliliter of
react with a definite weight of the substance. For example, one normal alkali solution will neutralize one milliequiva-
grams of any acid. If an acid is titrated with normal alkali and exactly two milliliters of the latter are required, it follows that two gram-milliequivalent weights of the acid must be present. If two milliliters of two normal alkali are required, then four gram-milliequivalent weights of the acid must be present. Jri other words, the number of milliliters multiplied by the normal
lent weight in
value of the solution will give the number of milliequivalents (in grams) of substance reacted upon. The number of gram-milliequivalents thus found multiplied by the milliequivalent weight of the substance reacted upon will give the number of grams of
that substance.
is
the percentage is desired, all that is necessary to divide this weight by the weight of sample taken and multiply
If
by
100.
In general, therefore, if a substance x requires a certain number of milliliters of a solution s of normality and if e is the milli-
equivalent weight of the substance,
174
and
iTr
XN, X inn = X 100 n r^ per cent* Weight sample

ml,
ex
,
oi
ml.,
of
X N* X
ex
= grams*
soda ash (impure Na2 CO3) is titrated with half-normal sulfuric acid. If the sample weighs 1.100 grams and requires 35.00 ml. of the acid for complete neutralization, what is the percentage of Na^COs in the ash, assuming no other active component to be present? SOLUTION: One milliliter of normal acid will neutralize one
EXAMPLE
I.
A sample
gram-milliequivalent weight of any base. Thirty-five milliliters of 0.5000 acid will neutralize 35.00X0.5000= 17.50 gram-
milliequivalent weights of
any base.
weight of Na2 CO 3 is Na 2 CO 3 /2,000 0.5000 sulfuric acid will react with
Since the milliequivalent 0.05300, 35.00 ml. of the
35.00
X 0.5000 X
0.05300
0.9275 gram of
Na C03
2
As
weight is contained in a sample weighing 1.100 grams, the percentage of Na 2 CO 3 in the sample is
this
X ^77^ l.luu
It is
100
84.32 per cent.
Ans.
important to remember that the normality of a solution merely expresses the ratio of its concentration to that of a solution containing one gram-equivalent weight of solute per liter Consequently, if the normality of a (i.e., a normal solution). of a definite volume of it in terms value the solution is known, of other elements, compounds, or radicals can be found directly, even though the solution may not be capable of reacting directly
with these elements, compounds, or radicals. Thus, the weight of hydrogen chloride in 10.00 ml. of 0.1000 hydrochloric acid is
10.00
X 0.1000 X TT^ =
0.1000
0.03G47 gram
The weight
of silver chloride precipitated
by adding an
excess of
silver nitrate to 10.00 ml. of
N hydrochloric acid is
0.1433 gram
10.00
0.1000
~=
The weight
175
of silver sulfate equivalent to the silver in the silver
chloride precipitated by adding an excess of silver nitrate to 10.00 ml. of 0.1000 hydrochloric acid is
10.00
0.1000
0.1559
gram
The weight
an excess
of
of
barium in the barium sulfate obtained by adding barium chloride to the silver sulfate above is
10.00
0.1000
X o-^ =
0.06868 gram
In other words, as in the case of gravimetric computations, it is not necessary to calculate the weights of the intermediate product From the milliequivalent weight of the substance of a reaction. required, the weight of that substance can be determined directly.
EXAMPLE IT. Given the same conditions as in Example what would be the percentage of CO 2 in the soda ash?
SOLUTION:
35.00
I,
0.5000
17.50 gram-milliequivalents of
CO2
17.50
X X
~=
z,uuu 10
0.3850 gram of
C02
C
2-
= 35
P61 cent
"
EXAMPLE
ide
is
III.
A 0.3000-gram sample of impure magnesium ox.
which 3.000 ml. =0= The end point is overstepped on the ad0.04503 gram CaCO 3 dition of 48.00 ml. of the acid, and the solution becomes neutral on the further addition of 2.40 ml. of 0.4000 N sodium hydroxide.
titrated with hydrochloric acid solution of
What
is
the percentage of
MgO in the
sample?
SOLUTION:
1
ml.
HC1
=0=
^55 ^ 0.01501 gram

of
of
CaCO3
Normality
48.00
HC1 =
14.40
milliequivalents of
milliequivalents of
X 2.40 X 14.40 -
0.3000 0.4000
0.96
'
= = =
HC1
0.96
13.44
NaOH
An,.
net milliequivalents
90.33 per cent
13 "4
72 000
X MO -
MgO.
176

Methods.
Instead of titrating a sub-
76. Volumetric Indirect
stance directly with a standard solution, it is frequently more feasible to allow the substance to react with a measured amount
a given reagent and then to titrate that part of the reagent over from the reaction. This is an indirect method and is characterized by the fact that, other factors being fixed, a greater degree of purity of the sample corresponds to a smaller buret
of
left
reading.
In acidimetry and alkalimetry an outstanding example of an indirect method is the Kjeldahl method for determining nitrogen
digested with concentrated 2 S04 in the presence of a catalyst and the nitrogen in the material thus converted to ammonium bisulfate. The resulting soluin organic material.
is
The sample
tion
is
made
distilled
and the liberated ammonia gas (through a condenser) into a measured volume of standard
alkaline with
NaOH
acid
(NH 3 + H+
the
NH4+ ). The
acid remaining in the receiving

is
flask, after all
NH
has been liberated,
then titrated with
standard
NaOH
solution.
Calculation of a volumetric indirect
method is usually best made

milliequivalents of reagent
of milliequivalents used in number of milliequivalents
by determining the
the titration.
number of added, and subtracting the number

total
This difference
is
the
of desired substance.
A sample of meat scrap weighing 2.000 grams is with sulfuric acid and a catalyst. The reconcentrated digested sulting solution is made alkaline with NaOH and the liberated
EXAMPLE.
ammonia
distilled into 50.00 ml. of
0.6700
N H SO
2
4.
The
excess
for neutralization. acid then requires 30.10 ml. of 0.6520 What is the percentage of nitrogen in the meat?
N NaOH
SOLUTION:
Milliequivalents of
H SO
2
Milliequivalents of
NaOH
=
= =
50.00
30.10
X X
>
0.6700
0.6520
= =
33.50
19.62
Net
milliequivalents
33.50
3
19.62
13.88
Since, in the lent weight of
above process,
NH + H+
inA 100
NH4+
the milliequiva-
NH
X
is
NH /1,000 and that of nitrogen is N/1,000.

3
'
13.88
N/1,000
'
vx
. n 9.72 per cent.

.
Ans.
Problems
177
616. Calculate the percentage of carbon dioxide in a sample of calcium carbonate from the following data:
Total volume of 0.5000 Total volume of 0.1000
N HC1 = N NaOH =
sample
35.00 ml.
17.50 ml. 1.000
Weight
Ans.
34.65 per cent.
of
gram
of
616. Given the following data, calculate the percentage purity of a sample cream of tartar (KHC 4 II 4O 6 ):
Weight
NaOH
II 2 S0 4
sample solution used solution used

2
of
= = =
2.527 grams 25.87 ml.

1.27 ml.
1.000 ml. of 1.000 ml.
H SO - 1.120 ml. of NaOH of H SO ~ 0.02940 gram CaCO

4
2 4
Ans.
517.
95.50 per cent.
3 ) weighing 2.000 grams the alkaline strength of the ash in terms of per cent of 2 O if 20.00 ml. of the HC1 will just neutralize the 3 that can be liberated from four millimoles of (NH 4 ) 2 HPO 4 ?
A sample of pearl ash
(technical grade of
K C0
2
is
titrated with
HC1, requiring 25.00 ml.
What
is
NH
Ans.
23.55 per cent.
518. Calculate the percentage of
K CO
2
in a
sample of pearl ash from the
following data:
Weight
of sample
IIC1 used
NaOH
1.000 ml.
used
= = =
=0=
2.020 grams
49.27 ml.
2.17 ml.
HC1
NaOH =
Ans.
519.
0.02926 gram
0.3172
CaCO3
96.25 per cent.
solution,
Given four 10.00-ml. portions of 0.1000 normal hydrochloric acid (a) How many grams of pure sodium carbonate will be neutralized one by portion? (&) How many grams of K 2 O are contained in that weight
of potassium hydroxide neutralized by another portion of the acid? (r) A of is a Calcuof calcium carbonate the acid. decomposed by portion sample
weight of CaCO3 decomposed, the weight of CO2 liberated, and the 2 4 .H 2 C 2 O 4 .2H 2 O weight of CaCl 2 formed, (d) Calculate the weight of
late the
KHC
equivalent in acid strength to a portion of the HC1.
Ans. (a) 0.05300 gram. (6) 0.04710 gram, gram, 0.05550 gram, (d) 0.08473 gram.
620. Strong
(c)
0.05004 gram, 0.02200
KOH will liberate NH

distilled
ammonia can be
and
The liberated 3 from ammonium salts. and determined by absorbing it in standard acid
titrating the excess acid with standard alkali. From the following data, calculate the percentage of 3 in a sample of impure ammonium salt:
NH
178

Sample
Standard acid used Standard alkali required
= = =
1.009 grams
50.00 ml. of 0.5127

1.37 ml. of 0.5272
N N
Ans.
42.06 per cent.

is and on ignition is converted to 6 .4II 2 4 4 original sample of 0.9546 gram is ignited and the product sulfuric acid. From the data given, calculate the purity of the
521. Rochelle salt
KNaC H O
KNaCO
sample:
3.
The
titrated with
10.27 ml.
H SO used = H SO *
2
41.72 ml.
10.35 ml.
NaOH
NaOlI = 0.1297
NaOH
.
used in titrating excess acid
1.91 ml.
Ans.
522.
76.95 per cent.
A
The
sample of zinc oxide

excess acid
is
is
is
digested with 50.00 ml. of normal sulfuric
arid.
titrated with 2.96 ml. of 0.1372
normal
alkali.
The
weight of sample
sample.
2.020 grams.
Calculate the percentage of purity of the
Ans.
99.89 per cent.
623. If all of the nitrogen in 10.00 millimoles of urea, by concentrated 2 SO4 into ammonium bisulfate and
CO(NH
if,
2 )2, is converted with excess NaOH,
the
NIT3
is
liberated
and caught
in 50.00 ml. of
HC1
=0=
(1.000 ml.
^ 0.03000'gram
CaCOs), how much NaOH solution (1.000 ml. would be required to complete the titration?
A?is.
0.03465 gram
H C O4.2H O)
2 2 2
18.18 ml.
524. The percentage of protein in meat products is determined by multiplying the percentage of nitrogen as determined by the Kjeldahl method by the arbitrary factor 6.25. A sample of dried meat scrap weighing 2.000 grams
2 SO4 and mercury (catalyst) until the nitrogen digested with concentrated present has been converted to ammonium bisulfate. This is treated with excess and the liberated 3 caught in a 50-ml. pipetful of 2 SO 4
is
NaOH
NH
(1.000 ml. =c=0.01860
gram Na O).
2
NaOH
Ans.
525.
(1.000 ml.
0.1266 gram
excess acid requires 28.80 ml. of 8 4 O 4 ). potassium acid phthalate,
The
KHC H
Calculate the percentage of protein in the

53.11 per cent.
meat
scrap.
sample of milk weighing 5.00 grams is digested with concentrated 2 4 (plus a catalyst) which converts the protein nitrogen in the milk to ammonium bisulfate. Excess NaOH is added and the liberated 3 is evolved and caught in 25.0 ml. of dilute H 2 SO 4 The excess acid then requires 28.2 ml. of NaOH of which 31.0 ml. are equivalent to 25.8 ml. of the dilute H 2 SO4 The acid and base are standardized by evolving the 3 from 1.00 gram of it into H NH of the above 25.0 ml. dilute 4 C1, passing 2SO 4 and titrating pure the excess acid with the above NaOH. A volume of 11.3 ml. of the NaOH is
H SO
NH
NH
required.
The
179
arbitrary factor for converting nitrogen in milk and milk products to protein is 6.38. Calculate the percentage of protein in the above sample of
milk.
Ans.
3.30 per cent.
526.
of
From
:
the following data, calculate the percentage purity of a sample

1.000 ml.
KHSO4
1.000 ml.
HC1 o HC1 o
used used
1.206 ml.
NaOH
Na CO
2 3
Sample
HC1
NaOH
627.
= = =
0.02198 gram 1.21 18 grams

1.53 ml.
26.28 ml!
sample of Rochelle salt (KNaC 4 4O6.4H 2 0), after ignition in it to the double carbonate, is titrated with sulfuric acid, methyl orange being employed as an indicator. From the following data, calculate the percentage purity of the sample:
platinum to convert
Weight
sample 2 4 used NaOH used
of
H SO
= = =
0.9500 gram 43.65 ml.

1.72 ml.
1.000 ml. II 2 SO4
1.064 ml.
NaOH
Mg(OH) 2
j
NaOH =0.1 321 N

528.
A sample of milk
is
of
magnesia [suspension of
weighing 5.000
requiring 40.10 ml. What is the perin the sample if 20.11 ml. of the 3 will just neutralize the centage of 3 that can be liberated from five millimoles of (NH 4 ) 3 AsO 4 .5H 2 O?
grams
titrated with standard
HNO
3,
NH
MgO
HNO
529. The saponification number of a fat or oil is defined as the number of milligrams of potassium hydroxide required to saponify one gram of the fat or oil. To a sample of butter weighing 2.010 grams are added 25.00 ml.
of 0.4900 solution. After saponification is complete, 8.13 ml. of 0.5000 HC1 solution are found to be required to neutralize the excess alkali.
N KOH
What
is
the saponification
number
of the butter?
530. Samples of oxalic acid mixed with inert matter are given out for student analysis to determine by acidimetric titration the acid strength in
terms of percentage
acid tartrate
of
2 2 4 4
2
H C O .2H O would the student report in this case?

631.
H C O .2H O. However, a sample of pure potassium KHC H O is included among the samples. What percentage
2 2
6,
sample of vinegar weighing 10.52 grams
is
point is overstepped, and the solution is titrated back with standard HC1. From the following data, calculate the acidity of the vinegar in terms of percentage of acetic acid (HC 2 3O2 ) :
NaOH. The end
NaOH
HC1
1.000 ml.
used used
= -
19.03 ml.
1.50 ml.
1.000 ml.
o NaOH o
HC1
0.02500 gram Na*CO 8 0.06050 gram benzoic acid (C6
H COOH)
6
180
632.

The
arbitrary factor 6.25 is used by agricultural chemists to convert of nitrogen in meat products to percentages of protein. percentages sample of dried pork scrap is sold under a guarantee of a minimum of 70.00 per cent
protein.
is digested with sulfuric acid and a catalyst, the nitrogen to ammonium bisulfate. Treated with excess NaOII, the ammonia is liberated and caught in a 25-ml. pipetful of 2 SC>4 What is the maximum volume of (1.000 ml. o 0.02650 gram Na2 CO 3 ).
one-gram sample
all
which converts
0.5110
N NaOH
required to titrate the excess acid
if
the sample conforms to
the guarantee?
Problems in Which the Volume of Titrating Solution Bears a Given Relation to the Percentage. In commercial laboratories where many similar titrations are made each day, it is often con77.
venient to simplify computation by taking each time for analysis a weight of sample such that the volume of standard solution
bear some simple relation to the percentage of desired The advantages derived from such a procedure are the same as those discussed in Sec. 55, and the computations involved are similar in principle. In the volumetric problem, it is
used
will
constituent.
also possible to fix the weight of sample and determine the normality of the titrating solution which must be used to fulfill a
similar condition, although this type of problem is less often met with in practice. It is easier in practical work to vary a sample
weight than it is to vary a solution concentration. In cither case, however, the required weight of sample or normality of solution is best found by directly applying the formula previously derived,
viz.,
ml..
N
of
ex
100
Weight
sample
it will
per cent*
always be found that, of the five be known and a ratio will be given between two others, thus making possible the determination of the
In this type of problem,
factors involved,
two
will
fifth factor.
weight of soda ash should be taken for analysis such that the percentage of Na 2 O present may be found by acid solumultiplying by 2 the number of milliliters of 0.2000
EXAMPLE.
What
tion used in the titration?
SOLUTION:
X ml.. X 100 = per cent, X 1An m r of Weight sample

a
N
,.
ex
.,
vv
In the problem given, N and e x are known. between the ml. and the per cent whereby
ml.
181
also exists
A relation
per cent
Upon
substitution,
ml. X 0.2000 X Na2 0/2,000 T x iuu = 117

.
mi. a
Weight
0.2000
ot
&
sample
62.00/2,000
of
1QO
Weight
sample
of
Weight
sample = 0.3100 gram.
Ans.
type of problem as were emphasized in the examples in Sec. 55, namely, that a numerical difference exists between a statement such as "the number of milliliters is three times the per cent," and the statement "the per cent is found by multiplying the number of milliliters by 3." Thus, in the above example, the weight of soda ash to be taken so that each millilitcr of 0.2000 N acid shall equal
in solving this
The same precautions should be taken
% of
per cent of
1
Na O
2
is
found as follows:
0.2000
0.03100
IOQ
î
2
Weight
of
sample
Weight
of
sample = 1.240 grams.

Problems
Ans.
633.
of
NaOII
Ans.
that
sample of oxalic acid is to he analyzed by titrating with a solution is 0.1000 N. What weight of sample should be taken so that
each
milliliter of
NaOH
will represent
3 2
of
P cr cent
of
IWÔÎÔ?
1.261 grams.
534. In the analysis of oxalic acid using a one-gram sample, what must be the normality of the alkali used for titration so that the buret reading will equal one-half the percentage of I^CaO^HÔ?
Ans.
0.3173 N.
535. In the analysis of a sample of soda ash, what weight of sample should be taken so that the volume in milliliters of 0.4205 normal acid required for complete neutralization and the percentage of Na 2 CO 3 in the sample will be in the respective ratio of 8:17?
Ans.
636.
1.049 grams.
0.2000
sample of a certain acid weighed 0.8250 gram and was titrated with After the purity of the sample was calculated in terms of the of constituent percentage A, it was found that the percentage obtained was
N alkali.
182

A
as
just equal to the equivalent weight of
an
acid.
What volume
of titrating
solution
was used?
41.25 ml.
Ans.
637.
A sample
of limestone
is
is
titrated for its value as
a neutralizing agent.
one-gram sample
always taken.
What must be
the normality of the
titrating acid so that every 10 ml. will represent 4J^ per cent of the neutralizing value expressed in terms of percentage CaO?
Ans.
0.1605 N.
acidity,
638. Samples of pickling solution are to be analyzed volumetrically for and results are to be expressed in terms of milliliters 2 SC>4 (sp. gr.
1.84, containing 95.60
per cent
H SO
2
by weight).
The
specific gravity of
the pickling solution is 1.270, and a 25-ml. pipetful is taken for analysis. (a) What must be the normality of the standard alkali so that each milliliter
used
will represent 0.100 ml. of the 2 SO4? represent 1.00 per cent of pure
H SO ?
2
(6)
So that every 10.0 ml.
will
Ans.
639.
(a)
3.59 N.
(b)
0.647 N.
0.5000
weight of soda ash must be taken for analysis so that by using IIC1 for titrating (a) the buret reading will equal the percentage of Na2O, (6) three times the buret reading will equal the percentage of Na2O, (r) every 3 ml. will represent 1 per cent Na2 O, (d) each milliliter will represent
What
3 per cent Na2 O, (e) the buret reading and the percentage of Na 2O will be in the respective ratio of 2:3? Ans. (a) 1.550 grams, (6) 0.5167 gram, (c) 4.650 grams, (d) 0.5167 gram, (e) 1.033 grams.
640. What weight of calcite (impure CaCO 3 ) should be taken for analysis so that the buret reading will be times the percentage of Ca in the sample? The solution used for the titratiori is IINOa of which 2.00 nil. 1.00 ml.
2^
Ba(OH) 2 (KHC 8H 4 O4). 641. What weight of soda ash (technical Na 2 CO 3 ) should be taken for analysis so that when titrated with HC1 [1.00 ml. o 2.00 ml. Ba(OH) 2 solution o 0.0254 gram KHC 2 O 4 .H 2 C 2 O 4 .2II 2 O] the buret reading will be threesolution
=0=
0.0400 gram potassium acid phthalate
quarters of the percentage of
Na2 O
in the ash?
642. In the standardization of an acid, it was titrated against 1.000 gram of calcium carbonate (98.56 per cent pure). If 46.86 ml. of HC1 were added, the CaCOa dissolved, and the excess acid titrated with 5.21 ml. of
NaOH
solution of which 1.000 ml.
0.7896 ml. HC1, calculate the weight of crude pearl ash to be taken for analysis so that each milliliter of this HC1 will 2 O. represent 2.00 per cent
=c=
643. If 1.500
grams
the strength of the the percentage of

644.
HC1
2
KO
2 3 are taken for analysis, what must be used in order that the buret reading will indicate twice in the sample?
of crude
K CO
2,000-gram sample of nitrogenous organic matter is digested with concentrated 2 SO 4 and a catalyst until the nitrogen in the sample has been converted to 4 HSO4 By adding excess NaOH, NHa is liberated and is
NH
183
completely caught in a cold 5 per cent solution of boric acid. It is then titrated directly with standard HC1. What must be the value of each milliliter of the acid in terms of pure Na2COs if the buret reading is 2% times the percentage of nitrogen in the material?
sample of quicklime is to be analyzed for CaO and CaCOs by N HC1. It is desired to start with a 10.0-gram sample,, mix with water, dilute, and take aliquot portions of such size (a) that when titrated with HC1 [phenolphthalein being used as an indicator, in which case
646.
titrating with 0.3572
only the Ca(OH) 2 is neutralized] the number of milliliters will represent directly the percentage of CaO and (6) that, when titrated by adding an excess of HC1, heating, and titrating back with NaOH of the same normality as the HC1,
the net
number
of milliliters of
of total calcium in terms of
CaO.
HC1 used will represent directly the percentage What portions should be taken?
Determination of the Proportion in Which Components Are Present in a Pure Mixture. Problems involving the determination from titration values of the proportion in which components are present in a pure mixture are identical in principle with the so-called double chloride problems of gravimetric analysis (see
78.
and the same algebraic method of solution The same type of analysis may be be used. may conveniently applied equally well to methods of oxidation and reduction. As shown in Sec. 57, the precision of the result of an analysis of this type is usually less than that of the data given, and there is often a decrease in the number of significant figures that ma^ properly be retained in the numerical answer. EXAMPLE. If 0.5000 gram of a mixture of calcium carbonate and barium carbonate requires 30.00 ml. of 0.2500 N hydrochloric
Sec. 57,
Example
II),
acid solution for neutralization, what
is
the percentage of each
component? SOLUTION
:
Let x
y
= number = number
(1)
of of
grams grams
of
of
CaCO 3 BaCO 3
Then
x
+y
0.5000
Number
of gram-milliequivalents of
CaC0 3
present
x
0.05004
CaCOa/2,000
Number
BaC03
present
=
y 0.09869
BaCO
/2,000
184

Number
HC1 used =
30.00
0.2500
Therefore
Solving equations
(1)
and
(2)
simultaneously,
0.247 0.253
x = y =
Percentage of
CaCO =
3
247 ;rk/^s
-
100
49.4 per cent
Percentage of
79. Analysis of
titration
is
0253 BaCO 3 = X
Fuming
100
50.6 per cent
Sulfuric Acid.
Case A.
An
important
that involved in the analysis of
fuming
2
sulfuric acid
(oleum). sulfur trioxide,
This substance
may
be considered to be a solution of
sulfate,
SO 3
is
in
hydrogen
H SO
is
4,
and when no
dissolving
other component
present, the analysis
made by
a weighed sample
titrating with standard alkali. EXAMPLE I. A sample of fuming sulfuric acid weighing 1.000 gram when dissolved in water requires 21.41 ml. of 1.000 N NaOH
in water
and
solution for neutralization.
What
is
the percentage of each com-
ponent?
SOLUTION Method
Since fuming sulfuric acid is a mixture of two pure components, the problem can be solved by the method of the
I.
preceding section.
Let x
y
x
= =
weight of free
SO 3
4
weight of
1.000
H S0
2
+ y=
2
SOÔOO
When
x
y
+ H S0
= 2L41 X
4
000
/2,000
the simultaneous equations are solved,
= =
= 22.2 per cent gram S0 3 0.778 gram H 2 SO 4 = 77.8 per cent

0.222
.
S
J
'
Method
II.
of the water to
H computed in terms of H S0
2
In dissolving the oleum, the SO 3 unites with part form If the total percentage of acid is 2 SO 4
4,
the following result
is
obtained:
21.41
185
1.000
T-
H S0 /2,000 w
2
t nn 100
n 105.0 per cent

,
Since, in the original mixture, S0 3 the difference of 5.0 per cent is caused
+ H SO =
2
100.00 per cent,

for
by the water which has
combined with the

mole.
5.0
SO 3
The S0 3 and
percentage of
HO
2
combine mole
X
-
^7-7! X12VJ
SO =
= =
100.0
22.2
SO 3 H 2SO4
Method III. In dissolving the oleum, the free SOs unites with water to form H 2 SO4 (SO 3 + H 2 O -> II 2 S04 ). The percentage of total SOs (combined and free) in the original solution is found
as follows:
-21.41
1.000
SOs/2,000
-
l.UUU
-v X
4
, nn 100
85.70 per cent
Since the original solution consisted of free SO 3 combined SO 3 , and combined 2 O, the percentage of combined II 2 in the solu,
tion
is
100.00
85.70
14.30 per cent.
Percentage of original
H SO
2
= = =
14.30
Jl il 2 ij
^
)
,
Percentage of free
SO 3
II 2
Case B.
of
titration:
Fuming
sulfuric acid often contains small
amounts
SO2 which
with water forms

2
SO 3 and
is
included in the alkali
H SO + 2OH- 3
SO 8- + 2H 2 O
used as the indicator.
This
is
when phenolphthalein
is
With
methyl orange, the color change takes place at the
bisulfite stage i
H S0 + OH~ -> HSOr + II

2
present, its amount is usually determined in a separate sample by titration with a standard oxidizing agent, and the other components are then computed from the alkali titra-
In case
S0 2
is
tion values in the usual way, with a correction for the

alkali
volume of
used by the
S0 2
186

II. A sample of fuming sulfuric acid containing and SO2 weighs 1.000 gram and is found to require 80s,
EXAMPLE
H S0
2
4,
23.47 ml. of 1.000 alkali for neutralization (phenolphthalein as A separate sample shows the presence of 1.50 per indicator). cent S0 2 Find the percentages of S0 3 and 2S0 4
.
SOLUTION:
Volume
of alkali used
by SO 2 = LOQO
47
mL
Volume
of alkali used for
Percentage of
= 23.47 - 0.47 = 4 3 = 100.00 1.50 = 98.50 per HaSCX + S0 3 Let x = weight of SO 3 y = weight of H2S04 x + y = 0.9850
H S0 + S0
2
23.00 ml.
cent
fcUs/ &, \j\j\)
<3
= 23.00 X rr qr/ mn + xi2^^4/ /9 MM ÎHJU

\
1,000
Solving,
x y
= =
= 63.5 per cent gram SO 3 0.350 gram H 2 SO 4 = 35.0 per cent

0.635
Problems
546. A mixture consisting entirely of lithium carbonate and barium carbonate weighs 1.000 gram and requires 15.00 ml. of HC1 for neutralization. Calculate the percentage of BaCO 3 in the sample.
Ans.
547.
71. 2 per cent.
A mixture of pure lithium carbonate and pure strontium carbonate 0.5280 weighs gram and requires 19.82 ml. of 0.5060 N acid for neutralization. What is the percentage of Li 2 O and SrO in the sample?
SrO = 41.8 per cent. 548. What weight of barium carbonate must be added to 1.000 gram of lithium carbonate so that the mixture will require the same volume of standard acid for neutralization as would the same weight of pure calcium carbonate?
Ans.
Li 2 O
16.3 per cent,
Ans.
549.
0.716 gram.
half-gram sample of a mixture of pure
CaCOs and pure SrCO3
sulfuric acid for neutralization, requires 30.00 ml. of 0.2726 (a) What would be the loss in weight of the original sample on strong ignition? (6) Calculate the combined weight of CaS0 4 and SrS0 4 obtained above, (c) What is
the weight of
CaCO 3
in the original
(b)
sample?
(c)
Ans.
650.
(a)
0.180 gram,
0.647 gram,
of
0.218 gram.
in a mixture
is
The combined weight

and 25.44 ml.
LiOH,
.5000 gram,
of 0.5000
KOH, and Ba(OH) 2
acid are required for neutralization.
The same amount of material with
filtered is
187
CO2 gives a precipitate of BaCO3 that when found to require 5.27 ml. of the above acid for neutralization.
2
KOH, and Ba(OH) in the original sample. Ans. 0.217 gram, KOH = 0.0567 gram, Ba(OH) 2 = 0.226 grain. 661. A sample of fuming sulfuric acid, containing no SO or other impurity, on titration is found to contain 108.5 per cent acid expressed in terms of H 2 SO Calculate the percentage of free SO 3 in the sample.
Calculate the weights of LiOH,
LiOH =
4.
Ans.
662.
is
37.8 per cent.
sample of fuming
titrated,
and the percentage
sulfuric acid containing only SO 3 of total SO 3 (free and combined) is
and H 2 SO4 found to be
84.00 per cent.
What
is
the percentage of 1I 2 SO4 in the original sample?
Ans.
87.1 per cent.
663. A sample of fuming sulfuric acid containing only SO3 and H 2 SO4 weighs 1.4000 grams and requires 36.10 ml. of 0.8050 normal NaOH for neutralization. What is the percentage of each constituent in the sample?
Ans.
654.
91.98 per cent II 2 SO 4 8.02 per cent

,
SO
3.
solution of
SO 3
in
H SO
2
requires 65.10 ml. of 0.9000 normal alkali
for the titration of
a sample weighing 2.604 grams. by weight of free SO3 to H 2 SO4 in the sample?
Ans.
666.
2
What
is
the proportion
0.850.
sample of fuming sulfuric acid consisting of a solution of SO3 and A sample weighing 1.500 4 is found to contain 2.06 per cent SO 2 KOH when of N 21.64 ml. 1.500 phenolphthalcin is used as the grams requires indicator. What are the percentages of free SO 3 and H 2 SO 4 in the sample? Ans. 22.4 per cent free SO 3 75.6 per cent H 2 SO 4
A
2
SO
in
H SO
mixture of pure sodium carbonate and pure barium carbonate acid for complete 0.2000 gram requires 30.00 ml. of 0.1000 weighing neutralization. What is the percentage of each constituent in the mixture?
666.
567. A sample supposed to be pure calcium carbonate is used to standardize a solution of IIC1. The substance really was a mixture of MgCO8 and BaCOs, but the standardization was correct in spite of the erroneous assumption. Find the percentage of MgO in the original powder. 658. A mixture of BaCO3 and CaCO3 weighs 0.5000 gram. The mixture From the following data, calculate is titrated with HC1, requiring 12.90 ml. the percentage of barium in the mixture:
30.40 ml.
2.000 ml. of
HC1 ~
45.60 ml.
NaOH
NaHC O
2
NaOH
2
3 2
will neutralize
0.07460 gram of
669. Glacial acetic acid often consists of a mixture of
pure acetic acid,

hydride,
HC H O
or
CH COOH,
3
two acids, namely, and a small amount of acetic an-
(CHjCO) 2 O.
When
dissolved in water, the anhydride forms acetic
188
acid:

(CH3 CO) O
2
+ H O -> 2CH COOH. A sample of the original substance

2 3
weighing A
grams
is
for neutralization.
and requires B ml. of C normal NaOH Set up an expression showing how the percentage of acetic
dissolved in water
this single titration.
anhydride in the sample can be determined from

clearly the correct milliequivalents involved.
Express
660. A sample of P2Os is known to contain H PO as its only impurity. A sample is weighed in a closed container, the container is opened under water (P20 + 3H O -* 2H PO and the solution is titrated with standard NaOH
8
4)
to form
set
Na HPO4
2
up an
were used, normal at the end point. If A ml. of how of P the number of in the to show O& 2 grams original expression
Express
all
NaOH
mixture could be determined.

661.
milliequivalent weights.
shows the presence
N NaOH for
sulfuric acid containing no SO 2 an equivalent of 109.22 per cent H 2 SO4 Calculate the percentage composition of the sample and the percentage of combined SO 3 662. A sample of oleum weighing 1.762 grams requires 42.80 ml. of 0.8905
The
titration of a
of
sample of fuming
neutralization.
Calculate the proportion by weight of free
SO 3
.
to combined S0 3
in the sample.
663. A mixture of SO3 and 2 SO4 contains 91.18 per cent of total SO3 Calculate the volume of half-normal alkali required to titrate a solution of 1.030 grains of the mixture. What is the percentage of free SO 3 in the mixture? What is the equivalent of the mixture in terms of aqueous sulfuric acid
containing 93.19 per cent II 2 SO 4 ?

664. A mixture of pure acetic acid and acetic anhydride is dissolved in water and titrated with NaOH. The acidity of the sample expressed in terms of HC 2 3 O2 is found to be 114.0 per cent. What is the composition of the original mixture? Acetic anhydride reacts with water to form acetic acid:
<CH CO) 2O
3
+H
~>
2HC H
2
2.
used in volumetric analysis for the purpose of detecting the point at which a reaction is just comThe indicators used in acidimetry and alkalimetry are pleted. usually organic dyestuffs which are of one color in acid solution
80. Indicators.
An
indicator
is
and
of a distinctly different color in alkaline solution. They are usually in themselves either weak acids (e.g., phenolphthalein) or
methyl orange), and the change in color that they undergo can be attributed to the fact that the arrangement of the atoms in their molecules is somewhat different from the arrangement of the atoms in the molecules of their corresponding salts. Consider a weak organic acid indicator of the general formula HX. This acid ionizes as follows: HX +> H+ + X~. The undis(e.g.,
weak bases
for example, colorless; the ion is colored, usually because of a rearrangement of atoms to form a
is,
sociated molecule
HX
X~
quinoid structure.
In water solution the ionization of the acid
is
189
so slight that the color of the ion is too faint to be seen. The addition of an alkaline substance to the solution, however, by reacting with the hydrogen ion, displaces the above equilibrium
to the right
and increases the concentration of the X~ ion to the point where its color becomes visible. The ionization constant of
the above indicator
is
as follows:
mrî [HAJ
= ^'
this
anc^ * s ca^ e(^
an
type of indicator a titration is stopped when one half of the un-ionized molecules have been converted by a base to the colored ionic form, then
If it is
indicator constant.
assumed that with
[HX] = [X~] and the indicator constant
is
equal to the hydrogen-
ion concentration of the solution at the end point. Similarly, a weak basic indicator of the general formula XOII + ionizes as follows: and the ionization constant <=
XOH
X + Oil"",
[AOHJ
rv L" LJ1
(= indicator constant)
color of the
is
= K.
In water solution the
XOH molecule predominates, but the addition of acid

X~
increases the concentration of the
form and the color changes. If it is assumed that the color change is seen when three-fourths of XOH has been converted to X~, then the hydroxyl-ion concentration at the end point is equal to ^K. With a given concentration of indicator, the color change takes place at a point where the hydrogen-ion or the hydroxyl-ion concentration in the solution has attained a definite value that is
characteristic of the indicator in question. Thus, a solution containing about 0.001 per cent of phcnolphthalein turns from color-
pink when the hydroxyl-ion concentration has attained the value of about 1 X 10~ 5 mole per liter, and the corresponding hydrogen-ion concentration has therefore been reduced to about 9 1 X 10~ mole per liter (pH = 9). Figure 2 shows the approximate
less to
hydrogen-ion and hydroxyl-ion concentrations at which dilute solutions of the common indicators change color. It will be noted that on this chart each color change is spread over a certain range
Each indicator may be said to have a "range of which doubt" over the transition in shade of color is gradual; the average analyst might stop a titration anywhere within the
of
pH
values.
range in question.
81. Equivalence Point.
is
the point where the
The equivalence point in any titration amount of titrating solution added is
190
191
chemically equivalent to the amount of substance being titrated; the analyst attempts to make the end point (i.e., the point where the indicator changes color) coincide with this. In an acidimetric
or alkalimetric titration the equivalence point is not necessarily For example, in the the same as the neutral point (pH = 7). titration of acetic acid with sodium hydroxide, when the latter
has been added in an amount equivalent to the former, the acidity of the solution is the same as that resulting from dissolving
the corresponding
is
amount
of
sodium acetate
in water.
Such a
basic owing to hydrolysis of the salt. solution Similarly, in the titration of a weak base with a strong acid, the equivalence
is at a point where the solution is slightly acidic (pH < 7). Other conditions being equal, the correct indicator for a given titration is one of which the color change takes place when the solution has that pH value which exists in a solution obtained by dissolving in the same volume of water the salt formed by the In other words, an indicator should be chosen neutralization. will that change color at a pH value approximately equal to the pH value at the equivalence point. Just how that pH value can be determined is shown in the following section. In 82. Determination of pH Value at the Equivalent Point.
point
the following discussion, let us consider four general types of acidimetric titrations:
Titration of a strong acid with a strong base, or vice versa B. Titration of a weak acid with a strong base
.
C.
Titration of a
D. Titration of Let us also make use
weak base with a strong acid a weak acid with a weak base, or
of the following
vice versa
symbols:
pH =
log
JL =
-log [H+]
pOH =
log
= -log [OH-]
constant
of
Kw
= ion-product
1014
water = [H+][OH"~] =
1.0
(at
25C.)
pW =
Ka =
log
îvw
= -log
Kw -
14.0 (at
25C.)
titrated
ionization constant of the
weak acid being
192
pA =
log ==Jva
= -log Ka
weak base being
titrated
Kb =
pB =
ionization constant of the
[X+][OH-]/[XOH]
log
= -log Kb
C=
molar concentration at the equivalence point, of the salt formed by the neutralization process
20
|
Ail.
N/2 solution
diluted to 100 ml.
and
titrated with
N/2 solution
HCl+NaOH
HC 2H 8
+NaOH-
HC.H.0 9 fNH,QH
n PhenolLJphthalein
Bromthymol LJblue
f~1
Methyl red
H Methyl orange
1-1
12
16
20
24
28
Titrating solution, ml.
FIG. 3.
Acidimetric titration curves.
Case Twenty milliliters N/2 HC1 diluted to 100 ml. with water and titrated with N/2 NaOIL At the beginning of the titration, [H+] = 20 X mole per = = 0.10 molar. Therefore pH 100 ml. 1.0. As the titration pro-
(pH increases), and as the equivalence point is approached the change becomes very rapid. At the equivalence point, the solution contains only sodium chloride dissolved in water, and, since there is no appreciable hydrolysis, solution is basic
point, the value to about 12. pH rapidly drops The graph for this titration, in which buret readings are plotted against corresponding pH values, is shown in Fig. 3, curve (A) (A). At the right of the figure are shown the approximate pH values
7.0.
gresses, the hydrogen-ion concentration decreases
pH =
Beyond the equivalence
and the
at which four of the
193
common
red,
indicators (phenolphthalein,
color.
thymol
blue,
methyl
and methyl orange) change
bromSo far
as the titration of a strong acid [curve (A) (A)] or the titration

is concerned, it is seen that not the at only equivalence point pH = 7.0, but near the equivalence point the change in pH is so rapid that any indicator chang-
of a strong base [curve (B) (B)]

is
ing color between about pH = 3 and pH =11 should be suitable. In other words, in titrations of strong acids with strong bases, and vice versa, although an indicator changing at pH = 7 is in-
dicated (e.g., brom thymol blue), yet the error involved in the use of such indicators as phenolphthalein or methyl orange is negligible being usually within the error of reading a buret.
Case B.
Twenty
milliliters
to 100 ml. and titrated with
N/2 acetic N/2 NaOH.
acid
(HC 2 H3O2 )
diluted
At the beginning
3.
of the titration, the
pH value is approximately
3
This can be calculated from the ionization constant of acetic
acid,
Ka =
1.86
10~ 5 thus:
,
H0 II [H+][0 H [HC H
2
2 <=
2-] 2]
H+ + C 2 H
=
Ka=
1.86
1.86X 10-6
10-6
[H+]
xXx
(0.10-z)
x
X
=
1.36
10~3
- 2 87
-
At the equivalence
:
point, the
pH
value of the solution can be

is
calculated from the following formula (which tions of this type)
general for titra-
This
may
be derived by considering the numerical equilibrium
relationships at the equivalence point in the titration just cited. The salt, sodium acetate, formed at the equivalence point at con-
centration C, hydrolyzes as follows:
NaC H O + H
2 3 2
HC H O + NaOH
2 3
2 3
2
or
C2 H 3O - + H O 4=i HC 2 H O + OH2 2
194

expression for this hydrolysis
is
The mass-action
m w
but
[HC 2 H 3Q2][OH-]
[C 2
(2)
2-]
[H+][OH-]
2-]
2]
Kw
and
[H + ][C 2H 3
[HC 2 H3
Dividing
(2)
by
(3) gives (1)
Hence
[HC 2 H 3 O2 ][QH-]
[C 2
Kw
Ka
2-]
but, as seen from the above hydrolysis equilibrium,
[HC 2 H 3
and,
if
2]
= [OH-]
not too great,
(approx.)
the extent of hydrolysis
is
[C 2
therefore,
H O-]
3
= C
Kw
Ka
Kw (^2 log C + }/2 log Kw y% log Ka)] = y<i log Kw Yi log Ka + % log C = A pw + y 2 PA + y 2 log c In the case at hand, we have Kw = 1.0 X 10~ Ka = 1.86 X 10""
-[log
1
14
,
pH =
5
,
and
0.010 mole
j
rr 120 ml. solution

1
NaC H O 2 3
U.Oooo molar
This
is
point C,on the titration curve (C) (C).
The common
point
tion.
like
is
195
indicator that changes color at approximately this phenolphthalein and is the indicator suitable for the titratitration graph, the use of
results.
4
As seen from the
an indicator
methyl orange would give erroneous
Case
Twenty
milliliters of
N/2
NH OH
diluted to 100 ml.
and
titrated with
N/2 HC1.
of the titration, the ionization constant of 4
At the beginning
NH OH
pH =
11.1, as calculated
from
(Kb =
1.75
X
:
10~ 5 ).
At the
equivalence point, the
pH
value can be calculated from the for-
mula (which
is
general for titrations of this type)
derived from the hydrolysis constant of ammonium chloride by a method analogous to that in Case B. = 1.0 X 10~ 14 Kb = 1.75 X In the case at hand, we have 10~5 and C = 0.0833.
This equation
is
Kw
14.0 -
4.76
(-1.08)
2~~
=
This
is
5.16
point
on the
titration curve (D) (D).
indicator that changes color at approximately this point is methyl red. As seen from the chart an indicator like phenolphthalein would give erroneous results. The change of color
The common
would be gradual, and the end point would occur considerably

before the true equivalence point. Case D. The titration curves for the neutralization of a
acid like acetic acid with a
weak
and
for the neutralization of a
represented by curves (E) The pH value at the equivalence point can be found by figure. substituting in the following formula (which is general for titrations of this type)
:
weak base like ammonium hydroxide weak base with a weak acid are (E) and (F) (F) in the accompanying
Such
titrations are of
no value
is
in general analytical
work,
for,
as
seen from the chart, there
no sudden
inflection of the curve
196
at the equivalence point, and no indicator has a sharp enough change in color to indicate the equivalence point with satisfactory
precision. 83. Calculation of the
Degree
of Hydrolysis of
Salt.
Not
only are the above formulas useful for calculating the pH value at the equivalence point in a given titration, but they can be used
to calculate the approximate extent of hydrolysis of a salt of a weak acid or of a weak base. For example, in the hydrolysis of
sodium acetate (C 2 H 8 O 2
IIC 2 H 3 O2 + OH~), the value of the concentration of OH~ can be found from the pH value calculated from the appropriate formula above; the value of the con2
"
+H
that of the concentration of the salt (0) [C2H 3 2~] indicates the of of the salt. degree hydrolysis EXAMPLE. What is the percentage hydrolysis of a 0.0010 molar + solution of 4 C1 (NH 4 2 O -> 4 11+)?
centration of acetate
is
in the formula.
The
ratio of [OII~] to
NH
+H
NH OH +
SOLUTION
where
-y 2 pB pH = % pW - Y z log C pW =14 pB = - log KNH4oH = - log 1.75 X C = 0.0010
10~ 5
Solving,
pH =
[H+]
G.12
log
6l2
7 6
'
X 1(H
[NH 4 +] =
0.0010
Percentage hydrolysis
rjj+i prf^-iTi
10
076 P er cent
Problems
666. What is the concentration of 4.2
pH value of a solution that at 25C. has a hydroxyl-ion X 10~ ? What color would be given to the solution by
8
a drop of methyl orange?

Ans.
666.
6.62.
Of thymol blue?
Yellow.
Yellow.
What
has a
pOH
is the hydrogen-ion concentration of a solution that at 25C. value of 8.85? What common indicator would change color at
approximately this concentration?

Ans.
667.
7.08
1Q-*.
Methyl
red.
certain
weak monobasic
acid
is
colorless in acid solution

is
and blue
in
alkaline solution.
Assuming that the blue
seen
when
two-fifths of the
indicator has been converted to ions
197
the solution
is 3.6,
Ans.
668.
2.0
2.7
X
If
what 10-u
.
is
and that at this point the pOH value of the indicator constant of the indicator?
A
10~4
.
certain
weak monobasic
is
acid
has
1/100 mole
dissolved in water
an ionization constant of and the solution diluted to
200 ml. and titrated with 0.250

to the equivalence point,
(r)
value of the soluNaOH, calculate the tion at the following points: (a) the original solution, (6) one-fifth of the way
at the equivalence point.
pH
Ans.
(a) 2.50, (6) 3.10, (r) 8.16.
569. What is the pH value of a 0.0100 molar solution of KCN? Of NH 4 C1? What common indicator is therefore suitable for the titratioii with HC1 of a
solution approximately
N/100
in
NH OH?
4
Ans.
570.
10.57.
5.62.
Methyl
red.
What
is
the percentage hydrolysis at
25C.
in a 0.0050
molar solution
of potassium acetate?
Ans.
0.032 per cent.
671. What are the pH value and the percentage hydrolysis at 0.010 molar solution of sodium formate (KncHOz = 2.1 X 10~ 4 )?
25C.
in
Ans.
672. of
7.84, 0.0069 per cent,
What
is
the percentage hydrolysis at

2
25C.
in
0.
10 molar solution
Na2C(MCQr + H o
A ns.
573.
4.5 per cent.
<=
iicor
on-)?
What
are the
pH
centage hydrolysis at
25C.
10~3
,
value, the hydroxyl-ion concentration, in a 0.10 molar solution of NaCN?

1.1
and the per-
Ans.
11.07, 1.1
per cent.
674. How many moles per liter of KC1O are required to give a solution with a hydroxyl-ion concentration of 2.0 X 10"6 at 25C.?
Ans.
1.6
10~5
576. sample of vinegar weighing 6.00 grams is dissolved in water, diluted to 50.0 ml., and titrated with 0.505 NaOH, phenolphthalein being used. After 12.40 ml. of the base have been added, it is found necessary to backtitrate with 2.00 ml. of 0.606 HC1. What is the acidity of the vinegar in terms of percentage of acetic acid, 2 3O2 ? Assuming that this is the only
HC H
acid present in appreciable amounts in the vinegar, calculate the pH value of the solution at the equivalence point at the end of the above titration. Is
phenolphthalein shown to be suitable for this titration?
Ans.
5.05 per cent.
8.82.
Yes.
676. If 400 ml. of a solution containing 4 OH are titrated with 0.250 N HC1, 40.0 ml. of the acid are required to reach the equivalence point. What
is
NH
the
pH
value of the solution at the start of the titration, halfway to the
198

What
indicator
is
equivalence point, and at the equivalence point?
thus
shown
to be suitable?
10.82, 9.24, 5.44.
Ans.
677.
Methyl
is
red.
Formic acid
(HCOOH)
a monobasic acid that
ionized in tenth-molar aqueous solution at constant of formic acid. If 50.0 ml. of 0.100
25C.
is 4.6 per cent Calculate the ionization
N HCOOH are diluted to 250 ml

pH
value at the equiva-
and
titrated with 0.200
N NaOH,
is
what would be the
lence point?
What
indicator
.
suitable for the titration?
Ans.
2.13
X
is
10-4
7.97.
Cresol red.
678.
of
What
the
pOH
is
which at 25C.
579.
9.0
value of a solution the hydrogen-ion concentration X 10~ 10? What common indicator would change
color at approximately this concentration?

is the hydroxyl-ion concentration of a solution that at 25C. value of 6.30? What color would be given to the solution by a drop of congo red? Of cresol red?
What
has a
pH
680. Derive the formula
the
pH
J/2 pB J^ Yt, log C, which represents value at the equivalence point in the titration of a weak base with a
pH =
pW
strong acid.
581.
certain
Assuming that the

is 4.8,
weak monoacidic organic base serves as an indicator. color change is seen when one-third of the indicator has
been converted to ions and that at that point the
pH
value of the solution
what
is
the indicator constant of the indicator?
682. In the titration of a solution of a certain monoacidic base with HC1, with methyl red as the indicator, the appearance of a shade of pink in the solution is taken as the end point. On the assumption that the concentration of the resulting salt is 0.100 N and that the indicator used is best suited for this titration, what is the approximate ionization constant of the base? 683. Benzoic acid (CeHsCOOH) is a monobasic acid with an ionization constant of 6.6 X 10~"6 A sample of the pure acid weighing 0.610 gram is dissolved in 500 ml. of water and titrated with 0.500 NaOH. Calculate the
.
pH value of the solution at the start of the titration, halfway to the equivalence
point and at the equivalence point. What indicator is shown to be suitable for this titration? Roughly sketch the titration graph.
684.
2
What
is
the percentage hydrolysis in a solution of 0.050 molar
NaNO ?
686.
By how many
times
is
when
its
0.10 molar solution
is
the percentage hydrolysis of diluted tenfold?
NH NO
4
increased
686.
What
are the
pH
at
0.10 molar in
687.
KHCO
25C.?
value and the percentage hydrolysis in a solution -
(HCO
+HO
2
<=>
H CO, +
2
OH~).
How many grams of each of the following substances must be dissolved in 100 ml. in order that the resulting solution shall have a pH value of 9.0; (a) NH (6) NaOH, (c) KN0 (d) NaHCO ?
8, 2,
3
588.
(a)
3
199
What
is
Na P04 (POr + H2PO4~ + OH-)?

689.
the percentage hydrolysis in 0.10 ~
solution at
25C.
2
of
H O * HPO +
2
OH-),
(6)
Na2 HPO4 (HPOr

like
+H
*
is
certain organic
amine
its
is
a monoacidic base
NtUOH
and
soluble in water.
Calculate
ionization constant from the fact that a tenth-
molar solution of the base
is 6.6 per cent ionized. What is the hydroxyl-ion concentration at the equivalence point in the titration of 200 ml. of a 0.20 molar solution of the base with 0.500 HC1? What indicator is suitable?
690.
certain organic
amine
is
.
ionization constant is 1.0
10~4
a weak monoacidic base like Its 4OH. If 100 ml. of a 0.020 molar solution is
NH
titrated with 0.020 HC1, what is the hydroxyl-ion concentration at the equivalence point? Which of the following four indicators would be best suited for the titration: methyl orange, phenolphthalein, methyl red, brom-
thymol blue? Carefully sketch the titration curve (pH against ml.) and show from it why the other three indicators would not be as satisfactory. Show clearly the positions of pH 4, 7, and 10 on the graph.
691. Propionic acid
1.6
10~5
If 0.100
with 4.00 NaOH, calculate the pH value (a) of the original solution, (b) of the solution when the acid is two-thirds neutralized, (c) at the equivalence
point.
is a monobasic acid with an ionization constant of mole of the pure acid is dissolved in 100 ml. and titrated
In Fig. 3 (Sec. 82) curve (G) (<7) represents the titration of a solution of sodium carbonate with a half-normal solution of hydrochloric acid. It will be noted that there are two points of inflection. The first is at about
84. Titration of
Sodium Carbonate.
pH =
9 and corresponds to the completion of the reaction
CO,-
+ H+ -* HCO 3
The second
is
at about
pH =
3
4 and corresponds to the comple-
tion of the reaction
HCO - + H+ -* C0 + H
2
Phenolphthalein should therefore indicate the conversion of sodium carbonate to bicarbonate, and methyl orange should change color
neutralization has taken place. Use is made of this principle in titrations of certain mixtures of substances as illustrated in the following section.
only
when complete
85. Analyses Involving the Use of Two Indicators. The fact that certain indicators change color at different stages of a neutralization
is
sometimes made use of

of the
in volumetric
work to
deter-
mine the proportions
components
of certain mixtures
by
200

This be brought about by means of two indicators, and the vol-
the employment of two end points in a single titration.
may
umes
of titrating solution required for the respective end points give a direct measure of the amounts of substances present. Only
the two
will
indicators, methyl orange and phenolphthalein, be considered. Assume a solution to contain only sodium hydroxide and inert impurities. The weight of NaOH present may be found by direct titration with a standard solution of any strong acid and with
either
common
methyl orange or phenolphthalein as the indicator. In either case, the color change will take place only when the alkali is completely neutralized, and the volume of standard acid used
in the titration is a direct
If
measure of the weight of NaOH present. a solution contains only sodium carbonate and inert impurities and is titrated with standard acid, methyl orange being used as the indicator, the color change takes place only when the Na 2 CO 3 has been completely neutralized.
C0 8- + H+ -* HCOr HC0 3- + H+ - II + C0 2
2
The volume
of acid required is
a measure of the total alkaline
strength of the sample and of the actual weight of Na 2 CO 3 present. In calculating, the equivalent weight of the Na 2 CO 3 would be taken as one-half of the molecular weight. On the other hand,
if
phenolphthalein were used as the indicator and the titration were carried out in the cold, the color change from pink to colorless
would occur when the carbonate had been changed to bicarbonate.
C0
The volume
+ H+
->
HC0 3
of standard acid required to titrate
sodium carbon-
ate to an end point with methyl orange as the indicator is twice that required if phenolphthalein is used as the indicator, since twice the number of hydrogen-ion equivalents is involved. The
equivalent weight of the Na2 C0 3 with the whole molecular weight
is
identical in the latter case
Na2 CO 3 /l, and the calculated the same in the two cases. present It is important to note that if, with phenolphthalein as the indicator, an excess of standard acid is added to the carbonate solution and the carbon dioxide is expelled by boiling the sodium carbonate will
weight of
Na CO
2
is
201
be completely neutralized. Neutralization of the excess acid with standard alkali will give a net volume of acid which will be the
same as that used with methyl orange as the indicator. If a solution contains sodium bicarbonate and inactive impuribe titrated with standard acid, methyl orange being used as the indicator, or in boiling solution with phenolphthalein, in the latter case by adding excess acid and titrating back with alkali.
ties,
the
NaHCOs may
HC(V + 11+ -> II

The equivalent weight
of
+ C0
NaHCO
in either case is identical to
the molecular weight. As stated above, a cold solution of pure sodium bicarbonate gives no color with phenolphthalein and therefore cannot be titrated with phenolphthalein as the indicator. There now remains the question of possible mixtures of the
three alkalies just discussed.

theoretical possibilities
(a)
(6)
(c)
:
Altogether, there are the following
NaOH Na C0
2
NallCOs
(d)
(e)
(/)
(0)
NaOH + Na C0 Na C0 + NaH(X) NaOH + NaHCOa NaOH + Na C0 + NaHCO

2
may be present in each case. The last two mixexist in solution, for sodium hydroxide and cannot tures, however, sodium bicarbonate interact mole for mole to form the normal
Inert impurities
carbonate
OH- + HCO - -> C0 - +

3 3
II 2 ()
Strictly speaking, these last

perfectly
two mixtures can exist when in the dry form, although this condition would be difficult to
realize in practice.
When
they are treated with water the reaction
takes place, forming the carbonate and leaving a possible excess of hydroxide or bicarbonate as the case may be.
The mixtures
y
ordinarily encountered in practice are those of

r
(d) and (e) viz., sodium hydroxide w ith sodium carbonate and sodium carbonate with sodium bicarbonate. Two end points being
used, it is possible to determine the proportions of the components of either of these mixtures even when inactive impurities are present.
202

I.
EXAMPLE
MIXTURE OF HYDROXIDE AND CARBONATE.

of
1.200-gram sample carbonate containing inert impurities is dissolved and titrated cold with half-normal hydrochloric acid solution. With phenolphthalein as an indicator, the solution turns colorless after the
addition of 30.00 ml. of the acid.
a mixture of sodium hydroxide and sodium
Methyl orange
is
then added,
of
and 5.00 ml. more

changes
color.
of the acid are required before this indicator

is
What
If
the percentage of
is
NaOH
and
Na CO 3
2
in the sample?
SOLUTION:
the acid
first,
(NaOH)
is
neutralized
added slowly, as follows:

2
the stronger base
OH- + H+ -+ H O
After this reaction
carbonate.
is
complete, the carbonate
is
converted to bi-
CCV*
+ H+
->
HCO 8
At this point, the phenolphthalein changes from pink to colorless and a total of 30.00 ml. of acid has been added. Then the bicarbonate formed is neutralized by 5.00 ml. more of acid.
HC0 - + H+ -> H
8
+ C0
1
Since each mole of

1
Na CO 3
2
reacts with
mole
of
HOI
to give
mole
HOI,
of
of
this, in turn, is neutralized by 1 mole it follows that the volume of acid required to convert
3
NaIIOO 3 and
into
the
Na2 OO
to neutralize the
NaHOO NaHCO
3,
the same as the volume required viz., 5.00 ml.

is
Therefore, the volume of acid necessary to neutralize completely the Na2 C0 3 is 10.00 ml. Since the total volume added was 35.00
ml., it is evident that 35.00
10.00
25.00 ml. were necessary
to neutralize the
NaOH.
=
Hence,
Percentage of
NaOH
X
25.00
0.5000
A
.
X X
100
J\J\J
41.68 per cent

x
Percentage of NazCOs
10.00
A v} 9
0.5000
X
X
100
22.08 per cent
203
These volume relationships are shown diagrammatically in

Fig. 4.
EXAMPLE
II.
MIXTURE OF CARBONATE AND BICARBONATE.
1.200-gram sample of an impure mixture of sodium carbonate and sodium bicarbonate containing only inert impurities is dissolved and titrated cold with half-normal hydrochloric acid soluPhenolphthalein
25 ml.
30 ml.
NaCl
35 ml.
5 mi.
Na 2C0 3
i
[
NaHCO3 [<
changes color Methyl orange added
5 ml.
NaC1
U... Methyl orange

I
changes color
FIG. 4.
tion.
as an indicator, the solution turns colorless after the addition of 15.00 ml. of the acid. Methyl
With phenolphthalein
orange is then added, and 22.00 ml. more of the acid are required to change the color of this indicator. What is the percentage of
Na CO and
2
of
NaHCO
When
.
in the sample?
is
SOLUTION:
verted into
the acid
added slowly, the
Na COs
2
is
con-
NaHCO 3 At this point, the phenolphthalein changes ml. of HC1 have been added. As in Example I, and 15.00 color, the same volume of HC1 as was used for the conversion of the Na2 CO3 into NaHCO 3 would be required to convert this NaIICO3 It follows formed from the Na2 C0 3 into NaCl, H 2 O, and C0 2
.
that 15.00
15.00
completely the being 15.00 + 22.00
Na2 CO
30.00 ml. of acid were required to neutralize The total volume 3 present in the sample.
it is
= 37.00 ml,
evident that 37.00
- 30.00 =
204

HC1 were
required to neutralize the
7.00 ml. of
NaHCOs
present
in the original sample.
Hence,
Percentage of Na2CO3
30.00
=
2,000
X 0.5000 X
1.200
100
66.25 per cent
Percentage of
7.00
NaHCO =
3
Ans.
0.5000
NaHCO
1,000
1.200
100
24.50 per cent

in
These volume relationships are shown diagrammatically

Fig. 5.
Na 2 CO3
|<-
Phenolphthalein added
15 ml.
Phenolphthalein changes color Methyl orange added

37 ml.
15 ml.
22ml.
Methyl orange changes color

FIG.
5.
Composition of Sample. In an analysis of the type discussed in this section, it is not always true that the analyst is previously aware of the exact composition of the sample. He may not know whether the sample contains hydroxide, carbonate, bicarbonate, or possible combinato
86. Relation of Titration
Volumes
tions of these components, and a qualitative test is not always conclusive. By means of a simple titration, however, and the
205
use of a double indicator or double end point, the composition of the alkali can be determined so far as these negative radicals
are concerned.
let A represent the volume of standard acid to titrate the cold solution to a change of color of phenolrequired phthalein, and let B represent the additional volume of the acid
In this connection,
to continue the titration to a change of color of methyl orange.
The
following relationships exist:
Problems
sample of sodium carbonate containing sodium hydroxide and only inert impurities weighs 1.197 grains. It is dissolved and titrated in the cold with phenolphthalein as the indicator. The solution turns colorless when 48.16 ml. of 0.2976 N HOI have been added. Methyl orange is added, and
692.
24.08 ml. more of the acid are required for complete neutralization. the percentages of NaOl I and Na 2 CO 2 in the sample.
Calculate
Ans.
693.
NaOH =
From
3
23.95 per cent,
Na CO =
2 3
63.46 per cent.
NaHCO
in a
1
Sample = end point
the following data, calculate the percentages of Na 2 CO3 and mixture in which they are the only alkaline components. IIC1 required for phenolphthalein .272 grains. Volume of 0.2400
26.92 ml.
After addition of an excess of the standard acid arid

,
the boiling out of the
CO2 net additional volume of the acid required end point = 50.21 ml. phenolphthalein = Ans. Na 2 OO 3 53.84 per cent, NaHCO 3 = 36.93 per cent.
694.
for the
A
,
sample of material contains

3,
for its active
components NaOH,
or possible mixtures of these. Two samples, each weighing 1 .000 gram, are dissolved in water. To one sample phenolphthalein is added and the solution is titrated cold with 1.038 acid, of which 17.96 ml. are re-
Na2CO 3 NaIICO
The other sample is and 21.17 ml. of the same

quired.
titrated cold with
methyl orange as an
indicator,
acid are required. Calculate the percentage of each.
What
alkalies are present?
Ans.
696.
NaOH =
A
61.28 per cent,
Na CO =
2 3
,
35.31 per cent.
that they contained either
chemist received different mixtures for analysis with the statement NaOH, NaHCO3 Na 2 CO 3 or possible mixtures
,
206
From the data given, identify materials and calculate the the respective percentage of each component. and 0.2500 normal HC1 were used in all cases. One-gram samples
of these substances with inert material.
Sample
I.
With phenolphthalein
as an indicator, 24.32 ml. were used.
duplicate sample required 48.64 ml. with methyl orange as an indicator. Sample II. The addition of phenolphthalein caused no color change.
With methyl
Sample
orange, 38.47 ml. of the acid were required. To cause a color change in the cold with phenolphthalein 15.29 ml. of the acid were necessary, and an additional 33.19 ml. were required
III.
for complete neutralization.
Sample IV. The sample was titrated with acid until the pink of phenolphthalein disappeared; this process required 39.96 ml. On adding an excess of the acid, boiling, and titrating back with alkali, it was found that the alkali
was exactly equivalent

Ans.
I.
to the excess acid added.

