1792
method can be adapted for wide use. The adaptation must take
Table VII. Sample Analyses of Certain Treated Ammonia
Still Wastes
Saii:L4c 1 Vntreated 500 p.p.rn. phenol-+amino antipyrine teat
Lntreated 509 p.p.m. phenol-bromine t.ut.i2i:netric rest
Sample 2 L'ntreatcd 1100 p.p.rn. phenol-hron.ine t,irbi iirnetric tcit
Jainlde 1 Tre2ted with increasing ai?ioii1its oi a n o x i c l i z i i i ~agent
Phenol Units of Oxidizing
Found, P.P.31. Agents Used
48 2.5
3.4 5 0
2.5 8.4
1.3 10.0
Sample 2 9.4 Treated with active charcoal
author's experience indicates, however, that this will seldom be
necessary.
The time required for determining phenols by the described
procedure varies from about 20 minutes for the bromine turbidi-
metric test t o about 2 hours for determining a 25 p.p.b. concen-
tration by the 4-aminoantipyrine procedure.
COiYCLUSION
h procedure has been developed for determination of any
concentration of phenols likely to be met in aqueous wastes of
I)y-product coke plants. I t seems highly probable that the
Determination of Sodium Carboxymethylcellulose in
Detergent Mixtures
By the Anthrone Method
HENRY C. BLACK, JR.
Burnside Laboratory, E . I . du Pont de Nemours & Co., Inc., Penns Grove,
A method was needed for determination of sodium
carboxymethylcellulose in household detergents.
The green color formed by reaction of anthrone with
carbohydrate materials in sulfuric acid solution pro-
vided the basis for the present method. Color in-
tensity is measured with a spectraphotometer.
Controlled heating is necessary for reproducible re-
sults. Color intensity varies inversely with degree
of substitution of the carboxymethylcellulose. The
I S 1946, Dreywood ( 3 ) described a qualitative method for the
detection of carbohydrates by the use of anthrone (9,lO-
dihydro-9-ketoanthracene) in concentrated sulfuric acid. The
formation of a green-colored complex indicated a positive test.
Other investigators (6, 9) attempted to adapt the method to the
quantitative estimation of carbohydrates. Viles and Silverman
(9) described a procedure for the determination of cellulose in the
dust of air samples collected in a textile mill. In this procedure,
the dust was dissolved in 60% (by volume) sulfuric acid and a
O.lyosolution of anthrone in 9570 sulfuric acid was added. The
heat evolved on mixing developed the color. The solution was
cooled after formation of the green color, and its transmittance
at 625 mp was measured with a photometric instrument. The
cellulose concentration was calculated from a calibration curve
prepared in the same manner using known quantities of cellulose.
Dreywood (3) demonstrated that positive results were obtained
not only with carbohydrates but with certain carbohydrate
ANALYTICAL CHEMISTRY
into consideration both the type of phenolic bodies to be deter-
mined and the impurities to be removed.
As might reasonably be expected, the results on the mixed
tar acid solutions (Table 11)are noticeably lower than those on
pure phenol (Table VI). This is presumably due in part to the
p-cresol which, in isolated condition, a t least, gives no color with
the 4-aminoantipyrine reagent, and to the difference in molecular
weight of the alkylated phenols.
The results given in Table VI1 on sample I, untreated, show the
turbidimetric bromine test and the antipyrine test to be in good
agreement, though the turbidimetric test is much quicker.
The remainder of the figures illustrate the manner in which the
effects of a progressive purification treatment of waste can be
followed by meany of the proposed analytical method.
LITER4TURE CITED
Baylis, J . Am. Wuter W o r k s Assoc., 19, 597-604 (1928).
Emerson, J . O r g . Chem., 8, 417-19 (1943).
Emerson and Kelly, Ibid., 13, 532-4 (1948).
(4) Martin, ANAL.CHEM.,21, 1419 (1949).
(5) Shaw, ISD. ENG.CHEM.,ASAL. ED.,1, 118 (1929).
(6)Ibid., 3, 273 (1931).
(7) Stevens, I n d . Eng. Chem.. 35, 655 (1943).
RECEIVED October 4, 1950. Contribution of the Fellowship o n Gas Purifica-
tion sustained a t Mellon Institute by Koppers Co.. Inc.
N. J .
accuracy is 2% relative, provided the degree of sub-
stitution is known. Other carbohydrates, carbo-
hydrate derivatives, furfural, 5-hydroxymethylfur-
fural, and certain polyoxyethylene derivatives of
fatty acids and phenols are the only known inter-
fering substances. The method should be useful for
determination of carboxymethylcellulose in other
mixtures and, with appropriate modification, of
other carbohydrates and carbohydrate derivatives.
derivatives as well. Samsel and DeLap ( 7 ) applied the an-
throne reaction to the determination of methylcellulose.
Initial attempts to apply the procedure developed by Viles and
Silverman to the determination of sodium carboxymethylcellulose
(NaCMC) in detergent mixtures were unsuccessful. Repro-
ducible results were very difficult to obtain, primarily because
of the lack of control of the heat evolved on mixing the sample
and the anthrone reagent. In order to improve the reproduci-
bility, it was necessary to eliminate the heat evolved on mixing
and then develop the color by heating under controlled condi-
tions.
APPARATUS AND MATERIALS
