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 fact that ammonium salts prevent the precipitation of magnesium
hydroxide was formerly explained as being due to the formation of
"double salts," such as MgCl_{2},NH_{4}Cl. It is true that such
double salts exist, but, if their formation should prevent the
precipitation of magnesium hydroxide, possibly by including the
magnesium as part of a negative ion or radical,[347] MgCl_{3}, then
the corresponding double salts of magnesium chloride with potassium
and sodium chloride (‹e.g.› MgCl_{2},KCl), which are just as stable
as the ammonium salts, should show the same behavior; but, as a
matter of fact, the addition of potassium chloride does not interfere
with the precipitation of the hydroxide by either [p169] potassium
hydroxide or ammonium hydroxide (‹exp.›). So the explanation is
untenable. Obviously, a ‹specific interference of ammonium salts
with the precipitating power of ammonium hydroxide is involved›.
But that is exactly what the law of chemical equilibrium, applied
to the ionization of ammonium hydroxide, would demand: As a weak
base, which is little ionized in pure aqueous solutions, it is ‹very
much weaker as a base, produces a far smaller concentration of the
hydroxide-ion, when readily ionizable salts of ammonium are added to
the solution›,[348] and the precipitation of magnesium hydroxide, and
of metal hydroxides in general, depends on the concentration of the
hydroxide-ion, which is a factor in the solubility-products of bases.
The precipitation of magnesium hydroxide, in particular, depends
on the relation of the product [Mg^{2+}] × [HO^{−}]^2 to the
solubility-product constant of magnesium hydroxide. For the
saturated aqueous solution, the product [Mg^{2+}] × [HO^{−}]^2 is
equal to the solubility-product constant, and from the solubility
of magnesium hydroxide (see the table) the value of the constant is
found to be 15E−12 at 18°. The concentration of magnesium-ion is
0.000,154 in this solution. In a 0.1 molar solution of magnesium
sulphate, which is ionized to the extent of 37.3%, the concentration
of magnesium-ion is 0.0373, and it would require a concentration
‹greater› than 2E−5 of hydroxide-ion to precipitate any magnesium
hydroxide.[349] Now, the concentration of the hydroxide-ion, in an
ammoniacal solution, can easily be reduced far below this value
by the addition of ammonium chloride, nitrate, sulphate or other
readily ionizable ammonium salt to the solution, and then magnesium
hydroxide will ‹not› be precipitated.
In solutions of ammonium hydroxide the concentration of hydroxide
ion for 18° is found from the relation [NH_{4}^{+}] × [HO^{−}] :
([NH_{4}OH] + [NH_{3}]) = 18E−6 (p. 161). (1) For ammonium
hydroxide, for instance in 0.2 molar solution, and in the absence
of any ammonium salt, [HO^{−}] = [NH_{4}^{+}] = 0.0019.[350] This
concentration of the hydroxide-ion should be more than sufficient
to ‹precipitate› magnesium hydroxide in a 0.1 molar solution of the
sulphate.[351]
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