.
II. 80.79 per cent 64.45 per cent Na2 CO3 cent CO 37.60 NaHCO IV. 39.97 per cent Na cent 2 3 3 per per
,
.
NaHCO
3.
III. 40.52
NaOH.
sample is known to contain either NaOH or NaHC03 or Na2 CO3 or mixtures of these, together with inert matter. A 1.200-gram sample possible 42.20 ml. of N/2 HC1, using methyl orange as indicator. The same requires of sample requires 36.30 ml. of the acid using phenolphthalein indicator. weight Calculate the percentage of inert matter in the sample.
696.
Ans.
23.27 per cent.
697. Pure dry NaOH and pure dry NaHCO 3 are mixed in the respective proportion by weight of 2:1, and the mixture is dissolved in water. Calculate to three significant figures the ratio of the volume of standard acid required with phenolphthalein as an indicator to the additional volume re-
quired with methyl orange.
Ans.
598.
4.20.
mixture that contains and 2 CO 3 weighs a grams and, in the cold solution with phenolphthalein, requires 6 ml. of c normal acid. After methyl orange is added, d ml. of the acid are required. Calculate the
KOH
percentage of
Ans.
KOH and of K CO Reduce to simplest terms. r> Per cent I-^TT KOH = 5.611(6 d)c
2
3.
Per cent
K CO
2
699. Solve the preceding problem with respect to a mixture of NallCOs. Reduce to simplest terms.
Na2CO3 and
Ans.
Per cent Per cent
Na CO
2
10.60 be
3
a
8.401 (d
NaHC0 =
3
6)c
600.
NaOH
A liter of an alkali solution is prepared from 38.00 grams of pure and 2.00 grams of pure Na^COs. What is the true normality of the
solution
if
207
completely neutralized?
If this solution
were used in a titration
in the cold with phenolphthalein as taken for the alkali?
an
indicator,
what normality should be
Ans.
0.9874 N.
0.9686 N.
601. Calculate the
a mixture that on analysis gives the following data: Sample = 10.00 grams. The sample is dissolved in water, the solution is diluted to 250.0 ml., and
25.00 ml. are taken for analysis. An end point with phenolphthalein in cold solution is obtained with 44.52 ml. of 0.5000 N HCL A new portion of the HC1 for an end point with methyl same volume requires 46.53 ml. of 0.5000
grams
of
NaOH
and the grams of
Na CO3
2
present in
orange.
602.
mixture of soda ash and caustic soda weighs 0.7500 gram.
It
is
dissolved in water, phenolphthalein is added, and the mixture is titrated cold with 0.5000 HC1; the color disappears when 21.00 ml. have been added.
Methyl orange
appears. of NaOH
then added, and the titration continued until the pink color This requires 5.00 ml. of acid in addition. Calculate the percentage and of Na2 CO3 in the sample.
is
603. A sample is known to contain NaOH or NaIICO 3 or Na2CO3 or possible mixtures of these, together with inert matter. Using methyl orange, a 1.100gram sample requires 31.40 ml. of IIC1 (1.00 ml. - 0.01400 gram CaO). Using phenolphthalein, the same weight of sample requires 13.30 ml. of the acid. Calculate the percentage of inert matter in the sample.
The qualitative analysis of a powder shows the presence of sodium, a carbonate, and a little chloride. Titrated with methyl orange as an indicator, 0.8000 gram of the powder reacts with 25.10 ml. of half-normal HC1, and the same weight reacts with 18.45 ml. of the acid with phenolphthalein in the cold solution. Compute the percentage composition of the original powder. 605. A substance reacts alkaline in aqueous solution, and the alkalinity is
604.
due
centage of each alkaline constituent
K2 C03 and KIIC03 Compute the perfrom the following data: When phenolphthalein is the indicator (in a cold solution), 1.160 grams of powder react with 26.27 ml. of 0.3333 N HC1, and with 59.17 ml. when
either to
2 3
K CO
and KOII or
to
methyl orange
606.
is
the indicator.
is
Sample = 1.5000 grams.
prepared from NaOH contaminated with Na2 CO3 With phenolphthalein in the cold, 36.42 ml. of the alkali are rer With methyl orange as 2 SO 4 quired to neutralize 50.00 ml. of 0.5280 N the indicator, 35.60 ml. of the alkali are required for the same amount of acid. How many grams of NaOH and of Na2 CO3 are contained in each milliliter
solution of alkali
of the alkali solution?
87. Analysis of
Phosphate Mixtures.
;
Phosphoric acid ionizes

.
in three steps. The ionization constant for the first hydrogen is 13 7 2 1.1 X 10~ for the second, 2.0 X 1Q- and for the third, 3.6 X 10~
;
208
In the titration of phosphoric acid with an alkali like NaOH, the replacement of the first hydrogen results in the formation of
At approximately The this point, methyl orange changes replacement of the ~ second hydrogen results in the formation of Na2 HPO4 (H 2 P0 4 + OH~ >HPO4= + H 20). At approximately this point, phenolphthalein changes color. The reverse titration of Na3 PO4 with a
2
2
NaH P04
(H 3 PO 4
+ OH- -> H PO ~ +
4
II 2 O).
color.
strong acid like
HC1
results first in the formation of
HPO^,
at
which
H 3 P04
point
changes color, formation of

point
color.
and then
2
phenolphthalein in the
4
H PO ~,
orange
at
which
methyl
changes
titration of this sort is
NaH2 P04
...
Methyl orange changes color
shown
in Fig. 6.
substances adjacent Only shown on the diagram can exist together in solution. Other comAs in the binations interact.
case of the carbonate titrations
of the preceding section,
it
__ Phenolphthalein
changes color
is
possible to analyze certain mixtures of phosphates by means
Na 3 PO4
FIG. 6.
of titrations involving the use of two indicators. Actually, the
titrations should
be carried out
on
fairly concentrated solutions
and at a temperature of about 55C. EXAMPLE. A sample, which is known to contain either
Na PO4
3
or possible mixtures of these, together with inert impurity, weighs 2.00 grams. When this sample is titrated with 0.500 HC1, methyl orange being used, 32.0 ml. of the
2
NaH P() Na HPO

4,
2
4,
acid are required.
The same weight
of
sample when titrated with
0.500
HC1, phenolphthalein being used, requires 12.0 ml. of the acid. What is the percentage composition of the sample? SOLUTION: From simple inspection of the diagram and consideration of the two volumes involved, it is evident that both SaaP0 4 and Na2 HPO4 are present. A volume of 12.0 ml. must lave been required to convert the Na 3PO 4 to Na2 HPO 4 and, since 12.0 ml. more would be required to convert the Na2 HPO 4 formed
;
to
209
is
NaH PO
2
4,
a volume of 32.0
2
(2
to convert the original

12.0
Na HPO
to
X 12.0) = NaH PO4

2
.
8.0 ml.
required
0.500
X
X
*'" 141J<1
100
49.2 per cent
Na3 P04
Ans.
8.0
0.500
2.00
Problems
607. A sample that contains Na PO4.12II O, or Na HPO 2II O, or NaH PO .Il2O, or possible mixtures of these weighs 3.00 grams. When it is
3
4. 1
titrated with 0.500
required.
phthalein.
HOI, methyl orange being used, 14.0 ml. of the acid are similar sample requires 5.00 ml. of 0.600 NaOH, with phenolWhat is the percentage composition of the sample?
Ans.
608.
of
13.8 per cent
NaH PO
2
.H2 O, 83.6 per cent
Na TTPO4 .12H
2
,
O.
certain solution
is
known
to contain any possible combinations
following substances: HC1, Titration of a sample with 0.500
the
Na ITPO
2
4,
NaTI 2 PO4
H PO
3
4,
NaOII.
NaOH,
phenolphthalein being used, reof sample arid methyl to obtain a color

of each are
quires 27.0 ml. of the base. With the orange indicator, 17.2 ml. of the 0.500
same weight
N NaOII are required H PO

3
change.
What components
0.135
are present,
and how many grams

4.
present in the sample taken?
Ans.
609.
IT 3
gram
IIC1, 0.481
is
gram
certain
solution
,
known
to
contain either IIC1

existing alone.
+ H PO
3
4,
or
is
PO4
NalI 2 PO 4
or the three
compounds
sample
ml. with methyl orange indicator; but the NaOH, requiring same weight of sample requires B ml. of the NaOH with phenolphthalein What relationship would exist between A and B to indicate the indicator.
titrated with
first combination, and what relationship would indicate the second combination? What relationship would indicate the presence of 3 PO4 alone?
Ans.
B>
A
A, but
B<
2A;
B >
2A.
B =
2A.
solution known to contain Na2 HPO4 or NaH 2 PO4 or 3 PO4 of mixtures 1.10 When it is titrated with these, weighs grains. possible ml. are 27.0 the to color of phenolphthalein, 0.520 NaOH, change required but only 10.0 ml. to change the color of methyl orange. What is the per610.
, ,
,
centage composition of the solution?

611. A certain solution is known to contain any possible combinations of the following substances: HC1, Na 2 3 PO 4 4 NaII 2 PO 4 NaOH, Na 3 PO4 Titration of a sample with 0.510 HC1, methyl orange being used, requires 28.1 ml. of the acid. With the same weight of sample and phenolphthalein
HPO
210

are required. What components are present, grams of each are in the sample taken?
indicator, 17.1 ml. of the
HC1
and how many

612.
A series of solutions are known to contain H PO

3
4,
NaII 2 PO 4 Na2HP(>4,
,
alone or mixed in varying proportions. In each case, the titration is made with 1.000 NaOH to a pink color with phenolphthalein and the solution is HC1 to a pink color with methyl orange. then back-titrated with 1.000
In each of the following four cases, determine which components are present
and the number of millimoles

a.
6.
c.
of each:
Initial titration 48.36
ml;
back-titration 33.72 ml.
Initial titration 37.33 ml.; back-titration 39.42 ml.
Initial titration 24.36 ml.; back-titration 24.36 ml.
d. Initial titration
36.24 ml.; back-titration 18.12 ml.
CHAPTER
XTII
OXIDATION AND REDUCTION (REDOX) METHODS (OXIDIMETRY AND REDUCTIMETRY)

Fundamental Principles. This phase of volumetric analyhas to do with the titration of an oxidizing agent with a standard solution of a reducing agent or the titration of a reducing agent with a standard solution of an oxidizing agent. This type of determination embraces the greater part of volumetric analysis, for the number of substances capable of oxidation or reduction is
88.
sis
comparatively large. Oxidation is the increase in the positive direction of the electrical valence or oxidation number of an element or radical; reduction is the decrease in electrical valence or oxidation number of an element or radical. Oxidation arid reduction must evidently
take place simultaneously, for in any reaction of this type the oxidizing agent is always reduced and the reducing agent is always The methods of expressing oxidized, and to the same degree.
concentration and the definitions given in Chap.
solutions of oxidizing
IV hold
true for
and reducing agents. Therefore, the relabetween these agents are the same as those tionships existing existing between acids and bases. However, it is necessary in the case of concentrations of solutions expressed in terms of normality to consider the hydrogen equivalent from a slightly different point
of view.
89. Equivalent As in acidimetry

of
Weights of Oxidizing and Reducing Agents. and alkalimetry, the concentration of a solution
an oxidizing or reducing agent is best expressed in terms of its relation to the normal solution, and the gram-atom of hydrogen
is
taken as the ultimate unit.
We
must, however, consider the
unit from the point of view of oxidation and reduction, thus:
H
Hydrogen ion
is
<=>
H+ +
an oxidizing agent and

(e.g.,
to hydrogen gas
Zn
+ 2H+
211
capable of being reduced Zn++ + 2 ). Free hydrogen

is
212
is
ion
a reducing agent and is capable of being oxidized to hydrogen - 2Fe++ + 2H+). (e.g., 2Fe+++ + H 2 The conversion of one atom of hydrogen to the ion, or vice versa, involves a change of 1 in oxidation number and a transfer
of one electron.
To find the equivalent weight of an oxidizing or reducing agent we must, therefore, take that fraction of its formula
weight so that in the oxidation or reduction process there will be involved the equivalent of a transfer of one electron. This will be accomplished (1) by dividing the formula weight of the substance by the total change in oxidation number involved in the oxidation-reduction process, or (2) by dividing the formula weight of the substance by the number of electrons transferred per for-
mula weight
of substance.
is
of
an
the equivalent weight in grams and is equivalent oxidizing agent in oxidizing power to 1.008 grams of hydrogen as hydrogen ion.
It is likewise equivalent in oxidizing
power to 8.000 grams

of
of
is
oxygen.
a reducing agent
equivalent in reducing power to 1.008 grams of elementary hydrogen gas. As will be seen later, a substance may have two
different equivalent weights depending on whether it is used as an acid or as an oxidizing or reducing agent. As in acidimetry,
a normal solution
of
an oxidizing or reducing agent contains one
gram-equivalent weight of substance per liter of solution, or one gram-milliequivalent per milliliter. Hence, as in acidimetry,
ml.
= number
ml. 8
of gram-milliequivalents
cx
and
X N, X
= grams*
grams of the following reducing substances constitute the gram-equivalent weight in each case:
I.
EXAMPLE
How many
,
KHC
(6) SnCl 2 (c) H 2 C 2 O 4 .2II 2 (oxalic acid), (d) .H O KHC 2 4 2 4 .H 2 C 2 2 4 .2H 2 O (potassium binoxalate), (e) (potassium tetroxalate), (/) H 2S (oxidized to S), (g) H 2S (oxidized to H 2 S0 4 ), (K) Na2 S 2 O 3 .5H 2 (oxidized to Na2S4 6 ), (z) H 2 O 2 ? SOLUTION: (a) FeSO 4 .7H 2 O. In solution, this gives ferrous ions which can be oxidized to ferric ions.
(a)
FeS0 4 .7II 2 0,
Fe++ ->
+ Br
-> 2Fe+++
+ 2Br~
OXIDATION AND REDUCTION METHODS

ferrous ion changes in oxidation number by one unit hence is equivalent in reducing power to the hydrogen unit.
213
Each
and
The
molecular weight of FeS0 4 .7H 2 is therefore the equivalent weight as a reducing agent, and, expressed in grams, is equivalent in
reducing power to 1.008 grams of hydrogen.
FeS04 .7H 2 O =
1
278.0 grams.
Ans.
In solution, this gives stannous ions which can be " oxidized to stannic ions: Sn ++ > Sn 4 "^ + 2e. The change in
(b)
SnCl 2
oxidation
number
is 2.
therefore, equivalent in reducing
The gram-molecular weight of SnCl2 is, power to 2 gram atoms of hy-
drogen, or one-half the molecular weight represents the equivalent

weight.
?
z
(c)
77.08 grams.
Ans.
H C204.2H2().
2
In solution, this gives oxalate ions,
O4
=
r
which can be oxidized to
CO
1
gas.
( 2<
- -
2CO 2 +
10CO,
2e
e.g.,
5C 2 O4 The
+ 2Mn0 ~ +
4
1GII+
of
+ 2Mn++ + 8IT O
2
average oxidation
number
carbon in the oxalate radical
is
+3
(actually one is of carbon in 2 is
+2, the other is +4). The oxidation number +4. Each carbon, on an average, changes by one unit in oxidation number; but, since there are 2 carbon atoms
CO
in the oxalate radical, the

is 2.
average change for the oxalate radical
The
radical
is,
therefore, equivalent in reducing
power to
2 hydrogen atoms.
HC
2
.2H S
z
(d)
Q nQ 03.03 grams.
,.
A Ans.
KHCoC^.HaO.
salt gives
Here again, each molecule of the dissolved an oxalate ion which is oxidized to CO 2 as in the pre-
ceding case.
KHC ~ .H O =
2 4 2
Z
It should
73.07 grams.
Ans.
acid
is
be noted that the equivalent weight of this salt as an the molecular weight, or 146.14. Hence, a solution of po-
214

is
tassium binoxalate which

agent.
(e)
0.1
N as an acid is 0.2 N as a reducing

Since each molecule of this salt in
KHC204.H 2 C204.2H 2 0.
solution gives 2 oxalate ions which are oxidized as above to C02, the equivalent weight of potassium tetroxalate as a reducing agent
is
KHC 04.H2C
2
-2 4
.2H 2
PQ 63.55 grams.
A Ans.
When
this salt is reacting as
an
acid, its equivalent
weight
is
one-
third of the molecular weight, or 84.73. given solution of potassium tetroxalate has four-thirds the normality as a reducing agent that it has as an acid.
(/)
H S. When
2
change
in oxidation
this substance is oxidized to free sulfur, the number of sulfur is 2.
=
Zt
17.04 grams.
Ans.
(g)
H S. When this substance is oxidized to sulfate, the change

2
in oxidation
number
of sulfur is
2
from -2 to +6.
A Ans.
HS=
~Q o
(h)
4.2M) grams.
In aqueous solution, this salt gives thiosulfate ions which can be oxidized to tetrathionate ions. -> S 4
e.g.,
Na2S 2O3.5H 2O.
=
6
+ 2e
2S 2 O 3~
+I
-> S 4
=
6
+ 21-
is
In the thiosulfate radical, the average oxidation number of sulfur +2; in tetrathionate, the average oxidation number of sulfur is
The average change for each sulfur is %\ but, since in +2J/2. thiosulfate there are two sulfurs, the total change in oxidation
number
is 1.
-Na S
2
.5H 2
= 01QO 248.2
grams.
Ans.
(i)
2.
When hydrogen
2
peroxide acts as a reducing agent,

e.g.,
it is
always oxidized to free oxygen; ->
5H O + 2Mn0
2
+ 6H+
5O 2
+ 2Mn++ + 8H O
2

Average change in oxidation number hydrogen peroxide molecule is from
the molecule
is 2.
215
of each
1
to 0.
oxygen atom in the Total change for
H
EXAMPLE
(a)
3
17.01 grams.
Ans.
II.
How many
(6)
4,
grams
(c)
of the following oxidizing sub-
stances constitute the gram-milliequivalerit weight in each case:
KMn0 to duced bromide), (/) H O ? SOLUTION: (a) K Fe(CN)

6, 2 2 3
K Fe(CN)
K Cr O
2
2
7,
(d)
I2 ,
(c)
KBrO
(re-
In solution, this salt gives ferricyanide ions which are capable of being reduced to ferrocyanide
6.
ions.
The change
in oxidation
3
number
6
-
of the iron
is
from
+3
to +2.
K Fe(CN)
fobf)
(ft)
^ n QOnQ 3293 gram
^
A
2
KMnOd.
When
reduced in
ions.
the presence of acid,
perman-
ganate ions
form manganous
MnOr + 8H f + 5e -> Mn++ + 4II O
MnOr + 5Fe++ + 8H+ -> Mn++ + 5Fe+++ + 4H ()

2
Change
in oxidation
number
of
manganese
gram.
is
from
+7
to +2.
KMnOi = rôi^ 0.03161

5QQO
A Ans.
In alkaline solution, permanganate is reduced to change in oxidation number of 3 (from +7 to +4).
MnO
with a
MnO ~ + 2H O + 36 -> MnO + 4011^

4 2
2
Here the equivalent weight is one-third of the molecular weight. Bichromate ions are ordinarily reduced to chromic (c) K 2 Gr 2 Or.
ions.
Cr2 O 7 =s Cr2
=
7
14H+
6e ->
2Cr^^-
+ 7II O
2
+ 6Fe^ +
14H+ -* 201^++
+ 6Fc+++ + 7H
216

in oxidation
The change
number
of
each chromium atom

it
is
from
+6
to +3, or the change of the dichr ornate ion (since

ions)
is 6.
contains 2
chromiun
=
(d)
I2
.
0.04903 gram.
Ans.
Iodine
is
reduced to iodide.
I2
+ 2c -> 21-
There
one unit change in oxidation number for each iodine atom, or two unit changes for the molecule.
is
2
0.1209 gram.
Ans.
in
2,000
0) KBrOa.
oxidation
Bromate reduced to bromide involves a change number of the bromine from +5 to 1, or a change
of
6 units.
Br0 3-
+ 6H+ + 6e -> Bi- + 3H O

2
KBrOs
6,000
(/)
0.02784 gram.
Ans.
II 2 02.
As an
oxidizing agent, hydrogen peroxide
is
reduced
to water.
H O + 2H+ + 2e - 2H O
2
Average change of each oxygen

for the molecule is 2.
is
from
to
2.
Total change
=
90. Calculations
of
0.01701 gram.
Ans.
and Reduction Processes. Since the concentration of solutions in oxidation and reduction titrations, like those in acidimetry and alkalimetry, is based on the hydrogen equivalent, the methods of calculation are identical. Thus, I liter of a normal solution of an oxidizing agent will exactly oxidize 1 liter of a normal solution of a reducing agent, or 2 liters
Oxidation
of a half-normal solution.
or
In titrating a reducing agent with a solution of oxidizing agent an oxidizing agent with a solution of reducing agent, reasoning

similar to that described in Sees. 73, 74, and 75 same general formulas as were there derived: viz.,
ml..
217
will evolve the*
X N, X
X
ex
ex
= grams*
,
and
ml., X N* / V X 100 = per cent* w Weight of sample
vx
x
.
The methods of solving the various types of problems described under Sees. 76, 77, and 78 likewise apply to oxidation and reduction titrations.
Problems
613. Refer to
Problem 35 and give the equivalent weights
of the following
oxidizing agents: (a)
KsAsO4
(6)
NaBrO
3,
(c)
NaNO
2,
(d) NuaOfe.
Ans.
(a) 32.02, (6) 25.15, (c) 11.50, (d) 39.00.
614. Refer to
Probelm 34 and state what fraction

(a)
of the molecular weight
represents the milliequivalerit weight in the case of each of the following
reducing agents:
Cr2 (SO4 ) 3
(6)
HC1,
(c)
(c)
H S.
2
Ans.
(a)
1/6,000, (6) 1/1,000,
1/2,000.
grams
616. Thirty milliliters of ferrous ammonium sulfate solution contain 1.176 of pure FeSO 4 (NH 4 ) 2 SO4.6II 2 O. Twenty milliliters of potassium
.
dichromate solution contain 0.2940 gram of

of the ferrous
K Cr O
2 2
7.
sulfate, (6) normality of the dichromate, (c) of 1.000 ml. of ferrous solution in terms of the dichromate solution.
ammonium
Calculate (a) normality value
Ans.
616.
(a)
0.1000 N,
(fc)
0.2998 N,
(c)
0.3335 ml.
of water
solution of nitric acid is 3.00 N as an acid. How many milliliters' must be added to 50 ml. of the acid to make it 3.00 N as an oxidizing agent? Assume reduction of HNO8 to NO.
Ans.
100 ml.
617. If 10.00 grams of E^Fe(CN) 6 .3H 2 O are dissolved in water and the volume made up to 500 ml., what is the normality of the solution as a reducing,
agent?
Ans.
0.04736 N.
618. From the following data, calculate the ratio of the nitric acid as an oxidizing agent to the tetroxalate solution as a reducing agent (assume reduc~ to NO). tion of 3
NO
1.000 ml.
HNO
4
2
=0=
1.246 ml.
1.000 ml.
KHC O .H C O .2H O
2 4
2 2
=0=
1.743 ml.
NaOH NaOH
Normality
Ans.
619.
l.f
NaOH =
of
0.1200
To
oxidize the iron in 1.00
5.00 ml. of
HNOs
(3Fe++
+ NO - + 4H+ 3
gram
FeSO4 .(NH4 ) 2 SO4 .6H 2 O

3Fe+++
2
requires.
+ NO + H 0). How
218

to 500 ml. of this acid to
much water must be added

as
make
the concentration
an acid exactly one-tenth normal?

Ans.
350 ml.
620. A certain volume of a solution of KHC2O4.H2O would be oxidized in How the presence of acid by an equal volume of 0.01000 molar 4 would be neutralized solution molar 0.01000 of milliliters 2 Ba(OH) by many
KMnO
20.00 ml. of the binoxalate?
Ans.
621. tion of
25.00 ml.
A method of standardizing KMnO solution against a standard soluNaOH has been suggested. This consists in dissolving a small (un4
weighed) amount of oxalic acid (or acid oxalate) in water and titrating with the standard alkali, using phenolphthalein indicator. The resulting solution If is acidified with 2 O4 .H 2 O were 4 2 SO 4 and titrated with the used as the intermediate compound and the titrations required 10.58 ml. of calculate the normality of the NaOH and 38.10 ml. of 0.2280 4
KMnO
KHC
KMnO
KMriO4
Ans.
622.
as an oxidizing agent.
0.1266 N.
KIIC 2 O4 .H2C2O4 .2H 2 O and Na 2 C 2 O 4
are to be mixed in the proper
proportion so that the normality of a solution of the mixture as a reducing agent will be 2.15 times the normality as an acid. Calculate the proportion.
Ans.
1:0.644.
623. Calculate the normality as
solution
made by
grams
of
KHC
an acid and as a reducing agent of a of 20.00 grams of mixture a 2 C 2 O 4 .2H 2 O, 10.00 dissolving .H .2H of O and 15.00 KHC20 2 C2O 4 2 O in water and 4 2 4 grams
diluting to exactly
,000 ml.
Ans.
0.5728 N, 0.7096 N.
624. Refer to
Problem 37 and give the gram-milliequivalent weights
of the
following oxidizing agents: (a)

625. Refer to
BiO 2
(&)
K Fe(CN)
3
6.
Problem 36 and state what fraction

2,
of the molecular weight
represents the equivalent weight in the case of each of the following reducing
agents:
(a)
KNO
(6)
UO C1
2
2,
(c)
MnSO4
(d)
VOSO
4.
626. In the analysis of
chrome
iron ore,
chromium
is
oxidized by fusion
to chromate and determined by titration with ferrous What is the equivalent weight in terms of (a) Cr2 O 3 and
627.
ammonium
(6)
sulfate.
Cr?
theoretically required to dissolve the air, if 3.00 ml. of the acid will with iron out of contact of pure gram neutralize that volume of KOII solution which will react with 6.00 ml. of a
of
What volume
HC1
solution
is
1.000
potassium acid oxalate solution that

628.
is
2.00
N as a reducing agent?
,
weighing 0.5465 gram
AgNO 3 a precipitate of AgCl obtained; 24.36 ml. of the IIC1 exactly react with 27.22 ml. of NaOH solution; 26.24 ml. of the NaOH exactly react with 30.17 How much water must be added to a ml. of 2 O 4 .H 2 C2O 4 .2H 2 O solution. as a reducing agent? liter of the oxalatg solution to make it exactly 0.02500
25.00 ml. of IIC1 are treated with
is
When
KHC

629.
219
"
10 volume" which
The hydrogen peroxide sold for medicinal purposes is often labeled means that on ordinary decomposition it yields ten times
of such
its
volume of oxygen. What would be the normality an oxidizing agent? As a reducing agent?
630.
a solution as
certain volume of KHC 2 O4.H2C2O4.2H 2 O solution would be neuby an equal volume of 0.01000 molar Na2CO3 solution. How many milliliters of 0.02000 molar K 2 Cr 2 7 would be required to oxidize 25.00 ml. of
tralized
the tetroxalate solution?
Permanganate Process. Potassium permanganate is extenIt serves as its own insively used as an oxidimetric standard. dicator. A normal solution contains one-fifth the gram-molecular
91.
weight per
of acid.
used in the presence standard solution of potassium permanganate is used in three ways: 1. It is used in the presence of acid in the direct titration of a
liter (see Sec. 89,
Example
116)
if
large
number
of oxidizable cations
and anions.
Among them
are
the following:
SUBSTANCE
OXIDIZED TO
vo++
C or
2
vo co
3
2
NO ~
2
so3-
NOr
sor O2
HO
2
MO+++
U++++
2.
MoO
UO2 ++
It is used in the presence of acid in the indirect titration of a large number of reducible substances. In each case a meas-
ured amount of a reducing agent

is
(e.g.,
added, and, after reduction is ing agent is titrated with standard permanganate (see Sec. 76). Among the many substances that can be determined in this way
are the following:
StrBSTAN
a ferrous salt or an oxalate) complete, the excess reduc-
REDUCED TO
Cr2O7 -
MnO Mn O
2, 3
Mn ++
Pb.,0,
PbO Pb2 O3
2.
220
3.

It is
used in neutral or alkaline solution in the titration of a In these cases the permanganate is reduced few substances. very to MnC>2, which precipitates. The permanganate, therefore, has an oxidizing power only three-fifths of what it has when used in the presence of acid (see Sec. 89). This fact must be made use of in the calculations of such analyses (see Example VI below).
SUBSTANCE
OXIDIZED TO
Mn ++ HCOOH
EXAMPLE
tetroxalate,
I.
MnO
(formic acid)
is
CO
What
if
2
permanganate
0.5000
the normality of a solution of potassium 40.00 ml. will oxidize that weight of potassium
2
KHC O4.H2C2O4.2H 0,
The amount
which requires 30.00 ml.
of
N sodium hydroxide solution for its neutralization?

of tetroxalate that requires 30.00 ml.
SOLUTION:
of 0.5000
or*
N NaOH for neutralization is

vx
30.00
f\f\
f\ cr\r\r\
0.5000
^. ^ *-^ X KHC2O4.H2C2O4.2H2O grams s~000

vx
.,
The normality
of the
permanganate
1.271
is
therefore
0.5000.
Ans.
40 00
X
4,000
The same
result is
more simply obtained by
setting
up the
entire
equation before performing any of the operations, when it will be found that the molecular weights of the potassium tetroxalate
cancel
and need not be
calculated.
Thus, the weight of potassium
tetroxalate neutralized
by
30.00 ml. of 0.5000
N NaOH is
30.00
0.5000
X
of
and the weight of potassium tetroxalate oxidized by 40.00 ml. x normal KMnO4 is
in flfl 40.00
y r y XxX
KHC 04.H2C 04.2H20

2 2
Since these two expressions are equal to each other, the equality may be expressed by an equation in which the molecular weights
of the
for the normality of the
potassium tetroxalate cancel and x gives the value 0.5000 permanganate.

EXAMPLE
II.
221
What
is
iron ore weighing 0.7100 gram if, after solution the iron with amalgamated zinc, 48.06 ml. of
the percentage of iron in a sample of and reduction of
KMnO
(1.000 ml.
=0=
0.006700 gram
Na2 C O4
2
many grams
solution?
of
KMn0
are required to oxidize the iron? How are contained in each milliliter of the
SOLUTION
Normality
of the
KMn0
=
JN a2L/2vJ 4
0.1000
48.06
X
:
~27KKT
0.1000
QJ^Q
X y^r -^-
100
37.79 per cent Fe.

contains
Ans.
Each
milliliter
of
normal
KMn0
4
KMn0 /5,000 =
4
0.03161 gram.
Each
milliliter
of this
KMnO
contains 0.03161
0.1000
0.003161 gram.
Ana.
EXAMPLE
III.
How many
grams
of II 2 02 are contained in
solution that requires for titratioii 14.05 ml. of 1.000 ml. =0= 0.008378 gram Fe (i.e., will oxidize that
iron
KMn0
of
a which
of
amount
from the divalent to the trivalent state)? How many grams and how many milliliters of oxygen measured dry and under standard conditions are evolved during the titration?
SOLUTION
Normality
KMn0 =
4
re/I,
/1
0.1500
N
Ans.
Grams
HO
2
=
of
14.05
0.1500
~~ = 0.03584 gram.
O
2
Each mole
Sec. 89,
HO
2
corresponds to a mole of
Therefore,
evolved [see
Example
2
!(*)]-
Grams
evolved
14.05
0.1500
X x~c =
A,UUU
0.03372 gram.
Ans.
Each mole
Therefore,
Milliliters
of
occupies 22,400 ml.
evolved
14.05
99 4OA
0.1500
23.60 ml.
A na.
222
IV. What is the percentage of MnO 2 in impure pya sample weighing 0.4000 gram is treated with 0.6000 gram of pure 2 C20 4 .2H 2 and dilute 2 S04 and after reduction has taken place (MnO 2 + H 2 C 2 O 4 + 2H+ -> Mn++ + 2CO 2 +2H 2 O)
EXAMPLE
if
rolusite
the excess oxalic acid requires 26.26 ml. of 0.1000

titration?
N KMn0
for
SOLUTION:
Milliequivalents of
HC
2
.2H 2 O used =
4
= 9.526
26.26
Milliequivalents of
KMnO
used
0.1000
2.626
6.900
Net
milliequivalents
9.526
_. __
2.626
A
6.900
MnOz/2,000 x 040QA
V.
,__ 10
74 -97 per cent
~ Mn0
,,
2.
Ans.
What would be the milliequivalent weight of Pb in the calculation of the analysis of red lead (impure PbsC^) by a method similar to that of the preceding ex= ample (Pb 3 4 + H 2 C 2 4 + 3S04 + 6H+ - 3PbS0 4 + 2CO 2 +
EXAMPLE
PbsO4 and
of
4H2 0)?
SOLUTION:
The
oxidation
number
of lead changes
from an
average of 2% (in Pb 3O4 ) to 2 (in PbSO 4 ). Each lead therefore changes by an average of unit; 3 leads change by 2 units. Hence,
Me.
wt.
Pb3 Pb
=
=
Z } \)(j(j
~=
0.3428.
Ans.
Me.
qpu
wt.
~=
0.3108.
Ans.
EXAMPLE VI. A steel containing 0.90 per cent Mn is analyzed by the three standard methods below, in each case with a 2.50gram sample, 0.0833 N KMnO4 and 0.100 N FeS0 4 solutions.
KMnO required. SOLUTION Bismuthate Method. The Mn is oxidized to KMnO and after reduction with 25.0 ml. of the standard FeSO (MnO ~ + 5Fe++ + 8H+ -> Mn++ + 5Fe+++ + 4H 0) the excess ferrous iron is titrated with the standard KMnO Let x = milliliters of KMn0 used in the titration.
Calculate in each case the volume of
:
4.

Milliequivalents of Milliequivalents of
223
FeS04 used =
4
25.0 2.50
X
-
0.100
2.50
KMnO
used
=xX
=
0.0833
Net
milliequivalents
0.0833s
x = 5.42 ml.
Ans.
to
Chlorate (Williams) Method. The is oxidized with KClOs MriO 2 which is filtered and dissolved in 25.0 ml. of the standard
Mn
FeS0 4 (MnO 2 + 2Fe++ + 4H+^Mn^ + 2Fe+++ + 2H 2 0). excess FeSO 4 is titrated with the standard KMn04 Let x = milliliters of KMnO4 used in the titration.
.
The
Milliequivalents of
FeSO 4 used =
4
25.0
X
-
0.100
2.50
Milliequivalents of
KMnO
used
Net
milliequivalents
= =
0.0833
2.50
0.0833z
x
Volhard Method. The Mn a solution kept neutral with
is
20.2 ml.
Ans.
ZnO (3Mn++ + 2Mn04~ + 2ZnO ->
titrated directly with
KMnO
in
5Mn0 +
2
2Zn++). Let x = milliliters of KMn04 used in the titration. Tn this case the normality of the KMnO 4 cannot be taken as 0.0833 because it is used in neutral solution where the change
in oxidation
number
of its
manganese
of
is
3 instead of
5.
In other
words, the oxidizing power

three-fifths as great as it
KMnO
in neutral solution is only
case the normality ber of the titrated
s(0.0833
- -is
is
in acid solution.
0.0833
X %.
In this particular The change in oxidation num-
Mn is 2.
X___ ?flMn/2,000
luu
=
=
u.yu
16.4 ml.
Ans.
EXAMPLE
per cent
VII.
is
Mn
1.00-gram sample of steel containing 0.90 analyzed by the persulfate method whereby the
manganese is oxidized to permanganate by ammonium persulfate and the resulting permanganate is titrated with a standard soluIf 7.68 ml. of arsenite solution (0.0400 tion of sodium arsenite.
224
molar in NasAsOa) are required and the arsenite is oxidized to arsenate in the titration, to what average oxidation number was the manganese reduced in the titration? SOLUTION:
0.0400 molar
Na AsO =
3
0.0800 normal
of
Let x
= change
in oxidation
number
Mn during titration
=
0.0090
7.68
Solving,
0.0800
X
x
1,000
3.75
Oxidation number of
Mn in reduced form = 7
a solution of
2
3.75
3.25.
4
Ans.
EXAMPLE
VIII.
If 1.000 ml. of
KMn0
is
equiva-
lent to 0.1000 millimole of
2 2 2 2 lowing titration: what is the of value the in of terms 4 5OH-, grams of CaO in the volumetric method for calcium in which that element is
NaCHO (sodium formate) in the fol3CHO ~ + 2MnO4~ + H O -> 3CO + 2MnO +
KMnO
precipitated as CaC 2 4 .H 2 O and the precipitate is filtered, dissolved in dilute and the oxalate titrated with perman2 S0 4
ganate?
SOLUTION:
0.1000 millimole
NaCHO =
2
0.2000 milliequivalent
(since in the titration the oxidation
number
of
changes from
+2
to
+4)
Normality
KMnO
= 0.2000
This normality applies only to the above type of titration in which the oxidation number of Mn in 4 changes by 3 units.
KMnO
=
Therefore,
Normality
KMn0
of
(presence of acid)
is
0.2000
% = 0.3333 N
1
Each atom
of oxalate.
is its
Ca
combined with and equivalent to
mole
CaO
Since the milliequivalent weight of the oxalate radical molecular weight over 2,000, the milliequivalent weight of must be its molecular weight over 2,000.
1.000
0.3333
0.009347 gram CaO.
Ans.
225
92. Bichromate Process. Potassium dichromate is occasionally used as an oxidimetric standard. With chemical indicators (e.g.,
potassium ferricyanide as an external indicator, or diphenylamine sulfate as an internal indicator), the use of dichromate in direct
titrations is restricted to the titration of ferrous iron.
Oxidizing substances can be determined by the dichromate process, as in the permanganate process, by the addition of a measured excess
of a ferrous salt
solution.
bility in
and the titration of the excess with the standard Potassium dichromate titrations have greater applicapotentiometric titrations where chemical indicators are
not necessary.
The normal
of the
solution of potassium dichromate contains one-sixth 2 Cr2 Or per liter (see Sec. 89). gram-molecular weight of
the percentage of FesOs in a sample of limonite ore (impure Fe 2 C>3) if the iron from a 0.5000-gram sample is reduced and titrated with 35.15 ml. of a potassium dichromate
I.
EXAMPLE
What
is
solution of which 15.00 ml. are equivalent in oxidizing power to 25.00 ml. of a potassium permanganate solution which has an
"iron value" of 0.004750 gram? (This last expression is a conventional means of signifying that 1.000 ml. of the solution will
oxidize 0.004750
gram
of iron
from
the divalent to the trivalent state.}
SOLUTION:
Normality of
KMnO
=
t
=
OQO'V Fe/1 000
0.08506
08506
Normality
35.15
of
K Cr
2
25.00/15.00
0.1418
0.1418
U.oUUU
x|^ X 100 =
'
79.60 per cent
Fe2
3.
Ans.
Fusion with Na2 2 oxidizes the chromium in a 0.2000-gram sample of chromite ore to chromate. The addition of a 50-ml. pipetful of ferrous sulfate solution reduces this in acid solution to chromic salt (Cr2 Or + 6Fe++ + 14H+ -> 2O+++ +
EXAMPLE
II.
and the excess ferrous ions are titrated with Each pipetful of ferrous solution 7.59 ml. of 0.1000 N K2 2O7 What is equivalent to 47.09 ml. of the standard K 2 Cr2 7 solution. is the percentage of Cr in the sample? What weight of sample
2
GFe 4 4 4
"
"
"
+ 7H O),
of the
chromite ore should be taken such that the
milliliters of
226
N K2 Cr2 07 that are equivalent to the ferrous minus the milliliters of K^CrOy used in the titration, will equal the percentage of Cr2 03 in the sample? Net K2 Cr2 07 solution (equivalent to the Cr in the SOLUTION
standard 0.1000
solution added,
:
ore)
47.09
7.59
39.50 ml.
39.50X0. 1000
nonnn (j.ZOOO
Xg~ X 100 = 34.23 per cent

'-
Cr.
Ans.
part of this problem merely states that the net volume of 0.1000 2 Cr 2 O 7 (i.e., the milliliters equivalent to the
The second
NK
Cr
in the sample) is equal in value to the percentage of
Cr2 0a.
"
aX0.1000xCr O 3 /6,000
2
/\ JLUU
O>
0.2533 gram.
Ans.
93. Ceric Sulfate or Cerate Process.
Cerium
in the valence of
4 is a very powerful oxidizing agent, the yellow 4-valent eerie or complex cerate ions being reduced to colorless 3-valent cerous ions.
Ce++++
or,
+e-
+ e _> CC+++ + 3S04
A solution
and has
of eerie sulfate is satisfactory for oxidimetry titrations
certain advantages over potassium permanganate, particularly with respect to its greater stability and its lesser tendency to oxidize chloride ions. In the titration of reducing substances
that in solution are colorless, the yellow color of the excess eerie ions serves as a fairly satisfactory indicator. Titration of ferrous
ions can be accomplished with orthophenanthroline ("ferroin") The potential of the indicator in its as an internal indicator.
two and
states of oxidation lies
between those
of ferrous-ferric iron
cerous-ceric cerium.
Fe++
Ferroin' (red)
<=>
<=
Fe+++
+e
+e
ferroin" (blue)
Ceric sulfate
tions.
is
particularly satisfactory in potentiometric titra-

