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ACID ADSORPTIOX AND STABILITY OF NITROCELLULOSE

BY D. R. WIGGAM*

Introduction It is well known that traces of acid adsorbed by nitrocellulose accelerate its thermal decomposition. The type of acid is unimportant, with the possible exception of the weakest organic acids. The stability is lowered in a degree proportional to the amount of acid adsorbed. The present work has been confined to strong acids, as it is these which are of principal importance to the manufacturer and user of nitrocellulose. Experimental
The determination of acid adsorption is direct. Two grams of nitrocellulose, dried to constant weight at 7ooC., were added to 50 cc. of N / I O Oacid and allowed to stand for 15-30 minutes with occasional stirring. Longer standing was not found necessary. An aliquot was withdrawn and titrated with standard base, using methyl orange as the indicator. The reading of the endpoint at these dilutions requires some practice but becomes quite precise after a few trials. Base consumption by the sample was carried out in an analogous manner. Adsorptions are reported as cubic centimeters of N '100 acid used up per gram of nitrocellulose. Thermal decomposition was followed by the 134.5'C. methyl violet test. Two and five-tenths gram samples of oven-dry (70C.) nitrocellulose are placed in special test tubes and tamped tightly. A methyl violet test paper is placed in the tube above the nitrocellulose and the mouth of the tube plugged with a perforated stopper. The tube is placed in a special constant temperature bath a t 134.5Oc. and heated until the paper has completely changed color to a salmon pink. The time required for this change in color is reported. Two types of nitrocellulose were first studied, designated as 5119with nitrogen content 13.09 per cent and 4200 with nitrogen content 13.47 per cent. These are smokeless powder types, and in the process of manufacture had been reduced to pulverulent condition. They were stabilized by usual methods of processing. With sulfuric, nitric and hydrochloric acids, adsorption data are given in Table I. Experiments I, z and 3 indicate how closely the results of successive determinations checked. Sulfuric and nitric acids are adsorbed to the same degree; hydrochloric acid somewhat less. The two nitrocelluloses were suspended in N/IOOa O H . Aliquots of the S supernatant liquid were removed and titrated with acid. Three one-hundredths cc. I ~ / I OXaOH were used up per gram of sample by 5119,and O
*Hercules Powder Company.

ACID ADSORPTION AND STABILITY OF NITROCELLULOSE

53 7

A
No.
I
2

cc.

?;/IOO

TABLE I acid adsorbed per gm. X.C.


A Exp. No.

Exp.

N.C.
5119 5119 5119 5119

Acid
1I

K.C.
jI19 4200
4200 4200

Acid

H ~ S O I 0.44

3 4

,,
HSO,

0.46 0.45 0.46

5 6 7 8

HC1 HtSO4 HNO3 HCl

A 0.41 0,37 0.36 0.29

Faint traces of acid 0 . 1 2 cc. ~ , J I O O KaOH were used up per gram by 4200. may be present on nitrocellulose from incomplete removal in its preparation or from incipient thermal decomposition on drying. At ordinary storage temperatures with moist material the latter reaction has almost zero rate. If the residual adsorbed acid had been removed before suspending in acid, the adsorptions would have been as follows : H2S0, HSO, HC1 HzSOi HSO, HC1
- 0.45

- 0.46

+ 0.03 = 0 . 4 9 - 0.41 + 0.03 = 0.44


- 0.37 - 0.36

+ o .03 = 0 . 4 8 cc./gm.

5 I 19
J )
1)

3 0.12 .

- 0.29 + 0 . 1 2

0.12

= 0.49 = 0.48 = 0.41

4200

To verify the above results, samples of 5119 and 4200 were enclosed in semi-permeable nitrocellulose membranes and suspended for 3 0 days in distilled water, which was replaced continuously. No. 5 I 19 then adsorbed 0.51 oc. K/IOOsulfuric acid and 4200 adsorbed 0.50 cc. X / I O Oacid. The resultis agree within the limit of accuracy of the method. Adsorptions were determined in the above manner on two further samples of nitrocellulose of different nitrogen contents. (Table II), KO. 734 was longfibre inaterial of nitrogen 12.15 per cent, No. 4467 was pulverulent, with 12.86 per cent nitrogen. TABLE I1 A = cc. X/IOOacid adsorbed per gm. X.C.
N.C. 734
734

