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THE DETERMINATION OF CALCIUM IN THE PRESENCE

OF MAGNESIUM AND PHOSPHATES: THE DETER-


MINATION OF CALCIUM IN URINE.

BY FRANCIS H. McCRUDDEN.
(From the Hospital of the Roclcefeller Institute for Medical Research.)

(Received for publication, August 3, 1911.)

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A year ago I published the details of a very accurate method for
the quantitative estimation of calcium and magnesium in the
presence of phosphates and small amounts of iron.1 In the devel-
opment of the method, accuracy was the first consideration, sim-
plicity and rapidity having been deemed of secondary importance.
During the past winter, in the course of investigations in which
many calcium determinations were necessary, a more rapid method
appeared desirable. The new method, therefore, has been studied
with a view to ascertain to what extent its details could be modi-
fied in the direction of ease and rapidity of execution without
essential loss of accuracy. The present paper gives a report of
these investigations. Part I deals with pure solutions; Part II
with modifications advisable in the case of urine.

PART I. THE DETERMINATION OF CALCIUM IN THE PRESENCE OF


MAGNESIUM AND PHOSPHATES.

The method as previously published is carried out as follows:


The solution is brought to a volume of about 100 cc. and two drops of
alizarin red are added. Ammonia is then added drop by drop until the red
color of the alizarin just disappears (or, in the case of urine, until a pre-
cipitate of phosphate just appears). Dilute hydrochloric acid is then added
drop by drop until the red color of the alizarin just reappears (or, in the
case of urine, until the precipitate of phosphate just disappears). If the
solution has become warmed by the neutralization, a few drops of acid

This Journal, viii, p. 33, 1910.


187
188 Determination of Calcium
in excess should be added to insure complete solution of the calcium phos-
phate, the solution cooled and the neutralization repeated. After the
solution is just acid to alizarin, 10 cc. of G hydrochloric acid and 10 cc. of
2.5 per cent oxalic acid are added and the solution is brought to the boiling
point and kept gently boiling until the calcium oxalate is coarsely granu-
lar. The flask should be kept covered with a watch-glass to prevent spat-
tering. Three per cent ammonium oxalate is then added, a few drops at
a time, to the boiling solution, waiting after each addition until the result-
ing precipitate has become coarsely crystalline. The amount of ammonium
oxalate to be added depends on the amount of calcium in solution. Twice
the amount necessary to combine with all the calcium is sufficient. After
the calcium oxalate has become coarsely crystalline and has settled to the
bottom of the flask, it should be frequently stirred up in the liquid to pre-

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vent the latter from boiling over suddenly. After the precipitate has be-
come crystalline and has settled, the solution is allowed to cool to room
temperature. When cold, 8 cc. of 20 per cent sodium acetate solution are
added to it slowly and with constant stirring. The solution is then allowed
to stand in a cool place from four to eighteen hours, filtered cold and washed
free of chlorides with cold 1 per cent ammonium oxalate solution. The pre-
cipitate is allowed to dry and then incinerated with the filter paper in a plati-
num crucible. It is finally heated in a blast lamp to constant weight.
Details for the determination of magnesium need not be given here.

The points investigated were the following: (1) The possible


substitution of ordinary concentrated hydrochloric acid for 4
hydrochloric acid; the possible omission (2) of ammonium oxa-
late; (3) of oxalic acid; (4) of heating; (5) of standing over night;
(6) the possible substitution of shaking for either heating or stand-
ing over night; (7) the determination of the calcium oxalate by
titration with potassium permanganate; (8) the separation and
washing of the calcium oxalate by means of the centrifuge instead
of by filtration.
Various combinations of these changes were tried. Each change
in detail was considered with respect to accuracy, simplicity and
rapidity.
A. GRAVIMETRIC DETERMINATIONS.

