C h a r l e s H.
Henrickson
Gravimetric Determination of Calcium as
Western Kentucky University
Bowling Green. 42101 CaC204 H20
P a u l R. Robinson
I
University of Illinois
Urbana. 61801 A tractable, inexpensive experiment for
undergraduate quantitative analysis laboratory
T h e gravimetric determination of calcium i n calcium car-
bonate samples has served a s a n attractive replacement for
the gravimetric determination of chloride a s silver chloride
and nickel as the dimethylglyoximate. A class of 249 freshman
chemistry majors a t t h e University of Illinois performed t h e
analysis using twenty-five different calcium carhonate sam-
.~-~-
nles ohtained from Thorn Smith. 1023 T r o v Court. Trov,
~ ~~~~ ~
Michigan 48084. T h e samples ranged in calcium content from
20-40 nercent. T h e accuracv obtained b y these students is
represented in the figure in terms of frequency versus relative
percent error.
T h e procedure used was b a d d on a n analysis originally
described by Ingols a n d Murray.' I n outline, dried, weighed
calcium carhonate samples were dissolved in HCI. Solid urea
,and acidified (NHdzCz04 were then added, and the urea was
hydrolyzed a t ca. 90°C to slowly and homogeneously generate
oxalate ion (eqns. 1-4). T h e resulting calcium oxalate was
filtered while h o t into tared sintered glass crucibles, washed
with water, then acetone, a n d dried for 60 min a t 105'C.
CaCOs + 2HC - Caz+ + Hz0 + COz (1)
Experimental
The instructions given to the students2 are summarized below.
Theanalysis is to hecarriedout in duplicate with theaverage value
reported as the result.
The impure calcium carbonate sample should he dried for one hour
at 11O0Cbefore use. Two clean, medium frit sintered glass crucibles
should be clearly labeled with a lead pencil.. .then brought to con-
stant weight by drying at llO0C [note 11. Cool to room temperature
in desiccator for about 30 minand then weigh the crucibles. Store the
tared (preweighed) crueihles in a covered beaker until needed.
In each of two 250-ml beakers, place a 0.35-0.38 g sample of the
calcium carbonate unknown and record the sample mass to the tenth
of a mdligram.
To eaeh sample add 100 ml of distilled or deionized water and slowly
add 6.0 ml of 6 M HCI as you swirl the solution to dissolve the sample
(eqn. 1). Once the sample is dissolved, check the pH of the solution
by using a clean stirring rod to remove a small droplet and touch it
toa piece of pH paper. If the pH is higher than pH I, lower the pH to
at least I by adding a drop or two of 6 M HCI [note 21. From this point
on, eaeh solution should be treated individually.
Add 4-5 droos of methvl red indicator and mix the solution bv
w~rl~ng.'l'hr wlutmn should be red st this puint.Thenadd ?tIml<rf
+atum~rdnmmmwm oxalate sdur~onts lcirlr c,,nrnrns 1.1, ml ofti .3f
HCIr [note:3l.. d l I>g~rfsol:durea. Swrl tlw wluticm t o d i w h t thr
urea [note 41.
Cover the beaker with a clean watchglassand heat thesolution to
near boiling. Hold it there [note 51 until the color of the methyl red
indicator changes from red to yellow [note 61, which indicates a pH
of ahout 6. This should reauire from 2&35 min. The formation of the
crystals of CaCzOIHzO will be complete at this time. Rinse theeon-
densation from the watch glass into the beaker using a wash bottle.
'R. S. Ingols and P. E. Murray, Anal. Chem., 21,525 (1949).
2C. H. Henrickson, S. Zumdahl, and G . P. Haight, Jr., "An Intro-
duction to Chemical Systems in the Laboratory," Stipes Publishing
Co., Champaign, Ill., 1977, pp. 113-120.
Hdding the hesker with a towpl, or using beskrr tongs. filter the
hot sdurim [note 71 through the sinrrrrd gIss9 c~ucibk~ 8 t suctiun h
L'le a rubber rmlictman and small wlumci of distilled ur deionbed
water from a-wash bottle to transfer the entire precipitate to the
crucible.
Wash
- t.h e~ervrtals
~ . with two 10-rnl oortions of cold distilled or
~, ~~
d e i m ~ e ds,atcr. S a t , rinw rhe cr).stsls with t w o 10-ml portions of
ncetmr. 1)rdu air through the prtsipirat~for five rninuws u, partially
dr) the ~,rystaljandremove trarciot acetone Inow 81.Then nilou the
sample t<,rtand11111 intheairfwab~utone-hall hour todry while thr
iecond liannpl~i, taken through the remsindrr of the analgsi..
