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
where ‹k›_{1} is some number. Now, if the concentration of one of
the components, ‹e.g.› ‹A›, should be doubled, then the chances
for collision and for action between molecules of ‹A› and ‹B› will
be twice as great as before and the velocity of the action will be
doubled. If only one-tenth of the concentration of ‹A› (one-tenth
mole) is used, the velocity will only be one-tenth as great as
originally, and, in general terms, if [‹A›] moles of ‹A› are used per
liter, the ‹velocity of the change will be proportional to› [‹A›],
‹and equal to› ‹k›_{1} × [‹A›]. If the concentration of the other
reacting component, ‹B›, is now doubled, the chances for action are
again doubled, and, in general, the velocity of the action will be
proportional also to the concentration [p093] [‹B›] of the second
reacting substance. For the velocity, ‹v›_{1} of the action for any
concentrations, [‹A›] and [‹B›], of ‹A› and ‹B› at any moment at a
given temperature, we have
‹v›_{1} = ‹k›_{1} × [‹A›] × [‹B›].
Hence, if by the symbols [‹A›] and [‹B›] the concentrations at any
given moment are represented, we may say that the velocity of the
formation of ‹C› and ‹D› at that moment[169] ‹is proportional to
the product of the concentrations of› ‹A› ‹and› ‹B›, ‹and to some
constant›, which is characteristic of the interaction of ‹A› and ‹B›.
The validity of this conclusion has been fully verified by
‹experiment›.[170] The case is an instance of the ‹law of mass
action, which states that in chemical changes the velocity
of the action is proportional at any moment to the molecular
concentrations›[171] ‹of the reacting components, and to a constant,
which is characteristic of the chemical nature of the reacting
components› (and of the temperature).
If we start with the reversed action
‹A› + ‹B› ← ‹C› + ‹D›,
the relation may be developed in the same way. Thus the two
substances ‹C› and ‹D› will react upon each other, at the given
temperature, with a velocity proportional to a constant, ‹k›_{2},
and, at any given moment, proportional also to their respective
concentrations at that moment:
‹v›_{2} = ‹k›_{2} × [‹C›] × [‹D›].
Equilibrium will be reached when the substances ‹A› and ‹B› are
formed at any moment from ‹C› and ‹D› just as rapidly as they are
used up to produce ‹C› and ‹D›, and ‹vice versa›. Such is the case,
[p094] when ‹the velocities of the two opposite reactions are equal
to each other›. For the condition of equilibrium, then, ‹v›_{1} must
be equal to ‹v›_{2} and therefore
‹k›_{1} × [‹A›] × [‹B›] = ‹k›_{2} × [‹C›] × [‹D›]
or
[‹A›] × [‹B›] / ([‹C›] × [‹D›]) = ‹k›_{2} / ‹k›_{1} =
‹k›_{equilibrium}.
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