MASTER

P^V UCRL-7873

University of California

Ernest O. Lawrence Radiation Laboratory

SOME ANALYTICAL METHODS FOR EXPLOSIVES AND EXPLOSIVE SIMULANTS

Livermore, California

DISCLAIMER This report was prepared as an account of work sponsored by an agency of the United States Government. Neither the United States Government nor any agency Thereof, nor any of their employees, makes any warranty, express or implied, or assumes any legal liability or responsibility for the accuracy, completeness, or usefulness of any information, apparatus, product, or process disclosed, or represents that its use would not infringe privately owned rights. Reference herein to any specific commercial product, process, or service by trade name, trademark, manufacturer, or otherwise does not necessarily constitute or imply its endorsement, recommendation, or favoring by the United States Government or any agency thereof. The views and opinions of authors expressed herein do not necessarily state or reflect those of the United States Government or any agency thereof.

DISCLAIMER Portions of this document may be illegible in electronic image products. Images are produced from the best available original document.

LEGAL NOTICE This report was prepared as an account of Government sponsored work. Neither the United States, nor the Commission, nor any person acting on behalf of the Commission: A. Makes any warranty or representation, expressed or implied, with respect to the accuracy, completeness, or usefulness of the information contained in this report, or that the use of any information, apparatus, method, or process disclosed in this report may not infringe privately owned rights; or B. Assumes any liabilities with respect to the use of, or for damages resulting from the use of any information, apparatus, method or process disclosed in this report. As used in the above, " person acting on behalf of the Commission " includes any employee or contractor of the commission, or employee of such contractor, to the extent that such employee or contractor of the Commission, or employee of such contractor prepares, disseminates, or provides a c c e s s to, any information pursuant to his employment or contract with the Commission, or his employment with such contractor.

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UCRL7873 DE88 004062

UNIVERSITY OF CALIFORNIA Lawrence Radiation L a b o r a t o r y Livernnore, California Contract No. W-7405-eng-48

SOME ANALYTICAL METHODS FOR EXPLOSIVES AND EXPLOSIVE SIMULANTS Walter Selig May 1964 DISCXAIMER
This report was prepared as an account of work sponsored by an agency of the United States Government. Neither the United States Government nor any agency thereof, nor any of their employees, makes any warranty, express or implied, or assumes any legal liability or responsibility for the accuracy, completeness, or usefulness of any Information, apparatus, product, or process disclosed, or represents that its use would not infringe privately owned rights. Reference herein to any specific commercial product, process, or service by trade name, trademark, manufacturer, or otherwise does not necessarily constitute or imply its endorsement, recommendation, or favoring by the United States Government or any agency thereof. The views and opinions of authors expressed herein do not necessarily state or reflect those of the United States Government or any agency thereof.

I . ' '

PREFACE This r e p o r t is a corapilation of methods for the a n a l y s i s of explosives and explosive s i m u l a n t s . All of the methods with the exception of Section I w e r e p r e p a r e d for routine a n a l y s i s by technicians and an attempt has t h e r e fore been made to keep t h e m as simple as possible. Where p o s s i b l e , solvent extraction methods have been used. Section I p r e s e n t s a method for the estimation of the explosives RDX and HMX by m e a n s of nonaqueous t i t r i m e t r y . Analytical methods for extrusible explosives a r e given in Sections II, III, and IV; Sections V, VI, and VII a r e concerned with p l a s t i c bonded explosives; some explosive simulants a r e covered in Sections VIII, IX, and X. W. Selig May 1964

