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
[79] The copper electrodes are polarized by the formation of
hydrogen on the cathode, but, in the course of a few seconds, the
current becomes rather constant and is then read. The polarization
may be considered as simply reducing the potential of the cell, and
since, within the range of concentrations of acid used,—4-molar
to 1/8-molar—the polarization current does not vary markedly,
as compared with the potential of the storage cell, the total
potential used through the series of dilutions may be considered
sufficiently constant for the purposes of the experiment. Readings
are made three or four seconds after each dilution, when the
polarization has been fully established. Polarization may be
entirely avoided by the use of a silver nitrate solution and silver
electrodes or of a cupric salt solution and copper electrodes
(Noyes and Blanchard). Hydrochloric acid is used here in order
to carry the discussion in the text as far as possible with this
typical ionogen. If one takes care to make readings as described,
the result is quite satisfactory, as is shown by the comparison
of the ratios of the readings with the ratios calculated from the
known conductivities of the various dilutions (see table below).
[80] Current = (Potential Difference) / Resistance, or
Current = (Potential Difference) × Conductivity. For a ‹constant
potential difference›, then, Current ~ Conductivity.
[81] The ‹specific conductivity› of a solution (commonly designated
by κ) is the conductivity of a cube of 1 cm. edge; the ‹molecular
conductivity› is the conductivity of a mole of the electrolyte; the
‹equivalent conductivity› (designated by Λ) is the conductivity
of a ‹gram-equivalent› of the electrolyte. Λ = κ × ‹v›, where
‹v› is the volume, expressed in cubic centimeters, containing
the gram-equivalent. For instance, the resistance of 0.1 molar
hydrochloric acid in a cube of 1 cm. edge is 28.5 ohms and its
conductivity (κ) therefore 1 / 28.5 or 0.0351 reciprocal ohms.
Since 10 liters or 10,000 c.c. of 0.1-molar hydrochloric acid is
the volume (‹v›) containing one mole of the acid (the molar and the
equivalent conductivities, for a monobasic acid being the same)
Λ = 0.0351 × 10,000, or 351.
[82] Kohlrausch and Holborn, p. 200.
[83] Cf. Kahlenberg, ‹Transactions of the Faraday Society›, «1», 42
(1905).
[84] Clausius, ‹Poggendorf's Ann.›, «101», 347 (1857) («Stud.»).
His theory replaced the older one of Grotthuss.
[85] ‹Phil. Mag.›, «5», 729 (1903), and‹ Transactions of the
Faraday Society›, «1», 55, (1905).
[86] ‹Vide›, Hudson, ‹J. Am. Chem. Soc.›, «31», 1136 (1909), for a
recent summary of results.
[87] ‹Lectures on Physical Chemistry›, «1», p. 131.
[88] ‹Vide› A. A. Noyes and Blanchard, ‹J. Am. Chem. Soc.›, «22»,
726 (1900).
[89] The concentrations are figurative, but may be taken to
represent actual concentrations, such as 0.015 molar, etc.
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