EXAMPLE.
after solution in
227
that
of a standard eerie solution required for titration will be one-half the percentage of Fe2O 3 in the sample (6.00 ml. of the eerie solution = 2.00 ml. 2 O4 solution - 3.00 ml. of 0.0800 NaOH)?
What weight of limonite should be taken so HC1 and reduction of the iron, the volume
KHC
SOLUTION:
KHC O
2
soln.
Ceric soln.
1
~~~~
= = = =
0.0800
0.120
0.240
3.00/2.00
N os an acid 0.240 N as a reducing agent

X
2.00/6.00
0.0800
0.0800
X Fe 2 () 3 /2,000 ^ ~~~ X
Ans.
nn 1UU
n &
x = 0.320 gram.
Problems
631.
A solution of permanganate contains 2.608 grams of KMnO

the normality of the solution and what
(a)
is
What
is
4 per 750 ml. the value of 1.000 ml. in
terms of
Ans.
(d)
Fe2 O3
(6)
Fe,
(a)
(c)
KHC O
2
4,
(d) TI 2
(6)
2,
(e)
U(SO4) 2
(oxidized to
(r)
UO ++)?
2
0.1100 N.
0.001871 gram,
632.
(c)
0.008784 gram, 0.02367 gram.
0.006144 gram,
0.007046 gram,
Given a solution of
=c=
solution
1.000 ml.
NaOH
acid phthalate). What is How many millimoles of
Mn
4 of which 1.000 ml. =c= 1.000 ml. 2 O4 0.1000 millimole of O 8 4 4 (potassium the value of 1 ml. of it in terms of grams of Fe 2 O 3 ?
=0=
KMnO
KHC
KHC H
are present in each milliliter?
Ans.
633.
0.01597 gram.
0.04000 millimoles.
of
How many
if
grams
KMnO
permanganate
a certain volume of
are contained in a liter of potassium it will oxidize a weight of potassium

of 0.2000
tetroxalate requiring one-half that solution for neutralization?
volume
potassium hydroxide
Ans.
4.214 grams.
634. What is the normality of a solution of potassium permanganate if 50.13 ml. will oxidize that weight of 2 O4 which requires 43.42 ml. of 0.3010 sodium hydroxide for neutralization?
KHC
Ans.
0.5214 N.
636. 1.000 ml.
1.000 ml.
KHC .H C2O4.2H O 0.2000 KMnO - 0.1117 gram Fe

2
4
2
=c=
ml.
KMnO
What
Ans.
is
the normality of the tetroxalate solution
when used
as an acid?
0.3000 N.
636. Given
two permanganate
4
solutions.
is
Solution
contains 0.01507
gram
of
KMnO
per
milliliter.
Solution B
of such strength that 20.00 ml.
228
0.1200
gram Fe. In what proportion must the two solutions be mixed in order that the resulting solution shall have the same oxidizing power in the 2 Cr2O 7 has? presence of acid as 0.3333
NK
A Ans
Vol.
-
v^Ts
A = _ 7A L576
*
'
637.
How many
milliliters of
anhydrous
Ans.
salt per liter
K 2 Cr2O7 solution containing 25.00 grams of would react with 3.402 grams of FeSO4 .7H2 in dilute
acid solution?
24.00 ml.
ml. of 0.100
638. If 25.0 ml. of ferrous sulfate solution in sulfuric acid require 31.25 7 solution for oxidation, how much water must be added 2 Cr2
NK
to 200 ml. of the reducing solution to
make
it
exactly one-twentieth normal?
Ans.
300 ml.
639. How many grams of pure K 2 Cr2 O 7 must be weighed out, dissolved, and diluted to exactly 700 ml. to make a solution which, when used in the titration of iron in a sample of ore, shall be of such a strength that four times the number of milliliters used with a half-gram sample will represent one-half
the percentage of
FeO
in the sample?
Ans.
640.
19. 12
grams.
How many
a mixture of 30 ml.
so that 30.00 ml.
N H SO and 2.000 millimoles of KHC O .II C2O .2H O of 0.1000 N KMnO will be required for the excess oxalate?
of 6
2
grams
of
pure
4
Pb
O = PbO .2PbO)
4 (
2
must be
2 4
dissolved in
2
4
2
Ans.
1.714 grams.
641. What weight of spathic iron ore (impure FeCO 3 ) should be taken for 4 (1.000 ml. =c= 0.3000 ml. analysis such that the number of milliliters of of potassium tetroxalate solution which is one-fourth normal as an acid) used
KMnO
in titration will
be twice the percentage of
FeO
in the ore?
Ans.
1.438 grams.
642. If 0.9000 gram of oxalic acid (H 2 C 2 O 4 .2H2 O) is allowed to react with 0.5000 gram of pyrolusite and the excess oxalic acid is titrated with permanganate, what must be the normality of the permanganate in order that one-half the percentage of MnO2 may be obtained by subtracting the buret
reading from the volume gram of oxalic acid used?
of the
is
permanganate equivalent to the 0.9000

the value of
What
A?
Ans.
643.
of
0.2300 N.
62.09ml.
of steel weighing 2.20
A sample
is
Mn
dissolved,
grams and containing 0.620 per cent and the manganese is eventually titrated in neutral
solution with standard
KMnO
2
4.
4H+.)
If 6.88 ml. are required,

4
(3Mn++ + 2MnO4 + 2H 2 O -> 5MnO2 + what is the value of each milliliter of the
KMnO
in
terms of
H C O .2HaO?
2
4
Ans.
0.00756 gram.

644.
229
Sodium formate, NaCHO2, can be
titrated in neutral solution accord2
ing to the equation:

If 10.00 ml. of the
3CHO-T
4
+ 2MnOr + H O -> 2Mn0 + 3CO +

2
2
50H~.
KMn0
what
by
(6)
is
this
method,
is
(a)
is
are equivalent to 0.08161 gram of sodium formate " the "iron value of each milliliter of the 4
KMnO
(c)
what
the value of each milliliter in terms of rnillimoles of
HO
2
2,
what
the value of each milliliter in terms of grams of CaO, and (d) what is the value of each milliliter in terms of grains of by the Volhard method?
Mn
Ans. (a) 0.02234 (d) 0.006598 gram.

646.
filtered,
gram,
(6)
0.2000
millimoles,
(c)
0.01122
gram,
Calcium can be precipitated as CaC 2 O4 .H 2 O, and the precipitate washed, and dissolved in dilute II 2 S0 4 The oxalic acid formed can
.
KMnO
(r)
solution of then be titrated with potassium permanganate. If a 0.1000 4 is used, calculate the value of 1.000 ml. in terms of (a) Ca, (&) CaO,
CaCO
Ans.
3.
(a)
0.002004 gram,
(6)
0.002804 gram,
(c)
0.005004 gram.
646. If the iron in a 0.1500-gram sample of iron ore is reduced and subsequently requires 15.03 ml. of permanganate for oxidation, what is the purity of the ore expressed as percentage of (a) Fe, (6) FeO, (c) Fe 2 O 3 ? (4.000 ml. 2 O4 .H 2 C,O 4 solution =c= 3.000 ml. 0.1000 N NaOII.) 4 o 3.000 ml.
KMnO
647.
KHC
Ans.
(a)
55.95 per cent,
(6)
71.96 per cent,
(c)
80.00 per cent.
the percentage purity of a sample of impure 2 C 2 O4 .2II 2 O if a sample weighing 0.2003 gram requires 29.30 ml. of permanganate solution, of which 1.000 ml. - 0.006023 gram Fe?
What is
Ans.
648.
99.53 per cent.
half-gram sample of pyrolusite is added a certain weight of After reaction in acid solution is complete, the oxalic acid (II 2 C 2 O 4 .2II 2 O). If the excess oxalic acid requires 30.00 ml. of 0.1000 4 for oxidation.
pyrolusite is calculated to contain 86.93 per cent 211+ -> oxalic acid added? (MnO2 2 C 2 O4
To a
N KMnO MnO
Mn++
2,
what
is
2
the weight ot
2
+H
+ 2CO + 2H O.)
A ns.
649.
0.8194 gram.
One hundred
5.00 ml. of 6
per
liter)
4.
KMnO
Ans.
K2 Cr2 O7 solution (10.0 grams per liter), and 75.0 ml. of FeSO4 solution (80.0 grams FeSO4 .7H2 O are mixed and the resulting solution is titrated with 0.2121 N Calculate the volume required.
milliliters of
N H SO
2
4,
5.63 ml.
660. In analyzing a one-gram sample of hydrogen peroxide with permanga4 in order that the buret reading nate, what must be the normality of the
KMn0
2
shall represent directly the percentage of
H O2?
Ans.
661.
0.5880 N.
A sample
is
of magnetite (impure
Fe3 O4 )
is
fused with
Na O
2
and
all
the
iron thus oxidized to the ferric state.
the total iron
After leaching with water andiacidifying, determined by reduction in a Jones reductor and titration with
230
= 30.10 ml. It is of such Volume of standard 4 required 4 solution o 2.000 ml. concentration that 2.000 ml. - 3.000 ml. 2 O4 NaOH =0= 1.000 ml. 2SO4 =0= 0.008138 gram ZnO. What is the normality of
KMnO
4
KMnO
KHC
the
KMn0
and how many grams of Fe3O4 are present
in the
sample of mag-
netite?
Ans.
0.2000 N, 0.4646 gram.
662. Six millimoles of
the resulting
is
25 ml. of 6 N reduced by the ferrous ions completely to the divalent form.
MnO are ignited in air (6MnO + O2 * 2MnsO4 ) and (= MnO2.2MriO) is dissolved in a solution containing H2 SO4 and A grams of FeSO4 .(NH4) 2SO4 .6H2O. The manganese
Mn O
3
If the excess
KMnO
ferrous ions require 12.00 ml. of 4 per ml.) calculate the value of A.
KMnO
(containing 0.05000 millimole of
Ans.
2.745 grams.
663. A sample of steel weighs 2.00 grams and contains 0.55 per cent Mn. After dissolving in 3 the manganese is oxidized to permanganate with solid BiO 2 and the excess BiO2 is filtered off. Excess FeSO4 .7H 2 O (dissolved
HNO
in water)
is
now added and

2
the excess ferrous ions require 20.0 ml. of 0.200

4
2
4 2
How many grams of FeSO .7H O were used? If the reduction had been made with Na C O instead of with FeSO .7II O, how many millimoles of Na C O should have been added in order for 20.0 ml. of the KMnO4 to be
4.
2
KMnO
2 2
required for the excess oxalate?
Ans.
1.39 grams.
2.50 millimoles.
.
664. A sample of chromite contains 30.08 per cent Cr2 O 3 After fusion of a 0.2000-gram sample with Na2 O2 and dissolving in acid, how many grams of FeSO4 .(NH4 ) 2 SO4 .6II 2 O should be added so that the excess ferrous ions will
require 15.00 ml. of 0.6011
N K Cr
2
7?
How many
If
=c=
milligram-atoms of Cr
does each milliliter of the dichromate contain? o 2.000 ml. of 2 O 4 .H 2 C 2 O4 .2H 2 O solution
3.000 ml. of this dichromate

1.000 ml.
KHC
KOH o
3.000 ml.
II 2 SO 4
of
how many moles of Fe 2 3 .xII2 O is each milliliter of the H 2 SO4 capable dissolving, and how many milliequivalents as an oxidizing agent would this
,
amount
Ans.
666.
of
Fe 2 O3 .xH 2 O represent?
0.2006 mg.-atoms.
4.467 grams.
0.00007514 moles, 0.1503 me.

is
analyzed for manganese by FeSO4 were used for the reduction of the oxidized manganese and 22.9 ml. of 0.0833 4 were used in the titration of the excess ferrous ions, what volume of the 4 would have been used if the same weight of sample had been analyzed (a) by the chlorate method (using the same 25-inl. pipetful of the above FeSO 4 ); (6) by the Volhard method on a Y^ aliquot portion of the prepared solution?
sample of steel weighing 2.00

If
grams
the bismuthate method.
25-inl. pipetful of
0.120
N KMnO KMnO
What
is
the percentage of
(a)
Mn
in the steel?
Ans.
666.
,
30.8 ml,
(6)
4.37 ml.
0.600 per cent.
A sample of chrome iron ore weighing 0.3010 gram is fused with leached with water, and acidified with The resulting solution 2 SO 4 of dichromate is treated with a solution containing dissolved crystals of
Na2 O2

FeSO4.(NH 4 ) 2 SO4.6H2 O, and the
dichromate (containing 5.070 grams
231
excess ferrous ions titrated with standard
A maximum of 2 Cr2 O7 per liter). 45.00 per cent Cr2 O 3 in the ore being allowed for, what minimum weight of FeSO4.(NH 4 ) 2 SO4.6II 2O should be used so that not more than a 50-ml. buretful of the standard dichromate would be required?
Ans.
4.124 grams.
,
667. A sample of pure sodium oxalate, Na2C 2 O 4 weighing 0.2500 gram, when dissolved in dilute IT 2 SO4 requires 40.15 ml. of eerie sulfate solution to give a permanent yellow color to the solution. What is the normality of the eerie
How many grams of pure Ce(SO4) 2 .2(NH4) 2 SO4 .2H 2 O should be dissolved in 500 ml. of solution in order to prepare a solution of this normality? If a sample of limonite weighing 0.3000 gram is dissolved in HC1, the iron reduced by metallic silver and then requires 25.03 ml. of the above eerie sulfate solution, orthophenaiithroline being used as indicator, what percentage of Fe 2 O 3 is shown to be present in the limonite?
sulfate solution?
Ans.
0.09294 N.
29.40 grams.
62.03 per cent.
668.
What
is
the normality of a solution of

2
of each milliliter in terms of

of
KMnCX and what is the value grams of Fe if when titrating a 0.1000-gram sample
oxidized to nitrate) the buret reading is one-half does many gram-atoms of
impure
KNO
(which
2
3
is
the percentage of each liter of the

669.
N O in the sample? How KMnO contain?

4
Mn
What must be
the value of
Fe2 O3 so that
in the titration of a half-gram
ml. of eerie sulfate in terms of grams of sample of impure sodium arsenite
twice the buret reading?

660.
(arsenite oxidized to arsenate), the percentage of As 2 3 in the sample will What is the molarity of the eerie solution?
be
A stock solution of KMnO

is
4 is
made up and
of
standardized.
It is
found
that each milliliter
10-ml. pipetful gram of O in the acid and the excess of the permanganate is reduced with 2 2 presence is solution then made neutral and The is O 2 2 resulting destroyed by boiling.
.
equivalent to 0.01597
Fe2 O 3
the manganous ions in the solution are titrated with more of the original stock KMnO4, the solution being kept neutral with ZnO (Volhard method). How many milliliters of KMnC>4 would be required in the titration?
and one of 661. A student standardized a solution of 4 against the same salt (KHC 2 O 4 .H 2 C 2 O4.2H2 0). The normality of the former was found to be 0.09963 as a base and of the latter to be 0.1328 as an oxidizing agent. By coincidence, exactly 50.00 ml. of solution were used in each standardization. Calculate the ratio of the weight of tetroxalate used in the
first
KOH
KMnO
case to that used in the second case.
acid (H 2 C 2 O4 .2H2 O), potassium is composed of oxalic Find the percentage of inert an and O4.H 2 impurity. (KHC O), each constituent from the following. A sample of the powder weighing
662.
powder
binoxalate
1.200 grams reacts with 37.80 ml. of 0.2500 solution; 0.4000 of ml with 43.10 reacts 0.1250 permanganate solution. powder
N NaOH
gram
of
232
663. It requires 15.27 ml. of SnCl2 solution to reduce an amount of iron that can be oxidized by 16.27 ml. of permanganate solution. This volume 2 O4.H 2 C 2 O4.2H 2 O of the permanganate will also oxidize that amount of NaOH. Calculate the solution which reacts with 16.24 ml. of 0.1072
KHC
normality of the SnCl2 solution. 664. Given the following data, calculate the percentage of
MnO
in a
sample of pyrolusite:
KHC O4.H C2O4.2II O added to react with MnO =

2
Sample
0.5217 gram
2
0.7242 gram
KMiiCX used
1.000 ml.
666.
KMnO ~
4
in titrating excess
22.42 ml.
2
2
4
0.009721 gram
is added to a sample of 50.00-ml. pipetful of acid requires 10.15 ml. of pure MiiO2 to reduce it. The excess of oxalic What weight of 2 is present? 0.2008 4 for its oxidation.
H C O .2H O 0.2016 N oxalic acid

2
N KMnO
MnO
666.
How many
grams
of
Cr2
when decomposed by
2CV"*4-
fusion with
4
with 3.000 millimoles of
Xa O KHC 2 O .H C O
2 2
are present in a sample of chromite ore if and treated acidified with 2 SO 4 2 2 ,
.2H 2 O(Cr2 O 7
H + 3C (V +
,
14H+
+
A
6CQ*
7H2 O),
the excess oxalate requires 20.00 ml. of 0.1000
KMn0
667.
4?
sample of spathic iron ore is analyzed for calcium by the permanganate method, following the precipitation of the calcium as oxalate. What weight of sample must be taken so that one-half the number of milliliters of KMnO4 may represent the percentage of CaO in the sample? 0.1000 668. What weight of iron ore should be taken for analysis so that the milliliters of 0.0833 N permanganate multiplied by 2 will give the percentage
of
Fe 2 Oa
669.
in the sample?
qualitative analysis of a certain silicate shows the presence of a large quantity of calcium and only traces of other positive elements. In the is precipitated quantitative analysis, the silica is removed and the calcium
The
calcium oxalate. It is found that the milliliters of 0.1660 required to oxidize the oxalate in a half-gram sample is almost exactly equal to the percentage of silica in the sample. What is the empirical formula of the pure mineral?
from the
filtrate as
X KMnOi
670. Hculnnditc
is
hydrous acid calcium metasilicate and yields on analysis
14.8 per cent water and 16.7 per cent alumina. If the calcium were precipitated 4 as calcium oxalate from a 1.00-gram sample, 32.8 ml. of 0.100 would be required for oxidation. Three-fifths of the water exists as water of
X KMn0
crystallization.
What
is
the empirical formula of heulandite?
sample of alloy containing manganese and weighing 4.35 grams is and the manganese eventually titrated in neutral solution with a standard permanganate having an "iron value" of 0.00640 gram (i.e., 1.000 ml. will oxidize that amount of ferrous iron in add solution). A volume of 13.05
671.
dissolved
ml.
is
required.
Mn
is
in the alloy.
672.
sample of magnetite (impure FeaCW
fused with
Xa O
2
and
all
the
iron thus oxidized to the ferric state.
After leaching with water, the iron in
UA1VAT1UJM
the solution
is
AND KUDUUT1ON METHODS

NK
.
233
nous
ions,
and
determined by reducing with SnCU, destroying the excess stanIf 30.00 ml. are required, 2 Cr2 O7 titrating with 0.3000
of
calculate the
number
grams
of
Fe3 O4
are present in each milliliter of the How many milligrams of 2 Cr 2 07? is each milliliter of the dichromate equivalent to as an oxidizing agent?
in the sample.
How many
grams
of
Cr
CeO2
673. From the following data, compute the weight of iron ore to be taken for analysis such that the percentage of Fe2 3 prasent is numerically equal to twice the number of milliliters of 2 Cr 2 7 used in the titration.
40.00 ml. 35.00 ml.
HC1 HC1
solution
o
=c=
solution
2.880 grams of AgCl. 40.00 ml. of 2 O4 .H 2 C 2 O 4 solution.
KHC
35.00 ml. of tetroxalate solution

674.
=0=
40.00 ml. of
K Cr O
2
2
solution.
prepared by dissolving 4.883 grams of to one 2 2 7 liter; a solution of ferrous salt is preexactly diluting FeSO of 39.46 4 .(NH4) 2 SO4 .6H 2 O and diluting to pared by dissolving grams one liter. What volume of the dichromate solution must be transferred to the
is
solution of dichromate
pure K Cr O
and
ferrous solution and thoroughly mixed so that the normality of one solution as a reducing agent will be the same as the normality of the other solution as an
oxidizing agent?
676.
An
fused material
oxide of iron weighing 0.1000 gram is fused with and the 4 The iron is reduced with stannous chloride, is dissolved in acid.
,
KHSO
mercuric chloride
titrated with 0.1000
formula of
676.
added to oxidize the excess stannous ions, and the iron is If 12.94 ml. were used, what is the the oxide FeO, Fe 2 O3 or Fe 3 O4 ?
is
N dichromate solution.
,
pure Pb 3O4 (= PbO2 .2PbO) are dissolved in a solution containing a mixture of 25 ml. of 6 2 SO4 and A grams of FeSO 4 .(NH4 ) 2 SO4 .6H 2 O, the 4-valent lead being reduced to Pb++. The excess of ferrous ions requires 12.00 ml. of 0.2500 4 for oxidation
Two
millimoles
of
N H
N KMnO
(a)
What
is
the value of
Al
(6)
How many
milligram-atoms of
Mn
are
KHC
4? (c) If potassium tetroxalate, present in each milliliter of the 2 O4 .H 2 C 2 O 4 .2H 2 O, had been substituted for the ferrous ammonium sulfate
KMnO
above,
grams
how many milliequivalents, how many millimoles, and how many of the oxalate would have been used for the reduction so that the excess
oxalate would have required 12.00 ml. of 0.2500

,
N KMnO ?
4
(d)
If lead
sesquioxide, Pb2 O 3 were analyzed by a similar method, what would be the milliequivalent weight of Pb 2 O3 ? 677. From the following data, calculate the percentage of iron in a sample
of limonite:
1.000 ml.
K O O o 0.006299 gram Fe
2 2
Dichromate solution used

Ferrous solution used Sample taken for analysis
1.000 ml. ferrous solution
678.
= = =
=0=
47.56 ml.
2.85 ml.
0.6170 gram
1.021 ml.
KOO
2 2
is known to contain 24.80 per cent Cr. with Na2 O2 leached with water, and is fused 0.2580 gram sample weighing of dichromate is treated with a solution The acidified with SO 2 4 resulting
certain
chrome iron ore

.
234
weight of FeSO4.7H2 O crystals which happens to be just 50 per cent more than amount necessary to reduce the dichromate. The excess of ferrous ions is 2 Cr2 O7 per titrated with standard dichromate (containing 0.02000 millimole is It not to calculate is volume What necessary required? (Hint: milliliter).
the
the
amount
of ferrous salt required.)
679. A solution of eerie sulfate is of such normality that 26.73 ml. are required to titrate the ferrous iron obtainable from 1.052 grams of FeSO4 .(NH4)2SO4.6H2 O. How many grams of Ce(S04 ) 2 .2(NH4 ) 2 SO4 .2H2 should be dissolved in 750 ml. of water and the resulting solution diluted to
one
is
order to prepare a solution of such normality that each milliliter 2 O 4 .Il2C 2 O4 .2H 2 O? equivalent to 0.006500 gram
liter in
KHC
680. (a)
will oxidize
many
What is the normality of a solution of 4 if each milliliter 0.008377 gram of iron from the ferrous to the ferric state? (b) How grams of Mn do 10.00 ml. of such a solution contain? (c) How many
KMn0
grams of Mn would 10.00 ml. of this KMnO4 oxidize to MnO2 by the Volhard ~ method (3Mn++ + 2MnO4 + 2ZnO -> 5MriO2 + 2Zn-f +)? (d) How many
milliliters of this KMn04 would be required to titrate 0.1200 millimole of ~ ~ sodium formate (NaCIIO2 ) according to the reaction: 3CHO2 + 2MnO4 H2O -> 2MnO2 + 3CO2 + 50H-? (e) How many grams of CaO would each milliliter of the KMnO4 be equivalent to in the volumetric method for calcium? (/) How many grams of As 2 O 3 would each milliliter of the KMnO4 be equiva-
lent to in the titration of arsenite to arsenate?
681. Find the percentage of Pb 3 4 in a sample of red lead that has been adulterated with PbO. 2.500 grams of the pigment are treated with 50.00 ml.
of potassium tetroxalate solution which is 0.1500 as an acid, and the excess of the latter requires 30.00 ml. of permanganate of which each milliliter is
equivalent to 0.005584
682.
gram
of iron.
sample of
steel
the chlorate method (see above). used to dissolve the precipitated
weighing 2.50 grams is analyzed for manganese by If a 25-ml. pipetful of 0.110 FeSO4 were
and 18.4 ml. of 0.125 N KMnO 4 were used to titrate the excess ferrous ions, what volume of the permanganate would have been used if the same weight of sample had been analyzed (d) by the bismuthate method (using the same 25-ml. pipetful of the above FeSO 4 ) (b) by the Volhard method on a J^ aliquot portion of the prepared solution?
Mn0
What
is
the percentage of
Mn
in the steel?
94. lodimetric
process
(or
is
The fundamental reaction in this that between iodine and sodium thiosulfate, with starch
Process.
sometimes chloroform) as the indicator.

I2
+ 28203= -> 21- + S^may
be divided into two groups, those involving direct titrations with standard iodine and those involving titrations with standard sodium thiosulfate.
Titrations
by
this process

Iodine solutions are prepared
235
by
dissolving iodine crystals, to-
gether with potassium iodide, in water. A normal solution contains I 2 /2 = 126.9 grams of iodine per liter. Standard solutions are used to titrate directly certain reducing agents of which the
following are typical:
SUBSTANCE
OXIDIZED TO
HS
2
so 3 ~
S2 o 3 -
sor so4
c
thiosulfate solutions are prepared by dissolving crystals normal solution contains Na2S2O3.5Il20/l = of the salt in water.
Sodium
248.2 grams of the hydrated salt per liter (see Sec. 89). Standard solutions of thiosulfate can be used to titrate almost any
oxidizing substance. The titration is made, however, by adding to the solution of oxidizing substance a large excess (roughly
measured) of potassium iodide. The oxidizing substance is reduced, liberating an equivalent amount of iodine, and the liberated iodine is titrated with thiosulfate. Typical oxidizing agents determined in this
SUBSTANCE ~
way
2
are as follows:
EQUATION
Cr2 O 7
Mn0
IOr
2MnO
BrO 3 -
O O - -+ 61- + 14H+ -> 2Cr

7
4
BKV
Cu++
C1 2
II 2
I0r +
2Cu++
2
2
3I 2 7H 2 O 16H+ -> 2Mn++ 5I 2 10I~ 8H2 O 6H+ -> Br~ 3I 2 3H 2 O 613II 2 O 611+ -> I3I 2 61-
+++
+ +
+ +
41- ->
Cu 2 I 2
+
2 2
I2
C1 + 21- -> 2C1- + I H O + 21- + 211+ - I + 2H O

2
2
Since an oxidizing agent liberates its own equivalent of iodine, the volume of thiosulfate required for the liberated iodine in any
given case is the same as would be required if the thiosulfate were used directly and reduced the substance to the form indicated.
In calculations, therefore, the equivalent weight of the substance titrated is found in the usual way by dividing the formula weight of the substance by the total change in oxidation number. In titrations in acid solution, a standard solution of potassium
iodate containing an excess of potassium iodide is a convenient substitute for standard iodine. It is a colorless, stable solution, but
236

it
comes in contact with acid the two ingredients immedi~~ I~ + ately interact and liberate free iodine (IO 3 + 61"" j- 6H+ 3I 2 + 3H 2 0). In the titration of a substance in acid solution, this standard solution, therefore, behaves as if it were a standard solution of iodine.
sulfur
in
steel.
when
It is used, for example, in the determination of
KI0
by
equivalent of 6 iodine atoms, = 3.567 grams of 3 /60

dissolving this
of
Since the iodate molecule has the oxidizing a tenth-normal solution contains
KIO3
amount
per liter and can be prepared of the pure crystals, together with
an excess
liter.
potassium iodide, in water and diluting to exactly one

I.
EXAMPLE
An
excess of potassium iodide
is
added to a
solu-
tion of potassium dichromate, and the liberated iodine is titrated sodium thiosulfate solution. How with 48.80 ml. of 0.1000
many grams
SOLUTION:
of
N K Cr 07 did the dichromate solution contain?

2
Potassium dichromate liberates an equivalent amount of iodine from an iodide (i.e., 6 gram-atoms = 6 gramequivalents of iodine per mole of dichromate)
:
Cr2 0r
and the
+ 61- +
14H+ -> 2Cr+++
+ 3I + 7H O
2
2
liberated iodine
is
titrated with thiosulfate
2S 2 O 3~
+ k -> S O ~ + 214
6
The volume
if
of titrating solution is the
same as
it
would have been
the original solution had been titrated directly to the indicated
products.
Grams
of
K Cr O
2
48.80
0.1000
0.2393.
An*.
EXAMPLE
as
II.
The
sulfur
from 4.00 grams
of steel is evolved
HS
2
and
iodine solution.
What
the percentage of S in the steel? 1.000 ml. of the iodine in terms of As2 O 3 ?
is
=c=
What is the value of How many milliliters
of the iodine will
which 1.000 ml.
be reduced by 40.00 ml. of Na2S 2 3 solution of 0.006357 gram Cu. What volume of iodate-
iodide solution containing 10.0 millimoles of KIO 3 and 50.0 grams of KI per liter would be required to titrate the 2 S from 5.00 grams of the above steel? The equations involved are as follows:
237
+ 2HCOr + !- As0 s + 21- + 2CO + H O 2Cu++ + 41- -> Cu I + I IO + 61- + 6H+ -* 3I + I- 4- 3H O

1
SOLUTION:
1.
60
0.05000
Xn-TjL
'
100
0.0320 per cent
S.
Ans.
Ans.
1.000
0.05000
-r^ = 0.002473
gram AszO3
The addition of KI to a copper solution the Cu and the liberation of an amount
will
cause reduction of
of iodine equivalent to the copper present. This iodine may be titrated with thiosulfate and the normality of the latter found from the amount of Cu
present.
In the above case,

of
Normality
Na S O 3
2 2
solution
=
|
000
=
Cii/1 000
'
1000
Volume
of 0.0500
I2
solution
40.00
1000
80.00 ml.
Ans.
10.0 millimoles
Normality
of
KIOs = 60.0 milliequivalents KIO, = 0.0600 N
1.67 ml.
Ans.
The
reaction
As0 8= +
I2
+HO
2
<=
AsOr +
21-
211+
is
revers-
ible, for
3-valent arsenic
is is
oxidized
whereas 5-valent arsenic
by iodine in neutral solution, reduced by iodide in the presence of

These reactions can be the two forms of arsenic when
2
acid with the liberation of free iodine.
made
use of in the determination of

III.
present in the same solution.
EXAMPLE
material.
A powder consists of Na HAs0 + As O + inert

3
2
A sample weighing 0.2500 gram is dissolved and titrated
with standard iodine in a solution kept neutral by excess dissolved NaHCO 3 (AsO 3s + I 2 + 2HCO 3- - AsO 4s + 21- + 2CO 2 + 2 O).
The
titration requires 15.80 ml. of 0.1030

of
NI
+
2.
Hydrochloric acid
and an excess
KI
are added (AsO<r
21-
+ 8H+ -
AS+++
-f
238
I2
2

and the
liberated iodine requires 20.70 ml. of 0.1300 Calculate the percentages of Na2HAsOs and
+ 4H O)
NajSaOs.
in the sample.
SOLUTION:
15.80
20.70
2.691
1.628
X X -
0.1030 0.1300
1.628
= = =
1.628 milliequivalents 3-valent 2.691 milliequivalents total As

1.063 milliequivalents 5-valent
As As
9 ono
0.2500
!
X
5
100
55.33 per cent

,
>
A Ans.
063
As2
'
U.ôUU
100
24.42 per cent
As2
Problems
683.
A
2
solution of iodine contains 15.76

milliliter as
r
the value of each

(c)
grams of I 2 per liter. an oxidizing agent in terms of (a) SO 2

,
What
(6)
2
is
H SOj,
Na 2S O
Ans.
3,
(d)
As?
(6)
(a)
0.003978 gram,
0.005097 gram,
(r)
0.01963 gram,
(d)
0.004655
gram.
684.
in terms of
What is the value of 1.000 ml. of 0.04000 N sodium thiosulfate solution Cu? What is the normality of a thiosulfate solution if 25.00 ml.
by 0.01563 gram
of copper?
are required to titrate the iodine liberated
Ans.
686.
0.002543 gram.
0.009833 N.
What
is
the value of 1.000 ml. of

2 2 3)
an iodine solution (1.000 ml.
o=
0.03000
gram Na S O
in
terms
of
As 2 O 8 ?
Ans.
686.
0.009386 gram.
From
3
Na S O
2
solution
the following data calculate the normality and molarity of the and the value of 1.000 ml. in terms of grams of potassium
bi-iodate[KH(I0 8 )l. 1.000 ml. K 2 Cr 2 7 o 0.005585 gram of Fe. 20.00 ml. K 2 Cr 2 O 7 liberates sufficient iodine from potassium iodide to require 32.46 ml. Na 2 S 2 3 solution for reduction.
Ans.
0.06162 N, 0.06162
M,
0.002003 gram.
<^ 0.005000 gram Fe) 4 solution (1.000 ml. 687. Forty milliliters of with sodium thiosulfate is titrated iodine are added to KI and the liberated of the thiosulfate ml. of 1.000 value is the solution requiring 35.90 ml. What
KMnO
solution in terms of copper?
Ans,
688.
0.006345 gram.
of sodium thiosulfate is freshly prepared, and 48.00 ml. are the iodine liberated from an excess of KI solution by titrate to required
A solution

0.3000 gram of pure KIOs. value in terms of iodine?
239
and
its
What
are the normality of the thiosulfate
Ans.
689.
0.1752 N, 0.02224 gram.
The thiosulfate solution of the preceding problem is allowed to stand, 1.00 per cent of the Na2 S 2 3 is decomposed by a trace of acid present in = What is the new normality of 2H+ -> 2 SO3 the solution (S2 3 S). the solution as a reducing agent, assuming oxidation of sulfite to sulfate?
and
Ans.
0.1768 N.
690. A steel weighing 5.00 grams is treated with NCI and the H 2 S is evolved and eventually titrated with a solution containing 0.0100 mole of KIO3 and 60 grams of KI per liter. If 3.00 ml. are required, what is the percentage of
sulfur in the steel?
Ans.
0.0576 per cent.
0.03750 gram CuSO 4 .5H 2 O) 691. If 20.00 ml. of thiosulfate (1.000 ml. are required for a certain weight of pyrolusite by the Bunsen iodimetric method, what weight of 2 C 2 O4 .2H2 O should be added to a similar sample to require
20.00 ml. of 0.1000

the Bunsen method
N KMnO
MnO
KI
2
latter is passed into
by the commonly used indirect method? In reduced by TTC1, the C1 2 liberated from the solution, and the liberated iodine is titrated with
4
is
thiosulfate.
Ans.
0.3154 gram.
692. Titrating with 0.05000 iodine, what weight of stibnite ore should be taken so that the percentage of Sb 2 S3 in the sample will be 1 J^ times the buret I2 2HCO3 - -+ SbCV 21- 2CO2 How 2 O). (SbOr reading? many millimoles of Na2 S2 O 3 .5H 2 O is each liter of the above iodine equivalent to?
+H
Ans.
693.
0.2831 gram.
50.00 millimoles.
sulfite
weighing 1.468 grams was added to was titrated with 42.40 ml. of ml. 1.000 was O of which O .5H solution S Na2 2 3 2 equivalent to the iodine liberated from 0.01574 gram of KI. Calculate the percentage of Na2 SO3 in the sample.
sample of sodium
100 ml. of 0.1000
iodine.
The
excess iodine
Ans.
694.
25.67 per cent.
containing 70.00 per cent Sb is given to a student with a solution of iodine of which he had found for analysis. be to 0.004948 to 1.000 ml. gram of As 2 O 3 The normality of the equivalent solution, however, had changed, owing to volatilization of iodine, and the student reports 70.25 per cent Sb. What are the percentage error and the present normality of the iodine solution, and how much 0.2000 N iodine solu-
A sample of stibnite
He
titrates
tion
must be added to one
strength?
(SbOr
I2
the solution to bring it back to its original 2 O.) 2HCOr -> SbO4 3 21- 2CO2
liter of
+H
Ans.
0.36 per cent, 0.09965 N.
3.5 ml.
696. A sample of impure potassium iodide weighing 0.3100 gram is treated with 0.1942 gram ( = 1 millimole) of 2 CrO4 and 20 ml. of 6 N H 2 SO4 and the solution is boiled to expel all the free iodine formed by the reaction. The
240
solution containing the excess chromate is cooled, treated with excess KI, and Na2 S 2 O 3 requiring 10.20 ml. Calculate the liberated I 2 titrated with 0.1000 the percentage purity of the original potassium iodide.
Ans.
696.
3
96.38 per cent.
A standard stock solution is made by dissolving 50.0 millimoles of and 100 grams of KI in water and diluting to 10.00 liters. A sample of Bureau of Standards steel weighing 5.00 grams and certified to contain 0.0530 per cent sulfur is treated with HC1. The sulfur is liberated as H 2 S, caught in ammoniacal zinc sulfate solution, and eventually titrated in the presence of acid with the above-mentioned stock solution. What volume is
KIO
required?
What is the oxidizing many grams of KI in excess of the

Ans.
697.
theoretical
normality of the iodate solution? How amount were used in preparing
the stock solution?

5.52 ml.
0.0300 N.
58.5 grams.
The copper
(1.000 ml.
solution with excess
in a 0.2500-gram sample of copper ore is treated in KI and the liberated iodine titrated with 16.50 ml. of
NaÔa
Ans.
0.003619 gram
KBrO ). What
3
is
the purity of the ore
expressed in terms of percentage of
Cu 2 S?
68.28 per cent.
698. If the arsenic trichloride from 50 grams of impure copper is distilled off, absorbed in dilute alkali, and finally oxidized by 20 ml. of 0.0200
iodine solution, find the percentage of arsenic in the sample.
Ans.
699.
tion
0.030 per cent.
A mixture of As O
2
and As2 O 6 and
inert matter
is
dissolved and titrated
in neutral solution with 0.05000

is
acidified
and excess KI
3.
I 2 , requiring 20.10 ml. The resulting soluis added. The liberated I 2 requires 29.92 ml. of
Na2 S2 0.1500 in the sample.

Ans.
Calculate the
number
of
grams
of
combined As 2 O 3
As 2 O 6
0.2498 gram.
700. A mixture of pure potassium permanganate and pure potassium chromate weighing 0.2400 gram, when treated with KI in acid solution, liberates sufficient iodine to react with 60.00 ml. of 0.1000 N sodium thiosulfate solution. Find the percentages of Cr and Mn in the mixture.
Ans.
Cr = 11.0 per
cent,
Mn =
20.5 per cent.
701. A sample of pyrolusite is treated with ITC1, the liberated chlorine is passed into potassium iodide, and the liberated iodine is titrated with Na2 S 2 O3 solution (49.64 grams of Na 2 S 2 O 3 .5H 2 O per liter). If 38.70 ml. are required, what volume of 0.2500 N 4 would be required in an indirect determina-
KMnO
tion in which a similar sample is reduced with 0.9000 and the excess oxalic acid is titrated with the 4?
gram
of
H^CaOÎÔ
KMnO
is
Ans.
702.
26.16ml.
One
milliliter of
is
a thiosulfate solution
of copper
and
also equivalent to 1.50 ml. of
a certain iodine solution.
equivalent to 0.005642 gram Cal-

culate the value of one milliliter of the iodine solution in terms of
(a) Sb, (b)
241
grams
of
As,
(c)
As2 S8
(rf)
Sb2 O8
703. Calculate the percentage of iron in a sample of crude ferric chloride weighing 1.000 gram if the iodine liberated by its action on an excess of potas-
sium iodide
required.
is
excess thiosulphate
reduced by the addition of 50.00 ml. of Na2 S2 O3 solution and the is titrated with standard iodine, of which 7.85 ml. are
45.00 ml. iodine
=0= =c=
45.95 ml. thiosulfate 45.20 ml. iodine
45.00 ml. arsenite solution

1.000 ml. arsenite solution
704.
0.00516 gram As 2C>3.
the copper
weight of copper ore should be taken for analysis so that when determined by the regular iodimetric method using 0.05000 sodium thiosulfate, the buret reading will be two-thirds the per cent CuS in
is
What
the ore?
What
(1.000
KMnO
3Mn++
+
A
the molarity of the thiosulfate solution? What volume of =0= 0.0005493 by the Volhard method: gram of 2II 8 O) will react with an 2Zn++ 2ZnO -> 5Mn0 2 2MnO4
is
ml.
Mn +
excess of soluble iodide in the presence of acid to require 20.00 ml. of the above
thiosulfate for reduction?
706. special analysis calls for the preparation of an exactly 0.1000 solution of sodium thiosulfate. The usual method is to prepare a solution of slightly greater strength and standardize it, subsequently diluting with a
calculated
and
carefully
measured amount
of water.
In this case a stand-
ardization of the diluted solution was also
made
to ensure its accuracy.
The data
follow:
FIRST STANDARDIZATION
SECOND STANDARDIZATION
Pure Cu, grams

0.2504
Thiosulfate, ml.
Pure Cu, grams

0.2492 0.2507
0.2631
Thiosulfate, ml.
37.98
39.24
39.09 39.27
0.2592 0.2576
39.04
41.28
Calculate the volume of water necessary to reduce 1,000 ml. of the first and calculate the amount that apparently was actually added.
solution to a normality of 0.1000,
an iodine solution are exactly equivalent in oxidizing of ml. a to 49.47 2 Cr2 O 7 solution of which 1.000 ml. will liberate power 0.004263 gram of iodine from KI, calculate the normality of each solution.
706. If 50.00 ml. of
weighing 0.3321 gram, was boiled with an excess of chlorine was passed into a soluton of KI, and the Calculate the I 2 liberated was titrated with 68.21 ml. of Na2S2O 3 solution.
707. Pure
2
K Cr
2 C>7,
strong HC1.
The evolved
normality of the
Na2S 2O3
solution.
708. What must be the normality of a standard iodine solution so that, a 0.5000-gram sample of stibnite (impure Sb2 Ss) is taken for analysis, the number of milliliters of solution may represent directly the percentage of " 2H+ 2I~). 2 O -> SbO4 It antimony? (SbO8
if
+H
242
709.
powder
consists of a mixture of
Na3AsO4.12H O, Na2HAsO 3 and

2
,
inert matter.
It is dissolved
and
titrated in neutral solution with 0.08100
I2 ,
requiring 15.60 ml. The resulting solution is acidified and excess KI is added. The liberated iodine requires 8.58 nil. of 0.1200 molar Na2 S2 O 3 solution.
Calculate the
amount
2
of 5-valent
of
Na AsO4 .12H
3
and grams
and of 3-valent arsenic in terms of grams combined As2O 3 respectively.

,
of
weight of sulfite liquor should be taken for analysis so that 0.0125 gram Na 2 S 2 3 .5II 2 O) the milliliters of I 2 solution required (1.000 ml.
710.
What
and the percentage

711. If the
total
SO 2
3
shall
be in the respective ratio of 20:3? a carbonate

if
amount
2
of copper in
is
ore, expressed in
terms of
percentage
Cu
(OIT) 2
CO
53.05 and
25.72 ml. of
Na2S2 O
are eventually
required to titrate the iodine liberated from excess KI by the copper from a half-gram s'ample, what is the value of 1.000 ml. of the thiosulfate in terms of
grams of
712.
(a)
KBrO
sulfur
3,
(b)
KII(IO 3 ) 2 ?
steel is
The
from a 5.00-gram sample of
evolved as II 2 S and
eventually titrated in the presence of acid with standard iodine solution (1.00 ml. o 0.004945 gram As 2 O 3 ), of which 1.90 ml. are required. What is the
percentage of sulfur in the steel? If a standard potassium iodate-iodide solution had been substituted for the standard iodine and a volume identical
with the above had been required, how many grams of KIO 3 would have been present in each milliliter of the solution? Could the iodate solution have been standardized against pure As 2 O 3 as the iodine solution was?
,
Explain your answer.
CHAPTER XIV PRECIPITATION METHODS

(PRECIPITIMETRY)
95. Equivalent Weights in Precipitation Methods. In precipitation (or "saturation") methods a substance is titrated with a standard solution of a precipitating agent. At the completion of the precipitation the precipitating agent reacts with an indicator
and a color change takes place. For example, in the Volhard method for silver, silver ions are titrated with a standard solution
potassium thiocyanate (Ag+ + CNS~ AgCNS) and the end point is determined by the red color formed when an additional " drop of the thiocyanate reacts with ferric alum indicator (Fe*4 1 +
of
"
4CNS--*Fe(CNS) 4-).
Similarly silver ions solution with standard
and halide ions can be
titrated in neutral
NaCl
or standard
AgNO3 using
certain so-
(e.g., fluorescein), which form colored on the surface of the particles of precipitate and give compounds a change of color at the equivalence point. In determining the equivalent weight of a constituent being precipitated, 1.008 grams of hydrogen ion is again taken as the stadnard of reference. The equivalent weight is that weight which in precipitation reacts with the equivalent of that amount of hydrogen ion. Here the point of view is that of general metathesis rather than that of neutralization (as in acidimetry) or of oxidizing power (as in oxidimetry). Knowledge of valence and a simple inspection of the equation usually suffice to determine the correct
called adsorption indicators
In a great majority of cases the gram-equivalent weight is found by dividing the formula weight by the net number of charges on the constituent actually taking part in the
equivalent weight.
reaction.
In the reaction between silver nitrate and sodium chloride AgCl) the equivalent weights of the reacting sub(Ag+ + Cl~
stances are
AgNOs/1 and NaCl/1,
between barium chloride
respectively. In the reaction and sodium sulfate (Ba ++ SO4 > 243
==:
244

in each case is one-half of the
BaSO4) the equivalent weight

lecular weight.
mo-
The equivalent weight

Na2HPC>4/l =
phosphate as an acid is Na2HPO4 /2 = 71.03; and as a phosphate, Na2 HP04 /3 = 47.35. Reactions in this class may be direct or indirect. That is, the titrating solution may be added in amounts just sufficient to precipitate all of the substance to be determined; or in certain cases an excess of the precipitating agent may be added and the excess titrated by means of a precipitating agent. Because of the difficulty of finding suitable indicators to show the completion of the reactions a great many precipitating reactions cannot be used
satisfactorily for quantitative titrations. The Volhard method for silver is a direct
anhydrous disodium 142.05; as a sodium salt,

of
trated in
Example
below.
method and The Volhard method can
is illus-
also be
applied as an indirect process to the determination of chloride,
bromide, iodide, cyanide, and thiocyanate. This is illustrated in Example II below. EXAMPLE I. What is the percentage of silver in a coin, if a
0.2000-gram sample requires 39.60 ml. of potassium thiocyanate solution (0.4103 gram of KCNS per 100 ml.) for the precipitation
of the silver?
SOLUTION:
of the salt.
Ag++CNS~~*AgCNS A liter of the KCNS solution contains

Its normality is
4.103 grams
4.103
4.103
39.60
KCNS/1 X 0.04223 X Ag
nqnnft u.ûuu
0.04223
97.17
^^ X 100 = 90.20 per cent Ag.
Ans.
EXAMPLE
0.5000 gram.
II.
sample of impure strontium chloride weighs
After the addition of 50.00 ml. of 0.2100
N AgNO
and
filtering out of the precipitated silver chloride, the KCNS to titrate the silver. requires 25.50 ml. of 0.2800 is the percentage of SrCU in the sample?
filtrate
What
SOLUTION:
Milliequivalents of Milliequivalents of
AgNOs added
KCNS required
=
10.50
Net
milliequivalents
7.14
= =
50.00
3.36
X 0.2100 25.50 X 0.2800 =
10.50 7.14
PRECIPITATION METHODS
3.<
245
Per cent SrCl2
. Kt U.OUv/U
^'
w X 100 = 53.3 per cent.
A sample of feldspar weighing L500 grams is and eventually there is obtained a pure mixture of decomposed, KC1 and NaCl weighing 0.1801 gram. These chlorides are disEXAMPLE
III.
solved in water, a 50-ml. pipetful of 0.08333
N AgNO
3 is
added,
and the
0.1000
precipitate filtered off.
The
filtrate requires 16.47 ml. of
KCNS,
ferric
alum being used as
indicator.
Calculate
the percentage of
Let x
= grams
of
KÔ in the silicate. KC1 obtained

0.1801
Then
x - grams
of
NaCl
Trri/1 QAQ
Total milliequivalents of mixed halides
+
0.1801-x
NaCl/1,000
so/boo
0.1517
+
'
l.oOu
K O/2KC1 ^ X
2 *
mm x
inn 100
of 0.1233
/
(5
08333>
~ (16 47 x (IG^
-
1000)
0.1517
,
gram KC1
,
A A 6.40 per cent.
A Ans.
Problems
713.
What volume
silver nitrate solution is required to pre-
cipitate the chlorine
from a sample of rock salt weighing 0.2280 gram and containing 99.21 per cent NaCl and no other halide?
Ans.
714.
31.37 ml.
What volume
20.36 ml.
of 0.08333
BaCl 2
solution
is
the sulfur from a solution containing 0.2358
gram
of
FeSO 4 .7H 2 O?
Am.
715.
a precipitating from a 1.000-gram MgNH4PO4 agent is is required? volume What sample of dolomite containing 14.01 per cent MgCO 3
solution of a soluble phosphate that used to precipitate the magnesium as
is
0.2000
N as
Ans.
716.
16.62 ml.
which is 0.1121 normal as an oxidizing agent What is the is used to precipitate BaCrO 4 from 0.5060 gram of BaCl 2 .2H2 O. volume and what normality of the solution of 2 Cr2 C>7 as a precipitating agent,
solution of
2
K Cr
is
required?
Ans.
0.07473 N, 55.42 ml.
246
717.

What volume
of oxalic acid solution
which
2
is
0.2000
as
an acid
is
required to precipitate the calcium as
cement containing 60.32 per cent

acid as a precipitating agent?
CaC O4.H 2 O from 0.4080 gram of CaO? What is the normality of the oxalic
Ans.
43.88ml.
0.2000 N.
718. In the volumetric analysis of a silver coin containing 90.00 per cent Ag, a 0.5000-grarn sample being used, what is the least normality that a potassium thiocyanate solution may have and not require more than 50.00 ml. of
solution in the analysis?
Ans.
0.08339 N.
3 719. Pure elementary arsenic weighing 0.1500 gram is dissolved in (forming HaAsO^. The resulting solution is made neutral and then treated
HNO
with 150 ml. of 0.06667
M AgNO* which precipitates
all
the arsenic as
Ag 3 AsO 4
The precipitate is washed, dissolved in acid, and the silver in the resulting solution of the precipitate is titrated with 0.1000 using ferric ions as
M KCNS
indicator.
How many
60.06 ml.
is
milliliters are required?
Ans.
720.
What
of the
grams
the percentage of bromine in a sample of bromide if to 1.600 AgNO 8 solution and the sample are added 52.00 ml. of 0.2000
excess silver requires 4.00 ml. of 0.1000 of AgCNS?
N N KCNS solution for the precipitation
Ans.
49.95 per cent.
721. The purity of soluble iodides is determined by precipitating the iodine with an excess of standard silver nitrate and titrating the excess AgNO 3 with thiocyanate solution. The silver nitrate is made by dissolving 2.122 grams of metallic silver in nitric acid, evaporating just to dry ness, dissolving the residue in water, and diluting to exactly 1,000 ml. From a buret 60.00 ml.
of this solution are
is
titrated with 1.03 ml. of thiocyanate solution of
added to 100.0 ml. of a solution of an iodide and the excess which 1.000 ml. will preof silver as
cipitate 0.001247
gram
AgCNS.
Calculate the grams of iodine
present as iodide in the 100-ml. portion of the solution.
Ans.
0.1482 gram.
722. A mixture of pure LiCl and Bal2 weighing 0.6000 gram is treated with 45.15 ml. of 0.2000 normal AgNO 3 solution, and the excess silver is then KCNS solution with ferric alum as an titrated with 25.00 ml. of 0.1000 indicator. Find the percentage of iodine present in the mixture.
Ans.
723.
44.61 per cent.
A
it
K 0.
2
What must
ml. of
sample of feldspar contains 7.58 per cent Na2 O and 9.93 per cent be the normality of a silver nitrate solution if it takes 22.71 to precipitate the chloride ions from the combined alkali chlorides
from a 0.1500-gram sample? Ans. 0.03005 N.
PRECIPITATION METHODS
724.
247
A sample of greensand weighing 2.000 grams yields a mixture of NaCl

After the chlorides have been dis-
and KC1 weighing exactly 0.2558 gram.
3 are added to precipitate the chlorine solved, 35.00 ml. of 0.1000 and the excess is titrated with 0.92 ml. of 0.02000 thiocyanate solution.
N AgNO
Calculate the percentage of potassium in the sample.
Ans.
726.
6.36 per cent.
10.0 per cent 2 a residue of NaCl
1.000-gram sample of feldspar containing 3.05 per cent NaÔ and O is decomposed with CaCO 3 4 C1 and eventually yields KC1 which is treated with 75.0 ml. of 0.06667 AgNO 8
+ NH
The
precipitate
is filtered off
and the
filtrate titrated
with 0.1000
M M KCNS.
How many
Ans.
milliliters are
required?
18.93 ml.
726.
How many
all
milliliters of
0.2500
N AgNO
precipitate
the
chlorine
from a solution containing 0.5680 gram
solution are required to of
BaCl 2 .2H 2 0?
727. How many milliliters of a solution of Na 2 HPO4.12H 2 O which is tenth normal as a sodium salt are required to precipitate the calcium as Ca 3 (PO 4 )2 from a solution containing 0.5000 gram of Ca(NO 3 ) 2 ? 728.
How many
milliliters of
K Cr O
2
will precipitate all the lead as
PbCrO 4 from
0.01597 gram Fe2 O 3 ) (1.000 ml. a solution containing 0.2510 gram
of
Pb(N0 3 ) 2 ? 729. To precipitate
the sulfur from a certain weight of ferrous
ammonium
of iron
sulfate contaminated with silica

of 0.2000
and water requires a number
of milliliters
barium chloride solution exactly equal to the percentage
in the sample.
What
is
the weight of sample?
of
730. In the analysis of a sample of silicate weighing 0.8000 gram, a mixture NaCl and KC1 weighing 0.2400 gram was obtained. The chlorides were
dissolved in water, 50.00 ml. of 0.1000 AgNO 3 added, and the excess of silver ferric alum titrated with solution, being used as an indicator. In the
KCNS
were used, in than the stronger normality and of Na2 in the silicate.
last titration, 14.46 ml.
and the reagent was exactly 0.30 per cent AgNO 3 solution. Find the percentage of K 2O
K O.
2
sample of feldspar contains 7.73 per cent Na2O and 9.17 per cent the normality of a silver nitrate solution if 25.18 ml. chloride ions from the combined chlorides in a sample weighing the precipitates
731.
What must be
0.1500 gram?
mixture of pure chlorides of potassium, lithium, and sodium weighgram is obtained from 1.600 grams of a silicate. The chlorine in this mixture is equivalent to 80.00 nil. of 0.1110 N silver nitrate solution, and the potassium is equivalent to 0.1052 gram of 2 PtCl 6 Compute the per732.
ing 0.4800
centage of
733.
K O and of Li O in the silicate.

2 2
mixture of LiCl and BaBr2 weighing 0.5000 gram
is
treated with
37.60 ml. of 0.2000
silver nitrate
and the excess
of the latter titrated with
248
18.50 ml. of 0.1111
thiocyanate solution.
Find the percentage of Ba
in the
mixture.
734. Express the calculation of the per cent
Na O
2
in
silicate
containing
sodium and potassium from the following data: Weight of sample = A grams. Weight of NaCl + KC1 obtained = B grams. Weight of AgN0 3 crystals added to precipitate the chlorine from these chlorides and give an excess = C grams. Volume of D normal KCNS required to titrate the excess silver
ions
= E
ml.
CHAPTER XV COMPLEX-ION FORMATION METHODS

(COMPLEXIMETRY)
Weights in Complex-ion Methods. Reactions in which complex ions are formed are common in chemistry, particularly in qualitative analysis, and many of them should already be familiar to the student. Typical cases where complex ions are formed are the following:
96. Equivalent
+ Ag+ + 2NH4 OH - Ag(NH,) a + 2H 2 Cd++ + 4CN- - Cd(CN) 4
6C1-
Unfortunately, because of lack of suitable indicators, few of the many reactions of this class can be used as a basis for a volumetric analysis. Most of those that are in common use are covered
by the examples and problems below. The gram-equivalent weight of a substance involved
in
a com-
plex-ion forming reaction is based as usual on 1.008 grams of H+ as the standard of reference. As in all previous cases, if one for-
hydrogen equivalents, The its equivalent weight is its formula weight divided by A. milliequivalent weights of the metal ions in the above four equations are Ag/2,000, Cd/4,000, Sn/6,000,
ively.
mula weight
of a substance reacts with
and Hg/4,000,
respect-
Conversely, the equivalent weight of

is
CN~
of
in the second
reaction
4CN/2,000 = CN/500, each atom sidered as equivalent to 2 atoms of H+

.
Cd
being con-
LIEBIG METHOD. How many grams of NaCN EXAMPLE are present in a solution that is titrated just to a permanent turbidity with 26.05 ml. of AgNO 3 solution containing 8.125 grams
I.
of
AgNO
per
liter?
SOLUTION:
2CN- + Ag+249
250

,
The next drop of AgNOs gives a permanent precipitate of Ag2(CN) 2

which serves as the indicator for the above reaction. ~ Ag(CN) 2 + Ag+ -> Ag2 (CN) 2 (indicator)
Normality of
812^ AgN03 =
0.04782
The
in this case is not NaCN/milliequivalent weight of 1,000 since two cyanide ions react with one silver ion in the titra-
NaCN
The milliequivalent weight of tion. here to be 2NaCN/l,000.

Then,
NaCN may
be considered
Grams NaCN =
26.05
0.04782
f^N = 0.1221 gram.
Ans.
Or, from another point of view, if 26.05 ml. are necessary to form the complex ion as shown above, then twice that amount is necessary to precipitate the cyanide completely.
2CN- +'2Ag+ -> A g2 (CN) 2

Therefore,
Grams
NaCN = 2 X 26.05 X 0.04782 X

II.
NnPN =
0. 1221
gram.
Ans.
EXAMPLE
with 0.1000
A solution contains KCN and KC1.

AgNOs
It is titrated
to a faint turbidity, requiring 15.00 ml.

of of
Then 32.10 ml.

0.08333
more of the AgNOa are added and the precipitates Ag2 (CN) 2 and AgCl are filtered off. The filtrate requires 7.20 ml.
N KCNS to give a red color with ferric indicator. How many grams of KCN and of KC1 are present in the original solution?
SOLUTION:
15.00
0.1000
TCPN X ^-^ = oUU

3
0.1953
gram KCN.
Ans.
Total volume
AgNO
added = 15.00
+ 32.10 = 47.10 ml.

X
15.00
AgNOs
47.10
KCN completely as
Ag2(CN) 2 = 2
30.00 ml.
giving
excess)
30.00,
17.10 ml.
AgNO
(reacting with
KC1 and
(17.10
X 0.1000)
(7.20
X 0.08333) X
0.08276 gram KC1.
Ans.
COMPLEX-ION FORMATION METHODS

EXAMPLE
49.80 ml. of
excess
III.
251
VOLUMETRIC NICKEL.
solution (0.007810
How many
is
grams
of
Ni
are contained in an ammoniacal solution that
treated with
KCN
The
6
gram per
milliliter)
3,
and the
being
KCN
N AgN0
KI
used as an indicator?
SOLUTION:
essential reactions are

2
+H-
+ 4CN- + 6H O - Ni(CN)r + 6NH OH 2CN- + Ag+-Ag(CN) 4

2
Unlike the Liebig method above, the formation of Ag2(CN)2 cannot be used as an indicator since this salt is soluble in 4 OH. is excess indicated the of formation which Instead, Ag+ by Agl
NH
is
insoluble in
NH OH.
4
Normality
5.91 ml.
KCN solution =
5.91
=
IvUJN / 1,UUU
0.1200
AgNO
3 =0=
X
49.80
9.85 ml.
KCN solution
(see
Net
milliliters of
KCN = 39.95 X 0.1200 X IV.
Example
I)
9.85
39.95 ml.
0.07032 gram Ni.
Ans.
EXAMPLE
ing
it
A volumetric
two
6
method
for zinc consists in titrat-
in acid solution with
a standard solution of K4Fe(CN)e.

steps, the net reaction being
2
The
reaction takes place in
3Zn++
+ 2Fe(CN) s + 2K+ -> K Zn [Fe(CN)

3
6 ]2
Ferric ions or uranyl ions are used to indicate the completion of the reaction (by forming a highly colored insoluble ferrocyanide). If 15.5 ml. of a solution of K4Fe(CN) 6 which is tenth-normal as
a potassium
is
salt is
used in a given titration, what weight of zinc
shown to be present?
F.W.
SOLUTION:
1
K Fe(CN)
4
as a salt
=0=
= 4 gm.-atoms H+
Therefore each gm.-atom Zn++

15.5
% gm.-atoms H+
Ans.
0.100
^^ = grams Zn
=
0.380 gram.
252

Problems
735.
faint
How many
50.00 ml.
milliliters of
0.1000
N AgNOa are required to titrate to a

KCN?
permanent turbidity a solution containing 10.00 millimoles of
Ans.
736.
solution containing
AgNO
solution to titrate the
KCN and KC1 requires 20.0 ml. of 0.100 N KCN to a faint turbidity by the Liebig method.
filtering,
After addition of 50.0 ml. more of the silver solution and

requires 16.0 ml. of 0.125 KCNS, ferric Calculate the number of millimoles of
solution.
the filtrate
alum being used as an indicator. KCN and of KC1 in the original
Ans.
4 millimoles
KCN,
millimole KC1.
737. A sample consists of 80.00 per cent KCN, 15.00 per cent KC1, and 5.00 per cent 2 SO4 half-gram sample would require how many milliliters of 0.1000 molar AgNOa for titration to a faint permanent turbidity? If
80.00 ml. more of the
KCNS would
Ans.
738.
AgNOa were added, how many milliliters of 0.2000 molar be required to complete the titration?
19.62 ml.
30.71 ml.
