192 ANALYTICAL EDITION Vol. 5 , No.

purity of the plasticizer was determined by refractive index
measurements, as well as by saponification values if the
plasticizer belonged to the ester type.
SUMMARY
A rapid method for the separation of plasticizers from or-
ganic cellulosic plastics, described in this article, has been
shown to be to cellulose, cellulose,
and cellulose acetate plastics.
Its accuracy, when- applied quantitatively to the determi-
nation of plasticizer content of organic cellulosic plastics,
was found satisfactory for practical purposes.
LITERATURE
CITED
(1) Bradley, IND. ENO.CHEM.,Anal. Ed., 3, 306 (1931).
(2) Gardner, “Physical and Chemical Examination of Paints,
Varnishes, and Lacquer,” 5th ed., pp. 491-550, 818-28, 850,
Institute of Paint and Varnish Research, Washington, 1930.
(3) Hickman and Sanford, J. Phys. Chem., 34, 637 (1980).
RECEIYBD
December 19, 1932.

Preparation of Sodium Hydroxide Solutions of

Low Carbonate Content by Centrifugation
NELSONALLEN AND GEORGEW. Low, JR.
Frick Chemical Laboratory, Princeton University, Princeton, N. J.

H AVING had occasion to prepare sodium hydroxide

solutions of low carbonate content, the use of a centri-
fugein connection with the oily alkali method (6) sug-
gested itself. This method has long been used for preparing
4.2 as determined by methyl orange indicator and a buffer
solution. The natural offset between the two end points
for pure water was found to be 0.140 ml. and this correction
was applied. Some typical data are given in Table I.
sodium hydroxide solutions and possesses the advantages of
simplicity and freedom from the introduction of contaminating DISCUSSION
OF RESULTS
ions. On the other hand it has the disadvantages of extreme
slowness and incomplete removal of carbonate. Clark (1) Nan and Chao (2) secured an average value of 0.15 per cent
speeded up the process by filtering the alkali through paper, for the hydrochloric acid used for the carbonate in their
and Kolthoff (4) filtered it through a Jena sintered-glass solutions, whereas the above data show a n average of 0.12
crucible. Han and Chao (g), who have recently made a per cent for the centrifuged alkali. This clearly indicates
comprehensive study of all methods of preparing alkali free that centrifugation gives a lower content of carbonate in the
from carbonate, clarified the solution by heating in a water alkali with a very much smaller expenditure of time and
bath (6) and followed this by filtration through glass. Ap- labor. Then, too, no elaborate heating or filtering devices
parently no one has made use of the centrifuge for the clari- are needed.
fication. Forty milliliters of a 0.1124 N sodium hydroxide solution
prepared by diluting the centrifuged alkali with carbon di-
EXPERIMENTAL oxide-free water required an average of 0.190 ml. of 0.0998 N
Samples of the oily alkali were prepared by dissolving 50 hydrochloric acid to go from the phenolphthalein end point
grams of pellet sodium hydroxide in 50 ml. of carbon dioxide- to pH 4.2. This value less 0.140 ml. (the natural offset)
free water. After cooling, each lot was transferred to a Pyrex equals 0.050 ml., which corresponds to the carbonate content.
centrifuge tube, made from a 125-ml. Erlenmeyer flask by Solutions prepared in this manner are perfectly satisfactory
rounding out the base and blowing out an opening to fit a No. for all ordinary titrations.
2 rubber stopper. The neck of the flask was drawn off and
a tube 5 cm. long and 0.8 cm. inside diameter sealed on. MODIFIEDTITRATION
HEAD
Centrifuging for 30 minutes a t 2200 to 2300 r. p. m. gave ab- In connection with the above work the titration head
solutely clear solutions with the undissolved carbonate and recommended by Hillebrand and Lundell (3) has been modi-
alkali tightly packed in the bottom. fied by leading the carbon dioxide-free air stream through a
tube passing through the cap by a ring seal and extending
I. CARBONATE
TABLE CONTENT
OF ALKALI
down about 8 cm. below the top of the head. This change
TOTAL VOL. ACID VOL.HCl FOR PERCENTHCI
SAMPLE AS 0.0998 N HC1 cos - - FOR cos-- insures that the titration flask will be completely swept out
M1. M1. by the air stream. The head was made of very heavy Pyrex
tubing and of a size to fit over a 250-ml. Erlenmeyer flask.
1
2
BEFORE CENTRIFUQINQ
273.36
270.67
2.40
2.42
0.88
0.88
. Such a titration head makes a very rugged and useful piece
3
4
306.66
276.24
2.48
2.26
0.81
0.82
of equipment,
AFTBR CENTRIFUQINQ
1 271.28 0.314 0.12
LITERATURE
CITED
278.37 0.284 0.10 (1) Clark, “Determination of Hydrogen Ions,” Williams and Wilkins,
2 309.36 0.610 0.16
3 276.33 0.280 0.10 1928.
4 330.64 0.450 0.14 (2) Han and Chao, IND. ENQ.CHEM.,Anal. Ed., 4, 229 (1932).
Av. 0.12 (3) Hillebrand and Lundell, “Applied Inorganic Analysis,” p. 141,
Wiley, 1929.
Samples of alkali were analyzed for carbonate before and (4) Kolthoff and Furman, “Volumetric Analysis,” Vol. 11, Wiley,
after centrifuging by titration in the absence of carbon di- 1929.
(5) Pregl, 2. anal. Chem., 67, 23-7 (1925).
oxide with standard hydrochloric acid. On reaching a (6) Sbrensen, Biochem. Z . , 21, 186 (1909).
phenolphthalein end point the titration was continued with
0.0998 N hydrochloric acid, from a microburet, to a pH of RECEIYED
January 31, 1933.