All transmittance measurements were made with a Beckman
Model DU spectrophotometer with 1.00-cm. Corex cells.
Samples of sodium carboxymethylcellulose of low (0.1 t o
0.8) degree of substitution, manufactured as technical grade by
V O L U M E 23, N O . 1 2 , D E C E M B E R 1 9 5 1
the Du Pont Co., were purified by precipitating the free acid
carboxymethylcellulose with strong mineral acid and washing
with water. The purity of the free acid carboxymethylcellulose
after washing and drying was assumed to be lOOy,. Refined
sodium carboxymethylcelluloses of high degrees of substitution
(greater than 1.0) were specially prepared by R. W. Sommers and
M. F. Fuller a t the Burnside Laboratory and were used without
further purification. Purity of refined sodium carboxymethyl-
cellulose was determined by ash and by the copper salt precipita-
tion method ( 2 ) .
100
1 1
BLANK
Q U A N T I T Y OF ' M A T E R I A L ' . I m g / 5 0 m l
I I
200 450 500 550 600 650
W A V E LENGTH IN my
Figure 1. Spectral Transmittance of Complexes of
Anthrone with Cellulose and with
Carboxymethylcellulose
The anthrone (melting point 154-155" C.) was obtained from
The Matheson Co., East Rutherford, N. J., and was used without
further purification.
The anthrone-sulfuric acid solution was prepared by dissolving
1 gram of anthrone in 1 liter of 95% sulfuric acid. The solution
was allowed to stand for a t least 4-hours before using and was
discarded after it was 24 hours old. Just before use, the con-
centrated acid reagent solution was diluted with water to 60y0
(by volume) sulfuric acid, and cooled to room temperature.
PROCEDURE
The sample, usually about 1 gram of a typical powdered house-
hold detergent, is dissolved (2 to 3 hours) in 607, (by volume)
sulfuric acid and made up to volume with 60% sulfuric acid in a
100-ml. volumetric flask. If the solution is not clear, it is filtered
through a dry medium porosity sintered-glass crucible into a dry
container. An ali uot containing not more than 1.0 mg. of
sodium carbox~me%~lcellulose is placed in a 50-ml. volumetric
flask, 30 ml. of the diluted anthrone reagent are added, and the
flask is placed in a boiling water bath for 15 minutes. The
C O N C E N T R A T I O N I N rng 50ml.
Figure 2. Transmittance of Anthrone Complex us.
Cellulose or Carboxymethylcellulose Concentration
1793
solution is cooled immediately and diluted to the mark with 60%
sulfuric acid. The transmittance a t 625 mF is measured with a
Beckman spectrophotometer or other photometric instrument.
A calibration curve is prepared by dissolving 0.1 gram of sodium
carboxymethylcellulose, of the same degree of substitution as
the sodium carboxymethylcellulose in the detergent, in 100 ml.
of 607, sulfuric acid, and repeating the procedure on 0.2-, 0.5-, *
and 1.0-ml. aliquots of this solution. A plot of transmittance
against concentration is made on one-cycle semilog aper and the
best straight line is drawn through the points. TRe concentra-
tion of sodium carboxymethylcellulose in the sample solution
is read from this curve.
I If the degree of substitution of the sodium carboxymethyl
cellulose in the sample is unknoiin, an estimate must be made on
the basis of experience or other information.
EXPERIMENT4L
Figure 1 shows the curve obtained Fvhen transmittance of the
green comples is plotted against wave length, for cellulose and
carboxymethylcellulose. Maximum absorption occurs a t 625
mp. The concentrations of cellulose and carboxyniethyIreIlu-
lose were identical.
Figure 2 shows the adherence to Beer's law when the logarithm
of the transmittance is plotted against concentration. I t can be
seen from Figures 1 and 2 that at a given concentration the
transmittances obtained u-ith cellulose and with carbosymethyl-
cellulose are very different. This difference is discussed below.
Effect of Temperature. I t had been recognized by previous
700 750
investigators that an elevated temperature was necessary to
develop the color and that the heating time had a critical effect
on the intensity of the color produced. Several determinations
were made using the same conditions throughout, except for the
time of heating. I t was found that minimum transmittance
occurred a t about 15 minutes (Figure 3).
- 0o IO 20 30 40 50
TIME I N MINUTES
Figure 3. Effect of Heating Time on Color
Development
Effect of Aging Reagents and Solutions. One of the main
disadvantages of the method is the instability of the anthrone-
sulfuric acid reagent. Variable results are obtained if the
reagent is used before it is about 4 hours old. Progressively
diminishing color intensities are produced as the age of the
reagent increases beyond 24 hours. Likewise, color intensity
decreases as the age of the sulfuric acid solution of cellulose
material increases. Table I illustrates the effect of the age of
the reagent, and Table 11, the effect of the age of the sample
solution.
After the green complex has been formed, the color is stable
for several hours. The transmittance increases only about 1%
in 24 hours. I t is not necessary to prepare a calibration curve
for each determination if sample solution and reagent are aged
1794 ANALYTICAL CHEMISTRY