1. Use of concentrated hydrochloric acid instead of + hydrochloric


acid. A number of determinations on different samples of acid
showed that ten drops of concentrated hydrochloric acid (sp.
gr., 1.20) from a 5 cc. pipette are practically equivalent to 10 cc.
of ; hydrochloric acid. Since good check results were always
obtained in a large number of determinations in which concen-
Francis H. McCrudden

trated hydrochloric acid was used instead of $ acid, this modi-


fication of the procedure was adopted and used throughout in
the analyses reported in this paper.
A solution of calcium chloride was prepared and the calcium in
50 cc. determined by the standard method already described
with the following results.
101 102
0.A o.& 0.436 0.1434 0.1435

The solutions filtered clear and no precipitate formed in the fil-


trate on standing. This solution was used in the subsequent

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analyses numbered 4-15 and 100-110.
2. Omission of boiling and omission of oxalic acid. Analyses
numbered 100 and lOOa, were carried out just as were analyses
1, 2 and 3, except that no oxalic acid was added and the solution
was not boiled. Nos. 1OOb and 100~ were carried out in the same
way except that they were shaken ten minutes after the addition
of the sodium acetate instead of standing over night.
100 1OOa 1OOb 1000
0.134!2 0.1203 0.1416 0.1433

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

1Certain observations were checked by independent determinations by


5 second chemist (Miss Fales). These check analyses are designated by
numbers above 100.
190 Determination of Calcium

that the liquid filters very slowly. Sometimes a slight cloudiness


is observed in the filtrate; this in time settles out a little and can
be seen when the filtrate is shaken. This is probably due to the
fraction of a milligram of calcium oxalate which passes through
the paper and is responsible for the slightly low results. The
fineness of the precipitate can be accounted for by the omission
of the oxalic acid. Calcium oxalate is somewhat soluble in an
acid solution so that when oxalic acid is,added a part only of the
calcium oxalate is precipitated. Boiling makes the precipitate
still more soluble. It is a well-known fact that if a crystalline
precipitate is somewhat soluble, the crystals grow larger-the

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smaller crystals going into solution, the larger crystals growing
by accretion. And so, in the case of the calcium oxalate, diges-
tion in the hot acid solution gives the precipitate an opportunity
to form in large crystals, and when the ammonium oxalate and
sodium acetate are subsequently added the rest of the calcium
oxalate comes down and precipitates partly, at any rate, on the
large crystals. The digestion over night brings about further
growth of the large crystals at the expense of the fine precipitate.
4. Omission of boiling. Two analyses were carried out just
as were Nos. 1, 2 and 3, except that the solution was not heated,
precipitation taking place in the cold. The results were:

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-

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nium oxalate being omitted, it was found thatthe precipitatewas
fairly coarsely crystalline, filtration was easy and no precipitate
appeared in the filtrate upon standing. Assuming that the results
would have been correct, the precipitates were not ignited and
weighed.
7. Omission of boiling; shaking instead of standing over night.
In analyses which were carried out exactly as were Nos. 6 and 7,
(i.e., boiling omitted) except that after the addition of sodium
acetate the flasks were closed with rubber stoppers, the solution
shaken for ten minutes and filtered immediately instead of after
standing over night, a very fine precipitate passed through the
paper as in analyses Nos. 6 and 7. For this reasonthe analyses
were not finished.
In analyses in which both boiling and standing over night were
omitted, the flasks being stoppered and the solutions shaken after
the addition of the oxalic acid, after the addition of the ammonium
oxalate and again after the addition of the sodium acetate, it was
found that the precipitate was coarsely crystalline, filtration was
easy and the filtrate remained clear upon standing. Assuming
that the results would have been correct, the analyses were not
finished. One advantage in shaking as compared with heating
is that the precipitate does not adhere to the sides of the flask
and hence is easily washed on to the filter. It is a question,
however, which is the simpler technique.
The same result was noted in analyses in which boiling and
standing over night were omitted, the flasks being shaken for ten
minutes twice, viz: after addition of oxalic acid and after addition
of sodium acetate:
O&4 O&5
192 Determination of Calcium

The results are correct, precipitates coarsely crystalline, filtration


easy, the filtrates remaining clear on standing. The precipitate
does not adhere to the sides of the flask.
The results thus far outlined indicate that, in carrying out the
method, 10 drops of concentrated hydrochloric acid may be used
instead of 10 cc. of $ acid; that the oxalic acid should not be omit-
ted; that boiling may be omitted if the solution is shaken for ten
minutes after the addition of the oxalic acid; and that standing
over night may be omitted if shaking for ten minutes after the
addition of the sodium acetate be substituted.