Aiter air drying, plarr the C ~ I I C I I ~ P iSn a C I ~ R I I V l.lbried 100-ml
beakrr and dry ar lfltl-1115" tno h,;her~ for 1 hr: weign them nfter
allowing themto cool in a desiccate; for 30 min. subsequent heating
nnd weiehine will not be necessarv since the laree calcium oxalate
Notes
(1) Students were asked todry their calcium carbonatesamples the
week before the experiment was performed, and to store them in
their desiccators until needed. They werealso asked to heat their
crucibles at least once, one week prior to theexperiment. On the
first week of the analysis, they were asked to qualitatively de-
termine possible interferences for the analysis using 3 M HzSOd,
0.1 M NaF, 0.1 M Na~COz,0.1M NaHzPO4,O.l M CaCh 0.1 M
Ba(N03)2,0.1 M MgClz, and 0.1 M Cu(NOd2. In addition to
teaching the students about interfering species, this assignment
helped to eliminate the tedium which is often associated with
heating crucibles to a constant weight.
(2) It was found that thisamount of HCI orovided a balance between
the longer time needed to hydrolyze the urea in more concen-
trated acid, and the tendency of CaC20aHn0 to precipitate in less
concentrated acid.
(3) Acidification of the ammonium axalate prior to its addition helps
to prevent the premature formation of CaCzOrHzO. In about
one-third of the determinations, some precipitations of calcium
oxalate did occur at this point, but since thesamples are digested
for 25-35 min, this did not affect the final results.
(4) Most students added the urea, ammonium oralate, and indicator
to both of their samples, and waited until their lab period one
week later to finish the experiment. A few students were able to
cnmplete one full determination in one 4-hr lab period, but none
of the students finished the whole experiment in 4 hrs.
(5) To prevent bumping of the heated solutions, the students were
told to place a glass stirring rod in the solutions.
(6) If less than 4 drops of indicator were used, the cnlor changed from
red to clear at pH 6.
(7) Cold filtrations took up to 30 min to complete.
(8) It is imperative that mast of the ACETONE BE REMOVED
to prevent a n explosion hazard in the drying oven.
Discussion
T h e chief advantage of t h e CaCzOaHZO gravimetric anal-
ysis over t h a t for AgCl is its lower cost; t h e estimated cost of
chemicals per 100 students for t h e calcium determination is
ca. $14, whereas that for t h e chloride analysis is ca. $70. Other
advantages are the absence of photochemical decomposition
of the precipitate and t h e reduced drying time. After a n ace-
tone wash and partial drying in air a t room temperature, t h e
mass of t h e o r e c i ~ i t a t edoes n o t chanee sienificantlv bevond
t h e 1-hr dr$ng pkriod a t 105'C. ~ r i n g i n ~ ' t hsampie
e tocon-
s t a n t weight can he done t o teach good methodology, h u t i t
Volume 56, Number 5, May 1979 1 341
 Statistics for the Gravimetric Determination of Calcium
Avg. %
N % of class deviation c Comment
249 100 -1.88 10.3% data for the whole class
228 91.6 -1.08 2.5% all values within +I0336
relative deviation
216 86.7 -0.73 1.75 all values within H a .
where o = 2.5%
207 83.1 -0.57 1.36 all values within i 2 c .
where n = 2.536
190 76.3 -0.43 1.03 all values within i o
where a = 2.5%

" ilr",>nor
Number of students versus relative error ( % ) N = 249
can he eliminated if time is unavailable. The chemistry in-
volved in the calcium determination is more complex, which,
deoendine - uoon
. one's point of view, can he an advantage or
a disadvantage.
The CaC20cH20 analysis does not suffer from the persis-
tent problem of "creeping" of the precipitate which is the chief
disadvantage of the dimethylglyoxime determination of
nickel.
~ ~ These
- ~
~~~ two.methods
~~ ~ ~
~ ~ are comnarahle
- - in cost (ca. $13 per
100 students for the nickel-DMG experiment).
The major hazard in the analysis is the possibility of over-
heating the CaC201.H20, which could result in removal of the
remaining water of hydration. However, the results of the
students' determinations (see figure and table) indicate that
this difficulty was minor. Anhydrous calcium oxalate is more
hygroscopic than common desiccants such as silica gel or
Drierite. and if it were formed it would regain the water of
hydrati& while cooling in the students2hesiccators. The
negative average deviation (-0.43%) may he attributed partly
to loss of water and partly to minor spillage and incomplete
transfer of orecioitate
. . which commonlv lead to small negative
deviations in gravimetric analyses.
The accuracy achieved by this freshman class is quite good
compared with that achieved for the gravimetric chloride
analvsis hv a similar class one year ago, especially since this
experiment was the very first "wet" chemistry laboratory
experience for these college students. If they had done trip-
licate determinations and had had more experience in the lab,
the students' results undoubtedly would have been better. We
feel that this exoeriment provides a tractable, inexpensive
alternative to the traditionally foolproof gravimetrfc silver
chloride determination. If coupled with qualitative tests for
interferences, it can serve as a rewarding and informative in-
troduction to gravimetric analysis.

342 1 Journal of Chemical Education