powder containing KCN, KCNS, and inert material weighs 1.200 grams, and the solution of it requires 23.81 ml. of 0.08333 AgNOs to titrate the by the Liebig method. A 50-ml. pipetful of the silver solution is then added, and the precipitated AgCN and AgCNS are filtered. The filtrate
KCN
requires 10.12 ml. of 0.09090
KCNS
used as the indicator.

powder.
Ans.
for the excess silver, ferric ions being in the and of
KCN
KCNS
21.53 per cent
KCN,
10.21 per cent
KCNS.
739. Zinc can be determined by direct titration with standard K 4 Fe(CN)6 and the net reaction is as follows: 3ZnCl2 + 2K4Fe(CN) 6 - K2 Zn8 [Fe(CN) 6 ]2 + 6KC1. If the KiFe(CN)6 is 0.1000 N as a potassium salt, what is the value of each milliliter of it in terms of grams of Zn? If the KiFe(CN)6 were 0.1000 N as a reducing agent (in reactions where it is oxidized to ferricyanide), what would be the value of 1 ml. of it in terms of zinc?
Ans.
0.002452 gram.
0.009807 gram.
740. Find the weights of dissolved KC1, KCN, and in 500 ml. of a solution that analyzed as follows: 30.0 ml. of the solution titrated for by the Liebig method reacted with 9.57 ml. of AgNO3 solution (15.0 grams per
KCNS
KCN
liter).
of the silver solution were added, and the solution contained enough silver to react with 9.50 ml. of 0.100 KCNS. The precipitate was heated with 8 to decompose the and AgCN AgCNS, the 2S04 formed was precipitated with barium nitrate, and the solution then reacted with 58.4 ml. of 0.100 KCNS.
Then
75.0 ml.
more
was
filtered.
The
filtrate
HNO
Ans.
KC1 -
0.85 gram,
KCN =
1.83 grams,
KCNS
6.73 grams.
COMPLEX-ION FORMATION METHODS

741.
253
millimole of
solution containing millimole of KC1, J millimole of KCN, and is titrated with 0.0667 AgNO8 to a faint turbidity,
KCNS
Then enough more of the AgNO3 is added to make a total of 30.00 ml. of the AgNO3 The precipitate is filtered off and the filtrate requires B ml. of 0.100 M KCNS to give a red color with ferric alum indicator. The
ml.
.
requiring A
precipitate is decomposed with concentrated HNO3 and the solution is diluted which leaves only AgCl as a residue. The nitric acid solution containing the silver from the Ag2 (CN) 2 and the AgCNS is titrated with 0.100 KCNS, requiring C ml. What are the values of A, B, and C?
Ans.
A =
2.50,
B =
9.17,
C =
5.83.
742. A nickel ore contains 10.11 per cent Ni. A half-gram sample is decomposed and the ammoniacal solution treated with 60.00 ml. of a 0.08333
solution of
of the
KCN. A
3
little
added as an indicator and the solution is AgNO3 to a faint permanent turbidity. What volume
is
KI
AgNO
is
required?
Ans.
11.65 ml.
if
743. Find the percentage of nickel in an ore
the sample weighs 0.3000
gram and the ammoniacal solution is treated with 20.00 ml. of KCN (31.2 grams per liter) and then requires 14.00 ml. of AgNOs (25.5 grams per liter),
KI
being used as an indicator.

26.4 per cent.
Ans.
744.
What weight of KCN is equivalent to 30.00 ml.
of
AgNO
solution con(&)
taining 15.00 grams per liter (a)
by the Volhard method for cyanide and
by
the Liebig method?

746.
sample of impure
of 0.0909
N AgNO
volume
percentage of
additional
746.
KCN?
weighs 0.950 gram and requires 22.0 ml. to obtain a turbidity in the Liebig titration. What is the If the sample contained also 0.102 gram of NaCl, what
KCN
of
AgNO
would be required
for complete precipitation?
sample containing
KCN
of 0.08333
N AgNO
weighs 1.000 gram and requires 24.00 ml.
solution to obtain a faint
permanent turbidity.
What
is
the percentage of KCN? If the sample also contained 10.00 per cent KC1, what volume of the AgN03 solution would be required to precipitate the
KCN
and KC1 completely?

747.
solution
is
is
known
to contain dissolved KC1,
KCNS, and KCN.

for cyanide
The
titrated to a faint turbidity with 25.00 ml. of 0.0880 3 solution.
solution
100-ml. pipetful of the AgN0 3 is then added and the solution is filtered; the excess silver in the filtrate requires 50.4 ml. of 0.0833 solution. The precipitate of the three silver salts is boiled with which decomposes the AgCN and AgCNS and leaves 3
N AgNO
by the Liebig method
N KCNS HNO
,
the AgCl, which
is filtered off.
The
filtrate requires 65.0 ml. of
the above-
mentioned
of
KCNS
solution of the silver.
Calculate the
number
of milligrams
KCN,
KC1, and
KCNS in the original solution.
254
748.
mixture of
30.0 ml. of 0.0500
N AgNO
Volhard
749.
titration.
is
weighing 0.687 gram reacts with and with 150 ml. more in the Find the percentage composition of the original powder.
3
KCNS, KCN, KC1
in the Liebig titration
What
of a 1.000-gram
the percentage of nickel in an ore if the ammoniacal solution sample is treated with 3.255 grams (= 50 millimoles) of
KCN
and the excess

turbidity with
KCN
KI
requires 50.00 ml. of 0.1000 molar indicator?
AgNO
to obtain a
750. The Ni in a 0.9000-gram sample of millerite is converted to the ammonia complex, and to the solution are added 0.25 ml. of AgNO 3 solution,
containing 20.00 grams

serves as the indicator.
(13.00
AgNO
By
liter)
3 per liter, and 5.00 ml. of a KI solution that solution addition of two 10-ml. pipetfuls of
KCN
grams
.
KCN
disappeared, but it AgN03 Calculate the percentage of Ni in the millerite.

761.
the turbidity due to the Agl is found to have per just reappears on addition of exactly 1.50 ml. more of the
How many
in the cyanide
each
milliliter
grams of copper are represented by each milliliter of KCN method for determining copper (see Part VI, under Copper), if of the KCN is equivalent to 0.01000 gram of silver by the Liebig
method?
PART IV ELECTROMETRIC METHODS

CHAPTER XVI
POTENTIOMETRIC TITRATIONS
In a potentiometric titration the principles discussed in Chap. VI are applied in a practical way. Suppose a solution of hydrochloric acid is to be titrated potentiometrically with a standard solution of sodium
97. Potentiometric Acidimetric Titrations.
One method is to use a hydrogen electrode (cona platinum electrode coated with platinum black and over which pure hydrogen gas is allowed to bubble) immersed in the solution. This is one half cell. The other half cell is a calomel cell. This consists of a tube containing free mercury in contact with a solution saturated with mercurous chloride and usually either one molar with respect to chloride or saturated with potassium chloride. The two half cells are connected by means of a capillary tube filled with potassium chloride solution. The whole cell (assuming one-molar chloride to be used) is expressed as
hydroxide.
sisting of
follows:
Hg
is
Cl|
(1
molar),
MHg Cl
2
2
1|
H+, i^H 2
(1
atmosphere)
Ft
|
At 25 the
electrode potential of this so-called normal calomel cell volt +0.285 (see Table XI, Appendix). Using saturated KC1,
is
the potential
(1) (2)
+0.246
2
volt.
2
Hg +
Cl(1
^Hg Cl + e
E =
l
+0.285
0.0591, -log
1
i
HH
atmosphere) = H+
+e
F ^2
i7o = /V
[H+] 7
(press.
~û H
!
2)
/2
E = Ei-Ei =
0.285
log [H+] 0.0591 log [H+]
+ 0.0591
255
256

of the e.m.f of the cell, the
.
By measurement
values of
pH value of the solu-
tion can be determined
from this formula. Furthermore, the pH the solution can be determined in the same way at suc-
and those pH values plotted against buret corresponding readings. There is obtained a curve similar to curve (A) (A) in Fig. 3, Sec. 82. If the nearly vertical line of
cessive points in the titration
inflection is bisected, the
volume
of titrating solution correspond-
ing to the equivalence point can be read off. Since the titration is independent of color indicators, the titration can be as successfully carried out in
colorless one.
a dark-colored or turbid solution as in a
weak acids
like acetic acid
Plotting the results of potentiometric titrations of and weak bases like ammonia gives
curves like (C) (C) and (D) (D) in Fig. 3, and the pH value at the equivalence point or at any other stage of the titration can be readily found in each case.
EXAMPLE.
If,
at the equivalence point in the titration of a
= 9.10, what e.m.f. should be certain solution of acetic acid, given by the cell made up of this solution in contact with a hy-
pH
drogen electrode and a normal calomel half
cell?
SOLUTION
EP
0.285
0.0591
9.10X0.0591
-#-0.285
0.823 volt.
E=
98.
Ans.
Simple Potentiometric Titration Apparatus. The essential a potentiometric titration apparatus of the type discussed above are shown in diagrammatic form in Fig. 7. An outer circuit consists of a storage battery S, a rheostat 72, and a slide wire 0, of uniform diameter. The inner circuit consists of a sensitive galvanometer G, a key for closing the circuit, and the cell to be measured. The direction of the current in the inner circuit
parts of
opposes that in the outer circuit so that, when the position of on the slide wire is adjusted so that the two voltages are equal, no current will flow through the galvanometer. In determining the voltage of the cell to be measured, the position of on the
slide wire is
flects
adjusted until the galvanometer needle no longer deis is
when the key
momentarily
closed.
The
distance
MN
along the slide wire
then a measure of the desired voltage.
If
a standard Weston
cell of
257
voltage is previously inserted in place of the cell to be measured, the resistance at R can be so adjusted that the scale divisions beside the wire will directly register
known
millivolts or
some simple
of
fact,
multiple thereof.
As a matter
vwwvyww
the purpose of a potentiometric titration is usually to establish the buret
reading at
the equiva-
lence point rather than to determine voltages or pll
values with a high degree of precision. Since the
the equivalence point can be established from the midpoint of the inflection of the curve obtained by
plotting either e.m.f. or
buret reading
at
FIG.
7.
Potentiometric titralion hook-up.
pH values against corresponding buret readings, the use of a simpler

apparatus than the one just described is possible. In this apparatus, a simple dry cell is substituted for the storage battery, and a simple voltmeter is used in place of the slide-wire arrangement. After the addition of each increment of titrating solution, the resistance at R
is adjusted until, on closing the key, the galvanometer needle does not deflect. The voltmeter is then read directly. When these
voltages are plotted against buret readings, a curve that inflects sharply at the equivalence point.
99.
is
obtained
Several substitutes for the hydrogen electrode are available, their principal advantages being the elimination of the cumbersome purifying trains necessary for the
Quinhydrone Electrode.
hydrogen electrode. Among these substitutes is the quinhydrone electrode. This consists of a few crystals of quinhydrone added A plain platinum wire directly to the solution to be titrated. serves as the metallic contact, and a calomel cell is used as the
other half
cell.
When
solves
quinhydrone
dissociates
is
and
added to water, a very small amount disinto an equimolecular mixture of quinone
258

These two substances shown by the equation
(C 6H4O 2 ) and hydroquinone (CeEUC^Hb).

are in equilibrium with each other, as
C6H4
The
potential of this electrode concentration.
is
+ 2H+ + 2e
a function of the hydrogen-ion
00591
, ,
-j-
log
=
Using a calomel
inner circuit)
0.700
-1-
0.0591 log [H+] at

cell
25C.
cell
as the other half
tive electrode in the outer circuit
and making it the nega(positive to quinhydrone in the
we have
E = +0.700 + 0.0591 log [H+] E = +0.285 E = E!-E2 = 0.415 + 0.0591

l
log [H+]
or
TT pH = ,
log [H+]
rrr+T
0.415 -
-E
In a titration, the quinhydrone electrode being used, the value of E becomes zero at about pH = 7; and on the alkaline side of
this point the calomel cell is
the values of
are given a negative sign. obtained in solutions where pH > 9.

100. Glass Electrode.
used as the positive electrode, and Correct values are not

glass electrode consists of a thin-
The
walled bulb of special glass containing an electrode immersed in a standard reference solution (e.g., a platinum wire in a quinhydrone-hydrochloric acid solution).
The
glass bulb serves as
semipermeable membrane between the reference solution and the solution to be tested. Because of the high resistance of the bulb, a galvanometer of high sensitivity or an electrometer potentiometer is required to measure pH. In some forms the glass electrode is rather fragile, but this disadvantage is more than offset by the facts that (1) there is no contamination of the solution being tested, (2) measurements can be made on very small volumes
and (3) the presence of oxidizing or reducing agents does not influence the results of a pH determination.
of solution,
259
Because of variations in composition of the glass used in the glass electrode, the formula for determining the pH value with a given electrode is usually provided by the manufacturer, but slight changes can occur over long periods of time owing to crystallization of the glass.
pH meters use glass electrodes and caloform and are of such construction that pH compact values can be read directly from the instrument. By means of such a meter a pll measurement can be made very quickly, and
mel
cells in
Most modern portable
the manipulative technique involved is hardly more than that of turning a knob a^d pressing a button.
101. Potentiometric
Redox
Titrations.
The hookup
for the
potentiometric titration of a reducing or oxidizing agent is similar to that of an acidimetric titration except that a plain platinum wire serves as the electrode.
solution of eerie sulfate (Fe++ Ce++++ - Fe+++ Ce+++). Before the equivalence point is reached, the principal equilibrium is that between ferrous and ferric ions (Fe ++ = Fe+++ e) and the
Suppose a solution
of ferrous sulfate is titrated
with a standard
ratio of the
of
two concentrations changes rapidly. titration the the cell is represented by

Pt
During
this part
Fe
HHg Cl
2
2,
Cl-
(1
molar)
Hg
= +0.748 + 0.0591
fTTp-l-K-1 J
log
cell)
Ez = +0.285
(calomel
E = E!-E2 = 0.463 + 0.0591
log
Beyond the equivalence point the predominating equilibrium is """ = that between cerous and eerie ions (Ce" Ce++++ Dur). ing this part of the titration the cell is represented by
1
1
Pt
Ce Ce
HHg Cl
2
2,
Cl-
(1
molar)
Hg
260

Elo
.,
+
,
0.0591
__
log
[Ce^ i___
j
= +1.45
+ 0.0591
log
[Ce+++j
E =
2
+0.285 (calomel
l
cell).
E-E -E 2
1.16
+ 0.0591
log
a typical titration of this type is shown hi Fig. 8. When dichromate is used for the titration of iron, the graph beyond the equivalence point depends on the hydrogen-ion concentra-
The graph
of
tion of the solution since in this case the predominating equilibrium

s
+ 7H
= Cr2 7= + 14H+ +
0.0591
.
Ge,
and
7
30
lo
[Cr2
~][H+]
2
14
[Cr+++]
In
all titrations of this
kind when the potentials are plotted

is
against volumes
+1.50
of titrating solution added, the equivalence point
found by bisecting
+1.40
+1.30
the nearly vertical part of the curve. As a
matter
Of
fact,
the
is
change
+1.20
in
e.m.f.
usually so great that it is often unnecessary to
+1.10
E
+1.00
tabulate the values for
the e.m.f. in order to
determine the volume

+0.90
of
Titration of 30 ml.
titrating
solution
+0.80
corresponding to the
FeS04
(N/10) with
+0.70
+0.60
10
N/10 Ce <S04 ) 2
equivalence point.
titrating
The
is
solution
20
30
40
50
60
70
80
ML
FIG.
8.
added in small increments until the voltmeter shows a very sudden deflection, and
the volume
read directly from ^he buret. Potentiometric titrations can, of course, be applied to oxidation reactions other than the change from ferrous to ferric ions. The
is
.
261
e.m.f at the equivalence point is different for different reactions, but the sudden change in voltage is common to all.
Precipitation Titrations. The potentiometric principle can be applied to certain precipitation titrations. For example, in the titration of silver ions with halide ions, the
102. Potentiometric
concentration of silver ions changes during the progress of the titration. Using a silver electrode and a regular calomel half cell,
we have
the
cell
Ag Ag+
MHg Cl
2
2,
Cl-
(1
molar)
Hg
E =
l
+0.799
o n^Qi
^p
log [Ag+]
#2
- +0.285 (calomel cell) E = Ei - #2 = +0.514 + 0.0591
log [Ag+]
The graph
of a titration of this type shows a sudden inflection at the equivalence point as in the case of acidimetric titrations and
oxidation titrations.
Problems
762. A cell made up of a certain basic solution and normal hydrogencalomel electrodes gives at 25C. an e.m.f. of 0.825 volt. What is the pH value and what is the hydroxyl-ion concentration of the solution?
Ans.
763.
of 3.60
9.14, 1.38
10~6 molar.
A X
certain solution of sulfuric acid has a hydrogen-ion concentration
10~3
What
is
the
pOH
value?
With regular hydrogen-calomel
electrodes,
what
e.m.f. could
be obtained at 25C.?
Ans.
11.56.
0.429 volt.
764. With quinhydrone-calomel electrodes, approximately what e.m.f. could be obtained at 25C. with a 0.0500 solution of acetic acid (ionization constant 1.86 X 10~5 )? What e.m.f. could be obtained from the same solution
containing an additional mole of acetate ion per 500 ml.?
Ans.
766.
0.237 volt.
0.041 volt.
electrodes,
With quinhydrone-calomel
a tenth-molar solution of a
certain monobasic acid at
25C.
gives an e.m.f. of 275
mv.
What
is
its
approximate ionization constant? Ans. 1.83 X 10~4

.
766.
What
1.07
is
the hydroxyl-ion concentration of a solution which at

anê.m.f. of zero?
25C.
and with quinhydrone-calomel electrodes gives

Ans.
10-7
262

25C.
obtainable from the
cell
757. Calculate the potential at connecting the half cell:
made by
Pt
with a calomel half
cell.
Sn++ (0.0600 molar) Sn++++ (0.00100 molar)
Ans.
0.208 volt.
N NaOH
768. Plot the foll&wing values of millivolts against milliliters of 0.100 in the potentiometric titration of 2.50 grams of vinegar, hydrogen-
calomel electrodes being used, and calculate the percentage of acetic acid in At what volume of NaOH is the solution neutral, and what volume corresponds to the equivalence point? What is the pll value at the
the vinegar.
equivalence point?
12.0 ml.
670; 19.8 21.0 ml. =

985. 55.
0.0 ml. 420 mv.; 4.0 ml. 475; 8.0 ml. 540; = 16.0 ml. 588; 620; 18.0 ml. = 638; 19.0 ml. = 650; 19.4 ml. = ml. = 790; 20.0 ml. = 830; 20.2 ml. = 856; 20.5 ml. = 875; 900; 22.0 ml. = 930; 24.0 ml. = 948; 28.0 ml. = 970; 32.0 ml. = 19.2 ml., 19.8 ml.
Ans.
769.
4.75 per cent.
8.55.
1.10 grams.
0.500
sample of sodium carbonate containing inert impurities weighs It is dissolved in water and titrated potentiometrically with HC1, normal hydrogen-calomel electrodes being used. Plot the
following values of milliliters against corresponding millivolts, and calculate the approximate percentage of Na 2 CO 3 in the sample. What are the
912; 12.5 ml. = 900; 15.0 ml. = 880; 17.5 ml. = 838; 20.0 ml. = = 710; 25.0 ml. = 696; 27.5 ml. = 682; 30.0 ml. = 669; ml. 22.5 762; 32.5 ml. = 650; 35.0 ml. = 607; 37.5 ml. = 484; 40.0 ml. = 452; 45.0 ml. = 427; 50.0 ml. = 416.
10.0 ml.
pH values at the two equivalence points?

=
0.01 ml.
928 mv.; 5.0 ml.
922;
Ans.
760.
87 per cent.
9.1, 4.5.
sample of Na2 C03 is known to contain either NaOH or NaHCO3, with inert matter. A sample weighing 1.50 grams is titrated potentiotogether with 0.600 HC1. Plot milliliters of acid against millivolts, and metrically determine the approximate percentage composition of the sample. 0.1 ml. = 930 mv.; 5.0 ml. = 918; 10.0 ml. = 899; 12.5 ml. = 872; 15.0 ml. = 820;
= 757; 20.0 ml. = 727; 22.5 ml. = 708; 25.0 ml. = 696; 27.5 ml. = 30.0 ml. = 668; 32.5 ml. = 648; 35.0 ml. = 606; 37.5 ml. = 485; 40.0 683; ml. = 452; 45.0 ml. = 427; 50.0 ml. = 416.
17.5 ml.
Ans.
761.
63.7 per cent
Na CO
2
3,
20.1 per cent

is
NaHC0
3.
sample of formic acid (IICOOTI)
dissolved in water
and
titrated
potentiometrically with 0.400 NaOH, quinhydrone-calomel electrodes being used. Plot the titration curve from the following data, and calculate the pH value at the equivalence point. Approximately how many grams of
HCOOH
10.0 ml.
are
shown
262; 25.0 ml.
to be present in the solution? 0.0 ml. = 273 mv.; = 242; 35.0 ml. = 225; 45.0 ml. = 195; 55.0 ml. =
135; 60.0 ml.
263
70.0 mi.
58; 62.5
ml.
0;
65.0 ml.
= -100;
= -223;
80.0ml.
Ans.
-308.
1.2
8.11.
grams.
762. In the potentiometric titration at
25C.
of 50.0 ml. of 0.100
N ferrous
eerie sulfate, what should be the sulfate (diluted to 250 ml.) with 0.100 voltage reading (a) at the equivalence point, (6) halfway to the equivalence
point?
Ans.
763.
(a)
1.10 volts,
(b)
0.748 volt.
A cell is made up
and
is
eerie ions,
and a regular calomel
of a platinum wire, dipping into a solution of cerous cell. At 25C. an e.m.f. of 1,190 mv.
obtainable.
Calculate the ratio of concentration of eerie ions to concentra-
tion of cerous ions in the solution.
Ans.
764.
3.22.
sample of limonite weighing 0.350 gram is dissolved in HC1, and the ferric ions are reduced by means of a slight excess of stannous chloride. Without removal of the excess stannous ions the solution is titrated potentiometrically with 0.100 N eerie sulfate solution, platinum-calomel electrodes
being used. Plot the following values of milliliters of eerie sulfate against corresponding millivolts, and from the graph calculate the approximate percentage of Fe 2 O 3 in the sample. The stannous ions are oxidized by the
218; 2.00 ml. = 223; = 350; 9.00 ml. = 3.00 ml. 325; 5.00 ml. 342; 6.00 ml. 240; 4.00 ml. = = = ml. = 417; 32.0 30.0 393; 388; 25.0 ml. 363; 15.0 ml. 382; 20.0 ml. = = = = ml. 910; 37.0 ml. = 570; 36.0 ml. 510; 35.0 ml. 450; 34.0 ml.
eerie sulfate
first.
0.0 ml.
190 mv.; 1.00
nil.
1,100; 39.0 ml.
=1,155; 45.0 ml.
1,217; 50.0 ml.
1,229.
Ans.
73 per cent.
766. Twenty-five milliliters of 0.200
N AgN0
are diluted to 250 ml. and
titrated potentiometrically with 0.200 KBr, a silver electrode and a normal calomel electrode being used. Assuming the solubility of silver bromide to be 5.9 X 10~7 mole per liter, calculate the theoretical value for (a) when a
fraction of a drop of bromide has been added, (fe) at the equivalence point, (Hint: Find the silver-ion (c) after 20 ml. of the bromide have been added. concentration in each case, and use the specific oxidation potential of Ag =
Ag+
given in the Appendix.)

(a)
Ans.
766.
+0.414
volt, (b)
+0.146
volt, (c)
-0.039
volt.
certain solution of
sodium hydroxide has a hydroxyl-ion concen-
With regular hydrogen-calomel electrodes, what e.m.f. could be obtained at 25C.? 767. With quinhydrone-calomel electrodes, a certain solution at 25C. gives an e.m.f. of 116 mv. What is the hydroxyl-ion concentration of the
tration of 5.20
10" 4
solution?
of
768. With regular hydrogen-calomel electrodes, a hundredth-molar solution a certain monoacidic base gives at 25C. an "e.m.f. of 946 mv. What is the
264
if
approximate ionization constant of the base? What e.m.f. would be obtained 2.00 moles per liter of cation common to the base were introduced into the
769. Plot values on graph paper showing the relationship between milliand pH values (a) when using normal hydrogen-calomel electrodes,
solution?
volts
(6)
when
pH =
=
using quinhydrone-calomel electrodes. 14 and pH = - 2.
Include the range between
770. Prove that in the potentiometric titration of ferrous ions with eerie
Ei
is given by the general expression At the equivalence point, not only is the reaction Fe^ + Ce+ ++ + = Fe+++ + Ce ++ + at equilibrium, and hence El = #2 but also [Fe++] = [Ce+++ + and [Fe+ ++ ] = [Ce ++ +].)
ions the voltage at the equivalence point

(Ei
+ -E
)/2.
(Hint:
771. In the potentiometric titration of 60.0 ml. of 0.100
ferrous sulfate
eerie sulfate, what should be the voltage (diluted with water) with 0.200 reading (a) after 10.0 ml. of eerie sulfate has been added, (6) after 30.0 ml. of
eerie sulfate
has been added?
titration of a 25-ml. pipetful of 0.268 2S04 solution gave the following values of millivolts for the corresponding volumes of NaOH: 0.0 ml. = 369 mv.; 5.0 ml. = 378; 10.0 ml. = 388; 15.0 ml. = 398; 20.0 ml. = 406; 25.0 ml. - 420; 28.0 ml. = 460;
772.
The potentiometric
NH
with
NaOH
-
516; 30.5 ml. = 690; 31.0 ml. = 860; 35.0 ml. = 949; 40.0 ml. = Plot the millivolts of potential as ordinates against 966; 45.0 ml. = 982. milliliters of as abscissas, and from the curve determine the pH value
30.0 ml.
NaOH
at the equivalence point
and the normality
of the
NaOH
solution.
773.
Make
of 0.213
N H PO
3
a graph for the following potentiometric titration of 40.0 ml. 4 diluted with water to 200 ml. and titrated with 0.200
NaOH
pH
H,PO4
at 25C., hydrogen-calomel electrodes being used. Calculate the value at which the replacement of the first and second hydrogens of
occurs.
0.0 ml.
385; 13.5 ml. = 398; 13.8 ml. = 405; 14.0 ml. = 415; 14.2 ml. = 450; 14.4 ml. = 525; 14.8 ml. = 555; 15.5 ml. = 566; 17.0 ml. = 580; 20.2 ml. = 603;
25.0 ml.
300 mv.; 5.0 ml.
315; 10.0 ml.
=*
350; 13.0 ml.
740; 35.0 ml.

774.
29.2
640; 27.5 ml. = 658; 28.5 ml. = 675; 28.8 ml. = 685; 29.0 ml. = ml. = 760; 29.5 ml. = 795; 30.0 ml. = 815; 31.0 ml. = 835; 870; 40.0 ml. = 890.
is known to contain, in addition to inert material, either or mixtures of these. The potentiometric titration of a
cleaner
NaOH, Na^COs,
1.00-gram sample in 100 ml. of water with 0.265 HC1, regular hydrogencalomel electrodes being used, give the following pH values: 0.0 ml. = 11.70; 5.50 ml. 11.68; 10.0 ml. = 11.66; 20.0 ml. - 11.60; 30.0 ml. = 11.44; 45.0 ml - 10.98; 55.0 ml. = 9.75; 60.0 ml. = 8.76; 62.0 ml. = 7.66; 64.0 ml. = 6.31; 66.0 ml. - 5.70; 68,0 ml. = 5.40; 70.0 ml. = 5.05; 72.0 ml. =
4.81; 73.0 ml.
85.0 ml.
4.10; 74.0 ml. = 2.44; 76.0ml. = 1.94; 78.0 ml. = 1.70; 95.0 ml. = 1.16. 1.41; the Interpret curve, stating which components are present and their
approximate percentages.
point of inflection?
265
first
What
voltage reading
is
obtained at the
775. The chromium in 5.00 grams of steel was oxidized to dichromate and then titrated potentiometrically with 0.1039 ferrous sulfate solution. Plot the curve, and compute the percentage of Cr from the following data which
show
volts
8.00; 15.0 ml.
= 8.78; 36.0 ml. * 8.85; 37.0ml. = 8.87; 37.5 ml. = 8.87; 38.0 8.85; 38.3 ml. = 8.84; 38.4 nil. 5.03; 39.0 ml. = 4.45; 40.0 ml. 45.0 ml. = 390.
35.0ml.
10 against milliliters: 0.0 ml. = 6.50; 5.0 ml. 7.90; 10.0 ml. = 8.10; 20.0 ml. = 8.20; 25.0 ml. = 8.40; 30.0 ml. = 8.60;
rnl.
4.15;
CHAPTER XVII CONDUCTOMETRIC TITRATIONS

Strong acids, strong bases, and most salts, dissolved in a relatively large volume of water, are pracThese ions are capable tically completely dissociated into ions.
103. Conductance.
when
of transporting electricity, and because of good conductors of the electric current.
solution
is
the reciprocal of
its electrical
them the solutions are The conductance of a resistance and is meas-
ured in reciprocal ohms or mhos. The specific conductance of a solution is the conductance of a cube of the solution of 1-cm. edge. The specific conductance at HC1 is 0.0394 mho; the specific conductance of 25C. of 0.100 HC1 is 0.00401 mho. 0.0100 Equivalent conductance is the conductance of a solution contain-
ing one gram-equivalent weight of dissolved electrolyte between electrodes 1 cm. apart. It is therefore numerically equal to the
product of the specific conductance of the solution and the number of milliliters containing one gram-equivalent weight of electroIIC1 is 0.0394 X lyte. Thus the equivalent conductance of 0. 100 HC1 10,000 = 394 mhos; the equivalent conductance of 0.0100 = 401 mhos. As a solution becomes more is 0.00401 X 100,000 conductance becomes somewhat greater owing its equivalent dilute,
to the fact that in more dilute solutions inter-ionic effects are

sened, which gives the apparent
ionization of the dissolved substance.
les-
effect of increasing the degree of
By
extrapolation
it is
possible to determine the equivalent con-
ductance of a solution at infinite dilution. For hydrochloric acid this value at 25C. is 425.8 reciprocal ohms. This is the theoretical conductance that would be given by a "perfect" solution containing 36.46 grams of HC1 between electrodes 1 cm. apart. 104. Mobility of Ions. Different kinds of ions have different that so when an electric current is passed through a velocities,
solution, the faster
moving ions carry a

266
relatively greater
amount
of the current.
267
In the case of very dilute hydrochloric acid, the hydrogen ions, moving much faster than the chloride ions, carry about 82 per cent of the current; the chloride ions carry only about 18 per cent. The mobility of an ion is the equivalent conductance of that ion, and the equivalent conductance of an elec-
sum of the mobilities of its ions. Thus, at 25C. of hydrochloric acid at inconductance the equivalent finite dilution (= 425.8) is equal to the sum of the mobility of the hydrogen ions (= 350) and the mobility of the chloride ions
trolyte
is
equal to the
(= 75.8) at that temperature. If several electrolytes are present in a solution, all the ions contribute to the conductance of the solution. Mobilities increase by about 2 per cent for each degree
centigrade increase in temperature. Table III gives the equivalent conductances, or mobilities, at 25C. of some of the common ions at infinite dilution. From it
can be calculated the equivalent conductances of corresponding

electrolytes at infinite dilution.
TABLE
III.
IONIC CONDUCTANCES OR MOBILITIES AT INFINITE DILUTION, 25C.

50.8
74.8
63.4
Na+
Cl~
75.8
77.7
K+
Ag+
Br~.*
I-
76.0
H+
350
4
OTI-
193
2
NH +
74.9
41.7
C 2 Il3O l / 2 SOr
C1O3
3
40.8
80.0
G3.3
70.9
55.0 65.2
NO Br03 -
61
71.0
53.6
55.3 39.6
73.5
I0r
J^CjOr
6
54
68.4
HFe(CN) MFe(CN) 6B
97.3
100.8
105. Conductometric Acidimetric Titrationsl
Consider the
ti-
tration of a dilute solution of
H+C1At the beginning
HC1 with NaOH solution: (Na+OH-) - Na+Cl- + H 2 O

HC1
solution has a high
of the titration, the
conductance value, owing principally to the extremely high mobility of the hydrogen ions. As NaOH is added, the concentration of the hydrogen ions is decreased and, although hydrogen
ions are replaced
by sodium
ions, the mobility of the latter is
268

less,
much
so that the conductance of the solution decreases
At the equivalence point, the solution contains only rapidly. NaCl, and the conductance is at a minimum for, on further addithe hydroxyl ions with their high mobility give a rapidly increasing conductance to the solution. If the titration
tion of
NaOH,
^4-"
,1
\
Volume of
NaOH
HC1
with
Fio.
9.
Conductometric titration of dilute
NaOH.
is
carried out under constant conditions of temperature, etc., and the volume of titrating solution is plotted against conductance, a curve of the appearance of line ABC in Fig. 9. is obtained
In this
figure, line
AH
of the solution contributed
represents that part of the conductance by the HC1 alone; DBJ represents
that part of the conductance of the solution contributed by the NaCl alone. Line A B is therefore the resultant of these two curves, the distance GI being equal to FI EL Line represents the conductance of the excess NaOH alone; line BJ is the conduct-
HK
ance of the
NaCl
point has been reached; and
present in the solution after the equivalence BC is the resultant.
269
Ideal titration curves applying to perfect solutions can be calculated from the mobilities of the ions involved. Thus, in the titration of a very dilute solution containing a gram-equivalent
a relatively concentrated solution of sodium hydroxide (so as to give no appreciable change in the total volume of the solution being titrated), the theoretical conductance of the original solution is 350 (11+) + 75.8 (Cl~) = 425.8 mhos. At the equivalence point the solution contains only NaCl and its
weight of
HC1 with
conductance is 50.8 (Na+) + 75.8 (C1-) = 126.6 mhos. An excess of one gram-equivalent weight of NaOH to the resulting solution would give a conductance of 50.8 (Na+) + 75.8 (C1-) + 50.8 (Na+) + 193 (OH") = 370.4 mhos. Plotting these conductance values against corresponding relative volumes of NaOH gives a titration curve like that of the resultant line ABC in the figure. The
equivalence point is the intersection of two straight lines. In an actual titration of this type the lines are likely to be slightly curved because of (1) variation in temperature, due, in
part at least, to the heat of neutralization, (2) increase in the volume of the solution because of added reagent, and (3) interionic effects.
Foreign ions in the solution
may
distort the curve
slightly, although their general effect is" to increase the total conductance by a constant amount. In spite of this, the inflection is sharp and three or four readings on each side of the equivalence
point are usually sufficient to establish the point of intersection
and hence the buret reading at the equivalence point. The titration of a weak acid like acetic acid with a strong base like sodium hydroxide is shown in the curve (a) (a) of Fig. 10. Here the first small amount of NaOH will, as before, cause a
decrease in conductivity but, since the concentration of hydrogen ions in acetic acid is small, the conductance of the solution soon
increases owing to the formation of sodium ions and acetate ions, the latter buffering the solution and thus cutting down the concentration of the highly mobile hydrogen ions. The conductance
values then follow closely those of the sodium acetate formed. Beyond the equivalence point the formation of hydroxyl ions does
not cause a sharp inflection in the titration curve. If, on the other 4 OH is used to titrate the acetic acid, a curve (6) (&) hand, is obtained with a sharper inflection at the equivalence point, for the excess 4 OH, owing to its slight degree of ionization, has
NH
NH
270

on the conductance of the solution.
In an actual
titra-
little effect
tion of this type, the two parts of the conductance curve do not meet sharply at a point because of hydrolysis effects, but the
equivalence point can be found by extending the straight parts of the titration graph to a common point [see part (c) of Fig. 10].
Volume of
FIG. 10.
titrating reagent
Conductometric titration of 0.01 N (a) with NaOH, (b) with NH 4 OH.
HC H O
2
3
and a weak acid with a standard base can often be carried out conductometrically and the amount of each acid determined from the graph (see Prob.
titration of a mixture of a strong acid
The
similar type of titration curve is obtained in the titration 781). of certain dibasic acids (see Prob. 789).
106. Conductometric Precipitation Titrations. Many precipitation titrations are also possible by Conductometric methods.
Consider, for example, a very dilute solution containing a
gram =
equivalent weight of sodium sulfate being titrated with a concentrated solution of barium acetate. The theoretical conductance
of the original solution
is
271
50.8 (Na+) 80.0 (MS04 ) = 130.8 mhos. At the equivalence point the conductance is 50.8 (Na4*) 40.8 = 91.6 mhos. If an excess of a gram-equivalent weight (C2H 3 02~)
of
barium acetate
is
added, the conductance of the solution
is
The is therefore a flat V-shaped one with the equivalence point at the intersection of two straight lines. Certain titration curves of this type are illustrated in the
titration curve
50.8 (Na+) 197.6 mhos.
+ 40.8
(C 2 II 3 O 2-)
+ 65.2
(HBa++)
+ 40.8
(C 2
H O -)
3
accompanying problems.
"NAAAAA/WWW
HH E
A/
1000
-a
K
FIG. 11.
Conductometric titration hook-up.
few complex-forming reactions can also be made the basis of conductometric titrations. 107. Conductometric Titration Apparatus. A simple hookup for determining the conductance of a solution is indicated in the is a slide-wire divided into 1,000 diagram of Fig. 11, where scale divisions, G is a galvanometer, E is a pair of electrodes so fixed as to remain at a constant distance apart and dipping into the solution to be measured. S is a source of alternating current, stepped down by means of a transformer to about 6 volts, and R is a rheostat. In measuring relative conductance values in a titration, the
MO
rheostat
is first
galvanometer when the
adjusted so that there point of contact
is
no deflection
is
of the near the center of
the slide-wire. From then on, the adjustment of the rheostat is not changed. The solution is then titrated, and bridge readings are
272
taken between each increment of added solution by adjusting the slide-wire until no deflection is observed in the galvanometer.
After any such adjustment,
a
1,000
resistance of cell
resistance of rheostat
but, since the resistance of the rheostat is a constant (K) resistance of the cell is the reciprocal of its conductance,
and the
=
whence,
a conductance of
1,000
of cell
*
cell
x o j Conductance
= /%
(
<A
JK
-^
Since in an ordinary titration we are not interested in the actual conductance values but only in the relative changes in conductivity as a
of establishing a titration curve, it is only necessary to plot the volume of titrating solution against the values
means
obtained from the bridge readings. Unlike the potentiometric graph, the conductometric titration curves are straight lines or nearly so, and they can therefore usually be fixed
(1,000
a) /a as
few volume readings on each side of the equivalence In for accurate values to be obtained and in order order point. for the lines to be straight or nearly so, it is important to keep the temperature of the solution as nearly constant as possible, and it is also theoretically necessary that the volume of the solution shall not change during the titration. This last condition is ful-
by a
relatively
filled
approximately enough for ordinary titrations if the total volume of reagent does not exceed 1 or 2 per cent of the solution titrated. The reagent should therefore be as concentrated, and 0.001 normal the solution as dilute, as feasible. A solution 0.01 titrated with a 1 normal solution of reagent would be a typical case.
Problems
776. If the specific conductance of
N/50
IIC1
is
0.00792 mho, what
is
the
equivalent conductance of
N/50 HC1?
Ans.
777.
396 mhos.
At 25C. what
143.4 mhos.
is
the equivalent conductance at infinite dilution of a
solution of silver sulfate?
Ans.
778.
273
dilution is titrated at
solution containing a gram-equivalent weight of BaCla at very high 25C. with Li 2 SO4 From mobilities of the ions involved
.
calculate the conductance of the solution (a) at the start of the titration, (6) at the equivalence point, and (c) at the point where a total of 2 gram-
equivalents of Li2SO4 have been added.

graph.
Plot these values to show the titration

for the titration of
Make
.
similar calculations
and graph
BaCl2 with
Na2SO4
Ans.
779.
Which
gives the sharper inflection at the equivalence point?
(a) 141.0, (6) 117.5, (c) 239.2; (a) 141.0, (6) 126.6, (c)
257.4 mhos.
A very dilute solution of sodium hydroxide is titrated conductometri1.00 N HC1. The following bridge readings of (100 with a) /a were cally in the titration. Plot the titration curve and indicated at the obtained points from it determine the number of grams of NaOH present in the solution. 0.00 ml - 3.15; 1.00ml. - 2.60; 2.00 ml. - 2.04; 3.00 ml. - 1.40; 4.00 ml. 1.97; 5.00 ml.
2.86; 6.00 ml.
3.66.
Ans.
780.
0.128 gram.
solution approximately HC1. ductometrically with 1.00
N/100
in
sodium acetate
is
titrated con-
From the following titration values showing
the curve to a point of intersection.) 0.00 ml. - 218; 4.00 ml. - 230; 8.00 ml. - 243; 9.00 ml. - 247; 10.00 ml. - 256; 11.00 ml. - 269; 12.00 ml. - 278; 380. Show from mobilities and relative degrees 14.00 ml. 325; 17.00 ml. form of curve is to be expected. this ionization of why
relative conductivities plot the curve and calculate the number of grams of NaC2H 3 O2 present in the solution. (Hint: Extend the nearly straight parts of
Ans.
781.
It
is
0.820 gram.
sample of vinegar has been adulterated with hydrochloric
acid.
titrated with 0.500
N NH OH
4
and the following bridge readings
of
a)/a were obtained at the indicated buret readings. Calculate the (1,000 number of grams of HC1 and of HC2H 3 O2 in the sample. (Hint: Find the point
of neutralization of the
shaped
part of the
2.50; 2.00 ml.
- 2.00; 4.20 ml. - 2.10; 4.50 ml. 3.50ml. 1.76; 4.00 ml. ml. - 2.16; 8.00 ml. - 2.18. ml. 7.00 2.14; 2.15; 6.00
Ans.
0.0580 gram HC1, 0.0336 gram HdH,Cfc.
HC1 by extending the nearly straight sides of the U-to a point of intersection.) 0.00 ml. 2.87; 1.00 ml. graph ml. ml. ml. 3.20 2.50 3.00 1.70; 1.70; 1.85; 2.10;
2.15; 5.00
ml -
782.
At 25C. what
is
the equivalent conductance at infinite dilution of a
solution of
BaCh?
783. Sketch the general form of the titration curve you would expect to 4 OII with (a) N/l HC1, get in the conductometric titration of N/100
NH
(6)
N/l
HC H O2.
2 8
784. Using the eqivalent conductance values obtained from the mobilities of the ions, show the general form of the titration curve in each of the following with 2 SO4 , a , (6) titration of BaCl 2 with cases: (a) titration of
NaOH
HNO
(c) titration of
BaCl2 with
H SO
2
4,
(d) titration of
Ba(OH) 2 with
K H SO
2
4,
274
(e)

MgSO4 with Ba(OH) AgNO with LiCl.
8
2,
titration of
(/)
titration of
NH C1
4
with
NaOH,
(0) titration of
785. In the titration of 80.0 ml. of a solution of NaOH 8 with 4.85 the following relative conductivities were obtained for the corresponding volumes of NaOH. Plot the curve and calculate the acid normality of the 0.00 ml. - 501; 1.00 ml. 340; 2.00 ml. original acid solution. 175;
HNO
3.00 ml.
786.
- 180; 4.00 ml. - 261 5.00 ml. - 338. A sample of vinegar weighing 5.00 grams
;
is
diluted to 500 ml. and
ti-
The following relative trated conductometrically with 0.500 4 OII. conductivities were obtained from the bridge readings of (1,000 a) /a at the indicated buret readings: 0.00 ml. - 1.20; 0.50 ml. - 0.95; 1.00 ml. - 0.80;
1.50 ml.
N NH
ml.
0.70; 2.00 ml.
1.75;
6.00ml.
0.70; 3.00 ml.
9.00 ml.
2.13; 7.00ml.
2.82; 10.00 ml.
2.48; 7.50ml. 2.87. 2.83; 14.00 ml.
0.95; 4.00 ml.
1.35; 5.00 2.68; 8.00ml. 2.78;
Plot these values and
determine from the graph the buret reading at the equivalence point. From this calculate the acidity of the vinegar in terms of percentage of IIC 2 H 3 O2. Explain the chemistry involved to give the U-shaped appearance of the curve prior to reaching the equivalence point. What would be the general appearance of the graph if 0.500 N NaOH had been substituted for the 4 OH in the titration? What is the advantage of using 4 OH?
NH
NH
N
in sodium acetate is titrated consolution approximately 0.01 HOI 1.25 with the and following relative conductivities ductometrically were obtained at the corresponding buret readings: 0.00 ml. 451; 1.00 ml.
787.
- 459; 2.50 ml. - 460; 2.75 ml. - 462; 3.00 ml. - 465; 3.25 455; 2.00 ml. ml. - 472; 3.50 ml. - 482; 3.75 ml. - 497; 4.00 ml. - 515; 4.50 ml. - 575; 5.00 ml. 776. Plot the curve and calculate the number 643; 6.00 ml.
of
grams of
788.
NaC H O
2
3
present in the solution.
acetate.
The
solution containing sodium bromide is titrated with 0.650 silver following relative values were obtained for the conductances of
- 262; 1.00 ml. - 241; 1.50 ml. - 227; 2.00 ml. - 213; 2.50 269; 0.50 ml. - 218; 3.50 ml. - 237; 4.00 ml. - 261; 4.50 ml. - 282; ml. 197; 3.00 ml. 5.00 ml. 301.
the solution during the titration. Plot the curve on a large scale and calculate the number of grams of NaBr originally present in the solution. 0.00 ml.
789. Oxalic acid is a dibasic acid and can be considered as an equimolar mixture of a fairly strong acid (H 2 C 2 O4 + 11+ + IlC 2 Or; K' = 4 X 10"2 ) ~ and a weak acid (HC 2 O4 * H+ C 2 O4 -; K" = 5 X 10~6 ). The following relative conductance values were obtained in the conductometric titration of a dilute solution of oxalic acid with 0.640 N Plot the curve and cal4 OH. culate the number of grams of H 2 C 2 O 4 .2H 2 O present in the solution. 0.00
NH
ml.
- 285; 0.20 ml. - 235; 0.40 ml. - 188; 0.60 ml. - 141; 0.70 ml. - 118; 0.80 ml. - 109; 0.90 ml. - 115; 1.00 ml. - 123; 1.20 ml. 147; 1.40 ml. - 1.81. What ml. 1.60 ml. 1.80 ml. 2.00 2.20 ml. 173; 184; 183; 181; does the lowest point of the curve represent? Show how it would be possible
in certain cases to analyze
(NaHC 2O4 ). What would be the
a mixture of oxalic acid and sodium binoxalate general appearance of the curve in this case?
CHAPTER XVIII AMPEROMETRIC TITRATIONS

108. Principle of an Amperometric Titration. Suppose a solution containing a reducible substance is subjected to electrolytic
reduction at an electrode consisting of metallic mercury dropping at a steady rate from a capillary tube, thus exposing a constantly fresh surface of the metal to the solution. If the applied e.m.f.
Diffusion current
&
Half wave
Residual current^
Applied voltage
FIG. 12.
Typical current- voltage curve (dropping-mercury electrode).
is
zero
increased gradually, the amperage of the current remains near and increases only slightly until the decomposition potential
of the substance is reached (see Sec. 58). At this point electrolytic reduction starts, and an increased e.m.f. causes a sharp increase in amperage in accordance with Ohm's Law, E = IR. As electrolysis progresses,
however, there
is
a depletion of the reducible
substance at the electrode and the potential necessary for decomposition is increased. A point is reached where an increasing
275
276

no increase
in
e.m,f. again causes practically
amperage.
These
three steps are shown in Fig. 12 where milliamperes as ordinates are plotted against applied voltages as abscissas. The nearly constant current corresponding to the upper right-
hand part magnitude
of the curve is called the diffusion current, and its is proportional to the concentration of the reducible
substance remaining in the solution.
Volume of
FIG. 13.
titrating reagent
Amperometric
titration curve (Pb+~*~
+ SO ~).
4
initial e.m.f.
Suppose a reducible substance in a solution is subjected to an which is of such magnitude as to give the amperage corresponding to the diffusion current, and suppose the solution is subjected to a precipitation titration with a nonreducible reagent. Such a case would be the titration of a solution of a lead salt with
of the reducible substance (Pb" 1") is steadily diminished as the sulfate is added. The current, being
sulfate.
1
The concentration
"
proportional to the concentration of lead ions, likewise steadily diminishes as the titration proceeds and, if amperes are plotted
volume of titrating solution added (as aba curve similar to that of Fig. 13 is obtained. The scissas), equivalence point corresponds to the point of intersection of the
(as ordinates) against
AMPEROMETRIC TITRATIONS
two arms
especially
of the curve.
if
277
the effect of dilution
These arms are essentially straight lines, is corrected for. In the above
Solu-
case, the nearly horizontal portion of the curve corresponds to the
diffusion current of a saturated solution of lead sulfate.

bility effects
may give a curved line in the close neighborhood of the equivalence point, but, as in certain conductometric titration curves [see Fig. 10(c)3, extension of the two straight parts of
NAAAAA/WVWW
-Dropping mercury electrode
Hg
Electrolysis
cell
FIG. 14.
Amperometric
titration hook-up.
the curve will give a the equivalence point.

centrated one.
point
As
in
corresponding to conductometric titrations, it is adof
intersection
vantageous to titrate a dilute solution with a relatively conequally satisfactory titration curve is given in the amperometric titration of a nonreducible ion when it is titrated with a
An
reagent capable of electrolytic reduction. This type is illustrated in the first part of the problem given below. The second part of the
a titration in which both the substance titrated and the reagent yield a diffusion current at the applied e.m.f.
problem
illustrates
Certain titrations involving neutralization, oxidation, and reduction, and complex-ion formation are also possible by ampero-
metric methods.
278
Current-voltage curves can be automatically recorded on photographic paper by means of a mechanism called a polarograph, but satisfactory curves can also be obtained manually with a relatively
simple dropping-electrode assembly which furnishes a means of applying a variable known e.m.f. to the cell and for measuring the resulting very small current. Several portable instruments of
this type are
on the market.
The
essential
hook-up
is
shown
diagrammatically in Fig. 14.

In general, although much work is still needed to bring about refinements of method and to extend the applications of the process,
amperometric titrations are in many specific cases capable of giving very precise results. The method is satisfactory in many precipitation titrations where the solubility of the precipitate is
too great for potentiometric or indicator methods to be used. Furthermore, foreign electrolytes which are often harmful in conductometric titrations do not usually interfere in amperometric
titrations unless they are present at high concentrations diffusion currents at the applied e.m.f.
and
yield
values in the following problem are taken from data and graphs obtained by I. M. Kolthoff and his co workers.
Problem
790. In each of the following two titrations, plot the titration graph and determine the volume of titrating solution corresponding to the equivalence
The numerical
Calculate the number of grams of titrated constituent shown to be point. present in each case and explain the appearance of the curve. 2 SO 4 is titrated amperometrically with (a) A certain volume of 0.0100
MK
volts. The following values are the milliamperes obtained at the corresponding volumes of titrating solution. Dilution effects have been corrected for. 0.0 ml. = 0.8; 1.0 ml. = 0.8; 2.0 ml. = = 0.8; 4.0 ml. = 0.9; 4.5 ml. = 1.3; 5.0 ml. = 4.2; 5.5 ml. = 0.8; 3.0 ml.
0.100
Pb(NO
3)
at e.m.f.
= -1.2
11.3; 6.0 ml.

(6)
0.0500
M K Cr O
2
2
20.0; 6.5 ml. - 28.9; 7.0 ml. = 37.5. 50-ml. pipetful of dilute Pb(NO 3) 2 (in 0.10
7
at e.m.f.
= - 1.0
M KNO
3)
is
titrated with
volt.
The
following values are the millititrating solution.
amperes actually obtained at the corresponding volumes of
Before plotting the titration curve, correct for dilution effect by multiplying each current reading by (V v}/V in which V = initial volume of solution,
= total volume of reagent added. 0.0 ml. = 81.56; 1.0 ml. = 66.22; 2.0 ml. = 48.34; 3.0 ml. = 31.66; 4.0 ml. = 15.25; 4.8 ml. = 3.79; 4.9 ml. = 2.09; 5.0 ml. = 2.9; 5.1 ml. = 5.1; 5.3 ml. = 12.03; 5.5 ml. = 21.86; 6.0 ml. =
and
v
43.86.
The large residual current at the equivalence point is due to (Note. the relatively high solubility of the precipitated PbCrO 4 in the acid formed Cr2 7 " 2O -> 2PbCrO 4 by the titration: 2Pb++ 2H+.)
+H
PART V
GAS ANALYSIS
CHAPTER XIX
CALCULATIONS OF GAS ANALYSIS
Fundamental Laws. Problems involving the determination of the proportional amounts of the components of a gaseous mixture and the determination of the amount of a given substance by measuring the quantity of gas which that substance
109.
may
be made to evolve in chemical reaction are the only phases
of gas analysis considered in this book. Calculations of gas analyses make use of the following gas laws, most of which apply strictly only to the so-called "perfect" gases,
but which
may be applied to ordinary analyses with results that are usually in keeping with the precision of analytical manipulation. These laws should already be more or% less familiar to the student.
Boyle's Law.
The volume
is,
of
a fixed mass of a gas at constant

it
temperature
is
is
inversely proportional to the pressure to which
subjected.
That
pv
p'v'
where pv and p'v' are pairs of simultaneous values of pressure and volume of a given mass of gas and k is a constant. EXAMPLE I. If a sample of gas occupies a volume of 500 ml. at a barometric pressure of 755 mm. of mercury, what volume would it occupy at a pressure of 760 mm.? SOLUTION: An increase in pressure must cause a decrease in volume. In this case, the new volume will be
500
Or,
=
7oU
49G.7 ml.
Ans.
by
substitution in the formula above,
755
whence,
500
= 760 X x
Ans.
496.7 ml.
279
280
Charles's Law. The volume of a fixed mass of a gas at constant pressure is directly proportional to the absolute temperature to which it is subjected; that is,
L" =
v
1
L T'
where vT and v'T' are pairs of simultaneous values of volume and temperature expressed on the absolute scale. Zero on the
absolute scale
units
is at 273C.; hence, the temperature in absolute be found may by adding 273 to the temperature in centigrade units. Charles's law may therefore be written
v
v'
= ~ 273
+ 273 +
t
//
where
and
represent the respective temperatures in degrees

If
centigrade.
a gas occupies a volume of 500 ml. at 20C. and the temperature is raised to 30C. at constant pressure, what
II.
is
EXAMPLE
the new volume of the gas? SOLUTION The temperatures on the absolute
:
scale are 293
and
303C., respectively. expand and the new volume becomes

500
Or,
If
the temperature
is raised,
the gas must
~
OfkO
517 ml.
Am.
by
substitution,
500 x
whence,
= 273 "273 = 517
+ 20 + 30
ml.
.
Ans.
.
The formulas
expressing the
two gas laws mentioned above may

__ ""
be combined to give ive

pv
"T
Dalton's Law.
The
equal to the sum and the pressure exerted by a single component is the same as the pressure that component would exert if existing alone in the
pressure exerted by a mixture of gases is of the pressures of the individual components,
same volume.

EXAMPLE
III.
281
Moist hydrogen gas is confined over water under mm. of mercury and a temperature of 26C. What is the actual pressure of the hydrogen? SOLUTION: At 26C., the vapor pressure of water is equal to 25 mm. of mercury (see Table V, Appendix). The partial pressure of the hydrogen is therefore 760 25 = 735 mm. Ans. Gay-Lussac's Law. Whenever gases unite or gaseous products are formed, the proportions by volume measured at the same temperature and pressure of all the gaseous products concerned can be represented by ratios of small integers. Thus, in the reaction
a pressure
of
760
2H + O
2
->
2H O
2
two parts
hydrogen unite with one part by volume of oxygen to give two parts by volume of water vapor. Avogadro's Law. Equal volumes of all gases under identical conditions of temperature and pressure contain the same number
of of molecules.
by volume
110. Gas-volumetric
Methods.
For convenience, gas analysis
may
be divided into the following groups:

(a)
(b)
(r)
Gas-volumetric methods
Absorption methods
Combustion methods
Under gas-volumetric methods may be included those methods which a gas is evolved by means of a chemical reaction, and from the volume of the gas the weight of the substance producing
in
it is
calculated.
it is
evident that the weights of equal volumes of gases will be in direct proportion to the respective molecular weights. The weight in grams of 22.4 liters of any
gas,
From Avogadro's law
when measured under standard
conditions,
i.e. 7
at
0C. and
under a pressure of 760 mm. of mercury, represents the molecular weight of the gas. If the molecular weight of a gas and the volume that a certain quantity of it occupies under standard conditions are known, the weight of that quantity can be readily determined. This is the principle underlying gas-volumetric analysis. Since it is usually inconvenient actually to measure the volume of a gas at 0C. and under 760 mm. pressure, it is customary to measure the gas at any convenient temperature and pressure and by means
282
and Charles's laws to calculate the volume that the gas would occupy under standard conditions. EXAMPLE. A gas occupies a volume of 42.06 ml. under 765.0 mm. pressure and at 20.0C. What is its volume under standard