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CONTENTS

I. The E s t i m a t i o n of S y m - C y c l o t r i m e t h l e n e t r i n i t r a m i n e (RDX) and S y m - C y c l o t e t r a m e t h y l e n e t e t r a n i t r a m i n e (HMX) by Nonaqueous T i t r i m e t r y . . . . II. The Analysis of HMX, Poly-Z, 2 - D i n i t r o p r o p y l a c r y l a t e , Silica, and Ethyl- and Methyl-4, 4-Dinitropentanoate in Explosives . . . . . . . . . III. The Determination of PETN and Silica in L X - 0 2 - 1 IV. The Spectrophotometric Determination of Acetyltributyl Citrate in an E x t r u s i b l e Explosive, LX-02-1 V. The Analysis of Mixtures of HMX, Viton, and Oxamide VI. An Analytical P r o c e d u r e for RDX in RX-05 VII. The Analysis of Tungsten and HMX in RX-12 VIII. The Analysis of Mock Explosive 90010 IX. The Analysis of a Mock Material for L X - 0 4 - 1 X. The Determination of Cyanuric Acid, Melamine, and Viton in Mixtures (LM-04-0) . . . . .

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SOME ANALYTICAL METHODS FOR EXPLOSIVES AND EXPLOSIVE SIMULANTS Walter Selig Lawrence Radiation L a b o r a t o r y , University of California Livermore, California

May 1964 I. THE ESTIMATION OF Sym-CYCLOTRIMETHYLENETRINITRAMINE (RDX) AND Sym-CYCLOTETRAMETHYLENETETRANITRAMINE (HMX) BY NONAQUEOUS TITRIMETRY*

Abstract
J

The nonaqueous t i t r a t i o n of RDX and HMX as acids with t e t r a b u t y l a m m o n i u m hydroxide (BU4NOH) is d e s c r i b e d . HMX 1 is d e t e r m i n e d in dimethylformamide (DMF); RDX may be deternnined in either DMF, methylisobutyl ketone (MIBK), or cyclohexanone, although the l a t t e r two solvents a r e p r e f e r r e d . The total amount of RDX and HMX in m i x t u r e s may be e s t i mated in DMF. Sample size is about 30 mg and a single d e t e r mination takes about 25 m i n u t e s . Introduction A t i t r i m e t r i c method for the m i c r o d e t e r m i n a t i o n of RDX and HMX by chromous chloride reduction has been used in this L a b o r a t o r y . however, has a number of disadvantages. titrants, minations. 2 It r e q u i r e s : of oxygen both during the t i t r a t i o n and in storage of the t i t r a n t s , The method, 2) two 1) complete absence

3) a l a r g e e x c e s s of chroinous chloride and close control of the In addition, any reducible i m p u r i t i e s cause high r e s u l t s .

raction t e m p e r a t u r e for the reduction of HMX, and 4) frequent blank d e t e r A rapid, simple t i t r i m e t r i c nnethod for RDX has been d e s c r i b e d by Kaye who t i t r a t e d it as an acid in dimethylformamide (DMF), using sodium methoxide in b e n z e n e - m e t h a n o l a s the t i t r a n t and azo violet as the indicator. Disadvantages of K a y e ' s method a r e that sodium methoxide is somewhat

