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 mathematical equations give us a measure of the extent to
which water must decompose or ‹hydrolyze› the salt in question, as
expressed in the chemical equations (p. 180). The ‹extent› of the
hydrolysis, clearly, depends on the relative ionization constants of
hydrocyanic acid and water, the ‹two acids competing for the base›.
From the known values of the constants, one may calculate that,
at 25°, in a solution of 6.5 grams potassium cyanide in a liter
(0.1 molar), almost 1.3% of the cyanide is decomposed into
potassium hydroxide and hydrocyanic acid. Since every molecule
of hydrolyzed salt forms one molecule of [p183] the hydroxide
and one molecule of the acid, we may put [KOH] = [HCN] = ‹x› and
[KCN] = 0.1 − ‹x›. The ionization constant, K_{HCN} = 7E−10,
and K_{HOH} = 1.2E−14, at 25°. Inserting these values into the
equation [KCN] / ([HCN] × [KOH]) = K_{HCN} / K_{HOH} we have:
(0.1 − ‹x›) / ‹x›^2 = 7E−10 / 1.2E−14. Here ‹x› = 0.0013. This is
1.3% of the 0.1 mole of cyanide used.
One may convince himself, as follows, that the constants are
satisfied when the decomposition of the cyanide has proceeded to
this point: the degrees of ionization of the potassium cyanide and
potassium hydroxide, α_{1} and α_{2}, may be taken as 85% (the
same as the degree of ionization of the similar electrolyte KCl
in 0.1 molar solution). Then [HO^{−}] = 0.85 × 0.0013 = 0.0011;
[CN^{−}] = 0.85 × (0.1 − 0.0013) = 0.083; [H^{+}] = 1.2E−14 /
[HO^{−}] = 1.1E−11. For [H^{+}] × [CN^{−}] / [HCN] we have then:
(1.1E−11 × 0.083) / (0.0013) or 7E−10, the value for the ionization
constant of hydrocyanic acid. It should be noted that, whereas in
pure water at 25° [H^{+}] = [HO^{−}] = √(1.2E−14) = 1.1E−7, in the
solution under consideration [HO^{−}] has increased to the value
0.0011 and [H^{+}] is only 1.1E−11.
The relation developed for the ‹hydrolysis› of potassium cyanide
is a general one, holding for the hydrolysis of salts, of the
type MeX, of a weak acid with a strong base. It may be expressed
in general as follows: for the hydrolysis of a salt according to
MeX + HOH ⇄ MeOH + HX, where HX is a weak acid and MEOH a strong
base, we have:[369]
[Salt] / ([Acid] × [Base]) = K_{Acid} / K_{HOH}.
It is clear, from the equation, that the weaker the acid of the salt
(measured by the ionization constant K_{Acid}, the numerator on the
right), the more will water, ‹ceteris paribus›, be able to drive it
out of its salt and form its own salt, ‹the base› (the smaller the
numerator on the right, the larger must be the denominator on the
left).
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