Table I. Effect of iging Reagent

Age of % Tof
.4nthrone Sollition Complex a t 623 nip
24 hours 29
2 days 31.5
6 days 39.5
9 days 37

Table 11. Effect of Aging Sample Solution

Age of 7a T o f
dsriiple Solution Complex a t 623 nip
3 hours 29
44 hoiirs 29
6 days 33
9 da$s 36

properly. It is convenient to prepare the anthrone reagent in

the Iate afternoon of the day before it is needed. The sample is
dissolved the next day and the color developed as soon as the
sample is completely dibsolved. Less than 2% error occurred
when the same calibration curve was used for 2 to 3 weeks. If an
error of more than about 2% was obtained, it could usually be
traced to improper aging or operator error.

>
D E G R E E OF S U B S T I T U T I O N
Figure 5 . Effect of Degree of Substitution of
Carboxymethylcellulose

stitution ranging from 0 to 2.2 were analyzed in 60% sulfuric

acid. It was found that the color intensity decreased as degree of
substitution increased. By calculating the extinction coefficient
a t 625 mg, and plotting this value against degree of substitution,
the curve shown in Figure 5 was obtained. The value of 285
a t a degree of substitution of 0 was obtained on the starting
material before etherification. From a value of 285 the ex-
tinction coefficient drops rapidly until a degree of substitution of
about 1.0 is reached. The rate of decrease in extinction coefficient
diminishes as the degree of substitution increases beyond 1.0.