of Boyle's
conditions?
According to Boyle's law, if the pressure of the gas at a constant temperature is reduced from 765 to 760 mm., the volume would be increased in the same ratio, and, were the tem:
SOLUTION
perature the same, the
new volume would be
42.06
42.34 ml.
The temperature, however, is to be reduced from 20.0C. (293 Absolute) to 0C. (273 Absolute), and, according to Charles's
law, this change alone serves to decrease the volume of the gas by the ratio of 293 273. If both the pressure and temperature are changed to standard conditions, the volume of the gas becomes
:
Expressed according to the symbols used above,
VX x
v
P.
'
x X
p'
273+
which
is
identical to the general expression
Water Vapor. Evolved gases are frequently and measured over liquids which exert an appreciable vapor pressure, and in such cases the barometric pressure does not represent the pressure of the pure gas. It may be assumed
111. Correction for
collected
that the gas will be saturated with the vapor of the liquid over which it is measured, and in such cases the vapor pressure of the liquid depends only upon the temperature. According to Dalton's law, the pressure of the pure gas may be found simply by subtracting the vapor pressure of the liquid at the given temperature from the barometric pressure. The values of the vapor pressure of water at different temperatures are given in Table V (Appendix).
283
ations
112. Calculations of Gas-volumetric Analyses. These considerbe to determine the of a constituent may applied percentage
of a given substance
by gas-volumetric measurements.
0.500-gram sample of limestone on treatment with acid liberates 98.7 ml. of carbon dioxide when measured over water at 23C. and 761 mm. pressure. What is the percentage
of
EXAMPLE.
CO
in the
:
sample?
of water at
SOLUTION
Vapor pressure
23C. =
761
20.9
mm.
Pressure of the pure
CO 2 =
273
20.9
= 740 mm.
Volume
of
CO2 under standard conditions =

740
(44 grams) of CO 2 would occupy under a conditions of 22.4 liters = 22,400 ml. volume standard The
The gram-molecular weight

is,
weight of C02 evolved
therefore,
gram
Percentage of
CO
in the
sample
is
0.174 0.500
100
34.8 per cent.
Ans.
chemists prefer to solve problems involving molar relationships of gases by means of the following general formula:
Alternative Method.
Some
pv
where
= NRT. p = pressure _ pressure

v
of the gas,
atmospheres
in millimeters
= volume, = number
__
milliliters
of moles of gas weight of gas
molecular weight
R = "gas constant " = 82.07 T = temperature on the absolute
scale
284

this
Applying
formula to the problem under consideration,

OQ 7 y8 7
'
740 760
v X
of
_ ~ wt
of gas
44.0
v co n7 U ' N/ X ^' X
OOP b
Weight
C02 =
=
0.174 gram
'
Percentage
.^ U.OUU
100
34.8 per cent.
Ans.
Problems
791. If 500 ml. of hydrogen gas are cooled at constant pressure from 26 10C., what is the volume at the lower temperature?
to
440
792.
is
ml
The pressure on a gas that at 758 mm. occupies a volume of 600 ml. What is the resulting increased to 774 nun. at constant temperature.
588 ml.
volume?
Ans.
793. Three hundred
and
sixty
volumes
of
hydrogen are measured dry at
is
pressure. increased 10 per cent. What
13CX and 760 mm.

Ans.
794.
By
is
heating at constant pressure, the volume the increase in temperature?
26C.
One hundred grams
of pure calcium carbonate are dissolved in hydro-
chloric acid.
and 760 mm. (c) measured over water at 30C. and 748 mm. barometric
Ans.
796.
(a)
Calculate the volume of gas evolved (a) measured dry at 0C. pressure, (6) measured dry at 15C. and 780 mm. pressure,
pressure.
22 A
liters, (b)
23.0
liters, (c)
26.4
liters.
mm.
to
How many liters of oxygen gas measured over water at 17C. and 777 pressure can be obtained from 1.00 kilogram of pure KC1O 3 by ignition
290
liters.
KC1?
Ans.
796*
What
ml. of
CO
2,
weight of CaCOa must be treated with acid to produce 138.6 measured over water (saturated with CC>2) at 10C. and 773 mm.
pressure?
Ans.
0.599 gram.
of
797. In the analysis of dolomite, 0.0500 gram of ferric oxide, 0.6080 gram CaO, and 0.1505 gram of magnesium pyrophosphate were obtained. If
,
these were originally present as FeCOs, CaCO 3 and MgCOa, how many milliliters of CO2 measured dry at 20C. and 780 mm. pressure could have been
obtained from the same weight of sample?
Ans.
300.3ml.

798.
285
What
volume
Ans.
799.
in milliliters of
weight of limestone should be taken for analysis such that the CO2 measured dry at 20C. and 780 mm. equals the
percentage of
CO2
present?
0.1880 gram.
sample of pyrite (FeS 2 ) weighing 0.2000 gram yields 0.7783 gram How many cubic feet of air measured at 130F. and 27 in. of mercury pressure would theoretically be required to burn 1.00 pound of the pyrite? What would be the volume of the gaseous residue (sulfur dioxide and residual nitrogen) measured at the same temperature arid pressure?
of
A
.
BaSO4
(4FeS 2
in.
11O 2 -> 2Fe2

1 Ib.
8SO2
Air
20.9 per cent
16.39 ml.
O2 by
volume.
cu.
0.4536 kg.)
49.5 cubic feet.
Ans.
800.
52.4 cubic feet.
of H 2 O that can be obtained from 8.0 grams of at measured I^CaÂUSiioO^ (a) 20C. and 750 mm. pressure, (6) 750 mm. and 900C. (Two significant figures.) pressure
Compute the volume
Ans.
(a)
0.18 ml.,
(fc)
970 ml.
801. If a gas measured dry at 27C. and 758 mm. pressure occupies a volume of 500 ml., calculate its volume if the temperature is increased to 87C. and the pressure is kept constant.
802. If hydrogen gas when measured over water at 23C. and 772 mm. the volume under standard pressure occupies 97.3 ml., what would b conditions?
803.
pressure.
gas occupies a volume of 222 ml. over water at 12C. and 751 What volume would it occupy over water at 31 C. and 770
mm. mm.
pressure?
804.
BaCO and MgCO

3
Calculate the volume of 6.00
are mixed in the proportions by weights of 2:1. HC1 to decompose a 5.00-gram sample. Cal-
culate the volume of CO2 gas formed when measured dry at 22.4C. and 758 mm. pressure. What would the volume of the gas be if it were collected under the same conditions over water (saturated with CO2 )?
weight of impure calcite (CaCOs) should be taken for analysis in milliliters of CO2 obtained by treating the sample with acid and measuring the CO 2 dry at 18C. and 763 mm. pressure will equul the percentage of CaO in the sample?
805.
What
so that the
volume
806.
at
What volumes
of nitrogen
20C. and 755 mm.

807.
and carbon dioxide, each measured dry pressure, could be obtained by the combustion of
2 ) 2 ]?
0.2010 gram of urea
[CO(NH
What volume
could
pressure
l(C 2
be
6) 2
:N.N:N.N:(C 2 H 6 ) 2 ]?
of nitrogen measured over water at 30C. and 760 mm. obtained from 0.1860 gram of tetraethyltetrazone
286
808.

If, in the analysis of a 1.00-gram sample of a carbonate, 18.0 ml. of measured over water at 18C. and 763 mm. pressure were obtained, find
CO
the percentage of carbon in the sample.
weight of limestone should be taken for analysis so that the volume of CC>2 evolved measured over water at 15C. and 749 mm. pressure shall be three-fifths the percentage of CC>2 in the sample?
809.
810. Compute the volume of oxygen required to oxidize a sample of pure Fe weighing 0.9000 gram, assuming that the product of combustion is composed of 60 per cent Fe2O3 and 40 per cent FeaCU and that the gas is measured dry at 21C. and 756 mm. pressure. 811.
What
compound
measured in
155.5 times
are present
a volume of nitrogen which when 22C. and 767 mm. pressure is equal to the number of grams of sample taken. The carbon and hydrogen in the molar ratio of 1:1. What is the empirical formula of the
of C,
N, and
II yields
milliliters
over water at
compound?
812. Decomposition of a compound of carbon, hydrogen, nitrogen, oxygen, and bromine weighing 0.2000 gram yielded 8.70 ml. of nitrogen, measured over water at 18C. and 758 mm. pressure. Combustion in oxygen of the same weight of sample gave 0.1880 gram CO2 and 0.01924 gram H 2O. After
a precipitate of AgBr weighing 3 decomposition of 0.2000 gram with 0.2674 gram was obtained. The molecular weight was found to be about 275. What is the formula of the compound?
,
HNO
813. Decomposition of 0.1500 gram of indole gave 16.42 ml. of nitrogen when measured over water at 27C. and 758 mm. pressure. Combustion in oxygen of 0.2000 gram of the sample increased the weight of a potash bulb by 0.6026 gram and of a calcium chloride tube by 0.1078 gram. Calculate the
empirical formula of indole.
113. Absorption Methods. Absorption methods of gas analysis apply to the determination of the proportionate amounts of
the components of a gaseous mixture. The mixture of gases is treated with a series of absorbents, and the temperature and pressure are usually kept constant throughout the entire determinaIn cases where these are allowed to vary, corrections for tion.
their effect
applying the principles outlined in volume of the gas before and after it has been acted upon by each absorbing agent represents the amount of gas absorbed, and the amount is usually expressed on a percentage-by-volume basis. The many forms of apparatus
Sec.
109.
may be made by
The
difference in the
used for carrying out gas absorptions are described in the textbooks on the subject, but the fundamental principles are identical.
The reagents commonly employed
are
shown below.

GAS
REAGENT
Caustic soda
Caustic potash
287
Carbon dioxide
Unsaturated hydrocarbons
(" illuminants")
Bromine water
Fuming
sulfuric acid
Oxygen
Carbon monoxide
Alkaline pyrogallol solution
Yellow phosphorus
Ammoniacal cuprous
chloride
Hydrogen
Palladium sponge Palladous chloride solution

Colloidal palladium solution.
EXAMPLE.
of 80.0 ml.
is
A sample of illuminating gas occupying a volume treated in succession with caustic potash solution,
acid,
alkaline pyrogallol solution, and ammoniacal cuprous chloride solution. After each treatment, the volume of the residual gas at constant temperature and pressure is
fuming
sulfuric
measured as
is
78.7, 75.5, 75.1,
and 68.3
ml., respectively.
What
the percentage composition of the gas as shown by these results?
SOLUTION:
Volume of CO 2 Volume of illuminants Volume of 2 Volume of CO
= = = =
80.0
78.7
^ -
78.7
75.5
75.1
75.5
75.1
68.3
= = = -
1.3 ml.
3.2 ml.
0.4 ml.
6.8 ml.
The percentages
of the various
components are therefore

cent
^
3 2
5777:
oU.U
X
X
100
=1.6 per
CO
100
=
=
oU.U
0.4
4.0 per cent illuminants
80.0
r
X X
100
0.5 per cent
Ans.
100
oU.U
f\R
8.5 per cent
GO
577 X 100 = oU.U

114.
85.4 per cent inert gases
Combustion Methods. If a gas mixture contains one or more components capable of combustion with oxygen, it is usually
possible to determine the percentages of these components by allowing combustion to take place and measuring the contraction
288
in volume, the amount of carbon dioxide formed, the volume of oxygen used, or combinations of these measurements, depending upon the number and character of the combustible components
present. Gay-Lussac's law underlies calculations involving contractions in volume. Thus, in the combustion of carbon monoxide
with oxygen
2CO +
->
2C0 2
The combustion
is
two volumes of carbon monoxide unite with one volume of oxygen

to form two volumes of carbon dioxide.
fore
there-
accompanied by a contraction equal to one-half the volume of the carbon monoxide present and produces a volume of carbon dioxide equal to the original volume of carbon monoxide. Assume a gas mixture with hydrogen and methane as the only
combustible components.
Hydrogen
reacts with oxygen accord-
ing to the equation
in
which two volumes
of
hydrogen unite with one volume
of
oxygen
to form water vapor, condensing at ordinary temperatures to liquid water. Methane reacts with oxygen according to the equation
CH + 20
4
->
CO + 2H
2
which one volume of methane reacts with two volumes of oxygen to form one volume of carbon dioxide. Let x represent the volume of hydrogen and y the volume of methane present in the gas mixture. The volume of oxygen required for the hydrogen is ^z, and the volume of oxygen required for the methane is 2y. The total volume of oxygen required B is therefore given by the exin
pression
0)
B=yx + 2y
2
The
3
contraction in volume caused by the hydrogen reaction is and that by the methane reaction is 2y. The total contracx, tion in volume C is given by the expression
(2)
C = 3^ +
x
2y
of
whence
= C
:
B=
volume
1
hydrogen
r
y=
= volume
of
.u methane
289
It is evident that by allowing this gas mixture to react with a determinable volume of oxygen and measuring the resulting contraction which the gas undergoes it is possible to determine the
volume
of
hydrogen and methane present.

is
appreciably soluble in water, it is customary in accurate analyses to measure the contraction in volume after the carbon dioxide has been entirely absorbed. Under such
conditions, in the combustion of a mixture of hydrogen and methane the volume of oxygen required would be represented as before by the equation
(1)
Since carbon dioxide
B=
yx + 2y
2
but the total decrease in volume due to combustion and absorption would be
(2)
C"
%x + 3y
whence
x
= %C' 2B = volume of hydrogen = volume of methane y = B ]/^C

f
Instead of measuring the contraction in volume and the oxygen consumed, the amounts of hydrogen and methane present in a
mixture in which they are the only combustible components may be determined from the contraction in volume and the volume of carbon dioxide produced by combustion. Combustion of hydrox and progen of volume x causes a contraction in volume of duces no carbon dioxide; combustion of methane of volume y
causes a contraction of 2y and produces a volume of carbon dioxide equal to y. The total contraction in volume C is therefore given
by the equation
C = %x +
and the
total
2y
volume
of
carbon dioxide produced
is
given
by
D
Hence,
= y
,
= 2C-4/) = volume ^
o
--
of
,,, hydrogen
D=
volume
of
methane
In a similar way, the percentage composition of other mixtures of gases may usually be calculated, provided that as many inde-
290
pendent equations can be formulated as there are unknown components in the mixture. The equations in the following table represent combustion reactions more commonly encountered in gas analysis, and the accompanying columns show the volume relationships in each
case.
this table, little difficulty should be experienced in formulating the necessary equations for the determination by combustion of any mixture of the gases.
With
used for combustion, it may be assumed to consist *of 20.9 per cent of oxygen by volume. EXAMPLE I. A mixture of carbon monoxide and nitrogen occupies a volume of 100 ml. and on combustion with oxygen produces
In case
air is
40 ml. of carbon dioxide.

the mixture.
Calculate the percentage of nitrogen in
SOLUTION: Let x represent the volume of carbon monoxide and ?/ the volume of nitrogen. Since I volume of carbon monoxide on combustion gives 1 volume of carbon dioxide, the volume of carbon dioxide produced is equal to x. This volume is stated to be 40 ml., and the volume of nitrogen is therefore 60 ml. N 2 = 60 per cent. Arts. EXAMPLE II. A mixture of carbon monoxide, methane, and nitrogen occupies a volume of 20 ml. On combustion with an excess of oxygen, a contraction of 21 ml. takes place, and 18 ml. of carbon dioxide are formed. What is the volume of each component in the mixture?

SOLUTION:
Let x
291
= volume = volume y = c volume
of of
of
CO
CTT4
N%
Total contraction in volume, C = ]/^x + 2y Total volume of CO 2 produced, D = x + y
= x-
4D ~ 2C =
3
72
~
3
42
ion
Q ml. 8
(x
,
2C D 42-18 ,,.__,__z
= volume
III.
original gas
+ y)
=2
ml.
EXAMPLE
Sec. 113
is
The
residual gas
mentioned
in the
assumed to consist
entirely of hydrogen,
example in methane, and
a 20.0-ml. sample are added exactly 100.0 ml. of After the carbon dioxide is air, and the mixture is exploded. absorbed in caustic potash, the volume of the gas is found to be
nitrogen.
To
88.0 ml.; and after the excess oxygen is absorbed in pyrogallol, the volume of the gas is 82.1 ml. What is the percentage of each component in the gas mixture and in the original illuminating gas?
SOLUTION:
Volume
32.0 ml.
after adding air

after
120 ml.
Contraction
explosion
and absorption
120
88.0
C"
of
Volume oxygen taken = 100.0 X 0.209 = 20.9 ml. Volume of residual oxygen = 88.0 82.1 = 5.9 ml. 5.9 = 15.0 ml. = B Oxygen actually required = 20.9
On
substitution of these values of

viz.,
and C'
in the equations de-
rived above,
x = y =
the results obtained are
^C' - 25
x =
y
(% X 32.0) - (2 X 15.0) = 12.7 ml. = volume of = 15.0 - (M X 32.0) = 4.3 ml. = volume of CEU 20.0 - (12.7 + 4.3) = 3.0 ml. = volume of N2
100.
The percentages by volume of these components dividing these volumes by 20.0 and multiplying by
are found
by
292

H2
CH4
f
J
Ans.
In the original illuminating gas (Example, Sec. 113) the percentages of these components are
12.7
X X X
4.3
3.0
~ ~ ^ ~
^~ X
AS Q
inn
54.2 per cent
=
=
18.3 per cent
CH
Ans.
12.8 per cent
Problems
814. The following measurements are made under identical conditions. Calculate the percentages of CO 2 O2 CO, and 2 in a sample of gas containing no other components.
,
,
Sample taken
Volume Volume Volume

Ans.
CC>2
after
KOII treatment
after pyrogallol treatment after cuprous chloride treatment
= = = =
100.0 ml.
91.5 ml.
81 .4 ml.
81.1 ml.
0.3 per cent,
8.5 per cent,
O2 =
10.1 per cent,
CO =
N =
2
81.1 per cent.
known to contain 3.8 per cent O2 0.6 per cent CO, and the rest N 2 A 95.0-ml. sample is drawn into an 2 Orsat apparatus. What would be the volume reading after absorption in the
815.
flue
gas
is
15.0 per cent
CO
following absorbents in the order stated: (a) caustic potash, (c) ammoniacal cuprous chloride?
(6)
pyrogallol,
Ans.
816.
(a) 80.7 ml., (6) 77.1 ml., (c)
76.5 ml.
How many liters

(a)
of
of 5.0 liters of (a) methane, (6) acetylene,
oxygen are necessary for the complete combustion (c) hydrogen sulfide?
(c)
Ans.
10
liters, (6)
12.5 liters,
7.5 liters.
817. The following measurements are made under identical conditions. Calculate the percentage composition of a mixture of hydrogen and nitrogen.

Ans.
of gas taken of oxygen added
of
oxygen consumed by combustion
= = =
58.2 ml.
32.0 ml.
6.1 ml.
21.0 per cent,
79.0 per cent.
818. The following measurements are taken under identical conditions. Calculate the percentage composition of a mixture of hydrogen and nitrogen.

Ans.
819. of gas taken of oxygen added
of gas after
293
= = combustion =
95.3 ml.
40.8 ml.
40.1 ml.
H =
2
67.2 per cent,
N =
2
32.8 per cent.
is the percentage composition of a mixture of hydrogen and the contraction in volume due to combustion with oxygen is the nitrogen same as the volume of the sample taken?
if
What
Ans.
820.
II 2
66?^ per cent,
N =
2
33>
per cent.
What is the percentage of methane in

if
a mixture of hydrogen, methane,

excess of air
and acetylene
Ans.
16.0 ml. of the mixture
when exploded with an
cause a contraction of 26.0 ml.?

25.0 per cent.
821. The following measurements are made under identical conditions. Calculate the percentage composition of a mixture of hydrogen, carbon
monoxide, and methane.
Volume of gas taken Volume of air added

Total volume after combustion
Volume
Ans.
after
removing
CO
= = = =
10.5 ml.
137.4 ml.
136.1 ml.
129.6 ml.
38.1 per cent,
CO =
45.7 per cent, CII 4
16.2 per cent.
822. What is the percentage of propane in^ a mixture of propane, carbon monoxide, and methane if a 13.7-ml. sample on combustion produces 23.7 ml. of carbon dioxide?
Ans.
823.
36.5 per cent.
What
is
the percentage composition of a mixture of carbon monoxide,
ethane, and nitrogen, if, on combustion with oxygen, the contraction in volume and the volume of carbon dioxide produced are each numerically equal to the volume of the sample taken?
Ans.
824.
CO =
To
33)^ per cent,

,of
C H6 = 33^
2
per cent,
= 33^
per cent.
40.8 ml.
are added 150.0 ml. of
a mixture of hydrogen, nitrogen, and carbon monoxide If 4.8 ml. of CO 2 air, and the mixture is exploded.
are produced and the residual oxygen requires 42.0 ml. of hydrogen for combustion, what is the percentage composition of the original mixture, and what was the total volume after the first combustion?
Ans.
Volume =
39.0 per cent,
N =
2
49.3 per
cent,
CO =11.7
per cent.
164.6 ml.
826. A mixture of ethane (C 2 6 ), hydrogen, carbon monoxide, and nitrogen has a volume of 28.0 ml. After combustion with 72.0 ml. of oxygen, the
residual
volume
is
60.0 ml. and, after passing this into
residual gas occupies 34.0 ml.
When
solution, the this gas is passed over yellow phosphor-
KOH
294

left.
ous, only 4.0 ml. are

Q.
Calculate the percentage composition of the original
Ans.
C2H 6 =
What
is
35.7 per cent,
H =
2
28.6 per cent,
CO =
21.4 per cent,
N =
2
14.3 per cent.
826.
the percentage composition of a mixture of hydrogen, carbon
monoxide, and methane if the volume of the oxygen consumed in combustion and the volume of the carbon dioxide produced are each equal to threefourths of the volume of the original gas taken?
Ans.
827.
112
25 per cent,
CO =
58.3 per cent,
CH ~
4
16.7 per cent.
From
the following data, calculate the percentage composition of a
sample
of illuminating gas:
Sample taken
for analysis
Volume after KOH After Br2 treatment

After
treatment
After pyrogallol treatment
treatment Residual gas taken for analysis
Cu 2 Cl 2
= = = = =
==
100.6 ml.
98.4 ml. 94.2 ml.
93.7 ml.
85.2 ml.
10.3 ml.
Volume of air added Volume after explosion Carbon dioxide produced

Ans.
= = =
87.3 ml.
80.1 ml.
5.2 ml.
CO
2
Unsaturated
O CO
CH
H N
828.
2
2
= compounds = = = = = =

8.5 per cent

3.3 per cent
The
following measurements are
made under
identical conditions.
Calculate the percentages of carbon dioxide, oxygen, carbon monoxide, and nitrogen in a sample of gas containing no other components:
Sample taken

Ans.
after after
KOH
2
treatment
CO =
2
8.3 per
O absorption 64.6 ml. after CO absorption 64.5 ml. = 10.4 per cent, CO = 0.1 cent, O
2
= = = =
79.5 ml.
72.9 ml.
per cent,
N =
2
81.2 per cent.
A water gas is of the following composition: 33.4 per cent CO, 8.9 cent unsaturated hydrocarbons, 3.9 per cent CO2 7.9 per cent 2 10.4 per per cent saturated hydrocarbons, 34.6 per cent If a sample of 2 0.9 per cent O 2 100 ml. is passed through the following absorbents in the order stated until
829.
,
constant volume is reached in each case, what is the volume reading following each treatment: (a) caustic potash, (6) bromine water, (c) alkaline pyrogallol,
(d)
ammoniacal cuprous chloride?
295
830. A mixture of methane, air, and hydrogen having a volume of 130 ml. is conducted over gently ignited palladium asbestos, after which the volume of the gas is 105 ml. Both measurements are made at 20C. and 750 mm. pressure, a Hempel pipet filled with water being used. Compute the percentage (by volume) of hydrogen in the original gas mixture and the weight of H 2 O that could be formed from it. 831. If 12.0 grams of pure carbon undergo combustion in 31.3 liters of is the percentage-by-volume composition of the mixture
pure oxygen, what after combustion?

832.
Assume air to contain 20.9 volumes O2 and 79.1 volumes of nitrogen. 100 volumes of air are mixed with 95 volumes of hydrogen and the mixture exploded, what is the composition of the gas remaining and what are the
If
volumes of the various components after cooling to 20C. and 760

pressure?
833.
mm.
of a mixture of methane, carbon monoxide, and with an excess of air. Show by equations that the nitrogen exploded of the mixture cannot be determined by measuring percentage composition the contraction in volume and the volume of oxygen consumed.
is
A known
volume
834.
certain illuminating gas
is
known
CH4, CO, and unsaturated hydrocarbons. the percentage composition of the gas from the following data:
nents:
2,
CO N O
2,
2,
2,
to contain the following compoCalculate
Sample taken
for analysis
v
Volume after KOH treatment After Br2 treatment

After pyrogallol treatment After Cu 2 Cl 2 treatment
Residual gas taken for analysis
Volume of O 2 added 20.2 Volume after explosion =11.8 Combined CO2 + O2 produced = 11.4
(i.e.,
= = = = = = =
99.5 ml.
97.6 ml.
94.4 ml.
93.8 ml.
85.1 ml.
12.0 ml.
ml.
ml.
ml.
absorbed in alkaline
pyrogallol)
836.
carbon dioxide.
volume
certain natural gas is known to contain methane, nitrogen, and 50.0-ml. sample is passed into caustic potash, and the of the residual gas is found to be 49.6 ml. Of this residual gas, 20.0 ml.
are taken
and an excess
of air
is
the total volume of 38.4 ml.

original gas.
added. Combustion causes a shrinkage in Calculate the percentage composition of the
836.
cent,
A blast-furnace gas is of the following composition: CO = 12.5 per CO = 26.8 per cent, H = 3.6 per cent, N = 57.1 per cent. If a
2
2 2
100-ml. sample were passed through a solution of caustic potash, what would be the volume of the residual gas? If to 50.0 ml. of this residue were added 25.0 ml. of pure oxygen and the mixture exploded, what would be the new volume of the gas and what would be its percentage composition?
PART VI COMMON ANALYTICAL DETERMINATIONS

The following methods are those in common use in the gravimetric and volumetric determinations of the more common elements and radicals. They
are given here in barest outline principally to serve as a reference in solving problems in this book. Colorimetric methods and other special methods
involving
little if
any stoichiometry are omitted.
Aluminum
Precipitated with NII 4 OII as A1(OH) 3 ignited, and weighed as A1 2 3 Precipitated with 8-hydroxyquinoline ("oxine") as A1(C 9 H6NO) 3 ignited, and weighed as A1 2 03.
,
.
Precipitated with oxine as in the preceding case arid the precipitate disKBr then added and the solution titrated with standard solved in HC1.
KBrOa
to disappearance of red color of methyl red indicator [A1(O 9 3C 9 H 6 NOH; 5Br~ 611+ - 3Br 2 311+ -> A1++*BrOr 2Br~ 211+ 2Br 2 C 9 H 4 NBr2 OH]. C9
HNOH +
H NO) + + 3II O;
6
3 2
Ammonium
(See under Nitrogen.)
Antimony
Precipitated as
xus 81)283.
Sb 2 S 3
or
Sb 2 S5,
,
ignited in an inert atmosphere,
and weighed
air,
and weighed
<6Sb
4iir
Precipitated as Sb 2 S 3 or Sb 2 S 6 heated with as Sb 2 4

.
NII 4 OH
+H
2,
ignited in
(In alloys}
Left as a residue of hydrated Sb 2 06 on treating alloy with 5II 2 O). 10NO Residue ignited lONOr 1011+ -> 3Sb 2 O 5
HNO
in
to
Sb 2 O4
Tin must be removed.
Titrated in ice-cold
(oSbCV
excess
I2
+ 2MnOr +
.
HC1 solution from 3 to 5 with standard 12II 2 O -> 5H 3 SbO 4 2Mn++ 20C191 l+).
KMn0
Titrated from 3 to 5 with standard
I 2 in
a solution kept nearly neutral by
NaIICO3
3
+ 2HCO ~ -> SbCV +
The antimony
21-
is
often held as a tartrate complex (SbOs*

2
+ 2CO +
H,O).
3
Titrated from 3 to 5 with standard

of color of
KBr0
methyl orange indicator (3SbCl4
in IIC1 solution to disappearance
+ Br<V +
9II 2
O - 3H SbO +
a
Br~
12C1-
9II+).
Brought to 5-valent form and the HC1 solution treated with KI. The liberated I 2 titrated with standard Na 2 S 2 O 3 (H 3 SbO4 + 21" + 4C1- + 5H+ ->
I2
+ 4H O).
2
297
298

Arsenic
N HC1 with H2S and weighed as such. Arsenate solution as MgNH4As0 4 .6H 2 O, ignited, and ammoniacal from precipitated as Mg^s^. weighed Precipitate disArsenate precipitated from neutral solution as Ag*AsO4 f solved in HNO 3 and the Ag titrated with standard KCNS using ferric alum
Precipitated as As^S3 from 9
.
indicator (Ag+
+ CNS~ -> AgCNS).
Titrated from 3 to 5 with standard I 2 in a solution kept nearly neutral by I 2 + 2HCO 3 -* AsOr + 2I~ + 2CO 2 + H 2 O). excess NaHCO 3 (AsOr Titrated in strong HC1 solution from 3 to 5 with standard KIO S (2As+++ Free I 2 is formed as an IC1 + 4H+). Cl" + 5H 2 O - 2Il8AsO4 IO3 Titration is to chloroform. with color violet intermediate product and gives
disappearance of this color. Titrated in HC1 solution with standard + ++ BrCV methyl orange indicator (3As
KBrO to disappearance of color of + 9II2 O -> 3H AsO4 + Br~ + 91I+).

3
as AsH 3 (Smatt amounts) Reduced in acid solution with Zn and evolved Or AsH to standards. 3 abcolor As and to The arsine oxidized compared standard I with titrated Excess I solution. of 2 2 sorbed in measured volume
.
NaAQi
(AsHs
I2
+ 4H
,
->
H AsO +
3
81"
8H+).
Precipitated as Precipitated as Precipitated
8H+
4 Precipitated f+ (+H 2 SO4 ) and excess Fe titrated with standard - -> ++ ++ + 4H BaSO
.
BaSO4 ignited, BaCrO4 and weighed as such. with (NH4 ) 2 CO3 as BaCO ignited, and weighed as such. as BaCrO Precipitate dissolved in excess standard FeS04
3,
Barium and weighed as such.
KMn0
2
(BaCrO4
+ 3Fe f +
f
+ S0
3Fe
Cr^
O).
dilute IIC1. Precipitated as BaCrO 4 and precipitate dissolved in KI 16II + -^ O Na S 6I~ standard with 2 2 I 8 4 titrated (2BaCrO Liberated 2
2Ba++
3I 2
+ 8H2O).
,
Beryllium as with NIlÔH Be(OH) 2 ignited, and weighed as BeO. Precipitated solution with 8-hydroxyquinoline, as ammoniacal from Precipitated BeO. as and weighed Be(C 9Il6NO) 2 ignited,
,
Bismuth
Precipitated with
H S as
2
Bi 2 S 3 and weighed as such.
Precipitated as basic carbonate, ignited, and weighed as Bi 2 O. Precipitated as oxalate, (BiO) 2 C 2 O 4 the precipitate dissolved in dilute 2Mn04 " 4 (5H 2 C 2 O4 2 SO4 and the oxalate titrated with standard 2Mn ++ 8H 2O). 6H+ -> 10C02
,
,
KMnO
Boron
Borate heated with methyl alcohol and the volatile methyl borate passed CaO 3H 2 O -* through a weighed amount of ignited lime: 2B(OCH s )a
6CH OH
3
weight
Ca(BO 2 ) 2 = B2CV
-f
The material
is
reignited
and weighed.
Gain
in

+
299
Borate treated with methyl alcohol as above and the methyl borate hy3H 2 O -> H 3 BO3 + 3CH 3 OH. The CH,OH is redrolyzed: B(OCH 8 ) 3
3 BO3 titrated with standard NaOH in the presence of glycerol (or other polyhydric alcohol) which forms a loose compound with the HsBOs. Only one hydrogen of 3 BO3 reacts.
moved by evaporation and the
Bromine
(Bromide) Precipitated as AgBr and weighed as such. (Bromide) (Volhard method) Precipitated as AgBr with measured amount of AgNOs and the excess Ag+ titrated with standard KCNS using ferric alum
indicator (Ag+
+ CNS~ -* AgCNS).
Titrated with standard
(Bromide)
indicator.
AgNO
using eosin or other adsorption
Na2 S O3 (Br 2 +
2
Excess KI added and the liberated I 2 titrated with standard 21" -* I, 2Br~). Excess KI added in the presence of acid and the liberated L> (Bromate) ~ titrated with standard Na 2 S 2 O 3 (BrO 3 + 6I~ 6H+ -> 3I 2 Br~ + 3H 2 O).
(Free bromine)
(Bromate)
solution
I2
is
Measured amount
I2
of
As 2 O 3
(dissolved in
NaHCOj)
added.
The
acidified, boiled, neutralized with NallCOs, and the excess arsenite
+ 2HCO- -
(BrO"
AsO4 -
21-
2CO
+ 3H AsO + H O).
3
3HaAsO4
Br~; AsOs"
Cadmium CdS and weighed as such. Electrolytically deposited as Cd and weighed as such. Precipitated as CdS and the precipitate titrated with standard
Precipitated as
I 2 in
the
presence of IIC1 (CdS
I 2 -*
Cd++
+ 2I~).
.
Calcium
Precipitated as Precipitated as Precipitated as
CaC 2 O 4 .H O, CaC O4 .II 2 O, CaC O4.H 2O,

2
ignited at low heat, ignited strongly,

ignited,
2 2
and weighed as CaCOs and weighed as CaO. moistened with H 2 SO4> reignited, and
,
weighed as
CaSO 4
Precipitated as CaC 2 O 4 .II 2 O, the precipitate dissolved in dilute II 2 SO 4 and the oxalate titrated with standard 2MnO 4" 6H+ -* 4 (5II 2 C 2 O 4
KMnO
lOCOa
+ 2Mn++ + 8H O).
2
Precipitated as
precipitate
is
CaC 2 O 4 .H 2 O
as above.
filtered
4
with a measured amount of oxalate. The and the excess oxalate in the filtrate is titrated with
standard
KMnO
Precipitated as
CaO
CaCOs)
CaC 2 4 .H 2O, and the ignited material (CaO, or titrated with standard acid.
Carbon
Substance
CaC0
3,
or
is burned in O 2 and the C0 2 caught in (In organic compounds) an absorbing agent (e.g., "asoarite") and weighed. (In iron and steel) Alloy is burned in O 2 The CO 2 is caught in absorbing agent (e.g., "ascarite," = NaOH + asbestos) and weighed. Or the COa is caught in a measured volume of standard Ba(OH) 2 solution and (1) the
.
300
Ba(OH) 2
change

filtrate or
supernatant liquid
is
titrated with standard acid or (2) the
in conductivity of the
Ba(OH)
2 is
measured.
(C02 in carbonates) (Alkalimeter method) Sample is treated with acid in a weighed alkalimeter and the loss in weight measured.
(C02
in
in carbonates)
Sample
(e.g.,
is
treated with acid and the evolved
CO
caught
an absorbing agent
KOH (COZ in gas mixture) volume of gas mixture measured. (CO in gtis mixture) CO absorbed in ammoniacal cuprous chloride solution and the decrease in volume of gas mixture measured. Or volume change measured before and after combustion with O2
.
"ascarite") and weighed. CO2 absorbed in solution and the decrease in
(Oxalate)
(see
Precipitated as
CaC2O4
ignited to
CaO, or
-
CaCO
4
3,
or
CaS04
under Calcium), and weighed. Titrated with standard (Oxalate)
KMnO
(5C2 O4
+ 2MnO ~ +
,
16H+ ->
10CO 2
+
.
2Mn++
+ 8H O).
2
Cerium
Precipitated as
as
Ce(OH) 4
,
or Ce(OII) 3 or
Ce2 (C 2 O4) 3
,
ignited,
and weighed
CeO2
Precipitated as
Ce(IO3 ) 4 converted to Ce2 (C2 O4 ) 3
ignited,
and weighed as
Ce0 2 (2CeffOW4 + 24H 2 C 2 O4 -> Ce2 (C 2 O4 ) 3 + 4I ? + 42CO 2 + 24II 2 O; 2Ce2 (C 2 O 4 ) 3 + 4O2 - 4CeO2 + 12CO 2 ). Cerous oxidized to eerie with NaBiO3 or (NH4) 2 S2 Os and excess oxidizing agent removed. Measured amount of FeSO4 added and the excess ferrous with standard KMn04 (2Ce+++ + NaBiO 3 + 6H+ -> 2Ce++++ + titrated Na+ + 3H 2 O;
Chlorine
AgCl and weighed as such. (Chloride) (Volhard method) Precipitated as AgCl with measured amount of AgNO 8 and the excess Ag+ titrated with standard KCNS using ferric alum indicator (Ag + + CNS" -* AgCNS).
(Chloride)
Precipitated as
Titrated with standard (Chloride) indicator. sorption

(Chloride)
AgNO
using fluorescein or other ad-
(Mohr method, for small amounts)
Titrated in neutral solution
with standard
AgNO using K CrO

3 2
indicator.
(Free chlorine)
Na S
2
(C1 2
Excess 21- -+ I 2
KI added and the liberated I 2 titrated with standard
+ 2C1-).
O
Excess KI added in the presence of acid and the liberated (Hypochlorite) 21211+ -> I 2 I 2 titrated with standard Na2 S 2 3 (OC1Cl~ 2 O). Titrated with standard Na 3 AsO 3 using KI starch as (Hypochlorite)
+H
outside indicator (OC1~
Cl~ AsO4 s ). Reduced to chloride with Zn, FeSO4 or (Chlorate) determined gravimetrically as AgCl.
+ AsOr -
H SO
2
and chloride
Chromium
as
Chromic ions precipitated with Cr2O3

.
NH OH
4
as
Cr(OH) 3j
ignited,
and weighed
301
Chromate precipitated as BaCrO4 from neutral or buffered acid solution, ignited gently, and weighed as such. Dichromate reduced with measured amount of FeSO4 and the excess ferrous titrated with standard KMnO 4 K 2 Cr2 O7 or Ce(SO4 ) 2 (Cr2 7 + 6Fe++ + 14H+ -> 2Cr+" + + 6Fe+++ + 7H 2 O). Dichromate reduced with excess KI and the liberated I 2 titrated with standard Na2 S2O3 (CriOr + 6I~ + 14H+ -> 2Cr+++ + 3I 2 + 7H 2O).
, ,
Cobalt
Electrolytically deposited as
Co from ammoniacal
solution.
Precipitated with alpha-nitroso-beta-naphthol as Co[CioHeO(NO)]3 precipitate (1) ignited in O2 to Co3 O 4 and weighed, or (2) ignited in
and the
2
to
Co
and weighed.
Copper
Electrolytically deposited as Cu.
H SO + 2CNS- + H O 2
3
Precipitated with
H SO + KCNS and weighed as CuCNS 2CuCNS + SO ~ + 4H+).

2
(2Cu++
2
Excess
(2Cu++
tion
KI added and the 41- - CuJ, + I 2 ).
liberated I 2 titrated with standard
Na2 S O|
Ammoniacal solution titrated with standard
(2Cu(NH3 ) 4 ++
4
+ 7CN- + H O
2
->
KCN to the point of decoloriza2Cu(CN)r + CNO~ + 6NH +

3
2NH
+
).
Precipitated as
CuCNS
I2
(see
standard
KIO
(lOCuCNS
Titration continued to disappearance of this color (2T 2 6H + - 5IC1 3H 2 O). Net reaction: 4CuCNS 7IO8 2
+ 14H+ -+10CU++ + 10S<V + 7I + 10HCN + 2TT O). + IGjT + 5C1~ + + + + 14H+ + 7C1~ -^ 4SOr + 7IC1 + 4IICN + 5H O.
+
14TO3
2
forming -
above) and the precipitate titrated with which gives a violet color with chloroform
2
Cyanide under (See Nitrogen.)

Fluorine
Precipitated as Precipitated as
CaF2
ignited,
and weighed
as such.
PbFCl from
Titrated with standard indicator (4F~ + Th+++ -> ThF4 ). Evolved as SiF4 by action with quartz and concentrated the gas 2 SO 4 absorbed in water and the solution titrated with standard NaOH using 3H 2 -> 2H 2 SiF 6 phenolphthalein (4IIF + SiO 2 -> SiF 4 + 2IT 2 O; 3SiF 4 -> H 2 SiF6 6OH~ 6F~ 3H 2O). 2 Si0 3 2 SiO3
acid solution and weighed as such. Th(NO3 ) 4 using zirconium-alizarin
+H
Gold
Chemically or electrolytically reduced to Au and weighed as such. Reduced to metal by measured amount of reducing agent (e.g., oxalate) and excess titrated with standard 4
KMnO
302
Hydrogen and loss in weight of sample determined. Volatilized as water and measured by gain in weight of absorbing agent (e.g., CaCl 2 ). (Gas analysis) Absorbed on Pd sponge and loss in volume of gas mixture determined. Or volume change measured before and after combustion with O 2
Volatilized as water
.
Iodine
(Iodide)
(Iodide)
Precipitated as Agl and weighed as such. Precipitated as PdI 2 and weighed as such (Br~ and Cl~ not
precipitated).
(Iodide)
(Volhard method)
Measured amount
of
excess
Ag+
KCNS
AgNO
added and the
(Ag+
+ CNS~ -* AgCNS). +
Excess Fe2 (SO 4 ) 3 added, liberated I 2 caught in KI solution and (Iodide) titrated with standard 2Fe 4++ -> I 2 (2I~ 2Fe++) (Br~ and Cl~
NaÔa
not affected). Excess KIOS added in presence of acid and liberated I 2 boiled out. (Iodide) Excess I(V determined in cooled solution by adding KI and titrating the liberated I 2 with standard Na^S-A (5I~ 6H+ -> 3I2 3H 2O). ICV Titrated with in standard KIO (Iodide) 8 presence of concentrated HC1 using chloroform as indicator. I 2 is first liberated and colors CHC1 3 violet. ~ Color fades away at end point. Net reaction: 2I~ IO 3 3C1~ 6H+ -
3IC1
+ 3H 0.
2
(Iodide)
Titrated directly with standard
AgNO3
using eosin adsorption
indicator.
Excess KI added and the liberated I 2 titrated with standard 516H+ -> 3I 2 3TI 2 O). 8 Titrated with standard Na2 S 2 O3 using starch indicator (Free iodine) -* 212S S 2 Or 4 6 -). (I 2 Titrated with standard NasAsOa using starch indicator in (Free iodine) 13 solution kept nearly neutral with excess NaHCQe (12 2HCO 8 - -> AsOs " 21- + 2CO2 AsO4 2 0). Iron
(lodate)
Na*S2O (IQr +
+H
Precipitated as
Fe(OH) 3 with
NH OH
4
or
NaOH,
ignited,
and weighed
as
Fe2
8.
Precipitated with cupferron as
(CeHsNONO^Fe from
acid solution, ignited,
and weighed as Fe2O3

4
Ferrous titrated with standard
MnO - + 8H+ -> SFe+++ + Mn^ +

Na S O
Ferric treated with large excess + 21" -> I 2 2 3
KMnO K Cr
4,
7,
orCe(SO 4 ) 2
(e.g.,
5Fe++
4TI 2 O).
liberated I 2 titrated with standard
(2Fe
^+
KI and
2Fe^).
Ferric titrated with standard TiCl3 solution using
KCNS indicator
Lead
Precipitated as
PbSO4
2
or
PbCrO4
or
PbMoO
Electrolytically oxidized
(Pb++
+ 2H
- PbO
and deposited as
PbO2 and
,
and weighed as such. weighed as such

+ MoOr
303
Titrated with standard (NH 4 ) 2 MoO4 using tannin as outside indicator -> PbMoO4 ).
PbCrO4 the precipitate dissolved in acid and the Cr207~ determined volumetrically as under Chromium above.
Precipitated as
,
Magnesium
Precipitated from weighed as Mg2 P2O7.
ammoniacal solution as
MgNH P0
4
.
4,
ignited,
and
Manganese Manganous
in air
ions oxidized
3
by KC1O3 or KBrO3 to Mn02

ignited,
Precipitate ignited
and weighed as Precipitated as

of
Mn O4.
4
MnNH PO4,
and weighed as
Mn P Or.
2
(Bismuthate method)
Oxidized with
NaBiO 3
or
BiO2
to permanganate.
Measured amount
KMnO
(2Mn++
FeSO4 added, and excess ferrous titrated with standard 5NaBiO8 + 14H+ -> 2MiiO4- + 5Bi+++ + 5Na+ + 7TI 2 O).
Oxidized with
(Ford-Williams method)
KC1O3
in presence of concentrated
HNO
to
titrated
Measured amount of FeSO4 added, and the exceiss ferrous with standard KMn04 (MnO2 + 2Fe++ + 411+ -> Mn++ + 2Fe+++ +
2.
MnO
2H 2 O).
Oxidized with (Persulfate method) then with standard and titrated ganate,
(NH4 ) 2 S O 8 (+AgNO ) to permanNa3 AsO to indefinite valence of 3+.

2
3 3
Arsenite standardized against similar sample containing known Mn. (Volhard method) Manganous ions titrated directly with standard
in solution kept neutral with 2II 2 O). 2Zn++
ZnO (3Mn++
Mercury
+ 2Mn0 ~ +
4
*
2ZnO - 5MnO2
KMnO +
Precipitated as
HgS and
Electrolytically precipitated as Ilg
weighed as such. and weighed as such.
2CNS-
Titrated with standard -> Hg(CNS) 2 ].
KCNS
2
using ferric
alum indicator
"
1
[Tig"*"
Molybdenum
PbMoO4 or Ag MoO Hg MoO or as MoS

2 4
4
3,
and weighed as such. ignited, and weighed as
MoO
3.
Reduced with Zn and passed

then titrated with standard
directly into ferric alum.
The reduced
iron
KMiiO 4 (2MoOr
4
2
3Zn
+
4
1611+
- 2Mo f f +
3Zn++
+ 8H O; 5Mo+++ + 3MnO " + 8II O -> 5MoO - + 3Mn^ +

2
16II+).
Nickel
Precipitated with
dimethyl glyoxime as [(CH3 ) 2 .CNOH.CNO] 2 Ni
and
weighed as such.
Electrolytically precipitated as Ni and weighed as such. Measured amount of added to ammoniacal solution
KCN
;
and the excess
CN4CN-
titrated
with standard AgNO3 using KI indicator [Ni(NH3 )++ -> Ni(CN) 4- .+ 6NH3 2CN~ Ag + -^ Ag(CN) 2 -].
Nitrogen Converted by digestion with con(Organic nitrogen) (Kjeldahl method) Excess NaOH is then added, the centrated H2S04 HSO to 4 4 catalyst
NH
304
liberated
NH
distilled into
measured amount
of acid,
and the excess acid

3
(Ammonium)
measured amount
using methyl
NaOH using methyl red indicator. Excess NaOH added, the liberated NH
(NH4)
distilled
into
of acid, and the excess acid titrated with standard red indicator.
NaOH
(Ammonium)
toPt.
(Nitrate)
Precipitated as
PtCl6 and weighed as such, or ignited
Reduced to method above. Kjeldahl

(Nitrite)
NH +
4
with Zn or with Devarda alloy; then by
Titrated
with standard
5NO
KMnO
(5NO2
+ 2Mn0 ~ +
4
6H+
->
2Mn++
+ 3H2 O).
KCNS
Measured amount of AgNO8 added and the (Cyanide) (Volhard method) excess Ag+ titrated with standard using ferric alum indicator (2CN~ 2Ag+ -> Ag2 (CN) 2 ).
of
Ag2 (CN) 2 [2CN-
(Cyanide) (Liebig method) Titrated with standard Ag+ -> Ag(CN)r].
AgNO3 to faint turbidity
(Gas analysis) other gases.
Volume
of residual nitrogen
measured after absorbing
Oxalate
(See under Carbon.)
Oxygen
(Gas analysis)
Volume
of gas mixture determined before
and
after ab-
sorbing in alkaline pyrogallol.

Precipitated as
(Iron
MgNH PO
4
4,
ignited,
Phosphorus and weighed as

.
Mg P O
2
2
7.
and steel) Precipitated as (NH 4 ) 8 PO4 .12MoO3 and weighed as such, or ignited and weighed as P 2 O5.24MoO 3 (Iron and steel) (Ferric alum metlwd) Precipitated as (NH4 ) 3 P0 4 .12Mo0 8 dissolved, the Mo reduced with Zn in a Jones reductor and passed directly
,
into excess ferric alum.

4
The reduced
iron then titrated with standard
KMnO (2MoOr + 3Zn + 16H+ -> 2Mo +++ + 3Fe+++ + 4H O -> MoOr + 3Fe++ + 8H+).
2
3Zn++
8II 2 O;
MO+++
(Iron
occurs.
and
steel)
reduced solution
is
(Blair method) caught in an
in the preceding method except that the open flask where slight oxidation by the air
As
The Mo, now having an average valence corresponding

titrated to
to the oxide
Mo
24
37 , is
MoO "
4
with standard
KMnO
4.
(Iron and steel) (Alkalimetric method) Precipitated as (NH 4 ) 8 PO 4 .12MoO 3 , dissolved in a measured amount of standard and the excess alkali
NaOH
HNO
(NH4 PO .12MoO
)3 4
+
2
23OH- - 12MoO4 -
using phenolphthalein indicator. Net reaction: HP04 " 3NH4+ 11H20.
Platinum
K PtCl
and weighed as such. and weighed as such, 4 2 PtCl6 (NH )

6
or] ignited
to Pt
and
weighed.
Electrolytically reduced to
Pt and weighed as such.

Potassium
Precipitated as to Ft and weighed. Precipitated as
305
K PtCl6
2
and weighed as such, or the precipitate reduced

weighed as such.
KC1O4 and
See also under Sodium.
Selenium
Reduced by
H SO
2
8,
KI,
etc.,
to Se
and weighed as such.
Silicon
2 SiO 8 ignited to SiO 2 and weighed. The impure SiO2 is Precipitated as then treated with HF, evaporated, reignited, and impurities are weighed. 4HF -> SiF4 2H 2 O). Loss in weight = SiO2 (SiO 2
,
Silver
Precipitated as
cator (Ag+
AgCl and weighed as such.

Titrated with standard -> AgCNS).
(Volhard method)
KCNS
using ferric alum indi-
CNS-
NaCl
using fluoresceiii as an adsorption indicator.
Sodium
Silicate decomposed by heating (Silicates) (J. Lawrence Smith method) with CaCO 3 + Leached with water, Ca++ removed, filtrate evapo4 C1. NaCl KC1 weighed. then determined as rated, and residue ignited. KC1O4 or K 2 PtCl e Na determined by difference.
NH
.
(Small
amounts)
2 2
Precipitated
2
2
as
NaMg(UO )3(C H O )9.6^2H O and weighed as such

3
NaZn(UO2 )3(C2H 3O2 )9.6H 2O
or
as
Strontium
Precipitated as
SrS0 4 and weighed
as such.
Sulfur
(Sulfate)
Precipitated as
Excess acid solution of BaCrO4 added (SO4 ~ (Sulfate) (Hinman method) ~ Ba++CrO4 BaSO4 4 OH added to precipitate excess CrOr). Excess
BaSO4 and weighed
as such.
NH
Combined BaSO4 + BaCrO4 filtered. Filtrate acidified, treated ~ with excess KI, and liberated I 2 titrated with standard Na2 S2O8 (Cr2 O 7 + ++ + 61- + 14H+ -2Cr + 3I2 + 7H2O). In the titration each Cr2O7 is equivalent to 2SO 4 ~.
BaCrO4
H SO
2
Precipitated with benzidine hydrochloride giving Ci 2 8 (NH 2 ) 2 .Suspension of precipitate titrated with standard NaOH which acts 2 SO4 only on the Evolved as 2S by action of HC1 and (Sulfide) (Evolution method for alloys)
(Sulfate)
4.
The solution is acidified and the caught in ammoniacal solution of ZnSO4 KI using starch indicator 2 S titrated with standard I 2 or standard KIOs
.
(Sulfide)
Oxidized to sulfate, precipitated as
BaSO4 and
weighed.
306

I2
(Sulfite)
using starch indicator.
(SOs~
HO+
2
I*
->
SOr +
21-
2H+0.
titrated
Measured amount of FeS04 added and excess ferrous ~ KMnO with standard + 2Fe++ -> 2SO4 - + 2Fe^+). 4 (S 2 O 8
(Persulfate)
(Thiosulfate)
Titrated with standard I 2 (2S 2
12
S 4 O6
"
21 -).
(Thiocyanate)
Measured amount
of
with standard
KCNS (CNS- + Ag + Th(C 2 O4) 2

ignited,
AgNO
added and excess Ag+ titrated
AgCNS).
Thorium
Precipitated as
,
and weighed as
ThO2
Tin
(In alloys)
ignited to
1I 2
H SnO
2
by
SnS 2
ignited,
hydrolysis, ignited, and weighed as and weighed as Sn() 2

.
SnO2
Alloy treated with

weighed.
1INO3
leaving
H SnO
2
as residue.
This
3
is
SnO2 and
->
3H 2 SnQ3
Antimony must be removed. 4NO).
(3Sn
+ 4NO ~ +
standard
I2
Titrated from 2 to 4 in cold IIC1 solution in current of + I2 6C1- - SnClT 21"). (Sn-*
CO2 with
Titrated to yellow color with standard FeCl 3 (Sn++ 2Fe + + 2C1-).
+ 2FeClr
Sn-Cle~
Titanium
Precipitated as
Ti(OH) 4
ignited,
and weighed as Ti02
Zn - 2Ti+++ standard 4 (2Ti++++ +++ 4H 2 O). Mn++ MnO4 8H+ -> 5Ti ++ Zn++; 5Ti 4 CNS Reduced to Ti +++ and titrated with standard ferric alum using + -> Ti ++++ Fe^ indicator (Ti+++ Fe++).
duced
iron
titrated
Precipitated with cupferron, ignited, and weighed as TiO 2 Reduced by Zn (but not reduced by SnCl 2 ) to Ti+++ and titrated with restandard 4 or passed from zinc reductor into ferric alum and the
.
KMnO
with ~
KMnO ^+
NH
Tungsten
Precipitated with acid as ignited, and weighed as
H W0
2
3.
or with cinchonine as cinchonine tungstate,
WO
4
Uranium
Precipitated with
NH OH
as
(NH 4 ) U2 O
2
7,
ignited in air,
and weighed as
.
8.
UO2NII 4PO4 ignited, and weighed as (UO2) 2P2O7 Zn and titrated back with standard KMnO4 (UO2 + + + Zn Reduced with 4H+ -* U++++ + Zn ++ + 2H 2 O; 5U++++ + 2Mn04 + 2H 2 O -> 5UO2 ++
Precipitated as
,
4-
2Mn +4 +
-
4H+).
Vanadium
as
HgVO
3,
ignited,
Pb(V08 )2,
and weighed fumed with H2 S04
as
VO
2
6.
filtered, ignited,
and weighed
VO
2
6.
307
5V08 ~
Reduced from 5 to 4 by 862 or H 2 S and titrated back with standard KMn04 ~ " (2V08 + S02 + 4H+ -> 2VO++ + S04 + 2H20; 5VO++ + MnO4 + 6H 2 ->
Mn++
Zinc
Precipitated as ZnS, ignited, and weighed as ZnO. Precipitated as ZnNH 4 PO 4 and weighed as such or ignited to
Zn 2 P207
or
and weighed.
K4Fe(CN) 6 using FeS04 as internal indicator UO2 (NO8 ) 2 as external indicator. The net equation is: 3Zn++ + 2Fe(CN) 6 li 2K+->K2Zn3 [Fe(CN) 6 2
]
.
Zirconium
Precipitated as
QS
Zr(OH) 4
ignited,
and weighed as ZrO2
Precipitated with cupferron or phenyl-arsonic acid, ignited,
and weighed
ZrO 2
2 Se0 8 as Zr()ScO3 ignited, and weighed as Precipitated with Precipitated as Zr(HP0 4 ) 2 ignited, and weighed as ZrP2 7
t
ZrO2
PART
VII
PROBLEMS ON SPECIFIC GROUPS AND DETERMINATIONS

A.
QUALITATIVE ANALYSIS
Silver
Group
(See also Probs. 54, 66, 109, 126, 153, 155, 174.)
837. Silver
chloride
dissolves
in
NH OH
4
2NII 4OH -> Ag(NH 3 ) 2 + + Cl- + 2H 2 O. Calculate (a) number of gram-moles of NII 4OH equivalent to 1 F.W. of AgCl, (b) number of grams of NH3 equivalent to 1 F.W. of AgCl, (c) number of gram-ions of Cl"" produced by dissolving 1 F.W. of AgCl.
according to the equation:
AgCl
Assuming 20 drops to equal a milliliter, how many drops of 2.0 formal would be required to precipitate the silver from a solution containing 100 mg. of AgNO 3 ? How many millimoles and how many milligrams of NII 4 C1 does each milliliter of the reagent contain? How many milliliters of 5.0 normal NH 4 C1 should be taken in order to prepare 500 ml. of the
838.
4
NH C1
solution
2.0 formal solution
by
dilution with water?
839. A neutral solution containing 0.0170 gram of dissolved AgN0 3 is treated with an aqueous solution of 0.120 millimole of HC1 and the precipitated AgCl is filtered off. (a) How many gram-ions of Cl" and how many grams of Cl~ are present in the filtrate? (6) How many milliliters of 4
NH OH
0.96 containing 9.9 per cent neutralize the acid in the filtrate? (c)
(sp. gr.
NH
by weight) would be required

milliliters of 2.0
to
How many
N NH4OH
would be required to dissolve the AgCl precipitate?
Hg + HgNTI
Complete and balance the following equation: Hg 2 Cl2 + NH 4OH > What oxidation numbers does mercury show in 2 Cl + this reaction? How many grams of mercurous chloride would give 0.0100 F.W. of the amido compound by this reaction? How many gram atoms of free mercury would be formed at the same time, and how many grams of ammonium chloride could be obtained by filtering and evaporating the filtrate to dryness?
840.
.
.
How many
per cent
milliliters of
3
ammonium
hydroxide
NH
by weight) would be required
(sp. gr. 0.970, containing 7.31 in the reaction?

if
841. What is the solubility product of lead chloride, PbCl2 dissolve in 50.0 ml.? How many milligrams of chloride ions
,
550 milligrams
in order to
must be present
in 3.00 ml. of a solution containing 0.100 millimole of give a precipitate of lead chloride in the silver group?
Pb(N08 ) 2
309
310
842.

To
+ a solution containing 50.0 mg. of Ag and 50.0 mg. of Pb++ are 4 C1 solution to give precipitates of AgCl and PbCl 2 and added sufficient make the surrounding solution half normal in chloride ions. If the volume of
NH
the solution is 30.0 ml and the solubility products of AgCl and PbCl 2 are 4 1.0 X 10~ 10 and 2.4 X 10~ respectively, how many milligrams of silver and of lead will remain unprecipitated? How many milliliters of boiling water are if its solubility at 100C. is required to dissolve the precipitated lead chloride
,
0.120 F.W. per

dissolve
liter of
water?
if its
by
this
treatment
milligrams of silver chloride would solubility at 100C. is 0.150 millimoles per liter
Sulfide
How many
of water?
Hydrogen
176.)
Group
(See also probs. 55, 57, 67, 106, 108, 110, 123, 128, 162, 163, 167, 171, 172,
in hy843. If precipitation of suifides is carried out in a solution 0.30 is the What solution? the of value is the hydroxyl-ion pH drogen ions, what
concentration?
844.
A
3) 3
solution
contains dilute
HN0
and 0.0485 gram
of
dissolved
Bi(NO
3H 2 S
.5H 2 O. The bismuth is precipitated by H 2 S as follows: 2Bi+++ + Bi 2 S 3 + 6H+. Calculate (a) number of formula weights of bismuth
sulfide produced, (6) number of grams and number of milliliters (standard + 2 S required, (c) increase in the number of gram-ions of conditions) of
accompanying the precipitation. 846. The bismuth sulfide of the preceding problem is dissolved in HNOa ~ - 2Bi+++ + 2NO + according to the ionic equation: Ri 2 S 3 + 2NO 3 + 8H+ Calculate (a) number of formula 3S + 4H 2 O; 2NO + O 2 (air) ~-> 2NO2
.
weights of Bi(NO3 ) 3 .5H 2 O obtainable from the resulting solution, (fc) number of formula weights of 3 3 required; (c) number of milliliters of
HNO
HN0
(Sp. gr. 1.13,
of gram-atoms of sulfur produced, (e) 2 subsequently produced, (g) percentage of nitrogen (/) number of grams of
by weight) required, (d) number number of millimoles of NO gas formed;

3
HN0
NO
in the
NO
gas.
milliliters of
846.
How many
What
is
H S0
2
(sp. gr. 1.14,
H SO4
2
by weight) are
Pb++ ?
theoretically required to precipitate 10.0 milligrams of the normality of the above sulfuric acid and what is its com-
position in terms of percentage of combined 80s? How many formula weights of 4 C2H 3 02 would be required to dissove the resulting precipitate of lead sulfate? If the latter solution were diluted to 50.0 ml., what would be its
NH
normality in terms of lead acetate and

sulfate?
its
molarity in terms of
ammonium
847.
When
7,
K Cr O
2
2
2CrCU
2 S is passed into an acid solution containing 0.10 F.W. of the following reaction takes place: 3H 2 S 8HC1 -*> 2 Cr2 O7 2KC1 3S 7H2 0. (a) Write this equation in ionic form ob-
serving the usual conventions,
(b) Express the reaction as the difference between two half-cell reactions, (c) How many formula weights of chromic chloride and how many grams of potassium chloride could be obtained by
PROBLEMS
311
evaporating the resulting solution to dryness? (d) How many gram-atoms of sulfur are formed? (e) How many milUmoles of 2 S are oxidized? (/) How
many
milliliters
(standard conditions) of
of 100 ml.
HS
2
are oxidized?
(g)
If
the initial
and is 0.30 N in HC1, what is the acid northe above after reaction has taken place, assuming no solution of the mality in volume? appreciable change
solution has a
volume
H S, oxidizing agents like the H S and the latter is

2
2
848. In the precipitation of the copper-tin groups from acid solution with permanganate ions and ferric ions are reduced by
oxidized to free sulfur.
Write each of these two
redox reactions as the difference between two half-cell reactions, and calculate the number of millimoles and the number of milligrams of 4 and of FeCU thus reduced by 10.0 ml. of 11 2 S gas (measured under standard conditions).
KMnO
SOr. Assume that 0.233 gram of HgS is dissolved according to this equation and the solution diluted to 50.0 ml. If excess chloride ions are present in sufficient amount to make the chloride-ion concentration 0.510 molar, how many milligrams of
two half-cell
849. Balance the following equation ~ reactions: HgS C103
and express
Cl~ ->
it
as the difference
between
HgClr
mercury are present as simple

1.0
Hg
H f
ions?
(Dissociation constant of
HgClr =
10-
16
).
860.
made ammoniacal and treated with excess KCN, forming Cd(CN) ~ and Cu(CN)a~. The resulting solution is 0.80 molar in CN~ ions. What is the molar concentration of Cd++ and of Cu+ in the solution if the dissociation constant of Cd(CN) 4 is 1.4 X 10~17 and that of Cu(CN) 3 is 5 X 10~ 28 ? Are these values consistent with what happens when II 2 S is passed into the
4
A solution containing 0.010 F.W.
of
CdS04 and 0.010 F.W.
of
CuSO 4
is
complex cyanide solution?

851. Mercuric sulfide dissolves in a solution of
Na2S
NaOII (HgS
+ +
S- -> HgS 2 -) but not
a solution of (NII 4 ) 2 S This is due to the 4OH. difference in the degree of hydrolysis of the sulfide ion: S" IIS~ 1^0 OH". Calculate the numerical value of the mass action hydrolysis constant
in
+ NH
[HS~~][OH~]/[S~] by combining appropriate ionization constants given in

Sees. 27
and 3L
solution containing 30 milligram-atoms of bismuth as Bi 4f f is treated with I1C1 in sufficient amount to make the hydrogen-ion concentration
852.
"