General C h e m i s t r y Technical Note No. 65, dated November 7, I96I,

2-

unstable and t h e r e is some difficulty in a s c e r t a i n i n g the endpoint which i s found by t i t r a t i n g to a g r e e n color p e r s i s t i n g for 30 seconds. Also, a fairly l a r g e (300 mg) sample is r e q u i r e d for each titration. 3 Sarson has d e s c r i b e d a method in which RDX is t i t r a t e d as an acid in methylisobutyl ketone (MIBK) with t e t r a b u t y l a m m o n i u m hydroxide (Bu.NOH). When used as t i t r a n t s for acids in nonaqueous media, t e t r a a l k y l a m m o n i u m hydroxides have s e v e r a l advantages over previously us^d alkali m e t a l 4, 5 bases. ' They a r e easily p r e p a r e d and quite stable. The t e t r a a l k y l a m m o n i u m salts a r e mostly soluble w h e r e a s p r e c i p i t a t e s a r e frequently formed when alkali alkoxides a r e used as t i t r a n t s . Excellent p o t e n t i o m e t r i c c u r v e s a r e obtained in a v a r i e t y of solvents with the g l a s s - c a l o m e l electrode s y s t e m ; with alkali m e t a l b a s e s the c u r v e s a r e not as r e p r o d u c i b l e . While satisfactory for RDX, MIBK d i s s o l v e s insufficient amounts of HMX to be of any use in its d e t e r m i n a t i o n . Consequently, this work d e s c r i b e s a modification of S a r s o n ' s method for the e s t i m a t i o n of RDX, and the application of this modification to the e s t i m a t i o n of HMX alone and HMX and RDX in m i x t u r e s . Expe r i m e n t a l Apparatus Beckman g e n e r a l - p u r p o s e g l a s s e l e c t r o d e , No. 1190-80. Beckman sleeve-type calomel electrode No. 1170-71, modified by replacing the aqueous p o t a s s i u m chloride solution with a s a t u r a t e d solution of p o t a s s i u m chloride in methanol. P o t e n t i o m e t r i c t i t r a t o r : Beckman Model G pH m e t e r . Buret, 10 ml Machlett, with 1000 ml r e s e r v o i r , kept under nitrogen atmosphere. Magnetic s t i r r e r . Titration c e l l s : 200 ml t a l l - f o r m e l e c t r o l y t i c b e a k e r s without spouts covered with a No. 11 1/2 r u b b e r stopper provided with a gas inlet tube and openings for two e l e c t r o d e s and the d e l i v e r y tip of buret. The b u r e t tip is i n s e r t e d into the titration cell through a g l a s s tube which provides space for exit of the sweeper gas.

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Re agents A 0.1 N solution in 10 to 1 b e n z e n e 4 methanol w a s p r e p a r e d according to Cundiff and Markunas. Dissolve 40 g r a m s t e t r a b u t y l a m m o n i u m iodide in 90 ml absolute methanol. Add 20 g r a m s finely ground purified silver oxide, stopper the flask, and agitate for one hour. Centrifuge s e v e r a l m i l l i l i t e r s of the m i x t u r e and t e s t the supernatant for iodide. If the t e s t is positive, add two g r a m s m o r e of silver oxide and reagitate for 30 m i n u t e s . If the t e s t for iodide is negative, filter the m i x t u r e through a fine porosity s i n t e r e d - g l a s s funnel. Rinse the reaction flask and funnel with t h r e e 50-ml portions of dry benzene and add to the f i l t r a t e . Dilute the filtrate to one liter with d r y benzene. T r a n s f e r the solution to the r e s e r v o i r of the Machlett b u r e t and flush for five m i n u t e s with prepurified nitrogen. Keep the r e s e r v o i r under a constant nitrogen blanket to protect from m o i s t u r e and carbon dioxide. Standardize the t i t r a n t against benzoic acid. Thyraol blue indicator solution. 100-ml isopropyl alcohol. Benzoic acid. P r i m a r y standard (Baker Analyzed Reagent). Dissolve 0.3 g r a m of thymol blue in T e t r a b u t y l a m m o n i u m hydroxide.

Nitrogen. Prepurified by running through A s c a r i t e - m a g n e s i u m perchlorate trap. Methylisobutyl ketone .(4-methyl-2-pentanone) ( B r a u n - K n e c h t - H e i m a n n Co.). Dimethylformamide. Cyclohexanone. Reagent grade (Matheson, Coleman and Bell).

Reagent g r a d e , purified. 7

Purification of Cyclohexanone

Convert 50 g r a m s of Dowex 1-XlO, 100-200 m e s h , to the hydroxyl form by s t i r r i n g the r e s i n for s e v e r a l h o u r s with 10% NaOH. Wash the r e g e n e r a t e d r e s i n with distilled w a t e r until the washings a r e n e u t r a l , then with methanol. A i r - d r y the r e s i n . Place the d r y r e s i n in an E r l e n m e y e r flask provided with a glass stopper, add 500 ml r e d i s t i l l e d cyclohexanone, and stir for s e v e r a l h o u r s . Decant the cyclohexanone and filter.

