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
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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
When phosphoric acid is neutralized by one equivalent of a base, say
of sodium hydroxide, the salt formed, sodium dihydrogen-phosphate,
NaH_{2}PO_{4}, yields sodium-ion and dihydrogen-phosphate-ion,
H_{2}PO_{4}^{−}. The latter is ionized ‹somewhat› into H^{+} and
the bivalent hydrogen-phosphate-ion, HPO_{4}^{2−}. The ionization
of the ion H_{2}PO_{4}^{−} is now the chief source of supply of
hydrogen-ion (the further ionization of HPO_{4}^{2−} is practically
negligible here) and it is ionized so little that the solution
of NaH_{2}PO_{4} no longer changes the color of methyl orange
(see EXP. below). The solution is, however, acid to the indicator
phenolphthaleïn, which is much more sensitive to the hydrogen-ion
and will show the presence of much smaller concentrations of it than
will methyl orange. The addition of a second equivalent of sodium
hydroxide to the solution converts NaH_{2}PO_{4} into Na_{2}HPO_{4}.
This salt gives sodium-ion and the hydrogen-phosphate-ion
HPO_{4}^{2−}, which, in turn, is ionized only very slightly,
producing phosphate-ion PO_{4}^{3−}, and again hydrogen-ion.
The ionization of HPO_{4}^{2−} is so slight, however, and the
concentration of the hydrogen-ion, therefore, so minute, that
the solution does not react acid even to the sensitive indicator
phenolphthaleïn.
EXP. Methyl orange (very little) is added to 10 c.c. of a 0.1
molar solution of phosphoric acid and 10 c.c. of 0.1 molar sodium
hydroxide solution is added to the mixture; the color will be found
to change from the acid to the neutral tint just as the last drop or
two of the alkali are added. Phenolphthaleïn is then added to the
mixture and 10 c.c. more of the 0.1 molar sodium hydroxide solution
are required to change the color of the mixture to a pronounced pink
(alkaline) tint.
Even sulphuric acid, although its two hydrogen atoms are ionized
very easily, making sulphuric acid a strong acid, shows a difference
in the ease of ionization of the two hydrogen atoms. Since
ionization, in general, is favored by dilution, we find that in
the case of such a strong acid the difference is most marked in
more concentrated solutions, the smaller amount of water starting
the ionization in the more favored direction and producing first,
chiefly, hydrogen-sulphate ions, HSO_{4}^{−}. When the solution
is diluted, the hydrogen-sulphate ions are to a very considerable
extent dissociated into sulphate ions and hydrogen ions. The
described change in ionization can be roughly followed with the aid
of an insoluble sulphate like barium sulphate. Barium sulphate,
while very insoluble in water, dissolves in rather strong sulphuric
acid to form the acid sulphate, Ba(HSO_{4})_{2}, the SO_{4}^{2−}
ion of the sulphate being more or less suppressed by uniting with
hydrogen-ion. We have the action
BaSO_{4} ⇄ Ba^{2+} + SO_{4}^{2−} and
Ba^{2+} + SO_{4}^{2−} + H^{+} + HSO_{4}^{−} ⇄ Ba^{2+} + 2 HSO_{4}^{−}.
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