Henry P. Talbot.

# An Introductory Course of Quantitative Chemical Analysis With Explanatory Notes online

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Font size 67. Sulphide sulphur was determined in a sample of reduced barium
sulphate by the evolution method, in which the sulphur was evolved as
hydrogen sulphide and was passed into CdCl_{2} solution, the acidified
precipitate being titrated with iodine and thiosulphate. Sample, 5.076
grams; cc. I_{2} = 20.83; cc. Na_{2}S_{2}O_{3} = 12.37; 43.45 cc.
Na_{2}S_{2}O_{3} = 43.42 cc. I_{2}; 8.06 cc. KMnO_{4} = 44.66 cc.
Na_{2}S_{2}O_{3}; 28.87 cc. KMnO_{4} = 0.2004 gram Na_{2}C_{2}O_{4}.
Calculate the percentage of sulphide sulphur in the sample.

68. What weight of pyrolusite containing 89.21% MnO_{2} will oxidize
the same amount of oxalic acid as 37.12 cc. of a permanganate
solution, of which 1 cc. will liberate 0.0175 gram of I_{2} from KI?

69. A sample of pyrolusite weighs 0.2400 gram and is 92.50% pure
MnO_{2}. The iodine liberated from KI by the manganese dioxide is
sufficient to react with 46.24 cc. of Na_{2}S_{2}O_{3} sol. What is
the normal value of the thiosulphate?

70. In the volumetric analysis of silver coin (90% Ag), using a
0.5000 gram sample, what is the least normal value that a potassium
thiocyanate solution may have and not require more than 50 cc. of
solution in the analysis?

71. A mixture of pure lithium chloride and barium bromide weighing
0.6 gram is treated with 45.15 cubic centimeters of 0.2017 N silver
nitrate, and the excess titrated with 25 cc. of 0.1 N KSCN solution,
using ferric alum as an indicator. Calculate the percentage of bromine
in the sample.

72. A mixture of the chlorides of sodium and potassium from 0.5000
gram of a feldspar weighs 0.1500 gram, and after solution in water
requires 22.71 cc. of 0.1012 N silver nitrate for the precipitation of
the chloride ions. What are the percentages of Na_{2}O and K_{2}O in
the feldspar?

GRAVIMETRIC ANALYSIS

73. Calculate (a) the grams of silver in one gram of silver chloride;
(b) the grams of carbon dioxide liberated by the addition of an excess
of acid to one gram of calcium carbonate; (c) the grams of MgCl_{2}
necessary to precipitate 1 gram of MgNH_{4}PO_{4}.

!Answers!: (a) 0.7526; (b) 0.4397; (c) 0.6940.

74. Calculate the chemical factor for (a) Sn in SnO_{2}; (b) MgO
in Mg_{2}P_{2}O_{7}; (c) P_{2}O_{5} in Mg_{2}P_{2}O_{7}; (d) Fe in
Fe_{2}O_{3}; (e) SO_{4} in BaSO_{4}.

!Answers!: (a) 0.7879; (b) 0.3620; (c) 0.6378; (d) 0.6990; (e) 0.4115.

75. Calculate the log factor for (a) Pb in PbCrO_{4}; (b) Cr_{2}O_{3}
in PbCrO_{4}; (c) Pb in PbO_{2} and (d) CaO in CaC_{2}O_{4}.

!Answers!: (a) 9.8069-10, (b) 9.3713-10; (c) 9.9376-10; (d) 9.6415-10.

76. How many grams of Mn_{3}O_{4} can be obtained from 1 gram of
MnO_{2}?

77. If a sample of silver coin weighing 0.2500 gram gives a
precipitate of AgCl weighing 0.2991 gram, what weight of AgI could
have been obtained from the same weight of sample, and what is the
percentage of silver in the coin?

78. How many cubic centimeters of hydrochloric acid (sp. gr. 1.13
containing 25.75% HCl by weight) are required to exactly neutralize
25 cc. of ammonium hydroxide (sp. gr. .90 containing 28.33% NH_{3} by
weight)?

79. How many cubic centimeters of ammonium hydroxide solution (sp. gr.
0.96 containing 9.91% NH_{3} by weight) are required to precipitate
the aluminium as aluminium hydroxide from a two-gram sample of alum
(KAl(SO_{4})_{2}.12H_{2}O)? What will be the weight of the ignited
precipitate?

80. What volume of nitric acid (sp. gr. 1.05 containing 9.0%
HNO_{3} by weight) is required to oxidize the iron in one gram of
FeSO_{4}.7H_{2}O in the presence of sulphuric acid? 6FeSO_{4} +
2HNO_{3} + 3H_{2}SO_{4} = 3Fe_{2}(SO_{4})_{3} + 2NO + 4H_{2}O.