2 molar and the chloride-ion concentration 2 molar. Most of the bismuth is converted to BiCl 4 ~. The solution has a volume of 15 ml. and is made 0.10
molar in I^S. From the ionization constant of H2S calculate the concentration of S" and from the dissociation constant of BiCU~ calculate the concentration of Bi+++. Calculate the value of [Bi+++] 2 [S-] 3 and predict from the solubility product of Bi2Ss whether a precipitation of the sulfide is to be expected.
Ammonium
853.
Sulfide
Group
(See also Probs. 78, 120, 127, 140, 141, 154, 160, 161, 168, 169, 170, 173, 185.)
A solution contains 0.286 gram of dissolved Fe

(a)
of solution,
What
is
2 (S0 4 ) 3 .9H 2 O in 500 ml. the normality of the solution as a ferric salt?
312
(b)

is its
What
normality as a sulfate?
(c)
NH OH
How many
milliliters of 3.00
(d)
millimole of 2 2 per milliliter are required to precipitate the sulfate? 854. From the solubility products of Mg(OH) 2 and Fe(OH) 3 calculate the number of grams of ferric ions that can remain dissolved in 100 ml. of a solution of such alkalinity that 243 mg. of Mg++ will just fail to precipitate as Mg(OIT) 2
.
are required to precipitate all the iron as 4 milliliters of barium chloride solution containing
Fe(OH) 3 ?
How many BaCl .2H O
866.
salt?
If the
What is the molarity of a solution of CrCl 3 which is 0.10 normal as a How many milliequivalents of the salt are present in each milliliter?
chromium is oxidized to dichromate and the volume what would be the normality as a sodium salt
is
twice as great
as before,
of the
Na Cr O
2
present?
this
How many
inillimoles of
FeSO4 .7H 2O would be
dichromate to chromic ions in the presence of acid?
required to reduce Write the ionic equa-
tion as the difference between

866.
two
2
half-cell reactions.
4
How many
milliliters of
H SO
(sp. gr. 1.20)

is
to dissolve 0.010 F.W. of A1(01I) 3 ? molarity of the acid?

867.
What
3
are theoretically required the normality and what is the
How many
millimoles of
HNO
are required to dissolve 0.020 gram-
atom
of metallic nickel
(HNO3
reduced to
NO)? How many grams
of
NiS
could be precipitated from the solution? Show from appropriate mass-action constants why one would not expect precipitate to form from 100 ml. of the
above solution if it has been made 0.30 normal in H+ and 0.10 molar in H 2 S. How high a molar concentration of sulfide ion would be necessary before NiS would start to precipitate?
858. Starting with 0.010 gram-ion of Zn + +, how many millimoles of 3 are theoretically required to form the ammonio complex ion? If three times
this amount of ammonia are used and the total volume molar concentration of Zn+ + ?
is
NH
250 ml., what
is
the
Alkaline Earth and Alkali Groups

(See also Probs. 124, 135, 142, 158, 177.)
869.
A solution is 0.030 formal in Sr++ ions. What value must the chromateSrCrO4
3.0
ion concentration be in order for
to start precipitating (Ks.p. for grams of Ba++ could remain dissolved in each milliliter of such a solution (K s .p. for BaCrO 4 = 3.0 X 10~ 10 )? The =B II 2 O is 2H+ <= Cr2 O7 ~ mass-action constant for the equilibrium 2CrO4 10 14 If the above solution contains sufficient C 4.2 and 2 3 O2 4 2 3 02
SrCrO4 =
10~6 )?
How many
+ HC H
NH
to give a
860.
pH 5, How many grams of CaCl should be taken to prepare 100 ml. of 0.20 N solution? How many millimoles of H C O 4 .2H O would be required to precipitate all the calcium? How many gram atoms of magnesium could theo~ retically be held as Mg(C O ) 2 by this amount of oxalic acid? 861. How many milliliters of a solution of K Cr Oy which is 0.10 normal as a
value of
2
what would be the dichromate-ion concentration?
potassium
as
salt
would be required to precipitate 0.010 gram-atom
of
barium
BaCr0 4 ?
PROBLEMS
862.
3
313
3 4) 2 weight be the normality and the approxiwater and diluted to one liter, what would H2SO4 How many milliliters of 3.40 mate specific gravity of the solution?
How many grams of NH would be liberated from 1.00 gram-equivalent of (NH SO 4 by the action of NaOH? If this NH were absorbed in
would
it
neutralize?
Anion Groups
(See also Probs. 107, 125, 130, 156, 157, 159, 165, 178, 179, 182.)
and balance the following: NO3 + A 1 + OH- -> NH 8 + A1O2 ". Also write it as the difference between two half-cell reactions. If 250 mg. of NaNO 3 are reduced as above with excess aluminum in the presence of NaOH, how many milliliters of N/2 II 2 SO 4 would be required to neutralize the NH 8 liberated? How many gram-atoms of aluminum are theoretically re863. Complete
quired for the reduction?

864. If 100 milligrams of sodium oxalate Na 2 C 2 O4 are heated with concenwhat volume of mixed gases would be obtained when measured trated 2 SO 4 > Na 2 SO 4 2 SO 4 over water at 753 mm. pressure and 25C.? (Na 2 C 2 O 4 be obtained of would volume What II (under the same (JO _j_ CO 2 2 O.) gas
,
+H
conditions of temperature and pressure as above) if the 100 mg. of sodium 2 SO 4 ? 4 in the presence of dilute oxalate were treated with excess
KMnO
B.
QUANTITATIVE ANALYSIS
Water
(See also Probs. 259, 360, 361, 367, 368, 369, 372, 373, 374, 375, 377.)
866.
per cent
cars,
A manufacturer purchased 130 tons of material at 0.20 cent per pound A on a guarantee of 10.00 per cent A. The material was shipped in
V
manufacturer had it analyzed. The chemist reported but neglected to state that he had dried the sample at 100O. The manufacturer paid on a 10 per cent basis, figuring he had made money. In reality, he lost $520. What was the percentage of moisture in the material?
and on
arrival the
10.46 per cent
866.
at the
Ten
tons of
price.
Na SO
2
market
containing 6.30 per cent moisture were purchased During storage, 10.0 per cent of the sodium sulfite was
3
oxidized to sodium sulfate.

its
The
salt
when
weight of water. The salt was purchased. Calculate the gain or loss in the transaction figuring the market price as 3.25 cents per pound.
sold as C.P.
sold contained 3.20 per cent of Na2 SO 3 at the same price as
Sodium.
725, 730, 731, 732, 734, 1028.)
Potassium
(See also Probs. 283, 306, 307, 313, 314, 322, 539, 541, 542, 543, 723, 724,
NaCI and KC1 weighing 0.7500 a obtained from gram and if this 0.2500 gram was sample weighing cent 50.00 mixture of chlorides contained chlorine, compute the percentage per of What weight potassium perchlorate would have been of 2 O in the silicate.
867. If in the analysis of a silicate a mixture of pure
obtained
if
the chlorides had been analyzed by the perchlorate method?
868. In the J.
Lawrence Smith method
for
sample
of mineral, the analyst fails to expel all the
potassium using a 0.5000-gram ammonium chloride from
314
the NaCl KC1. The insoluble precipitate with chloroplatinic acid weighs 0.08921 gram. On ignition the weight is changed to 0.05969 gram. What would be the weight if the ignited precipitate were washed with water and
dried,
and what
is
the percentage of
K O in the mineral?
2
869.
With a 0.5000-gram sample
what would
of pure NaKCaSi 2 6 (mol. wt. 254.3), be the financial saving of the perchloric acid method over the
perchloric acid at $18 per liter and chloroplatinic acid method with 3.00 Assume these at $6 reagents to be added in sufficient gram? platinum per
amounts to react with both the sodium and potassium in the sample and that 80 per cent of the platinum is recovered. Neglect all other costs. 870. Caustic potash is to be produced by the electrolysis of a solution of
per liter is potassium chloride. A solution containing 100 grams of An average current of 900 amperes is used; and, at the end of 5.00 hours, 102 liters of caustic potash, 1.520 N as an alkali, have been produced. How much longer must the electrolysis be continued in order to produce the desired concentration, and what is the current efficiency at the cathode?
required.
KOH
871.
liters of
How many grams of Pt

HC1O4
(3.000
(dissolved in
acid)
as
an
aqua regia) and how many milliwould theoretically be required to pre3
cipitate the potassium from 0.5000 customary excess of reagent?
gram of K PO without allowing for the How much would the former precipitate weigh
4
after ignition?
872.
When an
electric current is passed
through a solution of sodium
chloride, metallic mercury being used as a cathode, metallic sodium is liberated and dissolves in the mercury, forming a hard gray compound which shows the
properties of an alloy and is called an amalgam. extensively as a reducing agent and contains a
Sodium amalgam is used compound of the formula
NaHg2
Five grains of the amalgam are placed in a flask containing about 100 ml. of water and allowed to stand with repeated shaking until the evolution of gas has entirely ceased. The solution is then titrated with 40.75 ml. of Write the of HC1, methyl orange being used us an indicator. 0.1067 O. Calculate the on of reaction the for 2 2 NaHg percentage of Na equation
in the sample.
Ammonium.
Ammonia.
Nitrogen
(See also Probs. 250, 258, 280, 520, 523, 524, 525, 532, 544, 1011.)
873. Ten milliliters of ammonium hydroxide (sp. gr. 0.960) are diluted to exactly 100 ml. in a calibrated flask; 10.00 ml. are withdrawn in a pipet, made acid with hydrochloric acid, and an excess of chloroplatinic acid is added. After evaporation and dilution with alcohol, the insoluble residue is
and found to weigh 1.240 grams. Calculate the percentage of 8 by weight in the original ammonia sample. 874. The nitrogen in a half-gram sample of urea, CO(NH 2 )2, is determined by the Kjeldahl method. The evolved ammonia is passed into 150 ml. of 0.1200 How many ml. of NaOH solution would be required for the 2 SO 4 excess acid if 1.000 ml. NaOII o 0.00700 gram of hydrated oxalic acid?
dried
NH
NH
PROBLEMS
875.
315
bisulfate.
nitrogen in 5.000 grams of leather is converted into ammonium After the sample has been treated with excess NaOH, the 3 acid and the excess acid titrated with evolved is passed into 90.0 ml. of 0.4990
The
NH
Find the percentage of nitrogen in the leather. 876. Nitrogen, existing as nitride in a crucible steel, is determined by decomposing a 5.00-gram sample with HC1. The resulting NH 4 C1 is decomposed with NaOH, and the liberated 3 is absorbed in 10.05 ml. of H 2 SO4 which is After acid. an N as 0.00990 absorption, the concentration of the exactly II 2 SO4 is determined by adding an excess of KI and of KIO 8 and titrating with standard Na2 S 2 O3 the I 2 liberated. The Na 2 S 2O3 is of such strength that 42.0 ml. are equivalent to the I 2 liberated from an excess of KI by 20.0 ml. of 0.0258 N KMnO4 and in the above titration 5.14 ml. are used. Calculate the percent22.05 ml. of 0.1015
N NaOH.
NH
age of nitrogen in the

877.
steel.
chloride is dissolved in water, and the divided into two equal portions. One portion is made alkaline with NaOH, and the liberated ammonia is distilled into 100 ml. of 0.1000 NaOH for sulfuric acid which is then found to require 43.90 ml. of 0.1320 solution
is
A sample of impure ammonium
neutralization.
The other portion is treated with sodium hypobromite solution

>
3Br~ + N 2 + 3H 2 0), and the liberated nitrogen is found when measured over water at 20C. and 753 mm. pressure. If the first method gives correct results, what is the percentage error of the gas-volumetric method?
(2NH 3
+ 3OBr~
to occupy 51.30 ml.
Silver.
Mercury.
Gold.
Platinum
(See also Probs. 333, 335, 338, 341, 346, 718.)
878. If a sample of silver coin weighing 0.2500 gram gives a precipitate of AgCl weighing 0.2991 gram, what is the percentage of silver in the coin and solution would have been used if the silver what volume of 0.05000
N KCNS
in the
same weight Volhard method?
of sample
had been determined volumetrically by the

an insoluble thiocyanate
[IIg
879. Mercury, like silver, forms

]
++
2CNS~~
>
Hg(CNS) 2 and can be determined by titration with standard KCNS. How many milliliters of 0.08333 N KCNS would be required to titrate the
solution of 0.6000
gram
of
an amalgam consisting of 70.00 per cent
Hg
and
30.00 per cent

880.
Ag?
weight of metal can be deposited at the cathode in 20 minutes by the electrolysis of (a) HAuCU, and (b) 2 PtCl6r using an average current strength of 1.50 amperes? What material would you use for the construction of the anode?
What
Halogens.
Cyanide.
Thiocyanate.
Halogen acids
(See also Probs. 249, 257, 268, 286, 288, 298, 308, 311, 316, 324, 325, 326, 327, 328, 329, 330, 331, 695, 713, 720, 721, 722, 726, 735, 736, 737, 738, 740, 741, 744, 745, 746, 747, 748, 1013, 1014, 1018, 1019, 1027, 1028.)
if
881. In the determination of fluoride in a given sample of a salt mixture, 0.01021 gram potassium acid phthalate) 20.00 ml. of (1.000 ml.
NaOH
316
were required, what weight of precipitate would be obtained if the same weight of sample were analyzed for fluoride gravimetrically by precipitating as lead
chlorofluoride?
Barium.
Strontium.
Calcium.
Magnesium
(See also Probs. 278, 282, 285, 286, 295, 312, 315, 317, 318, 319, 323, 362,
528, 537, 540, 545, 645, 667, 715, 717, 733, 891.)
882. A sample of calcite (impure CaCO 3 ) weighing 1.402 grams is titrated with HC1 and requires 25.02 ml. What is the alkaline strength of the sample in terms of per cent CaO if 20.00 ml. of the HOI will just neutralize the 3 that can be liberated from four millimoles of (NH 4 ) 3 PO4.2H 2 O?
NH
883. Given the following data: 35.27 ml. I 2 solution =c= 0.02991 gram As 2 O 3 30.00 ml. I 2 solution =0= 45.03 ml. Na2 S 2 O 3 solution; 25.82 ml. Na2 S 2 O 3 will
;
reduce the iodine liberated from an excess of KI by 31.05 ml. 4 solution; 15.42 ml. 2 O 4 .H 2 C 2 O 4 .2H 2 O 4 <* 16.97 ml. solution; 1.000 nil.
KMnO
KMnO
KHC
solution =0 12.00 ml.
KIIC 2 O4 .H 2 C 2 O 4 .2H 2 O solution =0= 1.074 ml. NaOH solution; 10.00 ml. NaOH HC1 solution. How many grams of CaCO 3 will be reacted
of this
upon by 29.83 ml.

884.
HC1
solution?
4 .7H 2 O. the 0.8000 of a sample weighing magnesium precipitated as gram, and ignited to Mg2 P2 O7 was found to weigh 0.3900 gram.
A sample of Epsom salts is supposedly C.P. MgS0
On analysis MgNH 4PO4
sulfate precipitated as BaSO 4 weighed 0.8179 gram. (6) If not, is the sample contaminated (a) Is the sample chemically pure? with excess magnesium salt, excess sulfate, or excess water? (c) Is the
The
magnesium equivalent to the

885. Basic
sulfate?
magnesium carbonate corresponds approximately to the formula 3 4MgCO .Mg(OH) 2 .6H 2 O (F.W. = 503.7). The substance is sometimes roughly analyzed by determining its loss 011 ignition, but more generally by
titration.
sample weighing 1.000 gram
is
dissolved in a 25-ml. pipetful of 1.000
the excess acid requires 5.01 ml. of 1.010 NaOH. Calculate the in the terms of of the above theoretical formula. sample percentage purity
HC1 and
What would be
substance?
886.
the loss on ignition of a 1.000-gram sample of the pure
A sample of dolomite is analyzed for Ca by precipitating as the oxalate
The ignited product is assumed to be CaO, and the analyst reports 29.50 per cent Ca in the sample. Owing to insufficient ignition, the product actually contains 8.00 per cent of its weight of CaCO 3* What is the correct percentage of Ca in the sample, and what is the perand
igniting the precipitate.
centage error?
887.
sample of magnesia limestone has the following composition:

Silica
Ferric oxide
and alumina
Calcium oxide
Magnesium oxide Carbon dioxide
= = = = =
3.00 per cent
PROBLEMS
In the manufacture of lime from the above, the carbon dioxide
is
317
reduced
4 will be required to 3.00 per cent. How many milliliters of 0.2500 to determine the calcium volumetrically in a 1.000-gram sample of the lime?
N KMnO
888. A sample of limestone containing 34.75 per cent Ca is given to a student for analysis. Using a 1.000-gram sample the student reports 35.26 per cent Ca. If the error was due to insufficient ignition of the calcium oxalate precipitate causing contamination of the CaO by CaCO 3 what was the percentage of CaCO 3 in the ignited product? What was the percentage
,
error?
of sulfuric acid (sp. gr. 1.06, containing 8.77 per cent be added to this product to convert all the Ca into should weight) by CaSO4 ? What would be the new weight of the ignited product?
What volume
H SO
2
Limestone.
Lime.
Cement
(See also Probs. 246, 363, 364, 376, 378, 1025, 1026.)
the following data, compute the percentage of SiO 2 A1 2 O 3> MgO, and CaO in a sample of cement weighing 0.6005 gram: Weight of A1 2 O 3 = 0.1201 gram. Weight of SiO 2 = 0.1380 gram. Weight of Fe2 O 3 = of 0.1429 4 for the Fe in the above Mg2 P2 O7 0.0540 gram. Volume = of this ml. Volume 2.05 4 required to titrate the ignited precipitate
889.
From
N KMnO KMn0
,
precipitated calcium oxalate
45.12 ml.
, ,
,
3 890. A limestone contains only SiO2 CaCO 3 FeC0 3 MgCO 3 Calculate the percentage of CO 2 from the following data: Sample = 0.800 = 0.0521 gram and requires 5.00 ml. of 0.1112 3 O4 gram. Fe 2 3
.
MnCO
+ Mn
KMnO
891.
for the iron.
CaSO 4 =
0.7250 gram.
Mg P2 O7 =
2
0.0221 gram.
A sample of limestone contains only silica, ferrous carbonate, calcium carbonate, and magnesium carbonate. From a sample weighing 1.200 grams there were obtained 0.0400 gram of ignited ferric oxide, 0.5003 gram of CO 2 and 0.5007 gram of magnesium pyrophosphate. Find the volume of ammonium oxalate solution [containing 35.00 grams of (NH 4 ) 2 C 2 O 4 .H 2 O per liter] required
,
to precipitate the calcium as oxalate. Also calculate the normality of if 38.00 ml. are required to titrate the oxalate precipitate.
Iron.
KMnO
Aluminum.
Titanium
(See also Probs. 245, 251, 271, 281, 284, 289, 293, 294, 301, 302, 303, 304, 305, 309, 320, 366, 375, 639, 641, 646, 651, 657, 668, 672, 673, 675, 677, 703,
764, 810.)
892.
How many
milliliters of
ammonium
hydroxide
(sp. gr. 0.946,
con-
3 by weight) are required to precipitate the iron as taining 13.88 per cent of a from pure FeSO4 .(NH 4 ) 2 SO4 .6H2 O which requires 0.34 ml. sample Fe(OH) 3 1 3 by weight) for of hot 3 (sp. gr. .350, containing 55.79 per cent
NH
HNO
A
HNO
oxidation? Assume reduction

893.
of
HNO
to
NO.
4 ) is
sample
of magnetite (impure
Fe3
leached with water, and acidified.

portions.
The
solution
fused with an oxidizing flux, is divided into two equal
In one portion the iron is precipitated as Fe(OH) 3 and ignited in the regular way. What was the weight of the original sample if the number of centigrams
318

is
found to be one-third the percentage of FesO4 in the

.
sample? In the other portion the iron is reduced with zinc and titrated with KMnO 4 What should be the normality of the KMnO4 so that the percentage of Fe8 O4 will be twice the buret reading?
894. A 1.000-gram sample of limonite containing inactive impurities solved in acid, and the solution is divided into two equal portions. 4 (1.000 ml. =0= 0.008193 portion is reduced and titrated with
is dis-
KMnO
One gram
The other portion is just neutralized, and 40.00 ml. of 1.500 2 are added to precipitate the iron. This is in excess of the necessary amount, and the number of milliliters in excess is equal to the number of What is the permilliliters of 4 required in the volumetric process.
2
2
H C O4.2H O).
ammonia
KMnO
centage of Fe in the sample?

896. If 60.00 ml. of
just to precipitate
all
BaCl 2 (0.1000 as a precipitating agent) are required the sulfate from a sample of pure ferric alum, Fe 2 (SO 4 ) 3
.
(NH4) 2SO4 .24H2 O, how many
28.33 per cent 3 iron from the same weight of sample?

896.
NH
containing by weight) would be required just to precipitate all the

4
milliliters of
NH OH
(sp. gr. 0.900,
What is the percentage purity of a sample of ferrous sulfate FeSO4 .7H 2O
weighing 1.000 gram, if, after it has been dissolved in water, 10.00 ml. of 0.1100 hydrochloric acid have been added to it, and it has been oxidized are required to neutralize the acid and with bromine, 11.73 ml. of 4 ? the iron as 3 Fe(OH) precipitate
N NH OH
897.
How many
milliliters of
0.1250
N KMnO
are needed to titrate a solu-
tion containing ferrous iron if by a gravimetric method 3.50 ml. of 6.00 ammonia water are required to precipitate the iron after oxidation to the ferric condition?
weight of mineral containing ferrous iron should be taken for that twice the number of milliliters of permanganate used for analysis so oxidation (20.0 ml. o 30.0 ml. of potassium tetroxalate solution which is
898.
What
as an acid) will be three times the percentage FeO? With this weight of sample, 15.0 ml. of the permanganate are required, and the water
0.0400
evolved by strong ignition weighs 0.0256 gram. What is the percentage of FeO in a finely ground sample in which the percentage of water is 1.05?
899. After decomposition of a half-gram sample of a certain mineral and the removal of silica, the addition of bromine and 4 precipitates these 0.1205 On 3 3 weigh A1(OH) ignition, Fe(OH) gram. They are then
NH OH
fused with
millimole
KHS0
2 2
4,
dissolved in dilute
H SO
2
amalgamated
zinc,
and the iron
titrated with
Na C O4 ),
requiring 22.46 ml.
passed through a column of 4 (1.000 ml. =0= 0.02500 What is the percentage of A1 2 O 3
4,
KMnO
and
of
FeO
in the original
sample?
gr. 0.970, containing 7.31 per cent precipitate all of the ferric iron and
NH
How many
3
milliliters of
NH OH
4
(sp.
by weight) were required just to aluminum from the solution after neu-
tralizing the acid?
PROBLEMS
900.
319
" Iron by hydrogen is obtained by reducing pure Fe2Os with hydrogen. It is a fine gray powder used analytically as a reagent for the determination The material should contain at least of nitrates by reduction to ammonia. 90 per cent metallic iron and is generally contaminated with an oxide assumed to be Fe 3 O4 as the reduction is not complete. The metallic iron in the sample
"
,
soluble in a neutral solution of FeCl 3 according to the equation Fe 2Fe+++ > 3Fe++, and the ferrous chloride formed is determined by titration
is
,
with KMnO4 In an actual analysis, 0.5000 gram is weighed into a 100-ml. measuring flask, the air displaced with C02 and water added, 2.500 grams (an excess) of anhydrous FeCls (free from Fe++) are added, and the flask stoppered and shaken for 15 minutes. The solution is diluted to the mark, mixed, and filtered. Twenty milliliters of the filtrate are titrated with 44.16 ml. of
.
0.1094
N KMnO
after the addition of sulfuric acid

dilution.
and manganese
sulfate
titrating iron in the sample.
solution and proper
Calculate the percentage of metallic
A sample of aluminum sulfate is known to be contaminated with and manganese. A sample weighing 3.362 gram is dissolved in dilute acid, and bromine and ammonia are added to precipitate A1(OH) 3 Fe(OII) 3 and MnO2 Treating the precipitate with concentrated HNO 8 dissolves This MnO 2 is the iron and aluminum hydroxides and leaves the MnO2 ignited in air (forming Mn 3 O4) and the product is found to weigh 0.0363 gram. The HNOs solution is evaporated with H 2 SO4 and the iron eventually reduced and titrated with 4.90 ml. of 0.1020 N KMnO4 An acid solution of 3.829 grams of the original salt gives with bromine and ammonia a precipitate that on ignition in air weighs 0.5792 gram. What is the percentage of Al 2 Oa and of Mn and Fe in the original material?
901.
iron
volumetric method for aluminum has been found useful in certain The aluminum is precipitated with 8-hydroxyquinoline ("oxine") and the precipitate is dissolved in acid and titrated with standard KBrOs (+KBr) (See Part VI, under Aluminum). If an excess of KBr is used and the
902.
cases.
titration requires 48.0 ml. of 3 (of which 1.00 ml. will liberate KI in the presence of acid sufficient I 2 to require 1.00 ml. of 0.100
KBrO
from excess
2
N Na S O
2
3 ),
what weight
903.
of residue
air?
would have been obtained
if
the oxine precipitate had
been ignited in
A solution of ferric chloride is prepared by dissolving 10.03 grams of in HC1, oxidizing, and diluting to a liter. If 50.0 ml. of this soluiron pure tion react with 40.0 ml. of a TiCl 3 solution, what is the normality of the latter
as a reducing agent? 904.
sample of titanium ore
is
treated in such a
way
that
all
the iron
is
present in the 2-valent condition and all the titanium in the 3-valent condition. The solution is then titrated with ferric alum solution of which 50.00 ml. yield
0.4000 gram of Fe 2 O3
ml. of ferric
906.
If
alum
solution were used, find the percentage of
the original sample weighed 0.6000 gram and 15.00 TiO2 in the ore.
The
iron in a solution of a 0.800-gram sample of titanium ore
was
320
reduced with stannous chloride and then reacted with 26.0 ml. of KMnC>4 (1.00 ml. =0= 0.800 ml. of potassium tetroxalate solution which is 0.08000 as an acid). The sulfuric acid solution of the same weight of sample was reduced with zinc, and the reduced solution was caught in an acid solution of ferric alum which then reacted with 48.0 ml. of the above KMnC>4. Compute the analysis on the basis that the original sample contained only Fe 3 O 4 TiO2 and SiO 2 (Zinc reduces Ti from valence 4 to 3; SnCl 2 does not.)
rock is shown to contain ferrous iron, aluminum, and sample weighing 0.6050 gram is decomposed by an oxidizing 4 OH filtered flux, the silica removed, and the precipitate obtained by of of the ferric this consisting aluminum, hydroxides iron, precipitate off, and titanium. The ignited precipitate weighs 0.5120 gram. It is fused with K 2 S2O7, and brought into solution, and the solution divided into two equal portions. One portion is poured through a Jones reductor containing amal906.
silicate
titanium.
NH
gamated
zinc
and the solution caught

is
directly in excess ferric

,
alum
solution.
then titrated with 0.08333 N KMnO4 of which 19.56 ml. are The other portion is reduced with SnCl 2 the excess stannous is required. titrated with 0.08333 N KMnO 4 of which 1 1.94 ml. the solution and destroyed, are required. Calculate the percentages of FeO, A12 O 3 and TiO 2 in the original
This solution
, ,
,
silicate.
Cerium. Thorium. Zirconium. Uranium. Beryllium. Bismuth. Boron

(See also Probs. 273, 371.)
907.
From
outline a possible iodimetric method for that element milliequivalent weight to be used.
the methods given for the determination of cerium in Part VI, and indicate the correct
One 908. A solution of uranyl nitrate is divided into two equal parts. 2 SO 4 diluted, and passed through a portion is evaporated to fumes with Jones reductor. The uranium forms uranous ions (U ++ H~). The solution is The uranium in the other titrated with 0.1200 4 requiring 20.50 ml.
"
N KMnO
ignited
as (NH 4 ) 2 U 2 O7 and the precipitate is and weighed (see Part VI). Write equation for the titration and for the ignition (NH 3 and N 2 are among the products in the latter case) and cal-
portion
is
precipitated with
NIT 4 OH
culate the weight of residue obtained in the ignition.

909.
An
iodimetric
method
for determining zirconium has
been suggested.
.
The element is precipitated with selenious acid precipitate is dissolved, treated with KI (SeOr
(H 2 SeO 3 ) as ZrOSeO 3
The
2
.
4I~ -> Se
2I 2
+ 3H O)
If and the liberated iodine subsequently titrated with standard Na 2 S 2 O 3 5.00 ml. of 0.0833 N Na 2 S 2 O 3 were required for a given weight of sample by this method, how many grams of residue would be obtained by igniting the ZrOSeO 3 obtained from another sample of the same weight (see Part VI, under Zirconium)?
910.
Anhydrous sodium tetraborate reacts with water according to the
following equation:
B O - + 5H O - 2H BO - + 2H BO
4
7
PROBLEMS
The anhydrous
salt
321
may be
of hydrochloric acid, with
dissolved in water and titrated directly by means methyl orange as indicator, as represented by the
2
3
3
following equation:
H BO - + H+ - H BO
After conversion of the sodium tetraborate to boric acid by careful titration with HC1, methyl orange indicator being employed, a suitable polyhydric
alcohol (inverted sugar, glycerin, mannitol, etc.) is added and the first hydrogen of the boric acid is titrated by means of standard sodium hydroxide,
with phenolphthalein indicator. The following data were obtained on a sample of tetraborate:
Sample = 0.3000 gram Volume of IIC1 required, with methyl orange indicator = 26.35 ml. Volume of NaOH required to titrate the boric acid = 58.10 ml.
Normality
40.00 ml.
NaOH = NaOH o
0.1030
36.35 ml.
HC1
Calculate the percentage of Na 2 B 4 O7 present in the sample (a) using the data from the acid titration, (6) using the data from the alkali titration.
Barium can be determined volumetrically (after precipitating as either by a permanganate process or by an iodi metric process (see Part VI, under Barium). If in the permanganate process 25.00 ml. of 0.1000 N ferrous ammonium sulfate were used and the excess ferrous required 10.50 ml. of 0.06667 N KMnO 4 what weight of BaSO4 would be precipitated during the If the iodimetric method had been used on the same titration reactions? of how weight many milliliters of 0.06667 N Na2 S2O3 would have been sample,
911.
BaCrO4 )
required?
Ans.
0.1400 gram.
27.00 ml.
912. Beryllium can be determined volumetrically by precipitating with oxine and titrating with KBrO 3 as in the case of aluminum (see Part VI, under Aluminum). Write the corresponding equations for the behavior of beryllium and calculate the weight of the ignited residue (of BeO) using the same
numerical data as given in Prob. 902.
determined by precipitating as bismuthyl oxalate and KMnO4 (see Part VI, under Bismuth), what is the value of each milliliter of 0.1000 N KMnO 4 in terms of grams of Bi 2 O 3 ?
913. If bismuth
is
titrating with standard
914. In the volumetric method for boron (see Part VI), what is the milliequivalent weight of B 2 O 3 ? Look up the ionization constant for boric acid and plot the titration curve to show its general appearance. Show how it compares in appearance with the curve for the titration of HC1 under similar
conditions of concentration.
Copper.
Lead.
Zinc.
Cadmium.
Brass
(See also Probs. 248, 261, 264, 274, 279, 332, 336, 337, 339, 342, 344, 345,
347, 349, 350, 352, 355, 356, 357, 358, 359, 360, 522, 640, 681, 697, 704, 711,
728, 739, 751, 1005, 1006, 1007, 1010, 1017.)
322
916.

How many milliliters of HNO
HNO
8 (sp. gr. 1.130, containing 21.77 per cent are 3 by weight) theoretically required to dissolve 5.00 grams of brass cent 0.61 Pb, 24.39 per cent Zn, and 75.00 per cent Cu? Assume per containing
reduction of the
HNO
to
NO
by each constituent.
What
fraction of this
volume
916.
of acid
is
used for oxidation?
of sulfuric acid (sp. gr. 1.420) is required to displace the nitrate radical from the mixture of salts obtained by dissolving 25.00 grams cent Cu, 31.50 per cent Zn, 0.21 per cent Pb) in nitric acid of brass (68.29
What volume
per
and evaporating to dryness?

the volume of
percentage of copper in a steel if with a 5.00-gram sample gas (measured under standard conditions) required to as CuS is 2.00 ml. more than the volume of 0.100 the copper precipitate Na2 S2 O 3 solution subsequently required for the copper by the iodimetric
917.
What is the
2
HS
method?
918. If 0.800 gram of a lead ore yields a precipitate of chromate that contains chromium sufficient to yield on treatment with an excess of KI in thiosulfate acid solution an amount of iodine to react with 48.0 ml. of 0.1000 in Pb the ore. of the find percentage solution,
weight of zinc ore should be taken for analysis such that the number of milliliters of 0.1000 molar ferrocyanide solution used will equal the percentage of Zn in the ore?
919.
What
920. If a copper ore on being analyzed yields 0.235 gram of Cu 2 S after being heated with sulfur in a stream of hydrogen, how many grams of KIO3 would react in the iodate method with the same weight of ore?
92L If 0.5000 gram of a copper alloy containing 25.00 per cent Cu requires for titration, what is the equivalent of 1.000 ml. of the 20.00 ml. of in terms of Ni? How many (a) in terms of Ag (using KI as indicator) and (b) milliliters of KIO3 solution would have been required by the iodate method
KCN
KCN
if
with an excess of KI, 15.00 ml. of the
KIO 3 would have liberated I
enough to
react with a volume of 0.1000
thiosulfate equivalent to 0.1000
gram
of
K Cr O ?
2
922.
3 2 2 Zn, the determination of copper by adding KI and titrating the liberated iodine? What volume of 0.05000 4 would be required for the lead if it is preFeSO4 cipitated as chromate, dissolved, reduced with 25.00 ml. of 0.04000 ? What 4 and the excess ferrous ions titrated with the weight of zinc
A brass weighing 0.800 gram contains 75.02 per cent Cu, 23.03 per cent and 1.95 per cent Pb. What volume of 0.1000 N Na S O would be used in
N KMnO
KMnO
pyrophosphate would be obtained in the determination of zinc?

923. In a certain volumetric
method
precipitated as CuCNS and the precipitate according to the net equation: 4CuCNS
for determining copper, the element is is titrated with standard 8
+ 7KIO +
3
3
14HC1
KIO - 4CuS04 +
7IC1
+ 4HCN +
7KC1
+ 5H 0.
2
If
the
KIO
is
of such concentration that
1.000 ml. will liberate from excess
KI
in the presence of acid sufficient iodine
PROBLEMS
to react with 1.000 ml. of 0.1000
323
is
N NaÔa, what
in the
the value of 1.000 ml. of
the
KIOs
in
terms of grams of
Cu
above method?
Ans.
0.0006054 gram.
Cu++ requiring 10.0 ml. of a method for copper, how many milliliters of KIO 3 solution (1.00 ml. =c= 2.00 ml. of the above NaÔs) would be required to reach that point in the titration by the iodate method (see
of
924. If a solution contains that
amount
Naj&Os
solution in the
common
iodimetric
Part VI, under Copper) corresponding to the

the
maximum
intensity of color of
CHC13
indicator?
Ans.
925.
42.0 ml.
Red
lead (Pb 3 O 4 )
it
is
made by
the direct oxidation of metallic lead.

,
Chemically may be regarded as 2PbO.PbO2 but owing to uneven heating in the manufacturing process commercial samples vary somewhat from the
theoretical composition and are likely to contain excess Pb0 2 When such the monoxide dissolves, leaving a 3 samples are treated with dilute
.
HNO
brown residue
which can be reduced by the addition of a measured 3 and the excess titrated with standard permanganate. A sample weighing 0.7000 gram is treated with dilute HNO3 and subsequently with a weighed amount of pure sodium oxalate (5.000 milliequivalents).
2
,
H PbO
excess of oxalate ion
After complete reaction, the solution is diluted with boiling water, manganous sulfate solution added, and the excess oxalate ion titrated with 28.56 ml. of 0.09987 permanganate. Calculate: (a) the total percentage of PbOa
and combined) in the sample; (6) the oxidizing power to percentage of Pb3O 4 (r) on the assumption that the sample is composed only of 2PbO.PbC>2 and excess Pb02 the percentage of each.
(free
;
,
(a) 36,70 per cent total Pb cent 3 (X, 2.82 per cent free per
Ans.
926.
PbO2 PbO 2
.
(b)
105.2 per cent

to be 2.00
Pb3O4
as an
(c)
97.18
solution of
(NH4 IIPO4
)2
is
made up
ammonium
Calculate'approximately the volume necessary to precipitate the zinc as ZnNH4 PO4 in a sample of brass (90.0 per cent Cu, 10.0 per cent Zn) weighing 5.00 grams.
salt.
made
927. If in the analysis of a brass containing 28.0 per cent Zn an error in weighing a 2.500-gram portion by which 0.001 gram too much
is
is
weighed out, what percentage error in the zinc determination would be made? What volume of a solution of diammonium phosphate, containing 90.0 grams of (NH 4 ) 2 HPO4 per liter, would be required to precipitate the zinc as ZnNH 4 PO 4 and what weight of precipitate would be obtained?
,
are obtained 0.0030

solution.
928. In the electrolysis of a sample of brass weighing 0.8000 gram, there gram of PbO 2 and a deposit of copper exactly equal in weight to the ignited precipitate of Zn 2 P2 7 subsequently obtained from the
,
What
is
the percentage composition of the brass?
Tin.
Antimony.
Arsenic.
Bronze
(See also Probs. 263, 270, 287, 297, 310, 321, 348, 692, 694, 698, 699, 708,
709, 719).
324
929. A sample of stibnite weighs 0.5000 gram. The percentage of Sb as found by titration in neutral solution with 0.1000 N iodine was 30.00 per cent. If the buret reading as recorded was 0.45 ml. too large, what was the true
percentage and what was the percentage error?

930.
A
is
centrated
solution
H SO4.
ml.
sample of type metal weighing 1.100 grains is dissolved in conConcentrated HC1 is added to the cooled solution, and the 2
boiled.
At
this point
antimony
is
4-valent state.
KMn0
and the solution
requiring 32.80 ml. More HC1 is added, boiled with powdered lead which reduces the antimony from valence 5 to valence 3 and the tin from valence 4 to valence 2. The tin is then
4
(1
The antimony in the =c= 0.00558 gram Fe),

is
cold solution
in the 3-valent state; tin is in the is then titrated rapidly with
quickly titrated in cold acid solution with I 2 (1 ml. =0= 0.0500 millimole As 2 O 3 ), requiring 9.27 ml. What are the percentages of Sb and Sn in the alloy? If the same weight of alloy had been treated with 6 3 and the residual metastannic and antimonic acids had been ignited, what weight of product
N HNO
would have been obtained?

931. A sample weighing 0.250 gram and containing arsenic is dissolved, and the solution containing the trivalent element is electrolyzed (method of iodine Hefti). Arsine is liberated and is conducted into 50.0 ml. of 0.125
solution.
The
excess of the latter reacts with 20.0 ml. of
Na2 S O 3
2
which 1.00 ml. = 0.00500 gram of copper. Find (a) percentage of As 2O 3 in the sample and (b) the time required for electrolysis if a current of 3.00 amperes is used and only 40.0 per cent of the current is used in reducing the arsenic.
932. An alloy containing arsenic weighs 5.10 grams. The arsenic is distilled as AsCI 3 from a strong HC1 solution of the alloy and eventually titrated in nearly neutral bicarbonate solution with standard iodine (1.00 ml. =0= 1.00 ml.
solution, of
Na S2Oa
2
==
0.0024 gram Cu).
Calculate the percentage of arsenic in the alloy
if
5.00 ml. are required. If the arsenic were evolved as arsine and the arsirie iodine (which oxidizes the arsenic to arsenate), absorbed in excess 0.100 how many milliliters of 0.0833 Na2 S 2O3 would be equivalent to the iodine
used up?
933.
mixture of As 2
+ As O + inert
2
5
=0=
matter
is
dissolved and titrated

4
=0=
in neutral solution with I 2 [1.00 ml.
1.00 ml.
KMnO
0.0500 millimole
FeSO4.(NH 4 ) 2 SO4.6H 2 O]
and an excess
[1.00 ml.
of
KI
is
requiring 20.00 ml. The resulting solution is acidified added. The liberated I 2 requires 30.50 ml. of Na2 S 2 O 3
0.0100 millimole of
KH(IO 3 )
2 ].
Calculate the weight in grams of
combined As2 C>3

Carbon.
As 2
in the sample.
Silicon.
Carbon Dioxide.
Tungsten.
Molybdenum
(See also Probs. 272, 276, 277, 515, 794, 796, 797, 798, 804, 805, 808, 890.)
934. If a 1.30-gram sample of iron containing 1.15 per cent carbon is analyzed by direct combustion, what would be the gain in weight of the ab-
sorption tube?
If the gas is
how many
milliliters of
0.100
passed through 100 ml. of 0.0833 N Ba(OH) 2 HC1 would be required to titrate the super,
natant liquid?
PROBLEMS
936.
325
sample of steel weighing 1.00 gram is burned in oxygen. The CO2 is caught in a 100-ml. pipetful of Ba(OH) 2 solution. The supernatant liquid requires 96.50 ml. of 0.100 N HC1. If the steel contains 0.57 per cent carbon, what is the normality of the barium solution used and how many grams of Ba(OH) 2 .8H 2 O are contained in each milliliter?
936.
What
is
the percentage of carbon in a 5.00-gram sample of steel
if
on
combustion the ascarite tube gains 0.1601 gram in weight? Using the same weight of sample and passing the gas into Ba(OH) 2 solution, what must be
the normality of an
HC1
solution so that the milliliters required to titrate the
BaC03
937.
precipitate will
be twenty-five times the percentage of C?

steel is
2-gram sample of
burned
in oxygen,
and the evolved
CO2
after passing through appropriate purifying trains is caught in 100 ml. of Ba(OH) 2 solution. The supernatant liquid requires 75.0 ml. of HC1 [1.00 1.12 ml. of the Ba(OH) 2 solution]. 1.00 ml. ml. =0= 0.00626 gram Na 2 3
CO
What the percentage of carbon in the steel and what would have been the gain of an ascarite bulb if a similar sample had been analyzed by the absorption
is
method?
938.
What volume
of 6.00
hydrofluoric acid
is
volatilize the silica
from 0.5000 gram of KAlSi3O 8 ?

pressure
is
theoretically required to What volume of SiF4
at
29C. and 765 mm.

939.
in
produced?
contains 3.00 per cent Fe 2 Si.
After
it
A 3.00-gram sample of steel
has
been dissolved
HNO
and
What volume of SiF4 under of 1IF + H 2 SO 4 on the SiO 2 ?

940.
evaporated, what weight of SiO 2 will be obtained? standard conditions will be evolved by the action
A 3.00-gram sample of steel containing 1.21 per cent Si and 0.23 per cent
1INO 3 and evaporated to dryness. What should
is
dissolved in concentrated
be the weight of the ignited acid-insoluble residue before and after treatment with HF? sample of tungsten steel weighing 5.000 grams is] dissolved in aqua The acid-insoluble residue regia, evaporated to dry ness, and dehydrated. HF with weighs 20.00 per cent less. weighs 0.0928 gram and after treatment
941.
What
are the percentages of Si and of
W in the steel?
37
the assumption that what percentage of the total Mo is in the 6-valent state?
942.
943.
On
Mo O
24
is
is in the 3-valent state
a mixture of MoO 3 and Mo2 O3 and what percentage

,
weight of molybdenum steel should be taken so that 1.00 ml. of 0.0600 4 will be used for each 0.50 per cent of Mo, on the basis of reduction of element to the trivalent condition and reoxidation by the per-
What
N KMnO
manganate to the oxidation number
of 6?
Chromium.
Vanadium
(See also Probs. 296, 654, 656, 666, 678, 775, 1012.)
944.
steel.
the following data compute the percentage of Cr in a sample of Weight of sample = 1.850 grams. After the chromium has been
From
326

KMnO4 and the
excess reagent removed, 150 ml.
oxidized to dichromate with

of 0.0800
ml.
N ferrous solution are added and the solution then reacts with 14.00 of 0.0900 N KMnO
4.
945. It
is
desired to prepare a solution of
chromium acetate to contain
8.00 per cent Cr2 3 by weight for use as a mordant. A batch of the material is made up to the approximate concentration and is found to have a specific 2.000-ml. sample is taken, and the chromium is oxidized gravity of 1.195.
to dichromate.
KMnO
solution, 4 for oxidation (25.00 ml.
one-half the solution are added 50.00 ml. of ferrous sulfate and the excess ferrous iron requires exactly 17.32 ml. of 0.1334 N
To
FeSO4 solution
=c=
21.73 ml.
KMnO
solution).
How many
pounds
of water
must be evaporated from one ton
of the liquor
to give the desired concentration?

946. A steel containing 0.90 per cent Cr weighs 2.000 grams. The chromium oxidized to chromate, and to the acidified solution is added an excess of KI. The liberated iodine requires 10.00 ml. of thiosulfate solution. What is the
is
normality of the thiosulfate solution?
Assuming that vanadium like nitrogen forms five oxides and that any is a mixture of two or more of these, compute the oxidation number of the vanadium in the reduced condition and show what combination of oxides could give this. Use the following data: 0.08500 gram of Na 2V4 O 9 after an abnormal reduction was oxidized to the 5-valent condition by 43.14 ml. of KMnO4 of which 40.00 ml. reacted with 30.00 rnl. of potassium tetroxalate solution which was 0.08000 N as an acid.
947.
other oxide
gram of Na2 4O 9 is reduced and requires 10.00 ml. of perml. 0.0536 gram Na 2 C 2 O4) to oxidize the vanadium back (1.000 manganate to vanadic acid, find the valence of the reduced vanadium.
948. If 0.394
sample of chrome-vanadium steel weighing 2.00 grams is dissolved and HNO3 is added to oxidize the iron and carbides. 3 4 In the presence of silver ions (catalyst), ammonium persulfate is added to oxidize chromic ions to dichromate, vanadyl ions to metavanadate, and manganous ions to permanganate. Excess persulfate is destroyed by boiling, and the permanganate is reduced with a small quantity of HC1. The addition of 25.0 ml. of 0.1010 N FeSO4 causes reduction of vanadate and dichromate, and the excess ferrous and the reduced vanadium are titrated with 0.1120 N KMnO4 of which 12.6 ml. are required. A small amount of FeSO4 is added to reduce the vanadium again and the excess ferrous ions destroyed with perThe vanadium alone is then titrated with the above-mentioned sulfate. KMnO4 of which 0.86 ml. are required. Write ionic equations for all chemical changes involving the above-mentioned elements, and calculate the percentage of Cr and of V in the sample.
949.
2
A
4
in
H SO + H PO
acid
(HV03 ) in the presence of molybdic fact that vanadic acid alone is reduced to the depends upon VO++ by sulfur dioxide in dilute sulfuric acid and can be reoxidized by standard permanganate solution. Both vanadic acid and molybdic acid are reduced by
960.
of vanadic acid
The determination
4)
(H MoO
2
amalgamated zinc, the former to V*4 and the latter to
"
Mo+ ++
These reactions
PROBLEMS
327
are carried out in a Jones redactor and the reduced constituents oxidized by being passed into an excess of ferric salt and phosphoric acid. An equivalent
reduction of the ferric iron to ferrous takes place. titrated with standard permanganate.
REDUCTION WITH SO2
The
ferrous iron
is
then
REDUCTION WITH Zn
= Grams of sample Normality of KMnO4 =

Ml.
a.
6.
0.4500 0.1092
8.23
Grams
KMnO
sample Normality of KMnO4 Ml. KMnO4
of
= = =
0.4500
0.1092
41.74
Complete and balance all the equations in this process. Express the amount of vanadate as percentage of V and the amount of molybdate as percentage of Mo.
vanadium
951. Calculate the percentage of chromium steel from the following data:
and
of
vanadium
in a
chrome-
A sample weighing 2.00 grams is dissolved in an acid mixture. convert iron to Fe +4 + manganese to Mn+ +, chromium treatments Subsequent to Cr 2 O7~ and vanadium to VO 3 ". A 25-ml. pipetful of standard ferrous solution [39.2 grams of FeSO4.(NII 4 ) 2 SO4.6H 2 O per liter] is added. Chromium is
Chromium.
"
The solution is titrated with thus reduced to Cr+++, vanadium to VO++. 4 (1.00 ml. =0= 0.92 ml. of the ferrous solution) requiring 14.28 ml. to give a permanent pink color. Only vanadium and the excess ferrous iron are
KMnO
oxidized in this step. To correct for overtitration and color interferences, the solution is boiled until the permanganate color is destroyed, and the solution
is
brought to the same shade of color as before with the standard perman-
ganate, requiring 0.08 ml.
The vanadium in the above solution is now reduced to VO 4 with dilute FeSO4 solution and the excess ferrous oxidized with a small amount ~ of persulfate. The vanadium is then titrated back to VO 3 with the above
Vanadium.
4"
KMnO
to the
4,
requiring 1.10 ml.
It
may be assumed that the solution is overtitrated

Manganese
same degree as
in the first titration.
(See also Probs. 266, 269, 351, 370, 379, 642, 643, 648, 652, 653, 655, 664,
671, 682, 691, 701.)

962. What weight of pyrolusite containing 75.0 per cent MnO2 will oxidize the same amount of oxalic acid as 35.0 ml. of a 4 solution of which 1. 00 ml. will liberate 0.0175 gram of iodine from an excess of potassium
KMnO
iodide?
953.
An
oxide of
Mn
weighing 0.4580 gram
is
treated with dilute
H SO
2
and 50.00 ml.
of 0.1000
ferrous
ammonium
sulfate solution.
is
After the
reduction of the manganese to the manganous condition of ferrous solution reacts with 30.00 ml. of 0.03333
N KMn0
complete, the excess Find the 4

.
symbol
964.
of the original oxide of
Mn.
Given the following data in the analysis of pyrolusite by the iodimetric process, find the volume of disodium phosphate solution (90.0 grams of
328

per
liter)
Na 2 HPO4 .12H 2O
MnNH P0
4
from 0.5000 gram
that would be necessary to precipitate the of the sample.
Mn
as
Na
The
Weight of sample 2 S 2 O 3 solution

is
= =
.000
gram
40.40 ml.
equivalent in reducing power to a stannous chloride solution that contains 29.75 grams of tin per liter.
thiosulfate solution
bromine water (30.0 grams Br 2 per liter) would theoretically be required to precipitate the manganese from an acetic acid solution of its salt, if the resulting precipitate of Mn0 2 gives on ignition
956.
What volume
of
0.1060 gram of
Mn O4? How many

3
milliliters
of sulfurous acid
(sp.
gr.
weight) would be required to dissolve the 2 P 2 O 7 would be obtained from 2 precipitate, and what weight of the resulting solution?
1.028, containing 5.00 per cent
SO 2 by
MnO
Mn
manganese in 50.0 ml. of 0.0833 N KMnO4 solution were reduced to the manganous condition, how many milliliters of 0.0833 N KMnO 4 would be equivalent to the Mn in the reduced solution by the (a) Volhard method, (b) bismuthate method, and (c) chlorate method?
966. If the 967. It has been shown that manganous ions can be titrated potentiometrically with standard KMiiO4 in nearly neutral pyrophosphate solution " 4Mn++ 8H+ 15II 2 P2 O 7 the 4 according to equation: 4 in 5Mn(H 2 P2O 7 )s- 4H 2 O. What is the value of each millilitcr of
+ MnO +
KMnO
terms of Mn by this method if each milHliter of the KMnO4 is equivalent to 0.002040 gram of sodium formate (NaCIIO2 ) when titrated according to the
equation:
3CHO,"
+ 2Mn(V + H
is
->
2MnO + 3CO + 5OH~?

2 2
Ans.
968.
e.g.,
0.004394 gram.
When
it is
a constituent
in a case where the
manganese content
to be determined with extreme accuracy, of a sample of steel may be in
dispute,
best to analyze for the constituent
by two
different methods.
It is also best to standardize the solutions used against a sample of like material of known composition rather than in the usual way. This procedure gives a
direct comparison under identical conditions with a standard. The purchaser of a quantity of steel has reserved the right to reject the lot, which is to be used for a special purpose, if the manganese content is less than
0.350 per cent. The sample must therefore be prepared and the analysis made with extreme accuracy. On the basis of a representative sample, the method
and
results of
an analysis
follow.
percentage of
manganese
in the steel
Calculate to three significant figures (a) the by both methods, (6) the normality of the
permanganate.
Persulfate Process.
0.1000-gram sample of Bureau of Standards steel
required 7.03 ml. of arsenite solution. containing 0.660 per cent of the steel under investigation required 4.36 ml. similar-weight sample
Mn
Bismuthate Process.
of Standards steel
A one-gram sample of the above-mentioned Bureau was used. A pipetful of FeSO4 was used, and the excess
ferrous salt required 16.96 ml. of standard
KMnO
4.
one-gram sample
PROBLEMS
of the steel
of the
329
under investigation, treated the same way, required 19.63 ml.

4.
KMnO
A
One
pipetful of
FeSO 4 ~
23.97 ml. of
KMnO
4.
carefully prepared steel is to be used as a standard in subsequent of other steels for manganese by the persulfate method. To determine analyses the correct percentage of manganese in the standard steel a sample weighing
959.
1.05
grams
is
ammonium sulfate is
0.00201
analyzed by the bismuthate method. A 25-ml. pipetful of ferrous 4 (1 ml. =c= used, and the titration requires 13.2 ml.
KMnO
gram Nu 2 C 2 O4 1 ml. =c= percentage of manganese in the

;
1.02 ml. of the ferrous solution).

steel?
What
is
the
In the routine analysis of a certain plain carbon steel by the persulfate method, the analysis is run in parallel with a corresponding analysis of the above standard steel. The same weights of sample are used in the two cases. The above standard steel requires 10.4 ml. of arseiiite solution; the unknown
steel?
17.1 ml. What is the percentage of manganese in the latter the persulfate method a one-gram sample was used and the arsenite solution contained 1.10 grams of As 2 O 3 per liter, to what average oxidation number was the manganese reduced in the titration?
steel requires
If in
A/is.
0.355 per cent.
0.584 per cent.

Cobalt.
3.4.
Nickel
(See also Prob. 334, 742, 743, 749, 750.)
sample of ore weighing 0.8900 gram yields by electrolysis 0.2670 Ni and Co, and from the deposited metal a precipitate weighing 0.9405 gram is obtained with dimethyglyoxime. Find the percentages of Ni and Co in the ore.
960.
gram
of
solution
nickel ore was analyzed by the volumetric method. The nickel was treated with KI solution and exactly 0.50 ml. of AgNO 3 solution containing 0.0125 gram of AgNO 3 per milliliter. The solution then reacted with 48.00 ml. of KCN solution containing 0.0140 gram of KCN per milliliter. What was the percentage of Ni in the ore if the sample taken weighed 0.900
961.
gram?
962. What weight of dried glyoxime precipitate would be obtained from 5.00 grams of steel containing 1.48 per cent Ni?
Phosphorus
(See also Probs. 256, 257.)
milliliters of magnesia mixture (1.00 with respect to are required to precipitate the phosphorus from 0.2000 gram of pure Assume the formula of the latter to be 3Ca3(P0 4 )2.CaCl 2 ? How apatite.
963.
How many
of
MgCl 2 )
many grams
(NH 4 ) PO4.12MoO
3
could theoretically be obtained from this
weight of apatite?
964. Calculate the percentage of phosphorus in a steel from the following
data:
Two grams
of steel furnished a yellow precipitate
which was dissolved
in
330
20.0 ml. of 0.500
sodium hydroxide
solution,
and the excess
of the latter
reacted with 27.0 ml. of 0.333
nitric acid.
Calculate the weight of a sample of steel to be taken for analysis so that 4 used in the titration by the Blair method every 100 ml. of 0.100
N KMnO
(see Part VI, under Phosphorus) will represent directly the percentage of P. Calculate in this process the equivalent weight of (a) P, (6) P2 O 6 (c) Mo,
,
(d)
normal yellow precipitate of ammonium phosphomolybdate from a sample of bronze weighing 1.00 gram is reduced with zinc. The reduced
solution requires 21.13 ml. of 0.100 denum to the hexavalent condition.
MoO 966. A
3,
(e)
Mo O
24
3 7.
permanganate to oxidize the molybthe alloy contains exactly 0.20 per
If
cent of phosphorus, to by the zinc?

966.
what hypothetical oxide was the molybdenum reduced
What
weight of steel should be taken for analysis so that the number
of milliliters of 0.125
permanganate required
in the ferric
alum method
(see
Part VI) will be two hundred times the percentage of

967.
in the steel?
is
2.00-gram sample of steel is dissolved in HNOa and the phosphorus precipitated with molybdate as the normal yellow precipitate. The molybdenum in the precipitate is reduced to a form corresponding to the oxide
to the
MoieO2 7 and requires 10.0 ml. of 0.100 N KMnO4 for reoxidation oxidation number of 6. Calculate the percentage of P in the steel.
]
968. A sample is prepared for student analysis by mixing pure apatite [3Ca 3 (PO4)2.CaCl 2 with an inert material. If 1.000 gram of the sample gives 0.4013 gram of Mg2 P 2 O 7 how many milliliters of ammonium oxalate solution [40.00 grams of (NH 4 ) 2 C 2 O4 .H 2 O per liter] would be required to precipitate
,
the calcium from the same weight of sample?

969. Calculate the percentage of phosphorus in a sample of steel from the
following data: 2.00 grams of steel furnished a normal yellow precipitate which when dissolved and passed through a Jones reductor reacted with
7.00 ml. of 0.0833
N KMnO
4.
970. In the analysis of
a sample
of steel weighing 1.881 grams, the phos-
phorus was precipitated with ammonium molybdate and the yellow precipitate was dissolved, reduced, and titrated with permanganate. If the sample contained 0.025 per cent P and 6.01 ml. of KMnO4 were used, to what oxide was the molybdenum reduced? One milliliter of KMnO4 was equivalent to 0.007188 gram of sodium oxalate.
