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
The equilibrium constant of the complex ion is, then, the ratio of
the velocity constants of its decomposition and formation (see p.
94). Now, the ‹velocity constant›, K_{Formation}, represents the
concentration, in moles, of the complex ion [Ag(CN)_{3}^{2−}],that
is formed in unit time from unit concentrations of its components
Ag^{+} and CN^{−}, and it may be considered as the ‹reciprocal›
of a ‹time constant›, T_{Formation}, the ‹time› required ‹to form
unit concentration› of the complex ion, while the components are
maintained at unit concentration. The analogous reciprocal relation
holds for the velocity constant, K_{Decomposition}, and a time
constant, T_{Decomposition}. The equilibrium equation, therefore,
expresses also the following relations:[468] [p234]
[Ag^{+}] × [CN^{−}]^3 / [Ag(CN)_{3}^{2−}] =
T_{Formation} / T_{Decomposition} = 1 / 10^{22}.
In words, the time required for the spontaneous decomposition of one
mole of the complex is 10^{22} times as long as the time required
to form one mole of the complex, from uniformly unit concentrations
of the components. If the concentration of silver-ion is reduced
to 1 / 10^{22} and the concentrations of the cyanide-ion and the
complex ion are maintained at 1, the formation of the complex takes
place 10^{22} times as slowly as when [Ag^{+}] = 1, and a condition
of equilibrium is produced, the time required to decompose and to
form the same amount of the complex being now equal.
This ‹relation› of ‹time constants› may be used to obtain some idea
of the consequences of assuming certain limiting values for one or
the other, the ratio being maintained at the value 1 / 10^{22}. If
the time constant T_{Formation} for the ‹formation of the complex›
be taken as one ten-thousandth of a second,[469] then, according
to Haber, a molar solution of potassium argenticyanide would not
be able to form in thousands of years sufficient silver ions to be
discovered by any direct test, a result which is not compatible with
the precipitation of silver sulphide and of metallic silver in a few
minutes, since silver ions could not be ‹supplied rapidly enough›.
It is evident, thus, that the ratio 1 / 10^{22} must indicate an
exceedingly small value for T_{Formation}, if only silver ions form
silver sulphide and silver.
Public-domain text, read in full here on John Shaqi.
Reviews
Reviews
No reviews yet
Be the first to share your thoughts on this work.
Elsewhere in the archive
Join the Discussion
Join the discussion
Sign in to leave a comment or review.
Sign InorCreate an account