14 ANALYTICAL EDITION Vol. 3, No.

Gravimetric and Direct Volumetric Determination

of Cadmium'
R. C. Wiley
UNIVERSITY COLLEGR
OF MARYLAND, MD.
PARK, .'.

ADMIUM is often de- Cadmium may be determined by precipitating as for converting c a d m i u m

C termined gravimetri-
cally by weighing the
pyrophosphate or sulfate. It
cadmium molybdate and weighing as such,
Cadmium may be determined volumetrically by
titrating with a standard ammonium molybdate solu-
molybdate to cadmium. The
results are the following:
is commodydetermined volu- tion, using a saturated solution of -pyrogallol
- - in chloro- Cadmium present, 0.1378 gram
form as an indicator. Cadmium found:
metrically - b y precipitating Assulfate, 0.1380,O.1390,O.1383,
it as the sulfide,treating the 0.1385; av. 0.1384gram
sulfide with hydrochloric acid and then titrating with iodine Molybdate method, 0 1376, 0.1380, 0.1389, 0.1381, 0.1384, 0.1380,
0 1371, 0.1374; av. 0.1379 gram
solution. This of course is an indirect method.
Cadmium molybdate is very insoluble in a neutral solu- These results show that the gravimetric molybdate is
tion. It is therefore possible to determine cadmium either quite accurate.
by precipitating it as the molybdate and weighing it as such In another solution there was present 0.2061 g a m of
or by titrating a neutral solution of a cadmium salt with cadmium and an average of four results shows 0.2062 gram
a standard molybdate solution. The end point of the titra- present by molybdate method.
tion may be determined by transferring some of the solu- Discussion of Gravimetric Method
tion being titrated to a spot plate and bringing it into con-
tact with a drop of chloroform saturated with pyrogallol. Cadmium molybdate as precipitated forms hard white
The solution tested must be nearly neutral. If the soluble crystals quite insoluble in water. It is, however, R little less
molybdate is in excess, the aqueous drop which has been soluble in a dilute solution of acetic acid than it is in water.
transferred will turn brown. Metals other than magnesium Upon drying it assumes a faint pink tinge. It may readily be
or the alkali metals will interfere with either method and filtered and does not tend to clog the filter. The cryst!als are
must be removed. very small when first formed, resembling those of barium
sulfate.
Cadmium Solution Used in Determinations Too much suction should not be used in filtering, es-
pecially a t the beginning, for the precipitate will tend to run
A cadmium nitrate solution was prepared by dissolving through if it has not been digested long enough. This
5.5150 grams of the metal in nitric acid, evaporating to precipitate is readily washed. The use of ground asbestos
dryness, and diluting to one liter. The cadmium in 25 cc. in the Gooch is a precautionary measure.
of this solution was determined as sulfate. No other metal Care should be used not to strike the sides or bottom of the
was present. beaker with the stirring rod when making the precipitation,
The Gravimetric Method since the crystals of cadmium molybdate will adhere tena-
cioudy to the beaker a t the point scratched and are detached
The reagent ammonium molybdate is prepared by stirring only with great difficulty.
up 30 grams of molybdenum trioxide with 400 cc. of water Cadmium molybdate is stable at 120"C. At about 500" C.
and a few drops of phenolphthalein and adding ammonia it turns brown and loses about 3 per cent of its weight.
with constant stirring until the oxide is dissolved. Acetic This compound is soluble in strong mineral acids and in
acid is then added until the pink color disappears but the concentrated solutions of bases. It is nearly insoluble in
reaction is acid to litmus. After filtering, the solution is water, but soluble enough to give a very faint color with
diluted to 1 liter. One cubic centimeter will precipitate the pyrogallol indicator.
0.02 gram of cadmium. Volumetric Method
Gooch crucibles should be prepared by covering the
layer of ordinary asbestos with a layer of ground asbestos, Prepare the standard as follows: Weigh out 7.4 grams
and dried at 120" C. of molybdenum trioxide, add about 100 cc. of water and some
phenolphthalein. Dissolve in ammonium hydroxide and
Procedure for Gravimetric Method neutralize with acid. Cool and dilute to a liter with dis-
The cadmium solution should be made just alkaline with tilled water. The solution may be standardized by dis-
ammonia and then just acid with acetic acid. It should then solving an exactly known amount of pure cadmium metal
be heated to boiling and the molybdate solution added a in nitric acid and evaporating to dryness over a water bath
drop at a time and with constant stirring. The presence and then titrating the resulting cadmium nitrate against it,
of an excess may be determined by transferring a drop to or it may be standardized by adding to a known volume of
the spot plate and testing with the pyrogallol indicator. the solution an excess of cadmium salt and weighing the
The solution containing the precipitate is kept near the resulting cadmium molybdate as in the gravimetric method.
boiling temperature until the supernatant is clear or nearly Procedure for Volumetric Method
so, and then allowed to stand for at least two hours and pref- The cadmium solution should be so treated that very
erably overnight. It is then filtered through the Gooch, little free acid is present. Ammonium hydroxide is then
previously dried a t 120" C. After the precipitate has been added until a precipitate begins to form. It is heated to
washed with warm water, the crucible containing it is dried boiling and the precipitate dissolved in the least possible
at about 120" C., and weighed. The factor 0.4122 was used amount of acetic acid. The solution is titrated and drops
1 Received August IS, 1930. tested from time to time on a spot plate, the depressions of
January 15, 1931 INDUSTRIAL A N D ENGINEERING CHEMISTRY 15

which contain a saturated solution of pyrogallol in chloro-
form. At the end point a deep brown color will appear.
The results are the following:
Cadmium present 0.1378 gram
Cadmium found by volumetric method, 0.1390,0.1380, 0.1395,0.1374,
0.1378,O.1390,O.1386,O.1390; av. 0.1385gram
The above recorded results are only a few of those ob-
tained and are given as typical. They show that cadmium
may be accurately determined volumetrically.
Comment and Discussion
Ammonium salts increase the solubility of cadmium molyb-
date. They should be kept a t a minimum. This increase in
solubility due to ammonium salts is so small as to be negligible
in the gravimetric method, but due to the great sensitiveness of
the indicator it is appreciable in the volumetric method.
When the end point of the titration is apparently reached
it should be boiled for about 30 seconds and retested, and if
necessary more standard molybdate added.
Just before the end point is reached, a very faint yellow
color may be noticed in the drop tested. This color is very
faint and should not be confused with the much deeper color
that appears when the true end point is reached.
A standard solution of ammonium molybdate appears to
give a sharper end point than the sodium salt, although
either may be used.

Potentiometric Determination of Saponification

Number of Mixtures of Asphalt
and Drying Oils'

reference and indicator electrodes, respectively. After each GILSONITE BERMUDEZ

titration the hydrogen electrode was treated with hot con- method Double maximum
centrated nitric acid and then made the cathode in the method Blank method
electrolysis of dilute sulfuric acid. After this treatment 11 2 12 3 26 9
it was ready for the next titration. It was found unnecessary 9
9
1
3
8 6
8 5
28 0
27 7
to replatinixe an electrode during the entire investigation. 10 0
A Leeds and Northrup student potentiometer was used. Mean 9 9 9 8 27 5 . -