81. If 0.7530 gram of ferric nitrate (Fe(NO_{3})_{3}.9H_{2}O) is
dissolved in water and 1.37 cc. of HCl (sp. gr. 1.11 containing 21.92%
HCl by weight) is added, how many cubic centimeters of ammonia (sp.
gr. 0.96 containing 9.91% NH_{3} by weight) are required to neutralize
the acid and precipitate the iron as ferric hydroxide?

82. To a suspension of 0.3100 gram of Al(OH)_{3} in water are added
13.00 cc. of aqueous ammonia (sp. gr. 0.90 containing 28.4% NH_{3} by
weight). How many cubic centimeters of sulphuric acid (sp. gr. 1.18
containing 24.7% H_{2}SO_{4} by weight) must be added to the mixture
in order to bring the aluminium into solution?

83. How many cubic centimeters of sulphurous acid (sp. gr. 1.04
containing 75 grams SO_{2} per liter) are required to reduce the
iron in 1 gram of ferric alum (KFe(SO_{4})_{2}.12H_{2}O)?
Fe_{2}(SO_{4})_{3} + SO_{2} + 2H_{2}O = 2FeSO_{4} + 2H_{2}SO_{4}.

84. How many cubic centimeters of a solution of potassium bichromate
containing 26.30 grams of K_{2}Cr_{2}O_{7} per liter must be taken
in order to yield 0.6033 gram of Cr_{2}O_{3} after reduction and
precipitation of the chromium?

K_{2}Cr_{2}O_{7} + 3SO_{2} + H_{2}SO_{4} = K_{2}SO_{4} +
Cr_{2}(SO_{4})_{3} + H_{2}O.

85. How many cubic centimeters of ammonium hydroxide (sp. gr. 0.946
containing 13.88% NH_{3} by weight) are required to precipitate
the iron as Fe(OH)_{3} from a sample of pure
FeSO_{4}.(NH_{4})_{2}SO_{4}.6H_{2}O, which requires 0.34 cc. of nitric
acid (sp. gr. 1.350 containing 55.79% HNO_{3} by weight) for oxidation
of the iron? (See problem No. 80 for reaction.)

86. In the analysis of an iron ore by solution, oxidation and
precipitation of the iron as Fe(OH)_{3}, what weight of sample must be
taken for analysis so that each one hundredth of a gram of the ignited
precipitate of Fe_{2}O_{3} shall represent one tenth of one per cent
of iron?

87. What weight in grams of impure ferrous ammonium sulphate should
be taken for analysis so that the number of centigrams of BaSO_{4}
obtained will represent five times the percentage of sulphur in the
sample?

88. What weight of magnetite must be taken for analysis in order that,
after precipitating and igniting all the iron to Fe_{2}O_{3}, the
percentage of Fe_{2}O_{4} in the sample may be found by multiplying
the weight in grams of the ignited precipitate by 100?

89. After oxidizing the arsenic in 0.5000 gram of pure As_{2}S_{3} to
arsenic acid, it is precipitated with "magnesia mixture" (MgCl_{2} +
2NH_{4}Cl). If exactly 12.6 cc. of the mixture are required, how many
grams of MgCl_{2} per liter does the solution contain? H_{3}AsO_{4} +
MgCl_{2} + 3NH_{4}OH = MgNH_{4}AsO_{4} + 2NH_{4}Cl + 3H_{2}O.

90. A sample is prepared for student analysis by mixing pure apatite
(Ca_{3}(PO_{4})_{2}.CaCl_{2}) with an inert material. If 1 gram of
the sample gives 0.4013 gram of Mg_{2}P_{2}O_{7}, how many cubic
centimeters of ammonium oxalate solution (containing 40 grams of
(NH_{4})_{2}C_{2}O_{4}.H_{2}O per liter) would be required to
precipitate the calcium from the same weight of sample?

91. If 0.6742 gram of a mixture of pure magnesium carbonate and pure
calcium carbonate, when treated with an excess of hydrochloric acid,
yields 0.3117 gram of carbon dioxide, calculate the percentage of
magnesium oxide and of calcium oxide in the sample.

!Answers!: 13.22% MgO; 40.54% CaO. 92. The calcium in a sample of
dolomite weighing 0.9380 gram is precipitated as calcium oxalate and
ignited to calcium oxide. What volume of gas, measured over water
at 20Â°C. and 765 mm. pressure, is given off during ignition, if the
resulting oxide weighs 0.2606 gram? (G.M.V. = 22.4 liters; V.P. water
at 20Â°C. = 17.4 mm.)