0
e o v o H Z 5 0 4 - i o m g . CELLULOSE / 5 0 m i . I Therefore, it is necessary to use a calibration curve which has
been pi epared from sodium carboxymethylcellulose of the same
0 5 IO I5 20 25
T I M E IN.MINUTE5
Figure 4. Effect of -4cid Concentration on Color
Development

Effect of Acid Concentration. To determine the effect of acid

concentration on color intensity and on the time required for the
development of maximum intensity, the procedure as described
tvas followed, using solutions containing, respectively, 60, 70, 80,
and 90", sulfuric acid. It was found (Figure 4) that the time
required for maximum color development decreases with in-
creasing acid concentration until the acid concentration reaches
about 80%. At 90To acid concentration the course of the
reaction appears to be altered.
Another effect of higher acid concentrations is to increase the
intensity of the color produced. Approximatelr the same
transmittance is obtained Rith 0 . 5 mg. of cellulose in 80% sul-
furic acid as with 1.0 mg. of cellulose in 6070 sulfuric acid.
Therefore, smaller quantities of cellulose can be determined by
increasing the acid concentration. I I I I

a00 240 280 320 360 IO

Effect of Degree of Substitution. As the calibration curves W A V E LENGTH I N mp
for cellulose and carboxymethylcellulose did not coincide, i t was
necessary to determine the effect of the degree of substitution Figure 6. . Spectral Transmittance
of the carbox3.methylcellulose on color intensity. Several 1. Hydroxymethylfurfural
2. Solution of cellulose in 60% sulfuric acid
samples of sodium carbo.;yrnethJ.lcellulose with degree of sub- 3. Solution of carboxymethylcellulose in 60 70sulfuric acid
V O L U M E 23, NO. 12, D E C E M B E R 1 9 5 1 1795

degree 01' FulBxtitution as sodiun~carboxymethylcellulose in the furfural than did the cellulose solution. I t may be that sub-
material to be analyzed. stituents in the 2 and/or 3 positions interfere with the formation
Probable Mechanism of Color Formation. The mechanism of 5-hydroxymethylfurfural.
of the i,eartiori betn-een cellulose, and anthrone is not fully under- Applications. Several commercial household detergents and
stood. .\?cording to Karrer ( 5 ) .anthrone reacts with aldehyde soaps were analyzed for sodium carboxymethylcellulose by the
01' ketone group.. Sattler and Zerban (8) postulated that the method. A weighed amount of sodium carboxymethylcellulose
waction with sugars involves conversion of the sugar to furfural TT-as added and the analysis repeated. The results, shown in
or a furt'ural derivative by deb>-dration and ring formation. Table 111, indicated substantially quantitative recovery of the
\\~olfroni.Schuetz, and Cavalieri ( I O ) demonstrated the forma- added sodium carboxymethylcellulose.
tion of j-h?-tlroxymethylful.Eural from glucose by refluxing in Interferences. Phosphates, silicates, and fatty acids appeared
neutral or. acid aqueous solution. Heuser ( 4 ) stated that t,he not to interfere with the determination of sodium carboxymethyl-
\.ield of gluco~cfrom the sulfuric acid hydrol>-sis of c-?llulow is cellulose in detergents and soaps. Carbohydrates, carbohydrate
R I I O U t '36';. derivatives, furfural, and 5-hydroxymethylfuI.iural all give
tolored complexes, anti each would interfere in the determination
of another member of the group. S o other int,erferences were
Table 111. Determination of Sodium Carbox\methjl- found here. Certain polyoxyethylene derivatives of fatt5- acids
cellulose in Detergents and Soaps and phenols have been reported to depress color formation ( 1 ) .
Original Sucah compounds can usually be removed from dry mixtures by
KaChlC IiaCJIC NaCh'lC NaCMC
Contenta, Added Present, Found, Diffrrrncr extraction with anhydrous alcohol.
c7
% % % % /c Although the method was developed primarily for the deter-
Detergent A 1.25 0.W 1.94 1.9; io.01 mination of sodium carhox?.meth!.l(~ellulose in detergent mix-
Detergent B 0.17 0.68 0.85 0.86 n oo
Detergent C 0.42 0.68 1.10 1.12 f0.02 tures. it is believed that it will be found useful for the determina-
Detergent D 0.53 0.68 1.21 1.23 t o , 02
Soap E 0.00 0.69 0.69 0.6Y 0.00 tion of sodium carboxymethylcellulose in other mixtures and for
Soap F 0.00 0.69 0.69 0.6Y 0.00 the determination of other cellulose derivatives.
* Ry a n t t r o n e method, sample size 0,1000 gram (in aliquot)
LITERATURE CITED
(1) C'oiiner, -4.Z.. private communication.
Solutions of cellulose and of rarboxymethylcellulose in 60% ( 2 ) Conner, &4.Z.,and Eyler, R. TV., AN-AL.CHEM.,22, 1129 (1950).
sulfuric acid were heated in the boiling water bath for 15 minutes (3) Dreywood, R., ISD.Eso. CHEM.,Asar. ED.,18, 499 (1946).
(4) Heuser, Emil, "Cellulose Chemistry," p. 520, Xew York, John
and cooled as in the analytical procedure. The ultraviolet Wiley & Sons, 1944.
absorption curves of these solutions were similar in shape t o that (5) Karrei., Paul, "Organic Chemistry," p. 405, ?;em T o r k . Norde-
of ~-h~tlroxyniethylfurfural!with an absorption maximum a t man Publishing Co., 1938.
290 mM (Figure 6). Although the indicated yields of b-h>-droxy- (6) Morse. E. E., ASAL. CHEY..19, 1012 (1947).
(7) Samsel, E. P., and DeLap, R. A . , I b i d . . 23, 1795 (1951).
methylfurfural ~ w r e much below theoretical, this evidence (8) Rattler. L.. and Zerban. F. IT., Science, 108, 207 (1948).
tends t o confirm the formation of 5-hydroxymethylfurfural (9) Viles, F. .J.. ,Jr., arid Silrerman, L.. - 4 s . k ~ . CHEZI.,21, 950
as an intermediate in the color-forming reaction. I t seems prob- (1949).
&le that ceilulose is hydrolyzed to glucose by sulfuric acid in the (10) TTolfrom, 11. L.. Schuetz. R. D., and Caralieti, L. F., J . Am.
C'hem. Soc., 70, 514 (1948).
cold, the glucose yields 5-h-droxymethylfurfural by deb!-dration
and ring formation on heating, and the 5-hydroxymethylfurfural RECEIVED M a y 19, 1931. Presentpd before the Analytical Chemistry Divi-
sion of the Third Delaware Chemistry Symposiuni. Delaware Section,
then wa(,t.swith anthrone to give the color. The carboxymethyl- AMERICANC H E M I C A L SOCIETI-.University of Delawnrr, S e w a r k . Del.,
olutioii gavr a loiver apparent yield of 5-h>-droxyinrth>-l- J o n r u r v 13, 1951.

