An Introductory Course of Quantitative Chemical Analysis, Henry P. Talbot [chrome ebook reader txt] 📗

cubic centimeters of CO_{2} obtained by treating with acid, measured dry at 18°C. and 763 mm., shall equal the percentage of CaO in the sample?

!Answer!: 0.2359 gram.

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?

!Answers!: 55.06 cc.; 25%.

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.)

!Answer!: 1.335 grams.

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.

!Answer!: 2.48 cc.

(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.

!Answer!: 0.83 cc.

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

!Answer!: 0.0152 gram.

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

!Answer!: 11.6116 grams.

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

!Answer!: 0.5705 gram.

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

!Answer!: 0.6573 gram.

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?

!Answer!: 9.07 cc.

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.

!Answer!: 0.992 gram; 1.97 cc.

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?

!Answer!: 21.30%.

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.

!Answer!: 6.13%.

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?

!Answers!: 1.135 grams; 0.4715 gram.

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 18°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