93. A limestone is found to contain 93.05% CaCO_{3}, and 5.16 %
MgCO_{3}. Calculate the weight of CaO obtainable from 3 tons of the
limestone, assuming complete conversion to oxide. What weight of
Mg_{2}P_{2}O_{7} could be obtained from a 3-gram sample of the
limestone?

94. A sample of dolomite is analyzed for calcium by precipitating
as the oxalate and igniting the precipitate. The ignited product is
assumed to be CaO and the analyst reports 29.50% Ca in the sample.
Owing to insufficient ignition, the product actually contained 8% of
its weight of CaCO_{3}. What is the correct percentage of calcium in
the sample, and what is the percentage error?

95. What weight of impure calcite (CaCO_{3}) should be taken for
analysis so that the volume in cubic centimeters of CO_{2} obtained by
treating with acid, measured dry at 18Â°C. and 763 mm., shall equal the
percentage of CaO in the sample?

96. How many cubic centimeters of HNO_{3} (sp. gr. 1.13 containing
21.0% HNO_{3} by weight) are required to dissolve 5 grams of brass,
containing 0.61% Pb, 24.39% Zn, and 75% Cu, assuming reduction of the
nitric acid to NO by each constituent? What fraction of this volume of
acid is used for oxidation?

97. What weight of metallic copper will be deposited from a cupric
salt solution by a current of 1.5 amperes during a period of 45
minutes, assuming 100% current efficiency? (1 Faraday = 96,500
coulombs.)

98. In the electrolysis of a 0.8000 gram sample of brass, there is
obtained 0.0030 gram of PbO_{2}, and a deposit of metallic copper
exactly equal in weight to the ignited precipitate of Zn_{2}P_{2}O_{7}
subsequently obtained from the solution. What is the percentage
composition of the brass?

!Answers!: 69.75% Cu; 29.92% Zn; 0.33% Pb.

99. A sample of brass (68.90% Cu; 1.10% Pb and 30.00% Zn) weighing
0.9400 gram is dissolved in nitric acid. The lead is determined by
weighing as PbSO_{4}, the copper by electrolysis and the zinc by
precipitation with (NH_{4})_{2}HPO_{4} in a neutral solution.

(a) Calculate the cubic centimeters of nitric acid (sp. gr. 1.42
containing 69.90% HNO_{3} by weight) required to just dissolve the
brass, assuming reduction to NO.

(b) Calculate the cubic centimeters of sulphuric acid (sp. gr. 1.84
containing 94% H_{2}SO_{4} by weight) to displace the nitric acid.

(c) Calculate the weight of PbSO_{4}.

(d) The clean electrode weighs 10.9640 grams. Calculate the weight
after the copper has been deposited.

(e) Calculate the grams of (NH_{4})_{2}HPO_{4} required to precipitate
the zinc as ZnNH_{4}PO_{4}.

(f) Calculate the weight of ignited Zn_{2}P_{2}O_{7}.

100. If in the analysis of a brass containing 28.00% zinc an error is
made in weighing a 2.5 gram portion by which 0.001 gram too much is
weighed out, what percentage error in the zinc determination would
result? What volume of a solution of sodium hydrogen phosphate,
containing 90 grams of Na_{2}HPO_{4}.12H_{2}O per liter, would be
required to precipitate the zinc as ZnNH_{4}PO_{4} and what weight of
precipitate would be obtained?

!Answers!: (a) 0.04% error; (b) 39.97 cc.; (c) 1.909 grams.

101. A sample of magnesium carbonate, contaminated with SiO_{2} as its
only impurity, weighs 0.5000 gram and loses 0.1000 gram on ignition.
What volume of disodium phosphate solution (containing 90 grams
Na_{2}HPO_{4}.12H_{2}O per liter) will be required to precipitate the
magnesium as magnesium ammonium phosphate?

102. 2.62 cubic centimeters of nitric acid (sp. gr. 1.42 containing
69.80% HNO_{2} by weight) are required to just dissolve a sample
of brass containing 69.27% Cu; 0.05% Pb; 0.07% Fe; and 30.61% Zn.
Assuming the acid used as oxidizing agent was reduced to NO in every
case, calculate the weight of the brass and the cubic centimeters of
acid used as acid.

103. One gram of a mixture of silver chloride and silver bromide is
found to contain 0.6635 gram of silver. What is the percentage of
bromine?

104. A precipitate of silver chloride and silver bromide weighs 0.8132
gram. On heating in a current of chlorine, the silver bromide is
converted to silver chloride, and the mixture loses 0.1450 gram
in weight. Calculate the percentage of chlorine in the original
precipitate.