971.
The Pincus method
for determining
phosphate
is
to titrate
it
in acetic
acid solution in the presence of ammonium ions with standard uranyl acetate ++ + -> solution according to the equation: 2 2 4 4 PO 4
PO^ + UO
+ NH
UO NH
The
color on a spot plate with as an ordinary acetate uranyl acetate solution is 0.100 salt and 10.0 ml. are used in the titration, how many grams of P 2 O 6 are shown to be present?
indicator
is
ferrocyanide which gives a brown
excess
UO ++.
2
If the
was treated with ammonium and an abnormal molybdate, yellow precipitate was obtained, which after
972. A, solution containing phosphoric acid
PROBLEMS
drying
331
may be assumed
to have consisted of
[(NH^sPOJXMoOs)^
This
precipitate was dried, weighed, and dissolved in ammonia water, and the solution was made up to 500 ml. Of this, 50.0 ml. were taken, made acid with H2 S04, reduced with amalgamated Zn, and passed directly into an excess of ferric alum which served to oxidize the trivalent molybdenum back to the hexavalent condition. To oxidize the iron reduced by the molybdenum required a number of milliliters of 0.125 N KMnO4 equal to 15.39 times the weight in grams of the original yellow precipitate. What values of x and y
may
be taken in the formula of the yellow precipitate?
973.
determinations.
obtained.
carefully prepared steel is to be used as a standard for phosphorus It is analyzed by an accurate ("umpire") method in which,
from a sample weighing 3.00 grams, a phosphomolybdate precipitate is This is dissolved and the phosphorus is subsequently precipitated as MgNH 4 PO4 On ignition this precipitate yields a pyrophosphate residue
.
weighing 0.0109 gram. In the routine analysis of a plain carbon steel by the alkalimetric method, the analysis is run in parallel with a corresponding analysis of the above standard steel. The same weights of sample are used in the two cases, and a 25-ml. pipetful of standard NaOH is used in each case. Back titration with
HNO
of the standard steel
using phenolphthalein indicator requires 10.2 ml. of the acid in the case and 8.6 ml. in the case of the unknown steel. If 1.00 ml.
1.08 ml.
If
what is the percentage of phosphorus in the plain 3 the concentration of the HNOa were 0.105 N, what weight of sample must have been taken in each case?
,
NaOH o
carbon
HNO
steel?
Ans.
0.0868 per cent.
3.0 grams.
Sulfur.
Selenium
(See also Probs. 243, 244, 247, 251, 252, 265, 294, 373, 690, 696, 712, 714,
729, 799, 1023.)
974.
by
A sample of ferrous ammonium sulfatc is prepared for student analysis intimately mixing pure crystals of FeSO4.(NH )2SO4.6H O with an inert
4
2
substance.
Using a 0.7650-gram sample a student correctly obtains 0.1263
gram
of
grams from the

976.
of
Fe 2Os. What volume of barium chloride solution containing 25.00 BaCl 2 .2H2 O per liter would be necessary to precipitate the sulfur
filtrate?
What
is
is
the percentage of inert material in the sample?

is
A sample of pure ferric alum, FesCSOOs^NH^SO^HsO,

and the iron
dissolved
If the ignited precipitate 4 OH. precipitated with 4 weighs 0.1597 gram, (a) what volume of the (sp. gr. 0.900, containing 28.33 per cent 3 by weight) is theoretically required for the precipitation
in water
NH NH OH
NH
milliliters of 0.1000 N BaCl 2 would be required to from the iron filtrate, and (c) how many milliliters of 0.1000 N Na2 S 2 Os would be required in the determination of this amount of sulfate by the iodimetric (Hinman) method?
of
Fe(OH) 3
(6)
how many
precipitate the sulfate
of
976. If nitrogen is reduced to the 4-valent state, compute the volume fuming nitric acid actually required to oxidize 5.000 grams of pyritic ore
332
containing 70.10 per cent FeS2. Neglect the quantity of acid required for the remainder of the ore. Assume the acid to be of 1.500 specific gravity and to Also assume complete oxidation of contain 94.10 per cent 3 by weight.
HNO
sulfide to sulfate.
Compute the weight of dry sodium peroxide required to same oxidation assuming the oxidation products to be NaFeO2 the out carry
and
2 is analyzed by fusing a 0.5000-gram sample and How large an error in the weight of the as BaSO the sulfur 4 precipitating to be made must produce an error amounting to 0.10 per cent of precipitate
.
Na SO4 977. A sample of pure FeS

2
.
the apparent
978.
amount
of
in the mineral?
soluble sulfate weighing 0.9261 gram is analyzed. The precipitate ignition is found to weigh 1.3724 grams. On further ignition the weight increases to 1.3903 grams, owing to the fact that the precipitate as first weighed had been partly reduced to BaS which on further ignition was Calculate the true percentage of S in the original sample. reoxidized to BaSO 4
of
BaSO4 on
Calculate the percentage of S present as sulfide and the percentage of S present as sulfate in the first ignition product.
979. In the determination of sulfur
by the evolution method, a notebook
contains the following data:
Weight
of
sample
Iodine used
Naa&Oi used
1.000 ml. iodine
1.000 ml.
2 2
= = =
5.0275 grams
15.59 ml. 12.68 ml.
1
o Na S O o
3
.086 ml.
Na
S 2 O3
0.005044 gram
Cu
Find the percentage of

980.
is
sulfur.
A steel weighing 5.00 grams is treated with HC1,

If 3.00 ml. are
and the evolved
HS
2
eventually titrated with a solution containing 0.0100 mole of KIO3 and 0.4 KI solution as an mole of KI per liter. What is the normality of the KIO3
oxidizing agent? of sulfur in the steel?

981.
used in the titration, what
is
the percentage
sample of steel contains 0.075 per cent sulfur. Using a 5.00-gram sample and determining the percentage of S in an analysis by the evolution method, calculate the molarity of KIO3 to be used so that an error of 0.20 ml.
in the titration will represent
an actual
error of only 0.001 per cent in the
reported percentage of sulfur.

982.
sample of A1 2 (S04) 3 .18H 2
crystallization
and
is
which has lost a part of its water of therefore specified as A12 (SO4 ) 3 .XH 2 O, is analyzed to
determine
instance
is
approximate composition. The calculation in this particular based upon a determination of total sulfur as follows: A 0.5000-gram
its
.
sample
dissolved in dilute hydrochloric acid and diluted, and the sulfate ion Calculate to precipitated as BaSO 4 yielding 0.5602 gram of ignited BaSO4
is
,
three significant figures the value of X.

983. It is desired to prepare a standard solution of iodine of such concentration that each milliliter will be equivalent to 0.010 per cent sulfur when the
PROBLEMS
latter is
333
determined on a 5.00-gram sample by the evolution method. The is to be prepared in the following way. A certain volume of 0.105 N KMnO4 is to be run from a buret into an aqueous solution containing an excess of KI, the solution is to be acidified with 2 SO4 and diluted to exactly 1 liter. What volume of the KMnO4 should be used?
iodine solution
Ans.
984.
297 ml.
method
carefully for sulfur.
prepared steel
is
to be used as a standard in the evolution

3
A sample is dissolved in IINO
and the
sulfur subsequently
precipitated and weighed as BaSO4.
The sample weighs
4.57 grams and the
BftSO4 weighs 0.0110 gram.

the evolution method the analysis analysis of the above standard steel.
are used.
In the routine analysis of a certain sample of Bessemer steel for sulfur by is run in parallel with a corresponding
The same weights
(5.00 grams) of
sample
solution; the Bessemer steel requires 8.3 ml. What is the percentage of sulfur in the Bessemer steel and how many grains of KIO3 does each liter of the titrating
3
The above standard
steel requires 3.3 ml. of
KIO
KI
solution theoretically contain?
Ans.
0.083 per cent, 1.12 grams.
986. What volume (two significant figures) of 15.0 3 would be used in dissolving the Cii2S precipitate from a 5.00-gram sample of steel containing 0.25 per cent Cu, if the precipitate were contaminated with 5 per cent of its
N HNO
weight of FeS (assume sulfur completely oxidized to sulfate and the reduced to 2 )?
HNO
NO
986. In the anlysis of 0.8000 gram of a substance for sulfur by the barium chromate method, 25.00 ml. of 0.1110 N sodium thiosulfate solution were used.
Compute the percentage of sulfur. 987. The H 2 S in a sample of illuminating
gas is determined by passing 10.0 cubic feet of the gas through an absorbing agent and oxidizing the sulfur to sulfate. By the Hinman method, there are used 12.00 ml. of thiosulfate
solution having two-thirds the normality as a reducing agent as a certain potassium tetroxalate solution. 6.00 milliliters of the tetroxalate will reduce
in acid solution 3.00 ml. of a
KMnO
solution containing 0.00632
KMnO
4 per (by volume)?
milliliter.
What is the H 2 S content of the gas in parts per thousand
gram
of
988. Sulfite liquor, used in the manufacture of sulfite paper pulp, consists Titration with 2 SO 3 essentially of a solution of Ca(HSO 3 ) 2 Mg(HSO 3 ) 2 and
, ,
normal sulfites (i.e., to SO 3 ~). Titration with " "Available S0 2 is iodine converts all sulfites and bisulfites to bisulfates. the actual free H 2 SO3 plus one-half the SO 2 in the bisulfites of calcium and magnesium, and is given by the alkali titration (using phenolphthalein). " Combined SO 2 " is one-half the SO2 in the bisulfites of calcium and magnesium " and is given by subtracting the "available S(V from the "total SO 2 (as
alkali converts all of these to
given by the iodine titration).
A 10-ml. pipetful of sulfite liquor (sp. gr. = 1.028) is introduced into a 100-ml. measuring flask and diluted to the mark. A 10-ml. pipetful of the
334
diluted solution is titrated with 0.03312 NaOH, requiring 30.11 ml. to change the color of phenolphthalein. At this point starch is added, and the solution iodine to give a blue coloration. then requires 13.82 ml. of 0.1050 of "available SO 2 ," and of "combined SO*". the Calculate percentage (a) " of "free SO the Calculate 2 (i.e., in the form of uncombined percentage (6) the an Show S0 2 8 ). pink color produced at the first by (c) equation why end point disappears at the beginning of the second titration.
989.
of the
Fuming sulfuric
acid
is
clear, colorless, oily,
monohydrate (H 2 S04) and
sulfuric
fuming liquid, a mixture anhydride (SOa) containing from
13 to 15 per cent of free SOa. Fuming sulfuric acid for special purposes, commercially called oleum, contains as high as 60 per cent free SO 3 and is often partly or completely crystallized. The analysis depends upon the determina-
ton of total acidity in a representative sample, carefully collected and weighed under conditions that assure no loss of material. The ordinary method of determining the acid strength does not take into account the effect of SOa which is always present in small quantities. When sulfurous acid, H 2 SO3 is titrated with base, methyl orange changes color when one hydrogen has been replaced; phenolphthalein changes color when both hydrogens have been re,
placed.
a. The analysis neglects the presence of S0 2 and assumes the mixture to be 1X2804 when 3.926 grams of oleum, dissolved in water, are diluted to exactly 500 ml. A 100-ml. portion requires 34.01 ml. of 0.5132 N NaOH for complete neutralization, methyl orange being used as indicator. Calculate the percentage of 2 SO4 and free SOa, expressing the answers to the number of significant figures justified by the data and method of
calculation.
b.
The
2
as
H SO
analysis includes the presence of
SO2 and
,
the mixture
is
calculated
4,
SO and SO2
3,
In this case, 3.926 grams of oleum dissolved in water are diluted to exactly 500 ml. A 100-ml. portion requires 34.01 ml. of 0.5132 N NaOH for complete neutralization, methyl orange being used as indicator. Another 100-ml. portion is titrated directly with 0.1032 N iodine solution, starch being used as indicator, and requires 4.93 ml.
Calculate the analysis in this case.
990. An oleum contains only 2 S04 are found to be present in equal parts
,
SO3 and S02 The H SO4 and S03 by weight. When a sample of the
,
.
oleum is titrated with NaOH, phenolphthalein being used as indicator, the volume of alkali required is found to be fifty times the volume of iodine of the same normality required to titrate the SO 2 in the same weight of sample. Calculate the percentage composition of the oleum (see preceding problem).
991. A sample of fuming sulfuric acid contains only H SO SO and SOa. A sample weighing 3.2030 grams is dissolved in water and requires 5.00 ml. of 0.2000 N iodine solution to oxidize the S0 Another sample weighing 4.0301
2
4,
2,
2.
with phenolphthalein as an indicator grams and requires 172.5 ml. What is the percentage composition of the acid, and what volume of alkali would have been used with methyl orange as the inis
alkali
PROBLEMS
dicator?
335
(Methyl orange changes color when one hydrogen of H2SO3 has been replaced; phenolphthalein changes color when both hydrogens have been
992.
is
replaced.)
To 5.00 ml.
of a solution of a mixture of
of
Na2S and
NaHS
2
(sp. gr. 1.032)
added a standard solution
HC1.
The
liberated
HS
is
determined by
adding excess iodine solution and titrating back with thiosulfate, and the resulting acidity is determined with NaOH. From the following data, calculate the percentage of Na2 S and the percentage of NaHS in the sample:
1.000 ml.
12.0 ml.
HC1
2
=0=
0.006005 gram
CaC03
NaOH o 10.0 ml. HC1 1.000 ml. I o 0.00601 gram Sb 10.0 ml. Na 2 S O o 12.0 ml. I
2 3
HC1
NaOH
I2
used used used used
Na2 S O3
2
* = = =
10.8 ml. 15.0 ml.
28.0 ml.
15.0 ml.
acidified
contain Na 2 S, NaHS, H 2 S or mixtures of these is and requires 20.00 ml. of 0.1000 N iodine solution for titration. The gain in acidity caused by the titration is equivalent to 10.00 ml. of NaOH (1.000 ml. =0= 0.006303 gram H 2 C 2 O 4 .2H 2 O). What does the solution contain? If 20.00 ml. of iodine had been required and the gain in acidity had been represented by 17.00 ml. of NaOH, what would the solution have contained?
993.
A solution that may
994.
solution of a mixture of
HS
2
and
NaHS
is
acidified
with a ml. of
N/10 HC1, and the total H 2 S then present is determined by adding b ml. of N/10 I 2 and titrating back with c ml. of N/10 Na2 S 2O 3 The acidity at the end of the titration is measured by d ml. of N/10 NaOH. Show that the number of grams of H 2 S present in the original solution is given by the formula
.
[c
2d
(6
2a)]0.001704
is
995. The Norris and Fay method for determining selenium with standard Na2 S 2 O 3 according to the equation: H 2 SeO 3 Na2 S4O6 4NaCl + 3H 2 O. 4HC1 -> Na2 S4SeO6
to titrate
+
>
4Na2 S 2O3
+ +
The Jamieson method
for determining arsenic is to titrate
with standard
KIO
KC1
according IC1 4HC1.
to
the
is
equation: 2AsCl 3
+ KIO3
5H 2O
2H 3AsO 4
If the
above
KIO
of such concentration that 3.00 ml. will liberate
from
excess
in the presence of acid that amount of I 2 which reacts with 3.00 ml. of the above 2S2 3 and 3.00 ml. of the Na 2 S 2 3 will react with 3.00 ml. of
KI
Na
is
0.100
NI
2,
(a)
what
and
(6)
what
the value of 1.00 ml. of the KIO 3 in terms of grams of As the value of 1.00 ml. of the Na 2 S 2 Os in terms of grams of Se?
is
General and Miscellaneous Analyses

996.
sample
CaO =
gram
of pyrolusite analyzes as follows:
= 4.00 per cent; Si02 5.60 per cent; in is dissolved HC1 (Mn02 4HC1 sample
MgO
MnO2 = 75.00 per cent; = 15.40 per cent. A one- MnCl 2 + C1 2 + 2H 20),
336
and the

silica is
removed
is
in the regular
way.
4
4
The
solution
is
neutralized and
the manganese
Br 2
+ 4NH OH
4
precipitated with -> MnO 2 2NH4C1
NH OH + bromine + 2NH Br + 2II 0.

2
water:
MnCl
the
From
is
filtrate
the calcium
is
precipitated as oxalate,
.
and the precipitate

is
dissolved and
The magnesium precipitated with ammonium phostitrated with 4 phate in the regular way, and the precipitate is ignited and weighed. Calculate and to 3 significant figures: (a) the number of milliliters of 3.00 4
KMn0
N NH OH
number of milliliters of 3.00 per cent Br2 solution cipitate the manganese according to the above equation,
(6)
the
(sp. gr. 1.10)

(c)
to pre-
all
N Na C
2
solution to form
Mg(C 2O4) 2 and
the total number =

precipitate 4 to titrate
the calcium, (d) the
number
of milliliters of 0.100 molar
KMnO
the precipitated calcium, (e) the weight of the ignited magnesium precipitate, in the material obtained by strongly igniting a sample (/) the percentage of 2 to 3 O 4 and of the original pyrolusite in air, assuming conversion of
Mn
MnO
Mn
no other changes.
Ans.
(/)
(a) 11.5 ml., (b)
41.8 ml.,
(<)
5.97 ml., (d) 4.00 ml.,
(e)
0.111 gram,
52.2 per cent.

997.
A certain mineral has the following composition: CaO = 28.03 per = 10.05 per cent; FeO = 7.12 per cent; CO = 44.77 per cent; cent; MgO = 10.03 giO per cent. A one-gram sample is dissolved in HC1 and the silica
2
removed
in the regular way.
to 3 significant figures: (a) theoretically 2 SO 4 (b) numrequired to volatilize the silica in the presence of concentrated cent 9.91 3 by ber of milliliters of 4 per (sp. gr. 0.960, containing as iron the all to Fe(OH) 3 precipitate weight) theoretically required just
Bromine number of
is
used to oxidize the iron.
Calculate
milliliters of 6.00
N HF
NH OH
NH
4 after exact neutralization of the acid, (r) number of milliliters of in the calcium =0= oxalate the titrate Fe to 0.00800 gram 3) 2 regular (1 ml.
KMnO
precipitate, (d) weight of ignited
magnesium
precipitate obtained in the usual
way from
998.
the calcium
filtrate.
certain mineral has the following composition:
FeO = MnO = CaO = MgO = SiO 2 =
C0 A
43.60 per cent
one-grain sample is decomposed without oxidizing the iron and put through a regular systematic analysis. Calculate to 3 significant figures: (a) number of milliliters of 6.00 N IIF theoretically required to volatilize the silica, (b) total number of milliliters of bromine water (sp. gr. 1.100, containing 3.00 per cent
Br2 by weight) and (c) total number of milliliters of 3.00 N NH 4OH to pre2Fe++ + cipitate the iron and manganese together according to the equations: Br2 + 6NH 4OH~>2Fe(OH) 3 + 2Br- + 6NH4 +; Mn++ + Br2 + 4NH 4OH -> MnO2 + 2Br" + 4NH4 f + 2H20, (d) weight of this precipitate after ignition,
'
PROBLEMS
(e)
337
N H 2 C 2O4 solution to form the soluble and 2 4) 2 completely precipitate the calcium, (/) weight of the complex material obtained by precipitating the magnesium with (NH 4 ) 2 HPO 4 in the regular way and igniting the precipitate, (g) number of milliliters of KMnO4
total
number
ra
Mg(C O
H O - 2MnO + 3CO +
2
required to titrate the iron in a one-gram sample of the original mineral after 4 is equivalent decomposition without oxidation. Each milliliter of the ~ 2MnO4 in titration: 3CHO the of to 0.006802 gram 2 2 following
KMnO
NaCHO
2
5OII(c)
Ans.
(/)
0.333 ml., (b) 9.70 ml., 0.113 gram, (</) 6.00 ml.
(a)
3.33 ml., (d) 0.236 gram,
(e)
140 ml.,
sample of limestone rock was analyzed, and the percentages of the constituents, expressed as SiO 2 Fe 2 O 3 A1 2 O 3 CaO, MgO, CO 2 and H 2 O, were
999.
,
,
obtained as follows:
SiO*. sample weighing 2.500 grams was dissolved in IIC1, evaporated to dryness, and dried at 110C. The ignited insoluble residue weighed 0.6650 gram, and all but 0.0015 gram was volatilized by 11F. This small residue was
and added to the main filtrate. The filtrate from the SiO 2 determination gave a precipitate + with ammonia weighing 0.2181 gram after ignition. CaO. One-fifth of the filtrate from the above-mentioned determination
fused, dissolved,
Fe'zOs
AkOz.
gave a precipitate of calcium oxalate that required 38.40 ml. of 0.1225
KMnO
gram
for oxidation.
MgO.
of
/^20s.
From
the filtrate of the
Ca
determination was obtained 0.1133
Mg2P
A
2 C>7.
sample weighing 2.000 grams required 12.24 ml. of the above4
mentioned
KMnO
to oxidize
all
the iron after reduction.
CO 2
.
7/ 2 0.
A sample weighing 0.5134 gram after strong ignition weighed
0.3557 gram.
C0 2 The same weight of sample on treatment with acid caused an ascarite bulb to gain 0.1541 gram in weight. What was the complete analysis as reported?
1000.
mineral analyzes as follows:
CaO = MgO = Fe2 O 3 = CO2 =

A/f~f\
23.9 per cent Q 1 nt\t. cent f*f*-n43.1 per 40.0 per cent
M.
33.0 per cent
A
up
one-gram sample
is
in just 10.0 ml.
HC1
(sp. gr. 1.10,
dissolved in HC1, evaporated to dryness, and taken containing 20.0 per cent HC1 by weight).
NH
(6)
Calculate: (a) Total milliliters 4 OII (sp. gr. 0.97, containing 7.0 per cent 3 by weight) to neutralize the acid and just precipitate all of the iron.
NH
Volume
of
KMnO
of
which 20.00 ml.
will titrate the iodine liberated
(having the same normality as a solution of thiosulfate from excess KI by 0.1113
gram
of KBrO 3 ) to titrate the iron in the resulting precipitate after the iron has been dissolved in 2 SO 4 and reduced with zinc, 4 to (c) Volume of
KMn0
titrate the calcium precipitate in the filtrate
from the iron (1.00 ml. of
this
338
4

1.00 ml.
KMnO o
HC1
=c=
KHC O .H C O .2II O ~
2
1.00 ml.
NaOH o
1.00 ml.
0.0106 gram Na 2 CO 3 ). (d) Weight of ignited Mg precipitate obtainable from the Ca filtrate, (e) Percentage of Fe in the material obtained by (/) Empirical completely igniting a large sample of the above material.
formula of the original mineral.

1001. Ankerite
ring in nature as
is essentially a calcium-magnesium-ferrous carbonate occura vein mineral. A chemical analysis of a specimen of this
mineral gave the following data: A well-mixed sample was dried at 105C. to constant weight. a. Moisture.
Weight Weight
b.
of
sample
after drying
10.000 grams 9.988 grams
A sample was dissolved in HC1, evaporated to dryness, heated one hour, and dissolved in IIC1, and the residue filtered, ignited, weighed, treated with HF, and reweighed. The small residue was fused with Na2CO 3 acidified and was added to the main solution.
Silica.
at
105C.
for
Weight Weight Weight

c.
of
sample
of residue
= =
5.000 grams 0.0417 gram
of residue after
HF =
0.0117 gram
Iron and Alumina. One-fifth of the filtrate from the silica determination was treated with bromine and made ammoniacal, and the precipitate
d.
and aluminum hydroxides ignited and weighed. The ignited oxides were then fused with Na 2CO3 and dissolved in acid, and the iron reduced with Zn and titrated with KMn04 Weight of oxides = 0.2845 gram; volume of
of ferric
.
0.1990
with the above-mentioned KMn04 Volume required = 47.50 ml. and the /. The filtrate from the calcium was treated with phosphate magnesium precipitate ignited. Weight ignited precipitate = 0.1430 gram. with HC1 g. A 0.1000-gram sample of the original mineral was treated and the evolved CC>2 purified and caught in a special apparatus and measured
.
used = 17.33 ml. e. The filtrate from the combined oxides was treated with ammonium 2 S04, and titrated oxalate and the precipitated calcium filtered, dissolved in
N KMnO
over water previously saturated with
C0
2.
Volume of CO2 = 23.78 ml. Temperature = 20C. Barometric pressure = 747 mm.
Vapor pressure
Calculate percentage of: (1)
(6)
2
of
H O at 20C. =
2
17
mm.
(4)
H O,
(2)
SiO2
(3)
FeO,
A12O3
(5)
CaO,
MgO,
(7)
C0
2.
h. Neglecting the small percentages of.H 20, Si0 2 , and A12 3 , calculate an empirical formula for the mineral. i. How many milliliters of 4 (sp. gr. 0.96, containing 10,0 per cent 3 by weight) would be required in step c above to precipitate the iron
NH OH
NH
and alumina
bromine?
after neutralization of the acid
and boiling out
of the excess
PROBLEMS
j.
339
If
the II2O and material?

1002.
a sample of the mineral were ignited in the absence of air so that all C0 2 were lost, what would be the percentage of Fe in the resulting
sample of manganese ore was submitted for analysis with the

:
following instructions
manganese, total phosphorus, total iron, and Previous oxidizing power. experience with similar samples of this ore has indicated that the manganese may be present in two forms, Mn() 2 and Mn 3 O 4 the phosphorus as phosphate, the iron as ferric iron, that no manganese is
total silica, total
,
Determine
combined as silicate, and that the oxidizing power is due to MnO 2 as such or in the form of Mn 3 O 4 (MnO2.2MnO). Calculate: (a) total silica expressed as of iron total as SiOo, (&) percentage of F(oO 3 (r) total phosphorus percentage
,
as percentage of PsOs, (d) percentage of 2 existing as such in the ore, of O in as such the ore. 3 4 existing (e) percentage
MnO
Mn
Four samples weighing 2.000 grains each were fused with Xa^COa. Two fusions were dissolved in HNO 3 + H 2 O and two in TTC1. The solutions were evaporated arid the residues dehydrated. The first two were taken up in HNO 3 and the last two in HC1. Silica was determined in each case in the
Silica.
usual way, yielding 0.6260, 0.6274, 0.6268, 0.6268 gram, respectively. Total Manganese. The filtrate from the nitric acid silica determination
was diluted to 1,000 ml. and 50-ml. portions used

bismuthate method.
0.1086
for
manganese by the
KMnO
4)
In each case a 50-ml. pipetful of was used, and the volumes of 0.1086
FeS04
(=0=
4
45.60 ml.
N KMnO
required in
three determinations were 9.77, 9.75, and 9.79. Two 100-ml. portions of the Total Phosphorus.
for the alkalirnetric
same
solution were used
method.
0.09249 3 ) of NaOH 25.04 ml. of 0.09249 N IINO 3

Total Iron.
N HNO
In each case a 25-ml. pipetful (o 29.30 ml. of was added, and the titrations required 25.00 and
.
from the hydrochloric acid silica determination was reduced and subsequently required 2.00 ml. of 0.1086
iron in the filtrate
The
KMnO
for reoxidation.
This was determined by reduction of duplicate Total Oxidizing Power. half-gram samples of the ore with 0.7000 gram of sodium oxalate in the presence of 1I 2 SO4 The excess oxalate required 27.00 and 27.06 ml. of 0.1086
.
KMnO
of
4.
sample of moist lime sludge, a by-product from the manufacture - Ca(OH) 2 + C 2 H 2 ] was submitted for acetylene gas [CaC 2 + 2H 2 O and the were results obtained: following analysis, A 2.000-gram sample treated with HC1 left a Acid-insoluble Residue.
1003.
residue weighing 0.0274 gram.
Combined Oxides (Fe 2 O3
HC1
solution
with
+ A1 O NH OH + NH C1
2
3 ).
Treatment
of the above-mentioned a gave precipitate that ignited to
0.0051 gram. Total Calcium. tioned

filtrate.
4.
The
This was precipitated as oxalate from the above-menoxalate in the precipitate required 58.60 ml. of 0.4960
N KMnO
340
Total

Magnesium.
4,
This was precipitated from the Ca filtrate as yielding only a trace. Total Iron. A 4.000-gram sample of the original material was dissolved in HC1, reduced with Zn, and titrated with 0.1067 N KMnO 4 the titration
MgNH PO
4
A 10.00-gram sample of the original material, treated with HC1, evolved an amount of CO2 to cause an ascarite absorption tube
to gain 0.1031 gram in weight. Total Ignited Solids. 3.000-gram sample of the original material, dried and ignited, yielded a residue weighing 1.2704 grams.
requiring 0.91 ml. Carbon Dioxide.
when
The above-mentioned residue was Total Alkalinity of Ignited Solids. dissolved in 100.0 ml. of 0.5927 HC1 and diluted to 500 ml. and a 250-ml.
(This determination and so used in the calculashould be and to of Calculate the analysis.) (a) tion analysis of the moist prove the accuracy lime .sludge in terms of percentages of: residue, Fe 2 3 Al 2 Oa, calcium as Ca(OH) 2 and as CaCO 3 and 1I 2 O (by difference), (b) Calculate analysis of
portion titrated with 13.73 ml. of 0.5724 that of total solids were made as a check
N NaOH.
the ignited residue.

1004. The analysis of a sample of coal ashes produced by the combustion of a soft coal in a power station of a public-utility company was carried on by the following procedure with results of duplicate determinations as indicated.
The
analysis is similar to that of any undecomposable silicate. Loss on Ignition. The loss was taken at 800 to 900 C., representing approximately the unburned fuel. Each sample weighed 20.000 grams.
made on portions of the ignited material. One-gram samples were fused with sodium carbonate, the entire fusion dissolved in hydrochloric acid, and the silica determined by the usual method of dehydration. No correction was made with hydrofluoric; acid, as the sample Wifs not considered to be representative enough to warrant such a
Silica.
Loss: 3.0951, 3.0960 grams. Sulequent determinations were
procedure.
Weight of ignited SiO 2 0.5284, 0.5302 gram. Combined Oxides. The filtrate from the silica determination was used for the precipitation of combined oxides, assumed to be entirely ferric oxide and
:
alumina.
of ignited oxides: 0.3927, 0.3920 gram. Calcium Oxide. The filtrate from the precipitation of the combined hydroxides was used for the precipitation of calcium as calcium oxalate, followed by the volumetric determination of the equivalent oxalate with 0.1020
Weight
N KMn0
4.
:
Volume of KMnO4 18.10, 18.05 ml. Magnesium Oxide. The filtrate from the precipitation of calcium oxalate was used to determine magnesia as MgNH 4 P04 .6H 2 O, ignited to Mg2 P2 O 7
.
Weight 0.0257, 0.0256 gram. Total Iron. Two-gram samples were fused with sodium carbonate and dissolved in HC1, the silica was removed and the total iron determined
of
2
7
:
Mg P2O
PROBLEMS
volumetrically
chloride.
341
reduction
with
0.1020
KMnO4,
after
with
stannous
Volume
of
KMnO
13.21, 13.21 ml.
Total Sulfur. Two-gram samples were fused with sodium carbonate and dissolved in HC1, and silica and combined oxides were removed and the sulfate content was determined by precipitation as BaSO4.
Weight
of BaSO 4 0.0020, 0.0025 gram. Calculate: loss on ignition, SiO2, Fe 2 O8

:
A12O3
CaO, MgO, SOa an
the
original sample.
Report
alkalies
by
difference.
qualitative analysis of an alloy indicates the presence of small tin, large copper, small lead, small iron, small phosphorus, and large zinc. The quantitative data follow:
1006.
The
Tin.
The sample weighing 5.000 grams
is
treated with
HNOs, evaporated
The residue, ignited to SnO2 to dryness, treated with HNOs, and filtered. and containing all of the phosphorus as P2C>6, weighs 0.0517 gram. Copper and Lead. The filtrate from the above is diluted to 500 ml., and
a 50-ml. portion 0.0034 gram.
Iron.
is
electrolyzed.
Cathode gains 0.2940 gram; anode gains

electrolysis is treated
The
residual solution
is
from the
4.
the precipitated Fe(OH) 3 with 0.46 ml. of 0.1007

Zinc.
redissolved,
and the iron
is
with 4 OII, reduced and titrated
NH
N KMnO
By
difference.
Phosphorus. A new sample weighing 2.000 grams is dissolved and the The ignited precipitate 4 PO4 phosphorus eventually precipitated as 0.0131 weighs gram.
MgNH
v
Calculate the percentage composition of the alloy.

1006. Given a sample of an alloy for the determination of tin, antimony, and lead. Calculate the percentages of these four elements from the
copper,
following data:
Volume
Determination of Sb (Volumetric method). Sample = 1.000 gram. = 17.70 ml. of 0.1078 4 required Sn (Residue from HNOs treatment). Sample == Determination of Sb 1.000 gram. Weight of ignited residue = 1.1478 grams.
KMnO
N KMnO +
Determination of
Cu and Pb
(Electrolysis of filtrate).
Sample
Increase in weight of cathode 0.0583 gram.

1007.
1.000 gram.
0.0428 gram.
Increase in weight of anode
analysis of a sample of bronze of indefinite composition, but a common commercial type, was carried out quantitatively of supposedly without a preliminary qualitative analysis, as follows:
The
one-gram sample of the alloy gave a white the indicating presence of tin. This filtered residue was to found and was 0.0615 weigh gram. ignited Determination of Copper and Lead. The filtrate from the determination of tin was electrolyzed by the usual procedure. Gain in weight of cathode =
residue in
Determination of Tin.
IINO
3,
0.8514; gain in weight of anode = 0.0512 gram. The fact that during the electrolysis no purple color developed at the
342
anode, indicated the absence of manganese. The solution after electrolysis was slightly bluish, but continued electrolysis with clean electrodes gave no
and washings from the electrolysis were combined and the iron oxidized with bromine. Ammonia precipitated the characteristic ferric hydroxide, which gave an ignited product weighing 0.001 1 gram. The filtrate was deep blue, showing the presence of nickel. Determination of Nickel. The regular dimethylglyoxime precipitate from
the iron filtrate weighed 0.0205 gram. Determination of Zinc. The addition of
filtrate
further deposition of metal. Determination of Iron. The solution
ammonium
sulfide to the nickel
gave a white precipitate, showing the presence of zinc.
This was
crucible as
redissolved
and the
.
zinc precipitated
and weighed on a Gooch
ZnNH4 P04
Weight
0.1385 gram.
Calculate and report the complete analysis. The sum of the percentages should serve as a check on the accuracy and completeness of the analysis.
A steel gave the following analytical data. Calculate the analysis. Carbon (Direct combustion method). Samples = 1.000 gram. CO2 ab= 0.0100 sorbed gram.
1008.
Manganese
tion
Samples = 0.1000 gram. Titra(Persulfate-arsenite method). used in the titration was presolution sodium ml. The arsenite 5.00
pared by dissolving exactly 0.3876 gram of pure As 2 O3 in dilute Na2C03 and diluting to exactly one liter (assume reduction of the manganese to an average
oxidation
number
of 3.50 in the titration).
Phosphorus
added
Samples = 2.000 grams. (Alkalimetric method). = ml. In the standardization of the ml. used 26.91 25.00 3
NaOH
4,
HNO
solutions, 30.51 ml. of
NaOH
neutralized 0.8000
gram
of
25.00 ml. of the
NaOH
Sulfur
(Evolution
were equivalent to 33.19 ml. of the method). Samples = 5.00 grams.
KHC H O HNO
8 4
3
.
and
solution required = 3.05 ml. 1.200 grams of KIO3 and 12
Volume of KIO3 The KIO3 solution was prepared by dissolving grams of KI in water and diluting to exactly
Samples
one
liter.
Silicon (Sulfuric acid dehydration).

silica
1.000 gram.
Weight
of
obtained
0.0009 gram.
Chromium
(Persulfate method).
Samples
2.000 grams.
Ferrous sulfate
solution added
In the Titration required 17.75 ml. of 4 O of Na C 2 2 4 and standardization, 40.65 ml. of theKMnO 4 oxidized 0.2500 gram of ml. the 4 25.00 ml. of the ferrous solution were equivalent to 18.31
25.00 ml.
.
KMnO
KMnO
1009.
sample of chrome-vanadium
method).
steel
was analyzed, and the following
mean
values were obtained: Carbon (Direct combustion
Sample
1.000
gram.
CO2
ab-
sorbed
0.0176 gram.
(Persulfate-arsenite
Manganese
method).
Sample
1.000 gram.
Titra-
standard steel weighing 0.100 gram and tion required 3.85 ml. of arsenite. of cent 0.66 manganese required 6.85 ml. of the same arsenite. containing per
Phosphorus
added
method). Sample = 2.000 grams. (Alkalimetric 3 of which Back titration required 31.4 ml. of 1 pipetful.
NaOH
HN0
PROBLEMS
the
33.70 ml. were equivalent to one pipetful of the above = 0.09493. 3
343
NaOH. Normality
of
HNO
Sulfur (Evolution method). 1.25 ml. of a standard solution of

to the sulfur in 5.00
Sample = 5.00 grams. Titration required KIO + KI of which 5.70 ml. were equivalent
3
grams of Bureau of Standards
steel containing 0.065 per
cent sulfur.
II 2 SO 4
Sample = 1.000 gram. Weight of Si0 2 after dehydration with and ignition = 0.0334 gram. Chromium (Persulfate method). Sample = 2.000 grams. FeSO4 added = Back titration required 3.30 ml. of 0.1070 N KMnO4 of which pipetful.
Silicon.
required = 1.30 ml. Calculate the percentage composition of the steel, and write equations for all fundamental reactions involved in the analysis, assuming the constit-
17.80 ml. were equivalent to one pipetful of the ferrous sulfate. Vanadium (Cr-V persulfate method). Sample = 2.000 grams.
Volume
of
above
KMnO
uents to be Fe, Fe 3 C,
1010.
MnS, Mn,
Mn Si O F P,
2
8,
Fe2 Si,
Cr,
and V.
small duplicate samples of galvanized sheet were submitted with the statement that the product was manufactured by The specifications galvanizing copper-bearing steel by the usual process. called for the determination of the amount of zinc galvanizing calculated as ounces of metallic zinc per square foot of total surface, not including zinc on the edge of the sheet. They also called for the complete analysis of the steel that had been galvanized. The small pieces submitted were duplicate samples from the same sheet. An examination of the edges indicated that the samples had been cut from a larger sheet and therefore contained no zinc except on the two flat surfaces. In the analysis, the coating of zinc was removed by dipping the sheets in NaOH, and the zinc determined in the solution. The residual sheets of steel were combined as one sample and milled. Average values obtained in the
for analysis
Two
analysis are given below. according to specifications.
Calculate the results of the complete analysis
ORIGINAL SHEET
Sample measuring Sample 2 measuring
2% by 2% 6 inches and weighing 45.4409 grams. 2% by 2% inches and weighing 46.9708 grams.
ANALYSIS OF ZINC
made acid, interfering constituents removed, aliquot portions taken. The zinc was determined in these aliquot portions by precipitation as ZriNH 4 PO 4 and weighing as such. Average 4 P0 4 in Sample 1 = 0.6393 gram; in Sample 2 = 0.6531 gram. weight of
caustic solutions were
The
and
ZnNH
ANALYSIS or STEEL
A 20.00-ml. Manganese (Bismuthate method). Sample = 1.000 gram. pipetful of FeSO4 was added, and the titration required 4.81 ml. of 0.1062 4 (20.0 ml. FeSO4 ^ 7.10 ml. 4 ).
N KMn0
KMnO
344
Phosphorus (Alkalimetric method). Sample = 2.000 grams. Volume of N NaOH added = 5.00 ml. Titration with 0.1592 N HNO 3 required 11.92 ml. A sample weighing 3.0 grams yielded 0.0008 gram of SiOa after Silicon. dehydration with H 2 S(X
0.4617
Sulfur (Evolution method).
Sample = 2.000 grams.

.
pipetful of iodine
was eventually added
to a solution of the evolved II 2 S
N Na2 S2O 3 A found to be equivalent to 18.08 ml. of the thiosulfate. Carbon. Combustion of a one-gram sample of the steel formed 0.0039
of
and the excess was pipetful of the iodine was
gram
CO
2.
Copper.
Volume
1011.
Precipitated as CuS, redissolved, and determined iodimetrically. of above thiosulfate for 10.0-gram sample = 1.04 ml.
submitted for analysis. The material and bone that has been processed by been has the and ground in a Wiley mill to a fairly fine consample heating, is used commercially as an important comthis Material of type sistency.
sample of meat scrap
is
consists principally of a mixture of beef
ponent of poultry food, dog biscuit, and similar products. The scrap from which the sample was taken was sold under the following
specifications:
Protein: not less than 45 per cent Ash: not greater than 35 per cent
Bone phosphate: within the
limits of 25 to 33 per cent Grease: not greater than 10 per cent Free fatty acid: not greater than 10 per cent of the grease Moisture: not greater than 9 per cent
Crude
fiber:
not greater than 2 per cent
The following numerical data represent the averages of duplicate determinations in each case. Calculate the analysis of the material as indicated. Does
it
conform to specifications? A 2.000-gram sample was analyzed by the Kjeldahl method Protein. (see Part VI, under Nitrogen). The evolved NII 3 was caught in a 5 per cent solution of boric acid and titrated with standard IIC1, requiring 19.40 ml. The IIC1 was standardized against the NII 3 liberated from pure (NH 4) 2 SO 4
[1.000
ml.
=0=
0.03490 gram
(NH4 ) SO 4
2
].
Arbitrary factor for converting
percentage of nitrogen to percentage of protein

Moisture.
6.25.
at 105 C.
sample weighing 5.000 grams was dried to constant weight Weight of dried material = 4.638 grains.
red heat.
material from the moisture determination was ignited at dull Weight of residue = 1.611 grams. Bone phosphate. This means phosphate expressed as Ca3 (PO 4 ) 2 The ash
Ash.
The
obtained above was dissolved in residue taken up in dilute 3
HNO
.
HNO
3 the solution evaporated dry, and the The solution was filtered and a Ko aliquot
,
.
portion was treated

precipitate
with
(NH 4 ) 2 Mo04
was
filtered
and dissolved in
NH OH, and the phosphate was then

4
The yellow phosphomolybdate
PROBLEMS
precipitated
as
345
Weight of
MgNH PO
4
and
ignited.
Mg P O =
2
0.0250
gram.
Grease.
3.000-gram sample of the original material was dried and ex-
tracted with anhydrous ether for 8 hours. Weight of residue = 0.2700 gram.
The
ether extract
was evaporated.
Crude Fiber. The grease-free material was digested with dilute 2 SO 4 and then with dilute NaOH according to exact specifications of procedure. The residue was filtered off on an alundum crucible and dried at 105C. Weight
inorganic material) plus crucible The crucible plus residue was then ignited at dull red heat. == 11.8016 grams. (inorganic material) plus crucible
of residue
(== fiber
11.8366 grams. Weight of residue
Free Fatty Acid.
The
grease from the above ether extraction was heated
with alcohol and titrated with standard NaOH, using phenolphthalein indiNaOH required = 2.16 ml. Free fatty acid is cator. Volume of 0.05050
usually expressed as percentage of oleic acid (milliequivalent weight present in the grease rather than in the original material.
0.282)
44.85 per cent. Moisture = 7.24 per cent. Ash = 32.22 = 9.00 per cent. Crude per cent. Bone phosphate = 27.87 per cent. Grease = 11.40 per cent. fiber =1.17 per cent. Free fatty acid
Ans.
Protein
sample of solution submitted for analysis is known to contain chromium sulfate, potassium dichromate, and free sulfuric acid. All other
1012.
constituents are eliminated
by information
as to the source of the solution.
Preliminary experiments indicate that the content of the various constituents to be determined is such that different volumes of the original must be used as samples. Fifty milliliters of the original are diluted to exactly 500 ml.
and portions used
for the analysis as specified. Determinatimi of Total Chromium Content. The chromium in 50.00 mi. of the diluted solution is oxidized by ammonium persulfate in acid solution, a measured excess of standard ferrous sulfate is added, and the excess titrated with standard permanganate solution.
25.00 ml.
75.00 ml.
FeSO4 o 23.38 ml. KMn04 FeSO4 solution added
7.93 ml. 0.1020
N KMnO
used
in titrating the excess
as
The chromium is precipitated of Trivalent Chromium. solution and the precipitate diluted of the from a 100.00-ml Cr(OH) portion = 0.1623 O Cr to 2 8 gram. Ignited precipitate ignited Determination of Total Sulfate. The filtrate from the above-mentioned trivalent chromium determination is diluted to exactly 250 ml., and a
Determination
3
.
BaSO4
is used to determine total sulfate gravimetrically as of Weight ignited BaSO 4 = 1.132 grams. Calculate: (a) Grams of Cr 2 (SO 4 ) 3 per 100 ml. of original sample, (b) grams 2 SO4 expressed of 7 per 100 ml. of original sample, (c) amount of free 2 Cr 2
100.00-ml.
.
portion
in
terms of acid normality.

1013,
analysis for chloride
sample of impure potassium perchlorate was submitted for an and chlorate content. On the assumption that only
346
these three acidic constituents were present, and only as potassium salts (which was justified by a review of the method of preparation of the original
material), the following analysis was made: The chloride present was precipitated from dilute
HNO
solution with
AgNO3 (chlorate and perchlorate are not precipitated). Weight of sample = 5.000 grams. Weight of silver chloride = 0.0118 gram. In another sample, the chlorate present was reduced in neutral solution
ferrous sulfate (perchlorate is not reduced). After the total chloride in the of 3 precipitated basic ferric salts in dissolving of with was solution the AgNOa. Weight sample = 5.000 grams. precipitated = 0.0501 chloride silver of gram. Weight
by prolonged heating with
HN0
Calculate the percentages of KC1, KC1O 3 and KC1O 4 (by difference). Calculate the amount of FeSO4.7H 2 O necessary to reduce the chlorate present.
,
is proposed to discharge the spent dye liquor from a dyehouse, at times to 126 gallons per minute, into a neighbouring stream. amounting indicate that this may be done satisfactorily if the volume of tests Laboratory the stream is sufficient to dilute the dye liquor one thousand times. Tests of the
1014. It
stream flow are made by adding to the stream a solution of sodium chloride at the rate of one gallon in 24 seconds. The chloride in the stream above the AgNO3 1.10 ml. of point of dosing is found by titrating 100* ml. with 0.01156
the silver solution being required. A 100-ml. sample taken below the point of dosing required 1 .22 ml. of the same solution. Each milliliter of the dosing solution required 73. 17 ml. of AgNO 3 (a) What is the stream flow in gallons per min.
ute?
(c)
(b) What is the normal chloride content of the stream in parts per million? What dilution would be obtained for the maximum discharge of dye liquor?
Ans.
(c)
(a)
153,000
gallons
per
minute.
(6)
4.51
parts
per
million,
1,214 times.
1015.
Most samples
of leather
when moistened
are acid to litmus.
This
reaction, however, unless extremely marked and in the presence of much sulfate, is not conclusive evidence of free mineral acid. Although there is
is
no simple chemical method that will give an accurate estimate of this acid, it possible to compare different leathers for acidity by a method of Proctor and Searle (Leather Industries Laboratory Book of Analytical and Experimental
Methods, page 371, 1908).
principle of this method follows: A sample of finely divided leather treated with standard sodium carbonate solution and evaporated, the leather carbonized, and the residue leached with water. The carbonization drives off the organic sulfur without an appreciable reduction of sulfur to
The
is
sulfide.
The solution is filtered, and the residue ashed and treated with standard hydrochloric acid. This solution is mixed with the original filtrate and the mixture titrated with standard alkali, methyl orange being used as indicator.
The data on an
actual determination follow:
Sample weight Na 2 C0 3 added HC1 added

Titration,
25.00 28.50
5.000 grams ml.

ml.
NaOH
14.50
ml.
PROBLEMS
347
The sodium hydroxide is standardized against 0.8000 gram of potassium acid phthalate, requiring 34.25 ml. If 25.00 ml. of the Na2 CO 3 0= 28.50 ml. HC1, calculate the free mineral acid as percentage of 2 SO4 by weight in the
sample.
1016.
sample of tanned
original.
sole leather
specification that the following determinations be

1.
was submitted made:
for analysis
with
Ash on
Total chromium on ash, calculated to percentage of Cr2 Oa in the ash and percentage of Cr2 0a in the original. 3. Total sulfur in the original, calculated as percentage of S. The analysis and data obtained were as follows:
2.
1.
until the carbonaceous
Duplicate 4.000-gram samples were incinerated at a dull red heat, matter was consumed.
Weight
2.
of ash
0.3912, 0.3915
gram
Duplicate 0.1500-gram samples of the ash were fused with a mixture 2 the fusion leached with water, the solution boiled to 3 2 2 remove excess peroxide and made acid, excess standard ferrous sulfate added, and the excess ferrous sulfate titrated with standard 4
of
Na C0 and Na O
KMnO
Volume
of
FeSO4 added
Normality of
KMnO
= =
100.00 ml.
Ratio: 50.00 ml.
FeSO4
4
0.1057
24.60
KMnO
Back
titratioii,
KMnO =
4.00; 3.98 ml.
3. Duplicate 1.000-gram samples were mixed with pure Na2 C03 the mixture covered with Na2 C0 3 and incineration carried on at a temperature below the
, ,
fusion point of Na 2 leached with dilute
CO
HC1 and
to prevent loss of sulfur compounds. The residue was the sulfate precipitated as BaSO4 after the re,
moval
of silica.
Weight
Calculate as indicated.
of ignited
BaS04 =
0.0755; 0.0747
gram
1017. Commercial zinc dust, or "blue powder/' is a fine, gray powder obtained as a by-product from the production of zinc and is generally composed of zinc (80 to 90 per cent), zinc oxide (9 to 10 per cent), lead (1.5 to 2.0 per cent), and traces of cadmium, iron, arsenic, and antimony. The amount of zinc oxide depends partly upon the care with which oxygen is excluded during storage. As this material is often used industrially as a
reducing agent
it is
usual to determine
its
K Cr O
2
2
reducing power with solutions of
7.
and .600-gram sample of the powder, 100.00 ml. of 0.5000 2 Cr 2 O 7 sulfuric acid are shaken in a bottle with additions of small amounts of acid until the sample is dissolved. The solution is then diluted in a measuring flask to exactly 500-ml., a 100-ml. portion is taken, 5 ml. HC1
1
,
NK
10 ml. of 6
and 10 ml.
of 10 per cent
KI
solution are added,
and the
liberated I 2
is
titrated
with 12.96 ml. of 0.1252
N thiosulfate solution,
starch being used as indicator.
348
Calculate the reducing power of this sample as percentage of zinc. Which of the metals listed above contribute to the reducing power of the sample?
1018. Bleaching
powder
(chloride of lime)
]
when
treated with water forms
calcium hypochlorite [Ca(OCl) 2 and calcium chloride. The calcium hypochlorite constitutes the active bleaching and disinfecting agent, and the analysis
is
therefore a determination of
of Cl
by weight, which is chlorine present as chloride. The original material must be kept in airtight containers and protected from air as far as possible, since bleaching powder is
available chlorine/' expressed as percentage the chlorine present as hypochlorite, but not the
"
acted upon by carbonic acid, which liberates hypochlorous acid with a correloss of available chlorine. Representative samples for analytical work are difficult to obtain and handle; but the material itself is inexpensive,
sponding
and
results obtained are sufficiently accurate for the purposes for

is
which the
material
used.
is
10.00-gram sample
until it is well ground.
The
triturated with successive small portions of water portions and residue are washed into a liter
measuring flask and thoroughly mixed, and an aliquot of 50.00 ml. taken for The sample should carry its proper proportion of sediment, for analysis. the supernatant liquid gives percentages below, and the sediment percentages The sample is slowly titrated with sodium arsenite above, the average. solution (4.425 grams pure As 2 O 3 13 grams Na 2 CO 3 diluted to exactly 1,000 ml.) until a drop of the solution gives no color to iodostarch paper as an outside ^ As04 "). indicator (OC1~ + AsO3 -> Cl From the data given in the problem, prove that the number of milliliters
,
of the arsenite used, multiplied

(at
by
2,
OC.
and 760 mm.) per kilogram
gives the number of liters of chlorine of substance. This corresponds to the
chlorometric (or Gay-Lussac) degree. Prove also that the chlorometric degree must be multiplied give the American degree (percentage of Cl by weight).
1019.
by 0.31698
to
A method
for
in the presence of each other, devised
the determination of chloride, bromide, and iodide by Julius Bekk [Che?n. Ztg., 39: 405-406
(1915); Chem. Abstracts, 9:2042 (1915)] as a result of research on this separation, invites the following procedure: 1. The halogens are precipitated and determined in total as silver salts.
2. A similar mixture of washed, moist silver halides precipitated from a second sample is digested with 2 grams of potassium dichromate in 30 ml. of concentrated sulfuric acid at 95 C. for 30 minutes. The iodide is oxidized to iodic acid; the chloride and bromide are liberated as chlorine and bromine and removed by passing a stream of air through the solution. The solution is diluted and filtered to remove anhydrous insoluble chromic sulfate and the iodic acid reduced to iodide by adding drop by drop a concentrated solution of sodium sulfite until a liberal excess is present. (Sulfurous acid causes the
separation of iodine until an excess has been added.) iodide is determined by filtration and ignition.
3.
The
precipitated silver
The
filtrate
bromide
is
from (2) containing the silver formerly with the chloride and determined as silver iodide by precipitation with a soluble iodide.
PROBLEMS
349
Write all equations involved in these reactions. In a given case the qualitative analysis of the original substance shows that Na and K are the only positive constituents. From the following data calculate
the milliequivalents of Cl, Br, and I in the original mixture. Calculate the in the sample, and by inspection of your answer calculate milliequivalents of the most probable percentage composition of the original.
(a)
Weight
of
sample
Precipitated halides (6) Weight of sample
(c)
(d)
Agl Precipitated Agl Weight of sample

Precipitated
KC1O4
= = = = = = =
0.5000
1.0643
gram
grams
0.5000
gram
0.07074 gram 1.5044 grams

0.5000 gram 0.04176 gram
1020. Lactic acid as a laboratory preparation can be produced by boiling cane sugar or glucose with a solution of sodium hydroxide. The acid can be separated by converting it into the calcium salt which can then be purified 2 SO4. by crystallization and reconverted to the acid by treatment with The acid is monobasic and has the formula CH 3 .CHOH.COOH. A sample of the calcium salt produced in this way is analyzed by ignition of the salt to CaO, which may be weighed directly, titrated with standard A one-gram sample of the calcium salt acid, or checked by both methods. an residue 0.2481 weighing ignited gram. This residue is then titrated gives ml. IIC1 and 50.00 of 0.5132 titrating back with 32.38 ml. of by adding NaOH. 0.5194 Calculate the purity of the calcium lactate by each of the two methods.
is a yellow, or brown, amorphous, somewhat not a true bismuthate but of variable composition, hygroscopic powder, 4 of about cent "active" or available oxygen, corresponding containing per is cent It insoluble in cold water but is decomposed by to 70 per NaBiOa. boiling water. The salt is used principally in the determination of man-
1021.
Sodium bismuthate
ganese.
Three grams of sample were mixed with 20 grams of KI and 30 ml. of water in a 100-ml. graduated flask. Twenty milliliters of dilute HC1 were added, the flask was well shaken, stoppered, and allowed to stand for one hour
The solute was diluted to the mark and mixed and an aliquot of 20.00 ml. taken for analysis. The titration required 29.42 ml. of 0.1022 thiosulfate, starch being used as indicator.
in the dark.
of available
Write the equation for the fundamental reaction. oxygen in the material.
1022.
Calculate the percentage
following data are taken from the chemical analysis of a solution containing copper sulfate and free sulfuric acid only. The color of the solution and a preliminary test for acidity indicate the presence of a large amount
of copper
The
and a slight degree of acidity. conventional volumetric acid measurement.

Determination of Copper.
The
color prevents the use of a

is
25.00-ml. sample of the original solution
350
diluted to 250 ml. in a graduated flask and thoroughly mixed, and 50.00 ml. volume of 33.72 ml. of taken for the analysis by the iodimetric method.
thiosulfate (33.35 ml. =0= 0.2241 gram Cu) is required. Determination of Total Sulfate. 25.00-ml. portion of the original solution is diluted to 250 ml. in a graduated flask and thoroughly mixed, and 50.00 ml.
taken for analysis.
BaSO4 obtained =
1.170 grams.
Calculate: (a) normality
of the thiosulfate solution; (6) grams of copper per liter of solution; (c) grams of free sulfuric acid per liter; (d) normality of the solution as an acid; (e) milliliters of
6.00
exactly 0.6000
N sulfuric acid to be N as an acid.

is
added to a
liter of
the solution to
make
it
1023. "Bisulfite liquor"

bisulfites
an aqueous solution of calcium and magnesium

]
[Ca(HSO 3 )2 and Mg(HSO3 ) 2 and
