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Number of Viscose
HENRYL. BARTHELEMY~
AND
LOVELEEN WILLIAMS
NhCS,
+ 3HaO
s=
NhCO,
+ 3H2S
The only reliable method known hitherto for the determination of total combined carbon disulfide consists in transforming
the total sulfur present into sulfuric acid through an oxidation
process and determining it quantitatively as barium sulfate.
The procedure requires skill, space, and considerable time.
For these reasons, in practice only occasional determinations
are made by it and they are not conducted routinely for control
purposes but for general production information, inasmuch as
the viscose has already been spun by the time the results become
available. These considerations have prompted an investigation of the possibilities offered by other published procedures.
The volumetric method of d'Ans and Jaeger (S),based on oxidation of total sulfur by hydrogen peroxide and subsequent titration as sulfuric acid, has been evaluated exhaustively. The
reaulta were invariably much higher than those obtained by the
application to viscose of the gravimetric procedure of Del&
chanal and hlermet, embracing oxidation with sodium hypobromite and determination of the sulfurir acid as barium sulfate
(4). This fact is not surprising, for it is probable that part of the
cellulose is also oxidized to acidic end products. Indeed, the
rmults are always 7 to 10% higher than those obtained by the
gravimetric procedure.
Other volumetric methods described in the literature have
generally been applied to sulfur combined only as cellulose xanthate, which does not indicate the extent to which the allotted
carbon disulfide has been utilized. Then, too, many contradictory findings have been reported. The method of Cross and
Bevan ( 2 ) , for instance, which is an adaptation of a reaction
discovered by Delachanal and Mermet (6),gives results which
do not always agree with the gravimetric determination of sulfur
in cellulose xanthate. The probable explanation is that the
transformation of the sodium cellulose xanthate into a dixanthylated derivative in the presence of iodine is not a complete reaction, as was brought out by Andre (1) while working on potassium ethyl xanthate. A complete survey of the literature on
analytical methods for viscose is given by Ott (10). Changes inI Present addreas, S/A Induntrim Reunidaa F. Mataranso, SPo Psdo,
Na&Sz
+ 2N&ZnOa + 2HsO =
22x1s + CaHSOH +Na&O: + 3NaOH
B r a d , 8. A.
624
ANALYTICAL EDITION
October, 1945
45
14
.-.-A
625
%
' CS,
2.344
2.353
2.353
2.363
2.344
2.335
2.344
2 353
I
2.358
2.352
2.363
2.360
2.355
2.353
2.351
2.358
Table 1.
Two check determinations, carried out according to the conventional gravimetric method already mentioned, afforded 2.365
and 2.360, respectively.
Not only are the results obtained with each of these two
methodein good agreement, but when speed is an important factor, as is always the case in a plant operation control laboratory,
this new volumetric procedure has a decided advantage over the
conventional one. The time required by a technician to run a
total carbon disulfide combined is approximately as follows:
Volumetric method: from 1 hour 40 minutes to 2 hours
Gravimetric method: from 16 hours t o 20 hours
DISCUSSION.
The preparation of the sample by taking an
aliquot from 25 grams of viscose seems unnecessarily cumbersome in contrast with the direct weighing of 1 gram. Experience, however, shows that the longer procedure invariably yields
better duplication, perhaps because it minimizes surface evaporation.
Adding the acidified iodine solution to the products of the
sodium zincate reaction, instead of flushing the products into
the iodine solution as recommended, gives high results, because
some iodine then reacts with caustic soda before complete neutralization takes place. Acidifying the products of the reaction before adding the iodine solution, and then titrating, is also
an undesirable procedure, for some hydrogen sulfide always
escapes, even under strong cooling.
The quantitative transfer of products and acidified iodine solution back into the original Erlenmeyer flask is also essential.
Often very small amounts of zinc sulfide adhere to the flask and
(Houra)
25
30
35
40
45
50
42.5
41.1
40.3
39.1
38.1
36.8
44.1
42.4
41.7
40.2
39.5
37.9
13.4
12.6
12.0
11.4
10.7
10.1
REAGENTS.
The solutions required for total sulfur determination and also a saturated solution of C.P. sodium chloride.
PROCEDURE.
Pipet 100 ml. of the diluted viscose prepared
for the determination of total sulfur (25 grams in 250 ml.) into a
500-ml. volumetric flask packed in ice and complete the volume
with an iced saturated solution of sodium chloride. Mix well
and allow to stand for 15 minutes. (In the caw of unripe viscoles, the rate of settling of coagulated xanthate is likely to be
low. A centrifuge may be advantageously used to hurry the
settling and speed up the analytical procedure.) Filter through a
dry fluted paper of rapid filtering characteristics. Pipet 50 ml.
of the filtrate into a 500-ml. Erlenmeyer flask and determine its
sulfur content as carbon disulfide by the method described.
Calculate the gamma number from the equation:
GammaNo. =
- % by-product CSn)
% cellulose
626
--r
1.50 -
Vlbcotr
753-BOl685
I-
2 1.40 -
--
3
ti
11.30
.-PoP
:*:1.20 N
The new volumetric procedure presented in this paper is satisfactory for determining the total cwbon disulfide combined in
viscose. I t is simpler and much faster than the conventional
gravimetric procedure.
It is particularly well suited for prompt location of any leaky
carbon disulfide reactor and therefore can contribute efficiently
to better plant control operation. Failure to appraise accurately
and at the proper time any deviation from standard is often the
cause of misdirected effort, deterioration of quality, and unnecessary expense.
Reproducibility and degree of accuracy compare well with the
conventional gravimetric method currently used in viscose plants.
The accuracy falls within permissible limits of variation.
In determination of the gamma number or of xanthate sulfur,
1.10
-I
I
I
l14
I
I
I
I
IO
Hcttanroth Index
the suggested procedure is obviously handicapped by the possibility of incompletely salting out the sodium cellulose xanthate,
or by the possibility that the precipitated sodium cellulose xanthate may retain by-product sulfur. Nevertheless, where great
accuracy is not required, this volumetric procedure makes possible the running of a set of determinations with ease and rapidity.
Another advantage over the conventional gravimetric method
is the fact that sulfates, if present, do not react, and consequently do not interfere with the result.
ACKNOWLEDGMENT