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
On the other hand, solution of an ionogen is evidently favored and
its precipitation rendered more difficult, if we suppress one (or
both) of its ions. Thus barium phosphate, calcium carbonate, silver
borate, and many salts of weak acids, that are very difficultly
soluble in water, are quite easily soluble in strong acids, which
suppress the anions by converting them into little ionized acids.
When a precipitate is dissolved by the addition of a reagent, such as
an acid, an alkali, ammonia, ammonium sulphide—chemical solvents most
frequently used in analytical work—we may, as a general principle,
consider that the reagent must affect one or both of the ions of
the precipitate in question, suppressing it (or them) and thereby
making solution possible. The problem of determining in what way
the suppression of the ion is effected, must then be faced. Many
occasions to determine such questions[318] will arise. [p153]
We have, therefore, a certain degree of control over the
precipitation and solution of electrolytes, the control depending
upon, and being limited by, the fact that the ‹factors of the product
of ion concentrations are variables›.
On the other hand, we have little control, in a given solvent, over
the question of solution or precipitation as affected by the value
of the ion product ‹constant›, the remaining term in the equation
of the solubility-product for saturated solutions. These constants
cover a very wide range of values for the various salts, which are
most frequently used in analytical work for the precipitation of the
common ions.[319] They are subject to variation with the temperature,
and, as a rule, as most salts are more soluble at higher than at
lower temperatures, the values of the constants increase with the
temperature. For exceedingly difficultly soluble salts, the increase
is commonly of no practical moment in analytical work, when, by an
excess of the precipitant, the ion, which is to be precipitated, can
be precipitated quantitatively; the solubility of the nonionized
salt, that is precipitated, is so minute (see p. 148) in this case,
even at high temperatures, that it is altogether negligible for
ordinary purposes.[320] On the other hand, precipitates are often
used which are not at all extremely insoluble but merely rather
difficultly soluble; they are used in spite of their relatively
slight insolubility because they are the best available forms
for our purposes. Such salts are, for instance, lead chloride,
magnesium-ammonium phosphate, potassium chloroplatinate. When these
are precipitated, not only must the fact that they are appreciably
soluble at ordinary temperature be taken into account, but also the
fact that they are very much more soluble at higher temperatures.
Lead chloride and potassium chloroplatinate are, for instance, quite
soluble in hot water.
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