JANUARY 15,1937 ANALYTICAL EDITION 27

I
with a sufficient quantity of the diluent to reduce the bis-
TABLEI. BISMUTH
RECOVERIES muth concentration. The alternative, when dealing with
Bismuth added, quantities above 0.20 mg. of bismuth per 100 cc., is to deter-
Bismuth
mg. found, 0 . 2 5 0.50 ‘.O0 2.00 mine the average density of the bismuth line corrected for
mg. :
O.Ool O.O1
:::
: 5::: : :i: :!; :8 ii 8 ::
variations in the density of the internal standard and to evalu-
ate the bismuth concentration from the straight-line portion
of Figure 2. These curves were plotted from the mean values
TABLE11. &COVERY OF BISMUTH FROM TISSUES AND EXCRETA . of repeated observations on a series of solutions prepared by
OF A RABBIT adding known quantities of bismuth and the required quantity
(Killed one week after the administration of 3.5 mg. of bismuth of the “internal standard” to suitable volumes of the stock
intravenously)
Tissue Weight Bismuth Found
Gams Mo.
Blood 76.1 0.001
Applicability, Sensitivity, and Accuracy of
Liver 54.8 0.013 Method
Spleen 0.7 0.000
Kidneys 11.5 0.08
The recoveries for known amounts of bismuth added to
Heart 4.1 0.000
Lungs
Central nervous system 6.2
14.0 0.001
0.000
digested portions of beef are tabulated in Table I. In Table
Testes 1.4 0.000 I1 are recorded the results obtained from the tissues and
Bile ... o.ooo ’ excreta of an experimental animal. The weights of tissue
Pancreas 2.1 0.004
Muscle
Bone 578.5
132.0 0.014
0.18 available have been recorded in order to indicate the size of
Skin 208.4 0.01 samples which can be utilized. The error of analysis, as
Intestinal tract 132.2 0.05
shown in Table I, naturally depends on the quantity of bis-
Contents of tract 164.0 0.03
Ears, tail, and feet
Remainder 130.0
348.0 0.10
0.05 muth encountered. For amounts above 0.20 mg. the error
Entire carcass
~

Urine
Feces 2.24
0.90
Total bismuth found in excreta - 3.140
__
Total bismuth found
tion has proved very satisfactory, in that the salts present are
good conductors and give a very steady arc when used with the
technic described (1). Moreover it is free from the excessive
creeping which may give rise to incrustations about the crater
of the electrodes. Such incrustations result in spectrograms with
very dark backgrounds because of the high concentration of in-
candescent salt particles in the arc.] Then a 0.2-cc. portion is
introduced into each of 4 cratered graphite electrodes which are
dried at 1200 e. and arced in accordance with the technic de-
scribed for lead (I), while t,he region A2600 to A3800 is
photographed.
Follo’ving the suggestion Of Lundegardh (’), two curves
have been found useful in evaluating the densitometric values
for the plates. The curve in Figure 1, in which the opacity
ratios (galvanometer throw for the zinc line/galvanometer
throw for the bismuth line) are plotted against the bismuth
concentrations, is employed when the average opacity ratio
of the four spectraindicates less than 0,0004 mg. (0.20 mg.
per loo Of bismuth On the arc‘ This lnay be
used in estimating higher amounts of bismuth by diluting
0.633 is = t l O per cent. For quantities from 0.01 to 0.20 mg. the
error is about 10.01 mg. The greatest proportional error
naturally occurs with quantities below 0.01 mg., but the errors
3.673 in the estimation of extremely small amounts down to 0.001
mg. rarely exceed *20 per cent. (Although much smaller
quantities can be detected, a t least as low as 0.00004 mg.,
quantitative estimations below 0.001 mg. do not appear suf-
ficiently accurate to be useful because of mechanical losses,
as those caused by adsorption, and the passage of colloidal
bismuth sulfide through the filter paper.) In the case .of
material free from iron and containing very little ash, the
separation of bismuth is of unnecessary, and it may
well be that quantities as low as 0.0002 mg. of bismuth can
be dealt with by further concentrating the solution of the ash,
Literature Cited
(1) Cholak, J., IND,
E ~ GCHEM,,
, Anal, Ed,, 7, 287 (1935).
( 2 ) Cholak,
J., J . A ~Chem., sot., 57, 104 (1935).
(3) Lundegardh, H., “Die quantitat>ive Spektralanalyse der Ele-
mente,” P a r t 11, Jena, G u s t a v Fischer, 1934.
(4) Olseh, J. c.9“Chemical Annual,” 7th ed., P. 477, NOW York,
D. Van Nostrand Co., 1934.
RECEIVEDJuly 11, 1936. Presented before the Division of Physical and
Inorganic Chemistry, Symposium on Spectroscopic Methods of Analysis, at
the 92nd Meeting of the American Chemical Society, Pittsburgh, Pa.,
September 7 to 11, 1936.

Determining Calcium in Blood Serum

H. K. MURER,’ Washington Agricultural Experiment Station, Pullman, Wash.

IN THE determination of blood serum calcium by the Rymer
and ~~~i~ (1) modification of the Tisdall (2) method, the
separation and washing of the calcium oxalate by Successive
centrifuging are very time-consuming. There is also pos-
sible loss while decanting and from creeping of the pre-
cipitate.
By the use Of 30-cc*sintered-glass Buchner
nation 3 G. 4),this centrifuging and decanting can be avoided.
Place 2 ml. of serum in the test tube, dilute with 2 ml. of water
and 0.5 ml. of saturated ammonium oxalate, shake, and allow to
stand overnight. Filter on the glass filters, and wash with
ammonia water (4 cc. of concentrated ammonia t o 250 ml.).
After removing the funnel, rinse out the portion below the filter,
1 Present addresa, 44 Irving St., Cambridge, Mass.
place the funnel on top of test tube in the suction flask, dissolve
the precipitate through the filter with three 2-ml. portions of
hot N sulfuric acid, applying suction after each addition of acid,
and fiTashthe filters with water. &move and rinse the test tube
and lower portion of filter into a 50-ml. beaker, heat to boiling,
and titrate with dilute permanganate from a Koch automatic
microburet.
Very satisfactory results were obtained with this method
which lends itself well to fast routine work,
Literature Cited
(1) Rymer, M.R., and Lewis, R. C., J . Bid. Chem., 95, 441 (1932).
(2) Tisdall, F. F., Ibid.2 56, 439 (1923).
RECEIVED
September 1, 1936.