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
In this way the meaning of the fundamental law of chemical
equilibrium may be developed from the consideration of the velocities
of the reversible actions, such as are involved in all conditions
of equilibrium, and the ‹equilibrium constant represents the ratio
of the velocity constants of the two opposite reactions›. This
conclusion has been fully verified by experiment, the equilibrium
constant being, as a matter of fact, found equal to the ratio of the
velocity constants.[172]
The relations, so far considered, have been those of the simplest
type of reversible reaction. We may now discuss the modifications
required for other types of reaction by the law of equilibrium.
When two molecules of any reacting component take part in a
reaction—for instance, in ‹A› + 2 ‹B› ⇄ ‹C› + ‹D›—‹the concentration
of this component is raised to the second power in the mathematical
expression of the law of equilibrium;› when three molecules of a
component take part, its concentration is raised to the third power,
etc.
For instance, hydrogen iodide is decomposed, reversibly, into
hydrogen and iodine, according to 2 HI ⇄ H_{2} + I_{2}. A condition
of equilibrium is reached, at a given temperature when
[H_{2}] × [I_{2}] / [HI]^2 = K.
At 440°, the results given in the following table were obtained by
Bodenstein. The concentrations are expressed in moles per liter.[173]
The constant is calcuated according to the equation just given.
Analytical errors affect the value of the constant most in the first
and last experiments, as a result of the very small concentrations of
one component, I_{2} or H_{2}.
[p095]
[H_{2}] [I_{2}] [HI] K
0.0268 0.000190 0.0177 (0.016)
0.00986 0.00203 0.0328 0.019
0.00308 0.00783 0.0337 0.021
0.00175 0.0114 0.0315 0.020
0.000653 0.0204 0.0236 0.024
0.000265 0.0242 0.0202 (0.016)
The mechanical significance of the raised powers of the
concentrations of components, two or more molecules of which take
part in a reaction as indicated, will be discussed further on, in
connection with a case of equilibrium between an electrolyte and its
ions (Chapter VI, p. 102).
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