The Elements of Qualitative Chemical Analysis, vol. 1, parts 1 and 2.: With Special Consideration of the Application of the Laws of Equilibrium and of the Modern Theories of Solution.Stieglitz, Julius
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The Elements of Qualitative Chemical Analysis, vol. 1, parts 1 and 2.: With Special Consideration of the Application of the Laws of Equilibrium and of the Modern Theories of Solution.
Stieglitz, Julius
Chemistry, Analytic -- Qualitative
[331] From equation (I) we obtain directly, by the application
of a simple mathematical transformation, that [NH_{3}] +
[NH_{4}OH] / [NH_{4}OH] = ‹k›_{NH_{3}} + 1 = ‹k′›, and, therefore,
[NH_{4}OH] = [NH_{3}] + [NH_{4}OH] / ‹k′›. Inserting this value
for [NH_{4}OH] in equation (II) and transferring ‹k′›, we have
[NH_{4}^{+}] × [HO^{−}] / ([NH_{3}] + [NH_{4}OH]) = ‹k›_{base} /
‹k′› = K.
[332] Water of crystallization, found in many of the precipitates
used in qualitative analysis, will, as a rule, be indicated only
in the formulas used in Part III, in the study of the reactions of
ions.
[333] See Part III as to the method of vaporizing magnesium.
[334] ‹Cf.› Findlay, ‹Z. phys. Chem.›, «34», 409 (1900).
[335] The solubility of barium sulphate at 18°, according to the
table, is 0.0023 / 233, or 1E−5 mole per liter, and the salt may be
considered completely ionized at this dilution.
[336] The solubility (see the table) is 0.114 / 183.6, or 6.2E−4
mole per liter, 84% of which is ionized (according to conductivity
determinations, Kohlrausch and Holborn, ‹loc. cit.›, p. 200). Hence
[Sr^{2+}] = [SO_{4}^{2−}] = 0.00062 × 0.84 = 0.0005.
[337] To establish equilibrium, prolonged "digesting" is sometimes
required. Double salts, solid solutions and mechanical enclosures
are liable to interfere with the completeness of such separations
by fractional precipitation. Resolution and reprecipitation will
then usually effect a sufficiently accurate separation for most
purposes. On account of the possibility of such complications, the
conditions for a successful separation, within limits such as those
described in the text, must in all cases be investigated.
[338] See the table at the end of Part IV.
[339] The salt may be considered completely ionized at this
dilution. Each molecule of silver chromate forms two silver
ions when it is ionized. See p. 141 in regard to the form the
solubility-product takes in the case of a salt of this type.
[340] The complication, resulting from the hydrolysis of the
chromate, is not included in this calculation.
[341] ‹Cf.› Findlay, ‹loc. cit.›
[342] Even Guldberg and Waage considered the ‹active› mass
to be the fundamental factor and simply considered the total
concentrations to be proportional to the "active masses," since
they had no means of determining the proportion of "active"
substances in the total concentrations.
[343] See Nernst, ‹Theoretical Chemistry›, p. 533, for a fuller
discussion of the relations between the new and the old views on
this subject.
[344] Dietrich and Wöhler, ‹Z. anorg. Chem.›, «34», 194 (1903).
[345] On account of the formation of an ammonium salt in the
reaction.
[346] Loven, ‹Z. Anorg. Chem.›, «11», 404 (1896); Herz and Muks,
‹ibid.›, «38», 138 (1904).
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