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
Science
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
[141] The formation of an ammonium salt in the latter action still
further reduces the concentration of the hydroxide-ion (Chapter VI)
and retards the action; but the solution, in equal measure, becomes
less active toward the indicator, phenolphthaleïn (p. 114). The
experiment shows, therefore, rather fairly, the relative activities
of the bases. The exact work of Arrhenius included consideration of
the effect of the ammonium salt, and the clearing up of the mystery
of this effect (p. 114) formed one of the greatest triumphs of his
theory.
[142] Arrhenius, ‹Electro-chemistry›, p. 184 (1902). A second
accelerative factor, the so-called "salt effect" (Chap. VI, ‹q.
v.›), is more pronounced in the case of 0.1 molar hydrochloric acid
than in that of 0.1 molar acetic acid, as the result of which the
activity of the hydrochloric acid should be increased about ten
per cent; the ratio, therefore, of the speeds of reaction, both
the degrees of ionization of the acids and the "salt effect" being
considered, should be approximately 83 : 1, whereas the ratio found
by experiment is 79 : 1.
[143] ‹Vide› also A. A. Noyes, ‹Report of the Congress of Arts and
Science›, Vol. «IV», p. 311 (1904).
[144] Haber, ‹Z. für Elektrochem.›, «10», 775 (1904); see Chapter
XII.
[145] This is, essentially, the old Berzelius view of chemical
action.
[146] ‹Vide›, for instance, Stieglitz, ‹Report of the Congress
of Arts and Sciences›, St. Louis, «IV», 276 (1904); W. A. Noyes,
‹Ibid.›, 285; Nef, ‹J. Am. Chem. Soc.›, «30», 645 (1908). For the
application of the electron theory to organic compounds, see Falk
and Nelson, ‹School of Mines Quarterly›, «30», 179, and ‹J. Am.
Chem. Soc.›, «32», 1637 (1910). (‹Cf.› also Chapter XV.)
[147] ‹J. Phys. Chem.›, «6», 1 (1902), and other papers in the same
Journal.
[148] ‹Cf.› Patten, ‹ibid.›, «7», 168 (1903), and Falk and
Waters, ‹Am. Chem. J.›, «31», 398 (1903). According to the latter
investigators, the evolution of hydrogen is slow and weak.
[149] Patten, ‹loc. cit.›
[150] Students will not be capable of following the argument given
in the succeeding passages and would better omit this part until
Chapter XV has been studied.
[151] Kablukoff, Z. ‹phys. Chem.›, «4», 430 (1889). See also
Nernst, ‹Theoretical Chemistry›, p. 373.
[152] In view of the low order of accuracy of the data, and of the
approximate method of calculation, this result is only qualitative,
but even with an error of 10^2 to 10^4 the argument in the text
would hold.
[153] For hydrogen under atmospheric pressure, the equilibrium
ratio, [Zn^{2+}] / [H^{+}]^2, is, approximately, 10^{27}.
[154] ‹Vide› Sackur, ‹Z. Elektrochem.›, «11», 387 (1905).
Kahlenberg holds a different view; ‹ibid›.
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