BY FRANCIS H. McCRUDDEN.
(From the Hospital of the Roclcefeller Institute for Medical Research.)
These results are very low, partly due to the passage of the very
fine precipitate through the filter paper. The next analyses were
designed to determine whether the low results were due to the
omission of the oxalic acid, of boiling, or of both.
3. Omission of oxalic acid. These analyses were carried out
just as were Nos. 1, 2 and 3, except that the addition of oxalic
acid was omitted and an equivalent amount of ammonium oxa-
late added instead.
104 104s 105 1058
0.14432 Oh32 0.1433 0.1433 0.1430 0.1434
The results are only slightly low, so that the omission of oxalic
acid alone does not account for the low results of analyses Nos.
100 and 100a. The precipitate is so fine, however, that it is trouble-
some to wash it out of the flask and it clogs the filter paper so
CL25 0.:420
Although low, they are not so low as the results of Nos. 100 and
100a. The low results of Nos. 100 and 1OOa are therefore not due
to omission of either oxalic acid or of boiling alone but to the omis-
sion of both. The precipitate is so fine that some may pass
through the filter. A filtrate which is apparently practically clear
at first may show a fine precipitate on standing over night. Fil-
tration is slow for the fine precipitate soon clogs the paper. The
fineness of the precipitate is accounted for by omission of diges-
tion in the hot liquid as explained above. One advantage in the
omission of heating was noted; viz: the precipitate does not stick
to the sides of the flask and hence less water is necessary in trans-
ferring it to the filter paper.
5. Substitution of shaking for standing over night. Four
analyses were carried out as were Nos. 1, 2 and 3, except that the
Francis H. McCrudden 191
flasks were closed with rubber stoppers and shaken for ten minutes
after the addition of sodium acetate instead of being allowed to
stand over night.
109 110
O&36 o&5 0.1434 0.1436
6. Shalcing instead of boiling before addition of sodium acetate.
When the procedure used in Nos. 1, 2 and 3 was modified to the
extent of shaking for ten minutes after the addition of ammonium
oxalate and again for ten minutes after the addition of sodium
acetate, boiling after the addition of both oxalic acid and ammo-
These conclusions are based not only upon results given here, but also
upon similar results of a number of other experiments in which calcium oxa-
late was precipitated in these various ways in preparation for the volu-
metric determinations. The results given above suffice to bring out the
points desired.
2PTOC. of the Amer. Acad. of Arts and Sciences, xxxvi, p. 277, 1901.
Lot. cit.
Francis H. McCrudden I93
2. Calcium oxalate, precipitated and filtered as before, was
washed with cold distilled water. Titration with permanganate
indicated the extent of loss caused by the solubility of calcium
oxalate in distilled water.
3. Calcium oxalate, precipitated and filtered as before, was
washed free from chlorides with 0.5 per cent ammonium oxalate
solution. This was followed by washing three times with cold
distilled water, each time using only enough to fill the funnel
one-half to two-thirds full and allowing thorough draining each
time.
For these analyses a new solution of calcium chloride was used.
0202 0.2:501
It was noted in these and other analyses that the size of the crystals
makes as great or greater difference than the nature of the washing fluid.
If the precipitate is coarsely crystalline, even cold distilled water alone
may be used for washing. If the precipitate is very finely crystalline, even
0.5 per cent ammonium oxalate carries a little into solution which precipi-
tates out later.
Determination of Calcium
determined. When calcium is precipitated as oxalate in neutral or slightly
acid solution and allowed to stand over night, uric acid may be precipitated.
Such contamination of the precipitate would not affect the accuracy of the
gravimetric method, since the precipitate is ignited before weighing. It
would, however, interfere with the volumetric method. The possible pre-
vention of the precipitation of uric acid will be discussed later. On the
assumption that it is precipitated, as a means of getting rid of it I have
thought of washing the calcium oxalate with sodium hydroxide solution.
It was found, however, that even fairly strong sodium hydroxide does
not easily dissolve the uric acid contaminating a calcium oxalateprecipitate;
furthermore, even dilute sodium hydroxide dissolves some of the calcium
oxalate. 1 have concluded, therefore, that if calcium oxalate, precipitated
from urine, is contaminated with uric acid, as indicated by a reddish color
a reason for this, the point is of interest, for the calcium can be
determined by titration with permanganate if it can be precipi-
tated free from uric acid.
4. Shaking instead of boiling. Analyses carried out as directed
in my previous paper, except that, instead of boiling the urine,
it was vigorously shaken in a stoppered flask, gave good results.
Filtration was easy and the filtrate remained clear.
&?42 O.&I
5. Shaking instead of boiling: omission of ammonium oxalate.
o.&* OS&
Filtration was easy and the filtrate remained clear on standing.
7. Urine not boiled or shaken. In the case of pure solutions,
in which calcium is fairly concentrated, it has been shown that
either boiling or shaking is essential. Neither is essential in the
case of urine as is shown by the results of analyses 17- 20 in which
both boiling and shaking were omitted. In 17 and 18 ammonium
oxalate was added; not in 19 and 20. In all, the urine was allowed
to stand over night, after the addition of sodium acetate.
SUMMARY.
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