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Determination of Calcium as

Oxalate.
By gravimetric method
Discussion.
 The calcium is precipitated
as calcium oxalate CaC2O4.H2O by treating
a hot hydrochloric acid solution
with ammonium oxalate, and slowly
neutralizing with aqueous ammonia
solution.
The precipitate is washed with dilute
ammonium oxalate solution
Weighed in one of the following forms

1. As CaC2O4.H2O by drying at 100-105 OC for


1-2 hours.
 This method is not recommended for
accurate work, because of the hygroscopic
nature of the oxalate and the difficulty of
removing the CO-precipitated ammonium
oxalate at this low temperature. The results
are usually 0.5-1 per cent high.
2. As CaCO3, by heating at 475-525 OC
 Inan electric muffle furnace.
• This is the most satisfactory method, since
calcium carbonate is non-hygroscopic.
CaC2O4(s) CaCO3(s) + CO(g)
3. As CaO by igniting at 1200 OC.
• This method is widely used, but the
resulting calcium oxide has a
comparatively small relative molecular
mass and is hygroscopic; precautions
must therefore be taken to prevent
absorption of moisture (and of carbon
dioxide).
CaCO3(s) CaO(s) + CO2(g)
 Calcium oxalate monohydrate has a
solubility of 0.0067 g and 0.0140 g/L at
25 O and 95 OC respectively.
 The solubility is less in neutral solutions
containing moderate concentrations of
ammonium oxalate owing to the common-
ion effect hence a dilute solution of
ammonium oxalate is employed as thewash
liquid in the gravimetric determination.
Procedure.
 Weigh out accurately sufficient of the
sample to contain 0.2 g of calcium into a
500mL beaker covered with a clock glass
and provided with a stirring rod.
 Add l0 mL of water, followed by about 15
mL of dilute hydrochloric acid (1 : 1).
 Heat the mixture until the solid has
dissolved, and boil gently for several
minutes in order to expel carbon dioxide.
 Rinse down the sides of the beaker and
the clockglass, and dilute to 200 mL: add
2 drops of methyl red indicator. Heat the
solution to boiling, and add very slowly a
warm olution of 2.0 g of ammonium
oxalate in 50 mL of water
 Add to the resultant solution (about 80 OC)
filtered dilute ammonia solution (1 : 1)
drop wise and with stirring until the mixture
is neutral or faintly alkaline (color change
from red to yellow).
 Allow the solution to stand without further
heating for at least an hour.
 Afterthe precipitate has settled, test the
solution for complete precipitation with a
few drops of ammonium oxalate solution.
The subsequent procedure will depend on
whether the calcium oxalate is to be
weighed as the carbonate or as the oxide.
Weighing as calcium carbonate
 Decant the clear supernatant liquid through
a weighed silica or porcelain filtering
crucible.
 Transfer the precipitate to the crucible with a
jet of water from the wash bottle; any
precipitate adhering to the beaker or to the
stirring rod is transferred with the aid of a
rubber-tipped rod ('policeman').
 Wash the precipitate with a cold, very
dilute, ammonium oxalate solution (0.1
-0.2 per cent) at least five times, or until
the washings give no test for chloride ion.
 Testing the chloride
 add dilute nitric acid and a few drops of
silver nitrate solution to 5 mL of the
washings.
 Dry the precipitate in the steam oven or at
100- 120 OC for 1 hour, and then transfer
to an electrically heated muffle furnace,
maintained at 500 OC for 2 hours.
 Cool the crucible and contents in
desiccator, and weigh. Further heating at
500 OC should not affect the weight.
 As a final precaution, moisten the precipitate
with a few drops of saturated ammonium
carbonate solution, dry at
 110 OC, and weigh again.
 A gain in weight indicates that some oxide was
present; this should not occur.
CaO(s) + (NH4)2CO3(aq) CaCO3(s) + 2NH3(g) + H2O(l)
Weighing as calcium oxide
 Decant the clear supernatant liquid
through a Whatman No. 40 or 540 filter
paper, transfer the precipitate to the filter,
and wash with a cold 0.1-0.2 per cent
ammonium oxalate solution until free from
chloride.
 Transferthe moist precipitate to a
previously ignited and weighed 10-15
minutes with a Meker or Fisher high-
temperature burner until two successive
weighings do not differ by more than
0.0003 g.
 Thecovered crucible and contents are
placed in a desiccator containing pure
concentrated sulphuric acid or
phosphorus(V) pentoxide (but not calcium
chloride), and weighed as soon as cold.