Colorimetric Determination of Methylcellulose

with Anthrone
E. P. S.IMSEL AUD R. A. DEL-IP
The Dow Chemical Co., Midland, Mich.

T HE rapidly increasing commercial importance of methyl-

cellulose ( 3 ) makes desirable the development of a colori-
metric method to be used in conjunction with the well-known
alkoxy1 determination ( 1 , 7 ) . Methods have been developed for
the identification of this paiticular cellulose ether when it is found
incorporated with other mnteiiale such as starch, gums, emul-
sions, and suspensions.
Methocel ( D o x meth: lcellulose) is an ether of cellulose formed
by interaction of methyl rhloride and cellulose n hich has been
saollen by treatment with a strong base. TWOtypes are avail-
able, a water-soluble material and an alkali-soluble material;
the latter has a lower degree of substitution. The tests described
herein are applicable to both types, but unless specifically men-
tioned, the water-soluble type is meant. The Tvater-soluhle ma-
terial is a white, odorless, tasteless powder n-hich is soluble in cold
water, but soluble to only a very slight degree in hot water, an in-
teresting and unusual property. The solubility of the several
viscosity grades in hot 1%-aterwas studied. Methocel is insoluble
in most saturated salt solutions and most organic solvents.
Methylcellulose (6) can be separated from starches and gums
by first dissolving in water and then adding alcohol to throw out
these materials. T e a k acids or alkalies may be added to remove
interfering substances.
Water-soluble impurities may be separated from methgl-
cellulose by hot water extraction. Sodium carboxymethylcellu-
lose, being soluble in hot water, can be extracted from methyl-
cellulose in this manner.
The use of anthrone as a qualitative and quantitative test for