105. A sample of feldspar weighing 1.000 gram is fused and the silica
determined. The weight of silica is 0.6460 gram. This is fused with 4
grams of sodium carbonate. How many grams of the carbonate actually
combined with the silica in fusion, and what was the loss in weight
due to carbon dioxide during the fusion?

106. A mixture of barium oxide and calcium oxide weighing 2.2120 grams
is transformed into mixed sulphates, weighing 5.023 grams. Calculate
the grams of calcium oxide and barium oxide in the mixture.

!Answers!: 1.824 grams CaO; 0.3877 gram BaO.

APPENDIX

ELECTROLYTIC DISSOCIATION THEORY

The following brief statements concerning the ionic theory and a few
of its applications are intended for reference in connection with the
explanations which are given in the Notes accompanying the various
procedures. The reader who desires a more extended discussion of the
fundamental theory and its uses is referred to such books as Talbot
and Blanchard's !Electrolytic Dissociation Theory! (Macmillan
Company), or Alexander Smith's !Introduction to General Inorganic
Chemistry! (Century Company).

The !electrolytic dissociation theory!, as propounded by Arrhenius in
1887, assumes that acids, bases, and salts (that is, electrolytes)
in aqueous solution are dissociated to a greater or less extent into
!ions!. These ions are assumed to be electrically charged atoms or
groups of atoms, as, for example, H^{+} and Br^{-} from hydrobromic
acid, Na^{+} and OH^{-} from sodium hydroxide, 2NH_{4}^{+} and
SO_{4}^{ - } from ammonium sulphate. The unit charge is that which is
dissociated with a hydrogen ion. Those upon other ions vary in sign
and number according to the chemical character and valence of the
atoms or radicals of which the ions are composed. In any solution the
aggregate of the positive charges upon the positive ions (!cations!)
must always balance the aggregate negative charges upon the negative
ions (!anions!).

It is assumed that the Na^{+} ion, for example, differs from the
sodium atom in behavior because of the very considerable electrical
charge which it carries and which, as just stated, must, in an
electrically neutral solution, be balanced by a corresponding negative
charge on some other ion. When an electric current is passed through a
solution of an electrolyte the ions move with and convey the current,
and when the cations come into contact with the negatively charged
cathode they lose their charges, and the resulting electrically
neutral atoms (or radicals) are liberated as such, or else enter at
once into chemical reaction with the components of the solution.

Two ions of identically the same composition but with different
electrical charges may exhibit widely different properties. For
example, the ion MnO_{4}^{-} from permanganates yields a purple-red
solution and differs in its chemical behavior from the ion
MnO_{4}^{ - } from manganates, the solutions of which are green.

The chemical changes upon which the procedures of analytical chemistry
depend are almost exclusively those in which the reacting substances
are electrolytes, and analytical chemistry is, therefore, essentially
the chemistry of the ions. The percentage dissociation of the same
electrolyte tends to increase with increasing dilution of its
solution, although not in direct proportion. The percentage
dissociation of different electrolytes in solutions of equivalent
concentrations (such, for example, as normal solutions) varies widely,
as is indicated in the following tables, in which approximate figures
are given for tenth-normal solutions at a temperature of about 18Â°C.

ACIDS
=========================================================================
|
SUBSTANCE | PERCENTAGE DISSOCIATION IN
| 0.1 EQUIVALENT SOLUTION
_____________________________________________|___________________________
|
HCl, HBr, HI, HNO_{3} | 90
|
HClO_{3}, HClO_{4}, HMnO_{4} | 90
|
H_{2}SO_{4} H^{+} + HSO_{4}^{-} | 90
|
H_{2}C_{2}O_{4} H^{+} + HC_{2}O_{4}^{-} | 50
|
H_{2}SO_{3} H^{+} + HSO{_}3^{-} | 20
|
H_{3}PO_{4} H^{+} + H_{2}PO_{4}^{-} | 27
|
H_{2}PO_{4}^{-} H^{+} + HPO_{4}^{ - } | 0.2
|
H_{3}AsO_{4} H^{+} + H_{2}AsO_{4}^{-} | 20
|
HF | 9
|
HC_{2}H_{3}O_{2} | 1.4
|
H_{2}CO_{3} H^{+} + HCO_{3}^{-} | 0.12
|
H_{2}S H^{+} + HS^{-} | 0.05
|
HCN | 0.01
|
=========================================================================

BASES
=========================================================================
|
SUBSTANCE | PERCENTAGE DISSOCIATION IN
| 0.1 EQUIVALENT SOLUTION
_____________________________________________|___________________________
|
KOH, NaOH | 86
|
Ba(OH)_{2} | 75
|
NH_{4}OH | 1.4
|
=========================================================================