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B. TITRATION WITH POTASSIUM PERMANQANATE.

The next experiments were designed to determine whether the


calcium could be accurately determined by titration of the oxalate
with potassium permanganate. This method is sometimes recom-
mended, but as ordinarily carried out it can not give absolutely
accurate results. It has been shown by Richards2 and myseW
that if the calcium oxalate precipitate be washed with distilled
water, some dissolves, making the results low. If the pre-
cipitate be washed with dilute ammonium oxalate solution in the
manner described, the ammonium oxalate clinging to the pre-
cipitate will react with the permanganate and the result will be
high. It seemed probable, however, that if the precipitate were
washed free of impurities with dilute ammonium oxalate and then
washed a few times with very small amounts of cold distilled water,
allowing thorough draining after each washing, these errors could
be minimized. Accordingly, three sets of analyses were made
as follows :
1. Calcium oxalate was precipitated, filtered and washed with
dilute ammonium oxalate in the usual manner. The precipitate
was then titrated with potassium permanganate to determine how
much too high washing with ammonium oxalate makes the result.

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.

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Three determinations of the calcium in 50 cc. by the standard
method yielded the following:

0400 o&4 o.lYo2


The results of the three sets of analyses outlined above were as
follows :
1. Washing with 0.6 per cent ammonium ozalate.
0445 0.254
2. Washing with distilled water.1
o.& o.&
3. Washing with ammonium oxalate and then with diistilled water.

0202 0.2:501

These results show that calcium may be determined by titra-


tion of the oxalate with potassium permanganate if washing with
dilute ammonium oxalate is followed by washing three or four
times with cold distilled water.

C. EFFECT OF UBIC ACID.

In consideripg the applicability of the method for the estimation of cal-


cium in the urine, the possible effect of the presence of uric acid had to be

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

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of the precipitate, the calcium should not be determined by titration.

D. USE OF THE CENTRIFUGE.


A number of experiments were undertaken to determine whether it
might not be of advantage to use the centrifuge in separating and washing
the precipitated calcium oxalate instead of filtering in the usual way. They
showed that while accurate results may be obtained by its use, the work
involved and time consumed is greater than when filtration is employed.

E. USE OF GOOCH CRUCIBLE OR HARDENED FILTER POINT AND SUCTION.


When Gooch crucibles were tried, it was found that thin layers of abes-
tos did not retain the precipitate. Where layers thick enough to retain the
precipitate were used, they soon clogged up and prevented passage of fluid.

F. EFFECT OF PHOSPHATES,MAGNESIUM AND SMALL AMOUNTS OF IRON


UPON THE RESULTS.
In order to convince myself that the presence of magnesium, phosphates
or iron would not affect the accuracy of the calcium determination if boil-
ing and standing over night were omitted, the following analyses were made.
Nos. 70 and 71 were carried out on a pure calcium chloride solution, Nos.
72 and 73 on the same solution to which were added equivalent quantities
of magnesium chloride and sodium phosphate, together with a little ferric
ammonium sulphate.
70
0.1377 0.1377 0.1376 0.1377

PART II. THE DETERMINATION OF CALCIUM IN URINE.

The method which has been described in Part I, when applied


to the estimation of calcium in urine, gave accurate results. Cer-
tain steps in it were, however, found to be unnecessary, even inad-
Francis H. McCrudden 195
visable, owing partly to the small amounts of calcium, partly to
the character of the urine.
Fresh urine from a number of subjects was mixed and the cal-
cium content in 200 cc. estimated by the method described last
year. The results follow:

1. Omission of ammonium oxalate. Two analyses in which


the addition of ammonium oxalate was omitted showed that this
reagent was superfluous in the estimation of calcium in urine.

