An Introductory Course of Quantitative Chemical Analysis: With Explanatory NotesTalbot, Henry Paul
Science
An Introductory Course of Quantitative Chemical Analysis: With Explanatory Notes
Talbot, Henry Paul
Chemistry, Analytic -- Quantitative
Comparison of this equation with that on page 30 will make it plain
that hydrolysis is just the reverse of neutralization and must,
accordingly, interfere with it. Salts of methyl orange with weak acids
are so far hydrolyzed that the end-point is uncertain, and methyl
orange cannot be used in the titration of such acids, while with
the very weak acids, such as carbonic acid or hydrogen sulphide
(hydrosulphuric acid), the salts formed with methyl orange are, in
effect, completely hydrolyzed (i.e., no neutralization occurs), and
methyl orange is accordingly scarcely affected by these acids. This
explains its usefulness, as referred to later, for the titration of
strong acids, such as hydrochloric acid, even in the presence of
carbonates or sulphides in solution.
Phenolphthalein, on the other hand, should be, as it is, the best of
the common indicators for use with weak acids. For, since it is
itself a weak acid, it is very little dissociated, and its nearly
undissociated, colorless molecules are promptly formed as soon as
there is any free acid (that is, free H^{+} ions) in the solution.
This indicator cannot, however, be successfully used with weak bases,
even ammonium hydroxide; for, since it is weak acid, the salts
which it forms with weak alkalies are easily hydrolyzed, and as a
consequence of this hydrolysis the change of color is not sharp.
This indicator can, however, be successfully used with strong bases,
because the salts which it forms with such bases are much less
hydrolyzed and because the excess of OH^{-} ions from these bases also
diminishes the hydrolytic action of water.
This indicator is affected by even so weak an acid as carbonic acid,
which must be removed by boiling the solution before titration. It is
the indicator most generally employed for the titration of organic
acids.
In general, it may be stated that when a strong acid, such as
hydrochloric, sulphuric or nitric acid, is titrated against a strong
base, such as sodium hydroxide, potassium hydroxide, or barium
hydroxide, any of these indicators may be used, since very little
hydrolysis ensues. It has been noted above that the color change does
not occur exactly at theoretical neutrality, from which it follows
that no two indicators will show exactly the same end-point when acids
and alkalis are brought together. It is plain, therefore, that the
same indicator must be employed for both standardization and analysis,
and that, if this is done, accurate results are obtainable.
The following table (Note 1) illustrates the variations in the volume
of an alkali solution (tenth-normal sodium hydroxide) required to
produce an alkaline end-point when run into 10 cc. of tenth-normal
sulphuric acid, diluted with 50 cc. of water, using five drops of each
of the different indicator solutions.
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