d by the fact that oxalic
acid is a stronger acid than acetic acid; when, therefore, the oxalate
is brought into contact with the latter there is almost no tendency to
diminish the concentration of C_{2}O_{4}^{--} ions by the formation of
an acid less dissociated than the acetic acid itself, and practically
no solvent action ensues. When a strong mineral acid is present,
however, the ionization of the oxalic acid is much reduced by the high
concentration of the H^{+} ions from the strong acid, the formation
of the undissociated acid lessens the concentration of the
C_{2}O_{4}^{--} ions in solution, more of the oxalate passes into
solution to re-establish equilibrium, and this process repeats itself
until all is dissolved.
The oxalate is immediately reprecipitated from such a solution on the
addition of OH^{-} ions, which, by uniting with the H^{+} ions of the
acids (both the mineral acid and the oxalic acid) to form water, leave
the Ca^{++} and C_{2}O_{4}^{--} ions in the solution to recombine to
form [CaC_{2}O_{4}], which is precipitated in the absence of the
H^{+} ions. It is well at this point to add a small excess of
C_{2}O_{4}^{--} ions in the form of ammonium oxalate to decrease the
solubility of the precipitate.
The oxalate precipitate consists mainly of CaC_{2}O_{4}.H_{2}O when
thrown down.]
[Note 5: The small quantity of ammonium oxalate solution is added
before the second precipitation of the calcium oxalate to insure
the presence of a slight excess of the reagent, which promotes the
separation of the calcium compound.]
[Note 6: On ignition the calcium oxalate loses carbon dioxide and
carbon monoxide, leaving calcium oxide:
CaC_{2}O_{4}.H_{2}O --> CaO + CO_{2} + CO + H_{2}O.
For small weights of the oxalate (0.6 gram or less) this reaction may
be brought about in a platinum crucible at the highest temperature of
a Tirrill burner, but it is well to ignite larger quantities than this
over the blast lamp until the weight is constant.]
[Note 7: The heat required to burn the filter, and that subsequently
applied as described, will convert most of the calcium oxalate to
calcium carbonate, which is changed to sulphate by the sulphuric acid.
The reactions involved are
CaC_{2}O_{4} --> CaCO_{3} + CO,
CaCO_{3} + H_{2}SO_{4} --> CaSO_{4} + H_{2}O + CO_{2}.
If a porcelain crucible is employed for ignition, this conversion to
sulphate is to be preferred, as a complete conversion to oxide is
difficult
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