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2. Shaking instead of standing over night. It has been shown
in Part I that shaking of the solution may be substituted for
standing over night when there is considerable calcium present.
The fine precipitate which comes down on shaking after the addi-
tion of sodium acetate has in that case a large amount of coarsely
granular precipitate to which to attach itself. In the case of
urine the amount of precipitate that comes down before add-
ing sodium acetate is small. Hence shaking for ten minutes
is insufficient to give a coarsely granular precipitate. In two
analyses, in which this modification was introduced, the calcium
oxalate was so finely divided that some passed through the filter.
The analyses therefore were not finished.
3. Effect of bo&ng the solution. In all these analyses filtra-
tion was slow and washing of the precipitate difficult because
the filter became clogged. When boiling was omitted this was
not the case. Boiling seems to precipitate a very small quantity
of sticky, slimy substance, possibly mucus, which coats the cal-
cium oxalate precipitate and the filter paper, impeding filtration.
Boiling also seemed to prevent the formation of a coarse precipi-
tate, for when the urine was not boiled the precipitate wascoarse
enough to be retained by the filter.
It was noted, further, that, if the urine is boiled and then
allowed to stand as usual over night, the calcium oxalate precipi-
tate is occasionally contaminated with uric acid. In no case did
this occur when boiling was omitted. While it is difficult to assign
196 Determination of Calcium

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.

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In the analyses, the results of which follow, vigorous shaking was
substituted for boiling and the addition of ammonium oxalate
was omitted. The results are good, filtration was easy and the
filtrate remained clear.
dir42 O.&I
6. Omission of boiling and of ammonium oxalate: shaking instead
of standing over night. In the analyses following, a mixed urine
was used which gave 0.0275 gram of calcium oxide in 200 cc. by
the standard method. It was found that shaking could not be
substituted for standing over night if the urine was boiled, because
the fine precipitate so obtained passed through the filter. This
was not the case when the urine was not boiled as the results of
analyses 15 and 16 show.

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.

cl.& o.& O.& o.c%l


Filtration was more rapid in those analyses in which ammonium
oxalate was omitted.
Francis H. McCrudden 197

In the analysis of urine, as in the case of pure solutions, the use


of hardened filter points or of Gooch crucibles and suction was
found to be impracticable. Concerning titration with perman-
ganate, the considerations previously outlined are applicable. It
is advantageous to use filtered urine for the analysis, and in urines
which contain small amounts of calcium, litmus paper should be
used in adjusting the reaction in the first step of the analysis.

SUMMARY.

I. For the determination of calcium in pure solutions, which

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may contain also magnesium, phosphates and small amounts of
iron, or in the ash of food or feces, the best procedures as developed
in this work are as follows:
SOLUTIONS REQUIRED : 2.5 per cent oxalic acid; 3 per cent
ammonium oxalate; 20 per cent sodium acetate.
1. The solution is brought toavolume of 75 to 150 cc. Concen-
trated ammonia water is added drop by drop till the solution is
just alkaline, as shown either by the appearance of a precipitate
of calcium and magnesium phosphates or by the use of an indicator
(aliaarin red or litmus paper).
2. Concentrated hydrochloric acid is added drop by drop until
the solution is just acid, as shown either by the disappearance of
the precipitate or by an indicator. In the presence of iron an indi-
cator must be used.
3. Ten drops of concentrated hydrochloric acid (sp. gr., 1.20),
approximately equivalent to 10 cc. of ; HCl, are added.
4. Ten cubic centimeters of 2.5 per cent oxalic acid are added.
5. Either of two procedures may here be used:
a. The solution is boiled until the precipitated calcium oxa-
late is coarsely crystalline,1 and then an excess of 3 per cent am-
monium oxalate is slowly added to the boiling solution and the
boiling continued until the precipitate is coarsely crystalline.2
b. The flask, closed with a rubber stopper, is shaken vigorously
for ten minutes. An excess of 3 per cent ammonium oxalate is
then added.

