Thomson has shown[84] that of the three hydrogen atoms in phosphoric
acid two must be saturated with alkali before the reaction with
phenolphthalein is neutral. Therefore, when the yellow precipitate
is broken up by an alkali, according to the reaction to follow, only
four of the six molecules of ammonium are required to form a neutral
ammonium phosphate as determined by the indicator employed. The
remaining two molecules of ammonium unite with the molybdenum forming
also a salt neutral to the indicator.
Phenolphthalein is preferred because, as has been shown by Long, its
results are reliable in the presence of ammonium salts unless they
be present in large quantity, and if the solution be cold and the
indicator be used in sufficient quantity.[85] To prepare the indicator
for this work, one gram of phenolphthalein is dissolved in 100 cubic
centimeters of sixty percent alcohol. At least one-half of a cubic
centimeter of the solution is used for each titration.
The advantages claimed for the method are its speed and accuracy. Much
time is saved by avoiding the necessity for the removal of the silica
by evaporation. The results of analyses with and without the removal of
the silica are practically identical. When the silica is not removed it
is noticed that the filtrate from the yellow precipitate has a yellow
tint.
The reaction is represented by the following formula:
(NH₄)₆(PO₄)₂(MoO₃)₂₄ + 46KOH = (NH₄)₄(HPO₄)₂ + (NH₄)₂MoO₄
+ 23K₂MoO₄ + 22H₂O.
From this reaction it is seen that the total available acidity of one
molecule of the yellow precipitate titrated against phenolphthalein is
equivalent to twenty-three molecules of potassium hydroxid.
_Calculation of Results._—The standard alkali is of such strength
that one cubic centimeter is equal to one per cent of phosphoric acid
when one gram of material is employed and one-tenth of it taken for
each determination. In a given case one gram of a sample was taken
and one-tenth of the solution used. Fifty cubic centimeters of alkali
were added to the yellow precipitate. It required thirty-two cubic
centimeters of standard alkali to neutralize the excess.
The alkali consumed by the yellow precipitate was 50 - 32 = 18. The
sample therefore contained eighteen per cent of phosphoric acid.
_Comparison with Official Method._—A comparison of the Pemberton
volumetric with the official method of the Association of Agricultural
Chemists has been made by Day and Bryant.[86] The comparisons were made
on samples containing from 1.45 to 37.28 per cent of phosphoric acid
and resulted as follows:
Per cent Per cent
P₂O₅, P₂O₅,
Substance. Official. Pemberton.
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