SALTS
=========================================================================
|
TYPE OF SALT | PERCENTAGE DISSOCIATION IN
| 0.1 EQUIVALENT SOLUTION
_____________________________________________|___________________________
|
R^{+}R^{-} | 86
|
R^{++}(R^{-})_{2} | 72
|
(R^{+})_{2}R^{ - } | 72
|
R^{++}R^{ - } | 45
|
=========================================================================

The percentage dissociation is determined by studying the electrical
conductivity of the solutions and by other physico-chemical methods,
and the following general statements summarize the results:

!Salts!, as a class, are largely dissociated in aqueous solution.

!Acids! yield H^{+} ions in water solution, and the comparative
!strength!, that is, the activity, of acids is proportional to the
concentration of the H^{+} ions and is measured by the percentage
dissociation in solutions of equivalent concentration. The common
mineral acids are largely dissociated and therefore give a relatively
high concentration of H^{+} ions, and are commonly known as "strong
acids." The organic acids, on the other hand, belong generally to the
group of "weak acids."

!Bases! yield OH^{-} ions in water solution, and the comparative
strength of the bases is measured by their relative dissociation in
solutions of equivalent concentration. Ammonium hydroxide is a weak
base, as shown in the table above, while the hydroxides of sodium and
potassium exhibit strongly basic properties.

Ionic reactions are all, to a greater or less degree, !reversible
reactions!. A typical example of an easily reversible reaction is that
representing the changes in ionization which an electrolyte such as
acetic acid undergoes on dilution or concentration of its solutions,
!i.e.!, HC_{2}H_{3}O_{2} H^{+} + C_{2}H_{3}O_{2}^{-}. As was
stated above, the ionization increases with dilution, the reaction
then proceeding from left to right, while concentration of the
solution occasions a partial reassociation of the ions, and the
reaction proceeds from right to left. To understand the principle
underlying these changes it is necessary to consider first the
conditions which prevail when a solution of acetic acid, which has
been stirred until it is of uniform concentration throughout, has come
to a constant temperature. A careful study of such solutions has shown
that there is a definite state of equilibrium between the constituents
of the solution; that is, there is a definite relation between the
undissociated acetic acid and its ions, which is characteristic for
the prevailing conditions. It is not, however, assumed that this is a
condition of static equilibrium, but rather that there is continual
dissociation and association, as represented by the opposing
reactions, the apparent condition of rest resulting from the fact that
the amount of change in one direction during a given time is exactly
equal to that in the opposite direction. A quantitative study of
the amount of undissociated acid, and of H^{+} ions and
C_{2}H_{3}O_{2}^{-} ions actually to be found in a large number of
solutions of acetic acid of varying dilution (assuming them to be in
a condition of equilibrium at a common temperature), has shown that
there is always a definite relation between these three quantities
which may be expressed thus:

(!Conc'n H^{+} x Conc'n C_{2}H_{3}O_{2}^{-})/Conc'n HC_{2}H_{3}O_{2} =
Constant!.

In other words, there is always a definite and constant ratio between
the product of the concentrations of the ions and the concentration of
the undissociated acid when conditions of equilibrium prevail.

It has been found, further, that a similar statement may be made
regarding all reversible reactions, which may be expressed in general
terms thus: The rate of chemical change is proportional to the product
of the concentrations of the substances taking part in the reaction;
or, if conditions of equilibrium are considered in which, as stated,
the rate of change in opposite directions is assumed to be equal, then
the product of the concentrations of the substances entering into
the reaction stands in a constant ratio to the product of the
concentrations of the resulting substances, as given in the expression
above for the solutions of acetic acid. This principle is called the
!Law of Mass Action!.

It should be borne in mind that the expression above for acetic acid
applies to a wide range of dilutions, provided the temperature remains
constant. If the temperature changes the value of the constant changes
somewhat, but is again uniform for different dilutions at that
temperature. The following data are given for temperatures of about
18Â°C.

==========================================================================
| | | |
MOLAL | FRACTION | MOLAL CONCENTRA- | MOLAL CONCENTRA- | VALUE OF
CONCENTRATION | IONIZED | TION OF H^{+} AND| TION OF UNDIS- | CONSTANT
CONSTANT | | ACETATE^{-} IONS | SOCIATED ACID |
______________|__________|__________________|__________________|__________
| | | |

Online LibraryHenry P. TalbotAn Introductory Course of Quantitative Chemical Analysis With Explanatory Notes → online text (page 15 of 17)