If but little calcium is present, nothing precipitates at this point.


*If but little calcium is present, it is not necessary to add oxalate.
198 Determination of Calcium

6. The solution is cooled to room temperature and 8 cc. of 20


per cent sodium acetate added. (In case of ash of feces, add 15
CC.)
7. The solution may either be (a) allowed to stand over night
or (b) stoppered and vigorously shaken for ten minutes.
8. The calcium oxalate is filtered off on a small ash-free paper
and washed free from chlorides with 0.5 per cent ammonium oxa-
late solution.
9. Either of two procedures may next be followed:
a. The precipitate and filter are dried, burned in a platinum
crucible to calcium oxide and brought to constant weight by heat-

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ing in a blast-lamp.
b. The precipitate is washed three times with cold distilled
water, filling the filter about two-thirds full and allowing it to
drain completely before adding more. A hole is made in the
paper and the calcium oxalate washed into the flask. The volume
of the fluid is brought up to about 50 cc. and 10 cc. of concentrated
sulphuric acid are added. The oxalate is titrated immediately
with standard potassium permanganate.
Determination of magnesium in the filtrate may be carried out
as described in my previous paper. Or the filtrate may be evapor-
ated to dryness in a porcelain dish after the addition of nitric
acid and the residue heated over a free flame until the ammonium
salts are destroyed and the residue fuses. After cooling, the resi-
due is taken up in water and a little hydrochloric acid, and the
magnesium precipitated as usual. Another simple method of
destroying the organic matter is to add 3 to 5 cc. of concentrated
sulphuric acid to the filtrate and evaporate in a small Kjeldahl
flask until the water is removed. The sulphuric acid may then
be neutralized with ammonium carbonate and the magnesium
precipitated as usual.
In the analysis of ash of feces, carried out by the usual method
the calcium oxalate is apt to precipitate in a very finely divided
condition. Filtration is slow and loss may result on this account.
This difficulty may be obviated as has been indicated, by the addi-
tion of 15 cc. instead of 8 cc. of sodium acetate. I have shown
that, if the solution is kept cool, no phosphate or magnesium is
brought down by this excess of sodium acetate.
Francis H. McCrudden 199
II. For the determination of calcium in urine, the following
method is recommended:
SOLUTIONS NEEDED: 2.5 per cent oxalic acid; 20 per cent sodium
acetate.
1. If the urine is alkaline it is made neutral or slightly acid.
2. The neutral or slightly acid urine is filtered.
3. Two hundred cubic centimeters of urine are used for analy-
sis. If only faintly acid to litmus paper, 10 drops of concentrated
hydrochloric acid are added.
If the urine is strongly acid, it may be made just alkaline with
ammonia and then just acid with hydrochloric acid. If the urine

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is turbid or contains little calcium, litmus paper should be used
in determining these changes; otherwise, the appearance and dii-
appearance of a precipitate of phosphates are sufhcientlyaccurate
indicators. Ten drops of concentrated hydrochloric acid (sp.
gr., 1.20) are then added.
4. Ten cubic centimeters of 2.5 per cent oxalic acid are next
added.
5. Eight cubic centimeters of 20 per cent sodium acetate are
added.
6. The urine is either allowed to stand over night at room tem-
perature or is shaken vigorously for ten minutes.
7. The calcium oxalate is filtered, and washed free from chlor-
ides with 0.5 per cent ammonium oxalate solution.
8. a. The precipitate may then be dried, ignited, heated in
a blast-lamp to constant weight and weighed as calcium oxide.
b. If free from uric acid, the calcium oxalate may be washed
three times with distilled water and estimated by titration with
permanganate as described in the outline of the method for pure
solutions.
Magnesium is determined in the filtrate just as in the case of
pure solutions.
THE DETERMINATION OF CALCIUM
IN THE PRESENCE OF MAGNESIUM
AND PHOSPHATES: THE
DETERMINATION OF CALCIUM IN
URINE
Francis H. McCrudden
J. Biol. Chem. 1911, 10:187-199.

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