Acid

734

His04 HS03 HCl

0.87 0.88 0.66

N.C. 4467
4467

Acid

4467

HzS04 HhT03 HCl

0.36
0.38

0.34

The results follow, in general, the same trend as shown with the higher nitrogen samples. Base consumptions for the above samples showed that 0.58 cc. N/IOObase were required per gram of 734 and 0 . j 4 cc. for 4467. Had the samples been purified by dialysis the sulfuric acid adsorptions would have been, 7 3 4 . . . . . . . . .0.87 0.58 = I .45 cc.
1467 . . . . . . . . . .0 . 3 6

+ + 0.54 = 0 . 9 0 ~ ~ .

538

D. R. TVIGGAM

The total acid adsorption is thus dependent on the nitrogen content of the nitrocellulose. The total surface of the individual samples of nitrocellulose was not determined. The specific surface would vary from sample to sample, due to different degrees of pulping, but for any one sample would be substantially constant. Known amounts of acids were deposited on nitrocelluloses 5 I 19 and 4200, and the stabilities determined by the methyl violet test. After suspension in N / I O O acid, the sample was filtered on a Buchner funnel and sucked as dry as possible. I t was then stirred into 1000 cc. distilled water and agitated for several minutes, filtered and dried. Acid adsorptions were run with sulfuric, nitric and hydrochloric acids. Knowing the total adsorptive capacities from previous data, the retained acid could be calculated. Table I V gives this data, together with the methyl violet heat. tests.

TABLE IV
N.C.
5119 519 519 519 5119
4200 4200

Kind of Acid

cc. N/roo Acid Ads. after Treatment


0.20
0.32

cc.N,roo Acid Retd.

Methyl Violet Test

Original* HzSO4 H2S04 HXOs HC1 Original* HzSOi

0.03 0.29 0.16


0.40

28 Min. 263
27

0.08

261

0.13 0.25

0.31
0 . 1 2 0.24

263
25

271

* This refers to untreated sample. Retained acid may be nitric or sulfuric or both.

Traces of free acid have a distinct effect in lowering the methyl violet test. In spite of their greater volatility at the temperature of the test, hydrochloric and nitric acid, when adsorbed, have approximately the same effect as sulfuric in lowering stability of nitrocellulose. Xone of the samples exploded in five hours in the bath. Larger amounts of sulfuric acid were deposited on nitrocellulose by evaporation of dilute acid solutions in contact with 5119 at low temperature. After drying, the stabilities were determined by the methyl violet test. The results are given in Table V and Fig. I .
TABLE

Equivalent 101. of Mols Acid/Gm. NirooAcidlGm. N.C. K.C. 0.00004793 4 793 2,647 o .00002647 I . 178 0 . 0 0 0 0 1 178 I ,096 0.00001096 0.649 0.00000649 0.29 * o .000002 9 * From Table IV.

Methyl Violet Test


j$

Min.

If

&me 19 Min.

Ex losion

45
j j

8 ;
IO$
264

82 A h .

+ Hrs. + Hrs. 5 + Hrs. 5 + Hrs.

ACID ADSORPTION AND STABILITY OF NITROCELLULOSE

539

If the acid adsorbed is of the order of 3 X IO^ mols. per gram of nitrocellulose or less, the effect on the resistance to decomposition (stability) is not serious. It should be noted that this figure applies only t o high nitrogen content nitrocellulose for use in smokeless powder. For the lower nitrogen content nitrocelluloses, much larger amounts of acid would be required to have a proportionate effect.

FIG.I
Effect of adsorbed Acid on Stability

summary

At the dilutions used in this work, nitric and sulfuric acids are adsorbed to approximately the same extent, while hydrochloric acid is adsorbed to a somewhat lesser degree. Base adsorption by nitrocellulose apparently does not take place. When nitrocellulose is dipped in dilute base, some of the latter is used up to neutralize the acid present on the fibre, accounting for an apparent adsorption. When this acid is removed by dialysis, the acid adsorption becomes equal to the acid plus base consumption of undialyzed fibre. Acid retained by the fibre lowers the resistance to heating of nitrocellulose with a given sample. The effect of equal amounts of the three strong acids used lowered the heat resistance to approximately the same degree. A smooth curve is obtained by plotting the results of the methyl violet test (stability) against the acid adsorption.

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