excess free sulfurous acid.
It is
passing SO 2 gas through a suspension of Ca(OH) 2 and Mg(OH) 2 and generally contains a small amount of sulfate because of the presence of S0 3 in the gas. The liquor is used in the sulfite digestion process for the production
made by
of paper pulp; it disintegrates the wood chips by rendering the noricellulose parts soluble. For control tests in the mill, a volumetric method is usually sufficient. Gravimetric methods are used for a complete and more precise analysis.
mine the
Determination of Specific Gravity. By means of a Westphal balance deterspecific gravity of the liquor. Value obtained = 1.050.
VOLUMETRIC CONTROL ANALYSIS

Into a 100-ml. volumetric flask transfer a 10-ml. pipetful of the liquor, dilute to the mark, and mix.
Determination of Total 80%.
of the
H 2O -^ HSOr 21- 2H+). (IISO 3 + I 2 Determination of Available S0 2 Titrate with standard NaOH (using phenolphthalein) a 10-ml. pipetful of the prepared solution. Volume of 0.1 100 NaOH required = 6.04 ml. (IlSOr OH- -> SOr 2 O).
above prepared
solution.
Titrate with standard iodine a 10-ml. pipetful Volume of 0.1010 I 2 required = 10.05 ml.
+H
GRAVIMETRIC ANALYSIS
Determination of Silica. Evaporate a 25-ml. pipetful of the original liquor with HC1 to dryness. Dehydrate, dissolve in HC1, filter, and ignite residue in the regular way. Weight of residue = 0.0027 gram.
tion
Determination of FeÔz AW*. Use the filtrate from the silica determinaand precipitate with NII 4 OII. Filter and ignite in the regular way.
Weight
0.0051 gram.
Determination of
original liquor with
CaO and
H SO
2
of MgO. Evaporate a 25-ml. pipetful of the to dryness. Weight of CaSO4 MgSO4 = 0.5875
gram.
Dissolve in HC1, add
NH OH and
4
(NH C
4) 2
4.
ignite. Weight of CaO = 0.2225 gram. Determination of SO*. Pipet 100 ml. of the original liquor into a flask, add HC1, and boil out the SO2 in a current of CO2 to exclude air. Precipitate the
Filter the precipitated
CaC 2O4 and
sulfate with
BaCl2
Weight
of
BaS04 =
0.0330 gram.
PROBLEMS
DISCUSSION ANT> CALCULATIONS
"Available
351
SO2 "
is
the free
H S0
2
magnesium
is
bisulfites
and indicates the SO2
It is given by NaOII. Total S02 " the iodine titration. Combined SO2 " is represented by one-half given by the SO 2 in the bisulfites of calcium and magnesium and is found by subtracting " "available SO 2 from "total SO2 ."
(a)
to form neutral sulfites.
plus one-half the SO 2 in the calcium and in excess of the amount necessary " " the titration with
SO
From the volumetric analysis calculate the percentages of "available "total SO2 " and "combined SO2 ." (6) From these values find the per2 ," " centage of "free SO2 (i.e., as free 2 SO3 ). (c) From the gravimetric analysis
calculate the percentages of SiO 2 , Fe 2 O 3 A12 O3 and S0 3 (d) From the gravimetric analysis of calcium and magnesium calculate the weight of SO 2 combined as Ca(HSO3 ) 2 and Mg(HSO3 ) 2 One-half of this is " combine<l SO2 ."
, .
.
Calculate this percentage and compare with the value obtained volumetrically. Ans. (a) 2.03 per cent, 3.10 per cent, 1.07 per cent; (6) 0.96 per cent; (c) 0. 10 per cent, 0.019 per cent, 0.011 per cent; (d) 0.5581 gram, 1.063 per cent.
1024. Commercial aluminum sulfate is used in the sizing of mordant, in water purification, and for various other purposes. times contaminated with iron and may be " acidic " (containing or "basic" (containing free A1 2 O 3 ). The following is an analysis
paper, as a
It is somefree
H SO
2
4)
of a typical
sample:
filtered.
25.00-gram sample was dissolved in hot water and 105C., weighed 0.0525 gram. The filtrate was diluted to exactly 500 ml. and mixed (Solution 1). Of this solution, 100 ml. were taken and diluted to exactly feOO ml. in another measuring flask
Insoluble Matter.
The
residue, dried at
(Solution 2). Total Iron
and Aluminum.
the iron oxidized with
HNO
3,
Weight of ignited precipitate = 0.07602 gram. 100-ml. portion of Solution 2 was made acid with HC1 and BaCl 2 added. Weight of ignited precipitate = 1.0250 grams. Total Iron. A 100-ml. portion of Solution 1 was made acid with II 2 SO4
NII 4 OH
Total
A 50-ml. pipetful of Solution 2 was made acid, and the iron and aluminum precipitated with
NI1 4 C1.
SO
S.
poured through a Jones redurtor, and titrated with 0.05272 which 1 .37 ml. were required.
Acidity or Basicity.
is
KMriO4
of
The method
[/.
Soc. Chem. Ind., 30:
184 (1911)]
based upon the following reaction:
A1 2 (SO4 ) 3
(H 2 SO 4 )
12KF
-> 2(A1F 3 .3KF)
+ 3K SO +
2
(H2 SO4 )
Potassium fluoride solution, titrated to neutrality (phenolphthalein being used) with acid or base, decomposes aluminum salts forming stable compounds reacting neutral to phenolphthalein; but any free acid that may be present remains as such. Of Solution 1, 68.00 ml. were taken, diluted, and heated to boiling, and 10.99 ml. of 0.5176 N An excess 2 SO4 were added.
of
KF solution was KOH were required

It is
solution, and 10.00 ml. of 0.5292 to neutralize the solution to phenolphthalein. customary to calculate the iron to FeS04 even though some of it may
added to the cooled
352

.
exist in the ferric state. The remaining SO 3 is calculated to A1 2 (SO4 ) 3 If the sample is "basic," the A1 2 O3 left over is reported as A1 2 O 3 If the sample is acidic, the SO 3 left over is reported as free SO 2 4 Express the results of the analysis in terms of percentage of insoluble matter, FeSO4 A1 2 (SO 4 ) 3 "basic aluminum" (A1 2 O 3 ) or "free acid" (H 2 SO4 ),
.
and water (by
difference).
1026. Lime mortar, made from sand and lime, hardens by taking up carbon Unlike hydraulic dioxide, the lime being changed to calcium carbonate. mortar or cement, it will not harden unless fairly dry and exposed to the
air.
Cement mortar is a mixture of Portland cement, sand, and water. Cement mortar is much harder and more durable than lime mortar, but some lime is often added to make it spread and work more readily. The proportion of sand to cement is not greater than 3:1. Cement mortar is more expensive than common mortar but is useful in masonry that is exposed to water or where great strength is required. The setting of cement mortar is a process of hydration. The analysis of mortar to obtain the composition of the original material must be made on a sample after ignition. A sample of mortar that has been in use "and therefore has absorbed CO2 or has been set by chemical action, or both, is analyzed in duplicate in accordance with the following procedure. The original material which is known to be representative is crushed gently
and thoroughly mixed.
a sample Sand.
portion of indefinite weight large enough to use as
for all determinations is ignited.
HC1
is treated with a considerable volume of dilute the solution warmed, decanted, and this process repeated until all the soluble matter has been removed. Though some silicic acid precipitated
weighed portion
arid
pensated to The residue
be included in the residue, the amount is small and is comsome extent by the iron and alumina dissolved from the sand. is filtered off and ignited as "sand." The filtrate is diluted to a definite volume and an aliquot taken that is small enough to allow the precipitation of a reasonable amount of calcium and magnesium.
by the
acid
may
Elimination of Silica. By evaporation to dryiiess in accordance with the usual method. Precipitate discarded. Elimination of Combined Oxides (Fe 2
3,
A12 O3).
By
precipitation with
titration
ammonia.
Precipitate discarded.
KMnO
tion to
Determination of Calcium. By precipitation as 4 in the presence of 2 SO 4
CaC 2 O4 and
4
with
igni-
Determination of Magnesium.
By
precipitation as
Mg2 P2O7
MgNH P0
and
Calculate and interpret the analysis from the data obtained as shown below. These are mean values from the duplicate determinations.
The interpretation of this analysis is based upon the usual assumption that the average sample of Portland cement contains 62 per cent CaO and that the ignited material consists entirely of sand, cement, and free lime
(with
MgO).
PROBLEMS
for sand Residue (sand)
353
5.000
Sample
Dilution of filtrate
Portion taken
Normality
Volume
KMnO KMnO Weight of Mg P O

of
2
4
7
used
= = = = = = =
3.9869 500.0
100.0
grams grams
ml. ml. ml.
0.1317
37.67
0.05521
gram
1026. Structural concrete consists of cement, sand, and rock to which water has been added in proper amount to bring out a process of hydration. The chemical analysis of concrete calls for a determination of the proportions by volume of the original mix previous to the addition of the water and may be exceedingly complicated or comparatively simple depending upon the extent to which data are required. The simplest type of analysis, in which the sand and rock are actually determined and the cement is assumed to be the difference, is illustrated in the following problem. A representative sample of material in wliich the cement adheres loosely to the rock and in which it is apparent that the concrete has failed because
of improper original mixture, or other factors, is weighed and the entire sample disintegrated with a hammer or mortar and pestle, care being taken to knock the cement off the coarse aggregate or stone without breaking or crushing the
stone or sand particles. The rock particles (those which will not pass a j^-inch The finer portion is thoroughly mixed and sieve) are weighed as "rock."
sampled, and the loss on ignition is determined on a small portion. Another small portion is treated with dilute hydrochloric acid to dissolve the cement, and the sand is collected by filtration and is ignited and weighed as such.
DETERMINATION ON ORIGINAL CONCRETE SAMPLE

Weight Weight
of original concrete of rock
= =
1,785 grams
575 grains
DETERMINATIONS ON ROCK-FREE SAMPLE

Sand:
Weight of sample Weight of sand Loss on ignition:

Weight
of
= = = =
15.00 grams 12.15 grams
sample
5.000 grams
0.2654 gram Ignition loss a. Calculate on a percentage-by-weight basis the loss on ignition sand on the rock-free sample.
b.
c.
and the
Determine the cement by difference. Convert this 100 per cent analysis on the rock-free sample to a 100 per cent basis on the original concrete by introducing the percentage of rock as a factor. d. Convert this 100 per cent analysis of the original concrete to a 100 per cent analysis on a water-free and CCVfree basis by eliminating loss on ignition as a factor.
354
e.

On
the generally accepted basis that
1
1
cubic foot of rock
cubic foot of sand

cubic foot of cement
= = =
100 pounds 90 pounds
94 pounds
convert the analysis from a percentage-by-weight to a parts-by-volume basis. a unit basis for cement to two significant figures. /. Reduce these data to
qualitative analysis of a sample of welding compound showed definitely the presence of Na+, K+, Ol~, and F~, the first three conThe stituents present in large amounts in comparison with the fluoride.
1027.
The complete
also proved conclusively the absence of all other constituents, including water in any form.
analysis
The following quantitative The determination of total
analyses were made:

Cl~, precipitated
and weighed as AgCl
Sample weight AgCl weight
= =
0.4000 gram 0.7794 gram
The determination
of total F~, precipitated
and weighed as CaF2.
Sample weight
CaF 2
The determination
constituent F~)
weight
= =
3.000 grams
0.3046 gram
of the interfering
of total Na+ and K+ (after removal by the usual perchlorate method.
Sample weight NaCl and KC1 weight
KC1O 4
weight
= = =
0.2000 gram
0.2095
0.1714
gram gram
calculation of the percentage of the constituents K+, Na+, Cl*~, and F~ gives no indication of the proportions of the salts actually mixed to make this
compound.
be
An
interpretation of the results to give this information should
made
a.
accordance with the following method: Calculate the weights of all precipitates, and convert to the basis of a
in
one-gram sample. b. Reduce all data to the milliequivalent basis. 1. Milliequivalents calculated from weight AgCl. 2. Milliequivalents calculated from weight CaF 2 3. Milliequivalents calculated from weight KCKX (1) Convert milliequivalents KC1O 4 to grams KC1 (2) Subtract grams KC1 from grams KC1 + NaCl (3) Calculate milliequivalents from weight NaCl. c. Total the milliequivalents due to + constituents. constituents. d. Total the milliequivalents due to
.
If these totals balance within the limits of experimental error, it indicates that a correct analysis has been made, barring the improbable possibility that a constituent of the compound was completely overlooked in the qualita-
tive
and quantitative analyses.
PROBLEMS
e.
355
all
Consider the seven possible mixtures of
the salts of the constituents

as
K+, Na+, Cl~, F~, starting with the simpler mixtures,

below*:
enumerated
balancing the milliequivalents it is possible to eliminate four of the mixtures listed as impossible from the data of the analysis and to prove two possible mixtures as a duplication of the sample. The possibility of the seventh mixture cannot be proved or disproved with the data of the analysis. Further examination, possibly of a microscopic
/.
By
first six
or complicated chemical nature, would be necessary to indicate the actual existence of the four separate salts. g. From the observations made in (/), calculate the percentage composition of the mixture, bearing in mind that all data are now based on a one-gram
sample.
The percentage mixture

by
their proportions
is an interpretation of the actual salts and to be used in duplicating the original welding weight
compound.
Ans.
KCl =
NaCl =

10.91 per cent
KF =
KCl = NaCl =
NaF =
1028.
qualitative analysis of a solution of brine used in a special refrigerating process indicates the presence of barium, potassium, and sodium in medium amounts and chloride in large amount. All other constituents
The
are eliminated.
The method
of quantitative analysis used in this particular
case, which specified an inexpensive commercial analysis, is as follows: This was determined with a hydrometer at 20 C. = 1.188. Specific Gravity. Total Barium. A 50.00-ml. portion of the original solution was diluted to exactly one liter, and a 100.00-ml. portion was used for the precipitation of barium as BaSO4 Weight ignited BaSO4 = 0.6169 gram. Total Chloride. A 50.00-ml. portion of the original solution was diluted to exactly one liter, and a 50.00-ml. portion was used for the precipitation
.
of chloride as AgCl. Weight AgCl = 1.2575 grams. Total Solids. Twenty-five milliliters of the original solution were evaporated to dryness and ignited at a temperature of 400C to remove the water
of crystallization in the BaCl2.
The
residue (assumed to be
of
BaCl 2 NaCl,
,
KCl) weighed 6.7912 grams.

Calculate the percentage the original solution.
by weight
BaCl2 .2H 2 0, NaCl, and KCl
in
The
1029. Acetaldehyde is a low-boiling liquid which is soluble in water. dilute aqueous solution when treated with a solution of sodium bisulfite
forms
3
CH CHO + NaHSO + H O - CH CHOHSO Na.
an addition compound as indicated by the following equation: It was desired to work 2 3 3 8
356
out a feasible iodimetric method for determining acetaldehyde making use of this reaction. Since both bisulfite ion and the above addition product under proper conditions of acidity can be oxidized by iodine, and since bisulfite in
the presence of acid loses S(>2, a satisfactory method would seem to require careful control of such factors as pit value and time of standing. The experi-
mental analyses tabulated below were conducted in an attempt to use such an iodimetric method. In each analysis a 25.0-ml. pipetful of a solution contain-
= 44.0) and a little 2 S04 per liter ing 3.324 grams of acetaldehyde (mol. wt. was used. The aldehyde employed was carefully prepared and was better than 99 per cent pure. To this aldehyde solution, after dilution with water,
was added the indicated quantity of a solution containing approximately 39.5 grams of NaHS0 3 in 3.5 liters. After standing the indicated time, the solution was titrated with 0.0926 N iodine, with starch as the indicator. In certain cases (as indicated below) IIC1 was added together with the bisulfite and in certain cases (as indicated) NaHC0 3 was added after reaching the end point with iodine. When NaHC0 3 was used, it was found that further iodine was necessary to restore the blue color, the total volume required being
indicated in the last horizontal columns.
Erlerimeyer flasks
titrations were conducted in taken to eliminate loss of were and no special precautions
The
SOa on standing. Convert all numerical data to
inilliequivalents
and from a study
of the
values obtained write out in detail a dependable method for determining acetaldehyde to a precision of two or three significant figures. Emphasize
those conditions that must be followed with care and formulate the method of calculating the results. State all the conclusions you can draw as to the
chemical characteristics of the reactions involved.
PROBLEMS
357
Niter cake" (commercial sodium acid sulfate), a by-product from one of the processes for the manufacture of nitric acid, is used extensively as an acid in the pickling of steel and other alloys. The usual impurity is a small amount of iron as ferric sulfate. A sample is submitted for analysis
1030.
"
and the following information requested: (a) the percentage of total iron, calculated to percentage Fe 2 (SC>4)3, (b) the acid strength of the sample calculated as percentage of NaHS0 4 (c) any free acid calculated to percentage of H2SO4 , (d) any deficiency of acid calculated as percentage of Na 2 SO 4
, .
Determination of Total Iron.

dissolved, reduced, grams. Volume of
and
titrated
4
was precipitated as Fe(OH)s, with 0.1050 N KMnO 4 Sample = 10.00

iron
.
The
required Determination of Total Sulfate. Precipitated as BaSO4 (without elimination of small iron) from a hydrochloric acid solution of the salt. Sample =
KMnO
0.20 ml.
2.000 grams.
Ignited Determination of Total
BaSO4
Solution diluted to 250 ml. and a 50-ml. aliquot portion taken. * obtained = 0.7760 gram.
NaOH
Add Strength. Direct titration with 0.5137 N on a two-gram sample, methyl orange being used as the indicator,
required 32.02 ml. of the NaOH. a. Calculate all data to a one-gram basis, and reduce to milliequivalents, being careful to designate the milliequivalents in the iron titration as obtained
by a process involving oxidation and reduction, in the case of BaSO4 as a sulfate, and in the alkali titration as an acid. 6. Convert the number of milliequivalents due to the iron content, which lias been calculated as an oxidizing agent, over to the number of milliequivalents as a salt (sulfate), and convert the milliequivalents obtained from the
alkali titration over to milliequivalents as
sulfate.
The
results should
indicate an excess sulfate as

c.
Na2S04
milliequivalents of iron to percentage of Fe2(SO 4 )s. Subtract the milliequivalents of iron expressed as a salt from the total
milliequivalents of
Calculate
the
BaSO4 and
,
calculate the milliequivalents of
NaHSO4
as
an acid or as a
d.
salt to percentage of
NaHS04
Calculate the residual milliequivalents of
BaSO4
to percentage of
Na2S04
1031.
deposit taken from a steam

characteristics:
boiler,
a typical "boiler scale," had
scales, apparently containing iron oxide; the center layer of the plates white in color, indicating the possibility of CaS04 ; general characteristics indicating some organic matter. The
the
following
dark-colored
358
specification of analysis called for
a typical analysis of the boiler scale and indicated that the sample contained nothing uncommon to such a product.
specification also called for
an interpretation of results. The following were made: analyses Sampling. The scale was broken up in a porcelain mortar, then quartered and a final portion ground to a fine powder in agate.
The
ANALYSIS OF OKIGINAL SAMPLE

Moisture.
A portion
of the original sample
was dried at 105 C.
to constant
weight.
Sample weight Weight of dried sample
= =
9.0000 grains 7.6303 grams
ANALYSIS OF THE DRIED SAMPLE

Oil.
portion of the dried
transferred to an extraction thimble
sample from the moisture determination was and extracted with ether in a Soxhlet
extractor in the usual way, the extract being collected in a weighed flask. The ether was distilled off and the flask dried at 105C.
= 3.0000 grams Weight of sample = 17.3296 grams Weight of flask and extract = 17.3027 grams Weight of flask
ANALYSIS OF THE ORIGINAL SAMPLE
Organic and Volatile Matter. A portion of the original sample was ignited at a low temperature until the organic matter was burned off. The temperature was sufficient to remove moisture, oil, organic matter, and C0. from carbonates but insufficient to decompose sulfates.
Weight Weight
of
sample
of residue
= 1.0000 gram = '0.7286 gram
ANALYSIS OF THE IGNITED SAMPLE
A portion of the ignited sample Insoluble in Acid (Siliceous material). was treated with dilute HC1 until only a white silica residue remained; the
residue
was
filtered,
washed, ignited, and weighed in the usual way.
Weight of sample Weight of ignited residue
= =
1.0000
gram
0.5370 gram
Iron and Aluminum Oxides. The filtrate from the silica determination was oxidized with HNO 3 NH 4C1 and NH 4 OH added, the NIT4 OH nearly all expelled by boiling, and the precipitated A1(OH) 3 and Fe(OH) 3 filtered and ignited. Weight of ignited oxides = 0.2280 gram. Calcium. The filtrate from the combined oxides precipitation was used to precipitate CaC 2 O 4 which was filtered, dissolved in H 2 SO 4 and titrated
,
,
with
KMn0
4.
Volume
= KMnO = of KMnO Normality

of
4
27.40 ml.
0.1070
PROBLEMS
Magnesia.
359
for
The
filtrate
from the calcium determination was used
The precipitate was ignited. 4 PO4 in the usual way. precipitation of Weight of ignited precipitate = 0.03181 gram. Sulfur Trioxide. 1.000-gram portion of the ignited material was treated
MgNH
A
with concentrated HC1, diluted, and
filtered
4
and the
BaSO4 and
Chlorine.
filtered
ignited.
Weight
of
BaSO =
sulfate precipitated as
0.4089 gram.
A portion of the ignited sample was treated with water and and the chloride content determined in the filtrate by the usual method of precipitating AgCl in the presence of HNO3 filtering, and drying at 105C. Weight of AgCl = none. Total Iron. A portion of the ignited sample was dissolved in HC1, the
,
iron reduced with stannous chloride, the excess reducing agent reoxidized with HgCl2 and the iron titrated with KMn(>4 in accordance with the usual
,
method.
= = Volume of KMnO4 Normality KMnO4 =

Weight of sample
1.0000
gram
26.77 ml.
0.1070
Carbon Dioxide. A portion of the original substance showed no effervescence with dilute HC1. 1. Using the data obtained from the analysis of the ignited sample, which is all on a one-gram basis, calculate on the ignited sample: (a) percentage by
weight of insoluble residue; (b) percentage by weight of combined oxides (Fe 2 O 3 .Al 2 O 3 ); (c) grarn-milliequivalents of CaO; (d) gram-milliequivalents of MgO; (e) gram-milliequivalents of S0 3 (/) gram-milliequivalents of Cl; (#) percentage by weight of Fe expressed as* Fe 2 O3 ; (h) gram-milliequivalents
;
of
CO
2.
Calculate: (a) milliequivalents Cl (if present) to percentage of NaCl by weight; (6) milliequivalents SO3 to percentage of CaSO4 if an excess of SO3 is present, to percentage of MgSO4 if SO3 is insufficient to combine with
2.
CaO, remainder
of
CaO
to percentage of
CaCO3
(c)
milliequivalents
MgO
in excess of the excess milliequivalents SO 3 , to percentage of (not to 3 , for this decomposes at the temperature of the boiler). percentage of
MgO
MgCO
3.
Consolidate the analysis on the ignited sample to percentages of Insoluble residue Iron oxide (Fe2 O 3 )
Alumina (A1 2 O3 ) Calcium sulfate (CaSO4) Magnesium sulfate (MgSO4) Magnesium oxide (MgO) Sodium chloride (NaCl)
(This analysis of the ignited portion, if correct, should total 100 per cent within the limits of experimental error.) 4. Calculate the percentage of organic and volatile matter (including oil,
moisture, organic matter, and C0 2 ) on the original sample, and convert the 100 per cent analysis on the ignited sample to a 100 per cent analysis on an original basis by introducing this factor.
360
5. Calculate the moisture content on the original sample, and introduce it as a factor in the analysis, deducting the percentage for the "organic and volatile oil + CO2 ." matter" and changing this term to "organic matter
Calculate the percentage of C02 in the original sample, and introduce it as a factor in the analysis, deducting the percentage for the "organic CO2 ," leaving now a factor "organic matter oil." oil matter 7. Calculate the percentage of "oil in the dried sample," and convert
6.
this percentage only to
an original sample
basis.
Deduct
this value for the
factor "organic matter

8.
Make
leaving the factor "organic matter." out a complete report of analysis on the original sample basis.
oil,"
Ans.
Moisture
Oil
CO
Organic matter
Insoluble in acid
Fe2O 3
Al2Os
CaSO4
MgSO
MgO
NaCl
= 15.22 = 0.76 = none = 11.16 = 39.14 = 16.68 = none = 14.53 = 2.50 = none = none
per cent
99.99 per cent

1032. Two samples of table or dairy salt, submitted for complete analysis, were analyzed in accordance with the method given below, with results as indicated. The analysis was made in duplicate by the standard methods to determine whether these samples conformed to the United States specifications which require that they shall contain, on a water-free basis, not more than the following amounts of impurities:
1.4 per cent
CaS04
0.5 per cent CaCl2 MgCl2 0.1 per cent insoluble in 2
HO
0.05 per cent
BaCl 2
(In addition to the substances specified, table salt sometimes contains small amounts of Ca3 (PO4 ) 2 Na 2 SO 4 and MgS0 4 Natural salt also may
, ,
.
contain small amounts of
Na2 C0
8,
KC1, and other minor impurities.)
METHOD OF ANALYSIS AND RESULTS

Appearance. Examine the material under a microscope and note its general appearance. It should be homogeneous and free from foreign matter. Add a drop of dilute HC1 to the salt on the slide, and note if there is any effervescence
due to the presence of carbonates. Sample 1: Homogeneous, clear color, no foreign matter.
line structure.
Definite crystal-
No
effervescence with
HC1
Sample
2:
Homogeneous,
structure.
clear color,
Grains vescence with HC1
much
no foreign matter. Definite crystalline smaller than Sample 1. No effer-
PROBLEMS
Solubility
361
water.
and Reaction. Make a nearly saturated solution with distilled Test with sensitive litmus paper. A turbidity which dissolves on the
addition of
1
HC1
:
indicates
CasCPO^
or
CaCO8
Clear solution, neutral to litmus Sample 2: Turbid Sample solution, neutral to litmus; turbidity disappears on the addition of acid. Moisture. Dry 10 grams to constant weight at 105C.
Sample 1: Sample Wt. dry

Loss
10.0000
10.0000
9.8603
9.8592
0.1397
0.1408
Phosphoric Anhydride. Dissolve 50.00 grams in distilled water, dilute to 500 ml., and pipet out 100-ml. portions of uniform solution and suspension. until the acid is nearly, then add Add 10 ml. of concentrated 4 S but not completely, neutralized. Add an excess of ammonium molybdate
HNO
NH OH
If the solution is colored solution, warm gently, and let stand one hour. bright yellow but gives no precipitate, report a trace of P2 Os. If a yellow precipitate forms, determine the phosphate by one of the standard methods
(see
Part VI, under Phosphorus).
Sample 1: Sample
Analysis
= =
=
10.00 grams no precipitate obtained
Sample 2: Sample
10.00 grams
KMnO =
4
30.25 ml. 30.10 ml.
= KMnO4 =
Blairmeth d
0.1067 N.
:
Iron Oocide and Alumina. (a) In the absence of P2 O 6 To a new 100-mL portion of the above-mentioned solution add a few drops of concentrated 4OH, and boil to oxidize the ferrous iron. Add a slight excess of 3 To A12O 8 (fc) In the presence of P2 O 5 filter, wash, and ignite to FeuOa
HNO
NH
:
FePO4 and excess iron as Fe(OH) 8 Filter, wash, and ignite to Fe2O 8 P2 5 From this weight, subtract the amount of P2O 6 previously A1 2O8 determined and the weight of Fe2O8 added. The remainder will be Fe2 8 A12 8
as
.
100 ml. of the original solution, add slightly more than enough ferric sulfate to combine with the P2 C>5. After adding the iron solution, add a slight excess This precipitates all the P2Os of 4 OH, and boil until barely ammoniacal.
NH
Sample 1: Sample weight

Ignited precipitate
= =
10.00 grams
none
362

= =
10.00
Sample 2: Sample weight Milliliters Fe2 (SC>4)3 solution added

(0.001275 molar)
T
.
.
grams
100.0
Igmted precipitate
Total Calcium.
=
filtrate
0.0269 * gram
00269
from the combined oxides, precipitate the calcium as CaC204.H 2O, dissolve in dilute H 2 SO4, and titrate the equivalent oxalate with standard KMnC>4.
In the
Sample
1:
Milliliters
KMnO =
4
^'j[J
KMnO
Sample
0.1067
2:
Milliliters
KMn0 =
4
j'^
KMnO
a i Sample
a
i
Total Magnesium. calcium oxalate as

i
0.1067 Precipitate the magnesium in the

2 2
filtrate
from the
1:
-A
Ignited
MgNH4PO4 .6H O; ignite to Mg P O 0.01751 B j ^ ^ = gram 2P O

2
Ti/r
7.
Mg
Q Q1757
o T M j ** r rt Sample 2: Ignited Mg2P2 7
0.07296 * gram
Q 073(X)
Sulfur Trioxide.
HC1 and
o
i
ml. of the original solution, add 5 ml. of dilute precipitate BaSC>4 in the usual way.
i
To 100
-n
Sample
Sample
TIT
:
Weight BaSO4 Weight BaSO4
T.J.
cn-v
= =
0.2446 * gram
Q 244g
2:
gram
{
JJjjg
Total Barium. If sulfate is present, Ba cannot be in the solution but might be present in the insoluble portion. If SO3 was not found, test for barium by adding 5 ml. of dilute H 2SO4 to 100 ml. of the original solution,
precipitating BaSO 4 , igniting in the usual way. Total Chloride. Dilute 100 ml. of the original solution to 500 ml., mix, and pipet out 25 ml. Dilute to 500 ml., add 5 ml. of dilute 3 , and precipitate as AgCl, drying at 105C.
HNO
Sample Sample
1:
Weight AgCl
=
{ |;JjgJ
*rams
2:
Weight AgCl
=
{
grams
};}JJJ
to boiling,
Dilute 100 ml. of the original solution to 150 ml. Heat and add, drop by drop with constant stirring, a slight excess of BaCl2 solution. Without filtering, add in the same manner Ba(OH) 2 solution in slight excess. Filter while hot, and wash until free from chloride. Add to the filtrate 1 ml. of concentrated NH 4OH and a saturated solution of until the excess barium is precipitated. Heat, and add 0.5 gram
Total Potassium.
PROBLEMS
363
of oxalic acid; filter, wash until free from chloride, evaporate the filtrate to dryness in a platinum dish, and ignite carefully over a free flame below red
heat until
all volatile matter is driven off. Digest the residue with hot water through a small filter. Acidify with HC1, and add H 2 PtCl6 solution in excess. Evaporate on a water bath; add 80 per cent alcohol. Filter on a Gooch crucible, and dry at 105C.
and
filter
Sample
2
1:
6
K PtCl
Sample
2
none
2:
6
0.4304 gram 105 C. directly to percentage of loss by weight. P2O 6 grams of A12O 3 6. Calculate grams of P2 O 6 grams of Fe2O 3 A1 A12 3 grams Fe2 3 and grams Fe 2O 3 3 per gram basis; reduce the 2
a. Calculate loss at
,
K PtCl = +
single terms to milliequivalents.

c.
Reduce
2
all
d.
Calculate:
Calculate:
4.
P2 O 6
SO
8
other data to milliequivalents per gram basis. to Ca3 (PO 4 ) 2 excess over CaO to Mg 3 (P0 4 ) 2 ; further
;
excess to
e.
Na HPO4.
to
CaSO4
excess over
CaO
to
MgS04
further excess to
Na2SO
/. Calculate CaO over P2 O 6 and SO 3 to CaCO 3 (if the salt solution is turbid and shows the presence of carbonates) or to CaO (if the salt is alkaline) or to CaCl2 (if the solution is clear and neutral). g. Calculate MgO over P 2 O 6 and SO 3 to MgCO 3 (if the salt solution is turbid and shows presence of carbonates) or to MgO (if the salt solution is alkaline) or to MgCl 2 (if the solution is clear and neutral). h. Report Fe 2 O3 and A1 2 O 3 as such. If BaCl 2 CaCl 2 MgCl 2 KC1 are present, subtract the equivalent i. amount of AgCl from the total AgCl before calculating the latter to NaCl.
,
j.
Calculate percentage by weight of each constituent of the original
sample. k. Calculate percentage by weight of each constituent (dry basis).
Ans.
APPENDIX
TABLE
IV.
DENSITY OP WATER AT TEMPERATURES 15 TO 30C.
365
366

TABLE V.
VAPOR PRESSURE OP WATER
APPENDIX
TABLE
VI.
367
15
-
SPECIFIC GRAVITY OF STRONG ACIDS AT
IN
VACUO
(According to G. Lunge)
(From Tread well and
Hall' a "Analytical Chemistry," Vol. II, published Sons, Inc., by permission)
&
by John Wiley
368

15
a
SPECIFIC GRAVITY OF STRONG ACIDS AT
-TO"
IN VACXTO.
(Continued)
(According to G. Lunge)
APPENDIX
TABLE VII.
SPECIFIC GRAVITY OF POTASSIUM
369
AND SODIUM HYDROXIDE
by John Wiley
SOLUTIONS AT 15C.
(From Treadwell and
Hall's "Analytical Chemistry," Vol. II, published <fc Sons Inc. by permission)
370
TABLE

VIII.
SPECIFIC GRAVITY OF
AMMONIA SOLUTIONS AT 15C.

by John Wiley
(According to Lunge and Wiernik)

(From Treadwell
&
Hall's "Analytical Chemistry," Vol. II, published & Sons, Inc. by permission)
APPENDIX
TABLE IX.
IONIZATION CONSTANTS, 25C.
Acids
371
372

TABLE X.
SOLUBILITY PRODUCTS, Approximately 25C.
3.7
8.1
Aluminum
hydroxide, Al(OH)s
Barium carbonate, BaCOs chromate, BaCrO4 fluoride, BaF2

iodate,
3.0
1.7
Ba (163)2
6.0
1.7 1.1 1.6
oxalate,
sulf ate,
BaC 204
BaSO4
Bismuth
sulfide, BisSa sulfide,
Cadmium
CdS
.
3.6
. .
Calcium carbonate, CaCOa

chromate, CaCrCh
fluoride,
1.6
2.3 3.2
CaF2
CaCsCh CaS04
iodate, Ca(IOa)2
6.4
2.6
oxalate,
sulf ate,
6.4
Cobalt
sulfide,
CoS
3.0
8.0
1.0 4.1
Cupric
sulfide,
CuS
Cuprous
CuCl bromide, CuBr iodide, Cul

chloride,
sulfide,
5,0
1.0
Cu2S
thiocyanate,CuCNS.
Ferric hydroxide,
1.6
1.1
Fe(OH)s
.
Ferrous hydroxide, Fe(OH)a

sulfide,
1.6
1.5
FeS
Lead carbonate, PbCOa

chloride,
5.6
PbCh
2.4
1.8
chromate, PbCrO4
fluoride,
PbF2
3.7
iodate,
iodide,
Pb(I0 3)2
Pbl?
9.8
2.4
3.3
.
. .
PbC2O4 phosphate, Pb3(PO 4 )2 sulf ate, PbS04

oxalate,
sulfide,
1.5
1.1
PbS
4.2
X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X
Magnesium carbonate, MgCOj.

1(T*
fluoride,
2.6
10- w
MgF2 ..... hydroxide, Mg(OH)j

oxalate,
8.4 3.4
8.6
10
10-1
Manganese hydroxide, Mn(OH>2

sulflde,
4.0
1.4
1.1
10^
10- 10
MnS .......
X X X X X X
X X X
10~*
10-*
10-"
10-*
10~ 10'
10-*
Mercurous chloride, HgsCh .....

bromide, Hg2Bra .....
iodide,
1.4 1.2
Hg 2 I
.
........
Nickel sulfide, NiS

Silver bromate,
1.4
10-*
10-*
bromide,
chloride,
AgBrOa AgBr
5.0
xio-
5.0 6.2
1.0
1010-'
carbonate, Ag2COs
10-*
101010-*
l2
AgCl chromate, Ag2CrO4

cyanide, Ag2(CN>2
9.0
1.2 1.5
X X X X
10-12
10-w 10-u lO-"
hydroxide,
iodate,
iodide,
nitrite,
AgOH
AglOa Agl
2.0
1.0
X10xioXlO-w
10
AgNO2
7.0
1.3
10-<*
oxalate, Ag2C2(>4
10
10-
phosphate, AgsPO4
sulf ate,
sulfide,
1.8
X X X x X X X X X X X
X X
10-*
10-"
10io-<
Ag2SO4
7.0
1.6
xio10-n
1010-*
10-M
A gsS
thiocyanate,
AgCNS
1.0
1.6
10-*
Strontium carbonate, SrCOs .... chromate, SrCrO* ....

fluoride,
3.0
2.8
5.6
10~"
10-8
oxalate,
sulf ate,
SrF3 SrC 2 04
SrSO4
1010~
10-7
10-"
10-
2.8 3.0
1.8 1.2
Zinc carbonate,
sulfide,
hydroxide,
lO-*
ZnCOa Zn(OH) 2 ZnS
10-*
10-"
10*28
APPENDIX
TABLE XI.
[Temperature
SPECIFIC OXIDATION-REDUCTION POTENTIALS
373
= 25C.
Solution concentrations are 1 molar unless other-
wise specified.
Gases
(g)
are at
atmosphere pressure]
Half-cell Reaction
E
-2.992 -2.92 -2.90 -2.87 -2.713 -2.40 -1.67
K*
Sr
<=*
K+ +
Sr ++
Ca1
+ 2e
1
Ca <=
"-
+2
Mg <= Mg++ + 26
Mn 3F* Mn++ + 2e ^ Zn++ + 2c Cr ? Cr+++ + 3e S + 2e S~ H C (aq) 2C0 (g) + 2H+ + 2e Fe Fe ++ + 2e H (g) ?=t 2H+ (10-* M) + 2e Cd ?=* Cd ++ + 26
Zn
<=*
2
2
4
- 1.05
-0.758 -0.71 -0.51 -0.49 -0.441 -0.414 -0.398 -0.277 -0.22 -0.136 -0.122 -0.045
0.000
<=*
?=
Co
*=
Co ++
1 -*-
+ 2c
Ni ? Ni ++ + 2 Sn ? Sn- + 2e Pb ?= Pb++ + 2e Fe -Ft Fe +++ + 3e
(g)
*^
2H+
+ 2c
Sn++ ?i 8n++++ + 2e H2S S + 2H+ + 2c Bi + 4C1BiCLr + 3e Sb + H2O 3=4 SbO + + 2H + + 3e Ag + 01- SF AgCl + e As + 3H 2O ?=t 8 + 3H+ +
&
HÔ
+
3e
cell)
2Hg Cu
+ 2C1Bi + H O
2
?=
*=*
2e (calomel HgjCls BiO + 2H+ 3e
?=
Cu ++
+ 2e + 2e
Fe(CN),= ?=t Fe(CN),- + e HaAsO, + H2 O <=* H^sO4 + 2H+

21-
MnO4
^~ + 2e
I2
*^
+ 2H+ + 26 C,H (OH) * C.H.Os + 2H+ + 2e (quinhydrone) MnO + 4OH- * MnO - + 2H O + 2 Fe ++ Fe+ Ag Ag + + 6 2H O O (g) + 4H+ (10- M) + 4e Hg Hg++ + 2e
2 2 ?=t 2
MnO - +
4
(g)
<=
"*"1-
;F
?=t
?=t
+0.13 +0.141 +0.168 +0.212 +0.222 +0.24 +0.285 +0.32 +0.344 +0.40 +0.49 +0.535 +0.66 +0.68 +0.700 +0.71 +0.747 +0.799 +0.815 +0.86
374
CHEMISTRY CALCULATIONS OF ANALYTICAL

SPECIFIC OXIDATION-REDUCTION POTENTIALS.
Half-cell Reaction
(Continued)
E
+0.94
NO + 2H HN0 + H
2
^ NO," + 4H+ + 3e ^ NO,' + 3H+ + 2e

2
+0.96
+J-065 +1-30
2Br-^Br (aq)+2<2Cr +^ + 7H O^Cr

2
Mn ++ + 2H
+ 14H + + 6t ^ Mn0 + 4H + + 2c
2
+1-33
Ce+++
2
^
2
2 2
Mn++ + 4H Mn0 + 2H PbS0 + 2H

4
^ MnOr + 8H + + 5 & MnOr + 4H+ + 3e ^ Pb0 + 4H + + SOr + 2c

2
+1-52
+1-63 +1-70
APPENDIX
TABLE XII.
375
FORMULA WEIGHTS
(These weights cover most of the compounds encountered in the problems of

this text)
AgBr .................... AgBrOs .................. AgCl ....................

Agl ......................
AgNO, ................... Ag3PO4 ................... Ag2SO4 ...................

AlBr, .................... A12O, .................... Al(OH), .................. A12 (SO4 ) S ................. A12 (SO4 ),.18H2O ...........
462.35 187.80 235.80 143.34 234.80 169.89 418.65 311.82

266.72 101.94 77.99 342.12
666.4
1
CeO2
Ce(SO4 ) 2 .2(NH4) 2SO4 .2H2O
172.13 632.56
60.05 102.09 122.12 44.01 60.06 76.12
158.38 152.02 389.20
CH,COOH
(CH,CO) 2O
2
(acetic acid)
CO CO(NH
CrCl,
CeHsCOOH
2) 2
(benzoic acid).
CS(NH 2) 2
Cr2O3 Cr2 (SO4 ),
CuO
As2O6 ....................
AsjS, .....................
197.82 229.H2
2-16.00
Cu2 (OH) 2CO, CuS Cu 2S CuSO4 .5H 2O

Fed,
FeCl3 .6H2
79.57 221.17 95.63 159.20 249.71

162.22 270.32 115.86 223.87 349.97 71.84 159.70 231.55 106.87 119.97 139.76 278.02 399.88 562.02 392.15
Ba3 (AsO4) 2 ................ BaBr2 ....................

BaCl2 .................... BaCl2 .2II2 ...............
689.90 297.19 208.27

244.31 197.37
BaQA ..................
BaCO, ...................
FeCO, Fe(CrO2) 2
Fe20, Fe3O4 Fe(OH), FeS2 Fe2Si
BaF2 .....................
BaI 2 ..................... Ba(IO 3 ) 2 .................
BaO .....................
Ba(OH) 2 ................. Ba(OH) 2 .8H2 ............
BaSO4 ...................
BeO.
225.38 175.36 391.20 487.20 153.30 171.38 315.50 233.42

25.02
Fe(N03 ) 3 .6H2O F6O
FeSO4 .7H2O
Fe2 (S04 ) 3 Fe2 (SO4 ),.9II 2O
.
FeSO4 (NH4) 2 SO4 .6H2O
Bi(NO 3) 3 .5H2O BiO2

BizOs
BiOHCO,
Bi 2S 3
485.10 241.00 466.00 286.02 514.18

110.99 100.09 78.08 164.10 56.08 74.10 310.20 1041.59 136.11
HBr
2
HCH0 (formic acid) HC HsO (acetic acid)

2 2
HCyHtOi
(benzoic acid)
HC1
CaCl2
CaCO, CaF2
Ca(NO,) 2
CaO
Ca(OH) 2 Ca3 (PO4 ) 2 3Ca 3 (PO4 ) 2 .CaCl2
CaSO4
H C O .2H O (oxalic acid) HCOOH (formic acid) IINO HO H H,P0 H P0 HjS H SO, H SO
2
HC1O4
2
3
80.92 46.03 60.05 122.12 36.47 100.46 126.07 46.03 63.02

18.02 34.02 82.00 98.00 34.08 82.06 98.08
2 2
376

FORMULA WEIGHTS.
(Continued)
2
HgjBrj
Hg2Cl 2 Hg2I 2
KA1(SO4) 2 .12H2O K,AsO4 KBrO,
561.06 472.14 655.06
Mn O, ................... Mn,O ................... Mn P O7 .................

4 2 2
157.86 228.79 283.82
474.38 256.20
167.01 74.56 122.56 138.55 65.11 97.17 138.20 194.20 294.21
KC1
KC1O,
143.95 2894.80 MoS, .................... 192.13
MoO, ....................
MoÔw ..................
KCN KCNS
2 2 2 2
KC1O4
NaaAsOa .................
...........
191.91
201.27 381.43
102.91 150.91 68.01 82.04 58.45 49.02 106.00 134.01 169.91 84.01 112.03 141.98 258.17 56.07 119.99 138.01 149.92 122.11 69.01 85.01 61.99 77.99 40.00 163.97 358.17 78.05 126.05 322.21 158.11
K CO, K CrO K Cr O
8
NaBr ....................
NaBrOa ..................
2 2
s
4
7
KsFe(CN),
K,Fe(CN),,.3H2O
KHCJÔ,
KHC H4O
KHCOa KHCjO4
(tartrate)
(phthalate)
329.25 422.39 188.18 204.16

100.11 128.12 146.14 254.19 389.94 136.16 166.02 214.02 158.03 282.23 122.11 85.10 101.10 94.19 56.10 212.27 486.16 174.25 948.76 998.84
NaCHO (formate) ........ NaC H O (acetate) ........

2
NaCl ....................
................... Na-iCOa .................. NazC2O4 .................. NaaHAsOa ................ NaHCO, ................. NaHC2O4 ................. NazHPO4 ................. Na2HPO4 .12H 2 .......... NaHS .................... NaH2PO4 ................. NaH2 PO4 .H 2 ............ Nal ..................... NaKCOa ................. NaNO2 ................... NaNOa ................... Na-iO .................... .................... NaOH ................... NasPO4 .................. Na8PO4 .12H 2 ............ Na^S .....................
NaCN
KHC O .H C O .2H
2 4 2 2 4
KHCzCVHzO
KHSO4
KI
KH(IO,) 2
KMnO
KIO,
KNaC4H O,.4H
4 2
KNO KNO K KOH

2
2 2 2
KNaCO,
NaA
K,PO4
KjPtCU
4 4.
K SO K SO A1 (S0 ),.24H K SO .Cr (SO .24H

2
4) 3
............
LiCl
LiCOa
Li 2
LiOH
MgCl 2
42.40 73.89 29.88 23.95

95.23 84.33 181.27 137.33 40.32 58.34 222.60 120.38 246.49
70.93 86.93
248.19
NH C1 ...................
4
NH, .....................
MgCO,
MgNH AsO MgNH PO

4 4
4
NH OH
NO NO N
MgO
Mg(OH) 2
MgzPjO?
MgSO MgSO
MnO.
4
4
.7H2
17.03 53.50 (NH 4) 2 C 2O4 .H2 ........... 142.12 132.07 (NH4) 2 HP04 .............. .................. 35.05 4 (NH4 ),PO4 .12MoO 3 ........ 1876.53 (NH4) 2PtCl, .............. 444.05 (NH4 ) 2SO4 ................ 132.14 ...................... 30.01 46.01 2 ..................... 76.02 2 O, .....................
MnO
PbCl 2 ....................
PbCIF ...................
278.12 261.67
APPENDIX
FORMULA WEIGHTS.
(Continued)
377
PbC2O4 ...................
PbCrO4 ..................
PbI 2 ..................... Pb(IO,) 2 ................. Pb(NO,) 2 ................. PbO ..................... PbO2 .................... Pb2O, .................... Pb,O4 .................... Pb,(PO4 )2 ................ PbS04 ...................
295.23 323.22 461.05 557.05 331.23 223.21 239.21 462.42 685.63 811.59 303.27
SnCl 2
189.61
SnCU SnO2
260.53 150.70
64.06 80.06
SO2
SO,
SrCl2 .6H 2
SrCO, SrO
266.64 147.64 103.63 79.90 286.14 842.21
TiO2
PdI2 ..................... P.OS .....................
360.54
141.96
UO ..................... U O8 .....................
S
3
Sb2O4 .................... Sb2O6 .................... Sb2 S 8 ....................

SiCU .....................
SiF4 ..................... Si02 .....................
291.52 307.52 323.52 339.70

169.89 104.06 60.06
WO, .....................
ZnO ..................... Zn2 P2 7 .................. ZnSO4 .7H 2 ..............
ZrO2 .....................
231.92
178.40 81.38 304.72 161.44
123.22
378

LOGARITHMS OF NUMBERS
APPENDIX
LOGARITHMS.
(Continued)
379
380

ANTILOGABITHMS
APPENDIX
ANTILOGABITHMS.
(Continued?)
381
382

INTERNATIONAL ATOMIC WEIGHTS
(1944)
INDEX
Boron, problems on, 320
Boyle's law, 279
Absolute error, 2 Absorbing agents, 287 Absorption methods, 286 Accuracy of a result, 2 Acid mixtures, titration of, 184 Acidimetry, calculations of, 158
Acidity, control of, in sulfide precipitations,
Brass, problems on, 321
Bromine, problems on, 315 Bronze, problems on, 323 Buffered solution, 52
Buffered solutions, applications separations, 67
of, in
68
on, 321 Calcium, problems on, 316
Activity, 55
Activity coefficients, 55
Cadmium, problems
Calibration
of
Adsorption indicators, 243 Alkali group, problems on, 312 Alkalimetry, calculations of, 158
Alkaline earth group, problems on,
measuring
instru-
ments, 153
Calibration corrections, table
of,
98
312
Calomel
on, 317
cell,
255
Aluminum, problems
Ammonium, problems
on, 314
Ammonium
sulfide group,
problems
on, 311 Ampere, definition of, 126
Amperometric titrations, 275 Anion group, problems on, 313

Antilogarithm, definition
of,
Carbon, problems on, 324 Carbon dioxide, problems on, 324 Carbonate mixtures, titration of, 201 Cement, problems on, 317 Ceric sulfate process, 226 Cerium, problems on, 320
Characteristic, definition of, 11 Charles's law, 280
12
Antimony, problems on, 323 Arsenic, problems on, 323 Atomic weights, calculation of, 109 Average deviation, 3 Avogadro's law, 281
Chemical balance, sensitiveness of, 93 Chemical equations, ionic, rules for

writing, 18
mathematical significance
of,
29
oxidation-reduction, rules for writing, 21
B
of, 93 Barium, problems on, 316 Beryllium, problems on, 320 Bismuth, problems on, 320 Bismuthate method, for manganese, 222
Balance, sensitiveness
Boiling point, raising
of,
142
purpose of, 16 types of, 16 Chemical factor, 104 Chemical formula, mathematical significance of, 28 Chlorate method, for manganese, 223 Chlorine, problems on, 315 Chromium, problems on, 325 Cobalt, problems on, 329
383
384

Electrolysis, analysis by, 126 Electrolytic methods, 125
Cologarithm, definition of, 11 Combustion methods, 287 Common ion effect, 52
Complex-ion formation, separations based on, 69 Complex-ion-formation methods, 249
Electrometric methods, 255 Elimination of a constituent, 135
Empirical formulas, 144
calculation of,
Complex
of,
ions, dissociation constants
End
56
36
cell,
Equations,
point, definition of, 191 for half-cell reactions,
Concentration, methods of expressing,
rules for writing,
79
18
of,
ionic, rules for writing,
of solutions, 36
mathematical significance
85
ing, 21
29
Concentration
oxidation-reduction, rules for writ-
Conductance, definition of, 266 Conductometric titrations, in acidimetry, 267 apparatus for, 271 general discussion of, 266 in precipitimetry, 270 Copper, problems on, 321 Coulomb, definition of, 126 Cubic centimeter, definition of, 153 Cumulative corrections, 99 Current efficiency, 129 Cyanide, problems on, 315 volumetric determination of, 249
purpose of, 16 types of, 16 Equilibrium constant, calculation from electrode potentials, 87 Equilibrium constants, 46
of,
Equivalence point, definition of, 190 determination of pH at, 191

Equivalent conductance, of, 266
definition
Equivalent weight, definition of, 38 Equivalent weights, in complex ion methods, 249 in neutralization methods, 158
in
D
Dalton's law, 280 Data, conversion to milliequivalents, 169 Decomposition potential, 125
Definite proportions, law Densities, table of, 96
of,
oxidation-reduction
methods,
211
in precipitation methods, 243 Erg, definition of, 130
Evolution method, for sulfur, 236
102
Deviation measure, 2 Dichromate process, 225 Diffusion current, 275 Digit, definition of, 5 Distribution law, 73 Distribution ratio, 73 Double-indicator titrations, 199
Factor weight sample, 110 Faraday, definition of, 127 Faraday's laws, 126 Ferrous sulfate, equivalent weight 212
Fluorine, problems on, 315 Formal solution, definition of, 37 Formula weight, definition of, 28
of,
E
Electrode potential, relation to concentration, 83
Formulas, calculations based on, 28 Fractional precipitation, 62 Freezing point, lowering, 142
Fuming
184
sulfuric
acid,
titration
of,
Electrode potentials, 78
INDEX
385
G
Gas absorption methods, 286 Gas analysis, absorbing agents
287
calculations of, 279
divisions of, 281
in,
Indicators, properties of, 188 table of, 190
Indirect methods, gravimetric, 118
volumetric, 176 Introduction of a constituent, 135 lodimetric process, 234

Iodine, equivalent weight of, 216
279 Gas combustion methods, 287 Gas-volumetric analysis, calculations of, 283 Gas-volumetric methods, 281 Gay-Lussac's law, 281 General analysis, problems on, 335 Glass electrode, 258 Gold, problems on, 315 Gram-atom, definition of, 28
laws
of,
problems on, 315 Ionic equations, method of writing, 18

oxidation-reduction, writing, 21
method
of
lonization of acids, bases, and salts,
17
lonization constant, 50
Iron, problems on,
317
Iron value, 225 Isomorphic replacement, 145
Gram-equivalent weight, definition of, 38 Gram-ion, definition of, 28 Gram-molecular weight, definition of, 28
Joule, definition of, 130
H
Half
cell,
K
Kjeldahl method, for nitrogen, 176
77
Half-cell reactions, rules for writing,
79
Halogens, problems on, 315 Hydrogen electrode, 78
Hydrogen
weight
peroxide,
of,
equivalent
Lead, problems on, 321 Liebig method, for cyanide, 249 Lime, problems on, 317
214, 216
Hydrogen
of,
sulfide,
equivalent weight
Limestone, problems on, 317 Liter, definition of, 153

tables, Logarithms, rules
214
sulfide group,
Logarithm
method of using, 13
governing use
of,
Hydrogen
310
problems on,
Hydrogen
sulfide precipitation, con-
trol of acidity in,
68
of,
M
Magnesium, problems on, 316 Manganese, problems on, 327
Mantissa, definition
of,
Hydrolysis, calculation of degree
196
Hydronium
ion,
47
11
Mass
Indicator constant, 189 Indicators, adsorption, 243
action, law of, 46 Mathematical operations, Mean deviation, 3 Mean value, 2
Measuring instruments,
of,
calibration
analyses involving two, 199
153
386

Oxidation-reduction methods, 211 Oxidation-reduction processes, calculation
of,
Mercury, problems on, 315

Milliequivalent weight, definition
of,
38
Milliliter, definition of,
216
reactions,
of,
153
Oxidation-reduction
in-
cal-
Millimole, definition
of,
Mixed
alkali titration, dicators, 199
29 with two
of
culation of extent
86
determination ponents in, 183 Mobility of ions, 266

Mixtures,
com-
Oxidimetry, 211 Oxidizing agents, equivalent weights of, 215
solution, definition of, 37 Mole, definition of, 28 Molecular formulas, calculation 141
Molar
Percentage
of,
purity,
calculation
of,
from titration values, 173

Percentages, calculation calculations from, 135
of,
105
Molybdenum, problems
on, 324
Permanganate Permanganate
solution,
process, 219 titrations, in neutral

for
N
Neutral point, definition of, 191 Neutralization methods, 158 Nickel, problems on, 329 volumetric determination of, 251 Nitrogen, problems on, 314
223
Persulfate method,
manganese,
223
Phosphate mixtures, titration of, 207 Phosphorus, problems on, 329

pll value, definition
of,
48
determination
point, 191
of,
at equivalence
Normal solution, definition of, 38 Normal temperature, definition

153
Normality, adjustment of, 163 determination of, 168
of
of,
Platinum, problems on, 315
pOH
solutions, 161 definition of, 3
re-
value, definition of, 48
Polarograph, 277 Polybasic acids, ionization
mixed
Number,
Numerical problems, conventions garding, 6
of, 18, 53 Potassium, problems on, 313 Potassium binoxalate, equivalent weight of, 213 Potassium bromate, equivalent weight
of, 216 Potassium dichromatc, equivalent weight of, 215 Potassium ferricyanide, equivalent weight of, 215 Potassium permanganate, equivalent weight of, 215 Potassium tetroxalate, equivalent weight of, 214 Potentiometric methods, 255
O
Ohm, definition Ohm's law, 130
Oleum,
of,
130
titration of, 184

of,
Oxalic acid, equivalent weight
213
Oxidation, definition of, 211
Oxidation number, 20 Oxidation potentials, 76

Oxidation-reduction, relation of current to, 76
Potentiometric titrations, in acidimetry,
255
for,
Oxidation-reduction
equations,
in
apparatus
256
terms of
half-cell reactions,
80
method
of writing, 21
in oxidimetry, 259 in precipitimetry, 261
INDEX
Precipitation methods, 243 Precision measure, 2
Substitution,
387
method
of,
97
Problems, conventions regarding, 6
Sulfur, problems on, 331 Swings, method of, 94
Q
Quinhydrone
electrode, 257
Thiocyanate, problems on, 315
R
Range
of doubt, 189
of,
Thorium, problems on, 320 Tin, problems on, 323

166
Reacting solutions, ratios Redox methods, 211

of,
Titanium, problems on, 317 True volume, calculation of, 153 Tungsten, problems on, 324
Reducing agents, equivalent weights

212
of,
Two
indicators, titrations involving
use
of,
199
Reduction, definition Relative error, 2
211
U
Uranium, problems on, 320
Reliability, factors influencing, 1
Reported
percentages, from, 135
calculations
S
Selenium, problems on, 331 Sensitiveness of a balance, 93
Significant figure, definition of, 3 Significant figures, rules governing
Vacuo, conversion to weight
in,
95
Vanadium, problems on, 325 Vapor pressure, correction for, 282

Volhard method, for halides, 244 for manganese, 223 for Silver, 244 Volt, definition of, 130
use
Silicon,
of,
problems on, 324 Silver, problems on, 315 Silver group, problems on, 309
Slide rule, use of, 14 Smith, J. L. method, for alkalies, 120
Volume, of reagent, calculation

113
relationship to normality, 166 relationship to percentage, 180
of,
Sodium, problems on, 313
Sodium carbonate, titration of, 199 Sodium thiosulfate, equivalent weight

of,
Volume
ratios,
37
of,
Volumetric analysis, divisions
158
214
Solubility product, 60 Solutions, adjusting to desired nor-
W
Water, ion product constant problems on, 313
of,
47
mality, 163 methods of standardizing, 168
Water vapor, correction

Watt, definition of, 130
of,
for,
282
normality of mixed, 161

Specific
conductance,
definition
266
Specific electrode potentials,
76
Weight, conversion to vacuo, 95 Weights, calibration of, 97 Williams method, for manganese, 223
for, 296 309 problems on, Stannous chloride, equivalent weight of, 213 Strontium, problems on, 316
Specific
elements, methods
Z
Zinc, problems on, 321
Zirconium, problems on, 320

Calculations of Analytical Chemistry

Uploaded by

Copyright:

Available Formats

Calculations of Analytical Chemistry

Uploaded by

Document Information

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Calculations of Analytical Chemistry

Uploaded by

Copyright:

Available Formats

What is the book about?

What is the book about?

What topics are covered in the book?

What topics are covered in the book?

> W s^

OU_1 58434 >m XW >

OSMANIA UNIVERSITY LIBRARY,

INTERNATIONAL CHEMICAL SERIES

CALCULATIONS OF ANALYTICAL CHEMISTRY

SELECTION OF TITLES FROM THE

INTERNATIONAL CHEMICAL SERIES

Demonstrations Chemistry Aithur and Smith

Mittard Physical Chemistry for Colleges

Semixuicro Qualitative Analysis

Morton in Organic Technique Laboratory Chemistry The Chemistry of Ileterocyclic

Laboratory Course in General Chemistry

Mathematical Preparation Chemistry

Elementary Qualitative Analysis Theoretical Qualitative Analysis

Daniels, Mathews, and Williams

Experimental Physical Chemistry

Robinson and Gilliland

Experimental and Theoretical Electrochemistry Eastman and Rollefson Physical Chemistry

Schoch, Felting, and Watt

and Biffen Commercial Methods

and Eyring Rate Processes

Technical Methods of Analysis

Hamilton and Simpson

Dunn, and McCullough Experiments in General Chemistry

Henderson and Fernelius

Experiments in General Chemistry and Qualitative Analysis

Chemistry of Engineering Materials Long and Anderson Chemical Calculations

William* and Homerberg Principles of Metallography

CALCULATIONS OF ANALYTICAL CHEMISTRY

Professor of Analytical Chemistry Massachusetts Institute of Technology

and STEPHEN G. SIMPSON, PH.D.

Fourth Edition Third Impression

McGRAW-HILL BOOK COMPANY, NEW YORK AND LONDON

CALCULATIONS OF ANALYTICAL CHEMISTRY

Calculations of Quantitative Chemical Analysis

COPYRIGHT, 1922, 1927, 1939, 1947, BY THE

McGRAw-HiLL BOOK COMPANY,

PRINTED IN THE UNITED STATES OF AMERICA

w, any form without permission of

greater part of the book

of quantitative analysis. amperometric titrations

Factors Influencing the Reliability of Analytical Results

Deviation Measures as a Means of Expressing Reliability

Rules Governing the Use of Significant Figures in Chemical

Conventions Regarding the Solution of Numerical Problems Problems 1-18

Purpose of Chemical Equations Types of Chemical Equations

11. lonization of Acids, Bases,

Equations Not Involving Oxidation

Oxidation and Reduction Equations

CALCULATIONS BASED ON FORMULAS AND EQUATIONS

Mathematical Significance Formula Weights

Mathematical Significance of a Chemical Equation Problems 44-70

CHAPTER IV. CONCENTRATION OF SOLUTIONS

Grains per Unit Volume

24. Equivalent 25. Simple

Calculations Involving Equivalents,