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Analytical P r o c e d u r e Accurately weigh 20 to 40 mg sample into a 200-ml e l e c t r o l y t i c t a l l form b e a k e r containing a Teflon-coated s t i r r i n g b a r . Add 20 ml of solvent and d i s s o l v e . Place the b e a k e r into the t i t r a t i o n a s s e m b l y and sweep with nitrogen for five minutes while s t i r r i n g . Add the t i t r a n t slowly under rapid agitation. After each addition of t i t r a n t , allow sufficient time to r e a c h a steady potential. In the d e t e r m i n a t i o n of HMX and RDX in DMF, add the t i t r a n t in 0.10-ml i n c r e m e n t s n e a r the equivalence potential. In the d e t e r m i n a t i o n of RDX in MIBK or cyclohexanone, add the t i t r a n t in 0.05-ml i n c r e m e n t s n e a r the equivalence potential. Continue the t i t r a t i o n until the cell potential r e a c h e s a m a x i m u m which r e m a i n s r e l a t i v e l y constant upon further addition of t i t r a n t . Maintain the nitrogen a t m o s p h e r e throughout the titration. P e r f o r m a blank t i t r a t i o n for each batch of solvent. D e t e r m i n e the equivalence point from a t i t r a t i o n curve of volume 7 t i t r a n t v e r s u s emf, or by calculation (see appendix). Calculations (V % RDX or HMX = where V,
^2 74.043

- V )(normality titrant)(100)(74.043) , mg sample

volume of t i t r a n t , volume of solvent blank, and equivalent weight of RDX and HMX. R e s u l t s and D i s c u s s i o n

Titration c u r v e s of RDX and HMX in DMF a r e shown in Fig. I- 1. The t i t r a n t was Bu.NOH. The potential b r e a k s for the two compounds occur at
4

voltages too close together to p e r m i t a differentiating titration; however, the total amount of RDX and HMX in a m i x t u r e may be e s t i m a t e d (Table I - l ) . Table 1-2 gives r e s u l t s of the a n a l y s i s of RDX using v a r i o u s solvents. a n a l y s i s of HMX in DMF gave the r e s u l t s shown in Table 1-3. The

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Table m e q RDX 0.2851 0.1504 0.3995

I-l.

A n a l y s i s of RDX p l u s HMX in D M F . meq total 0.6201 0.5560 0.5369 m e q found 0.6187 0.5578 0.5457 no. detns. 3 2 4 % recovery 99.8 100.3 101.6

Taken m e q HMX 0.3350 0.4056 0.1374

T a b l e 1-2, . Solvent DMF Cyclohexanone MIBK N u m b e r of determinations 4 4 3

A n a l y s i s of RDX ( W a b a s h ) . meq taken 0.4898 0.4740 0.4788 m e q found 0.4922 0.4760 0,4777 % recovery 100.5 100.4 99.8

T a b l e 1-3. A n a l y s i s of HMX* p u r i f i e d on J , O. 2072). N u m b e r of d e t e r m i n a t i o n s

in D M F (HMX, c l a s s A, H O L - S R - 2 0 4 - 6 0 , meq taken 0.5304 m e q found 0.5185 % recovery

97.8

M a t e r i a l contained i m p u r i t i e s a s d e t e r m i n e d by p a p e r c h r o m a t o g r a p h y .

NO, N ^^2 O^N-N^ CH. RDX -N-NO, 0.,N-N'

CH N-NO_

' I
2^ O^N-N. CH, HMX

'

CH^

I '
N-NO.

As shown a b o v e , t h e b a s i c u n i t of RDX and HMX i s - C H N N O ^ - , formula weight 74.043. RDX c o n s i s t s of t h r e e , and HMX of four s u c h u n i t s . One e q u i v a l e n t of RDX r e q u i r e s t h r e e e q u i v a l e n t s of b a s e f o r n e u t r a l i z a t i o n ; one e q u i v a l e n t of HMX r e q u i r e s f o u r e q u i v a l e n t s of b a s e for n e u t r a l i z a t i o n . T h e e q u i v a l e n t w e i g h t of the two e x p l o s i v e s i s i d e n t i c a l .

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The neutralization reaction of RDX and HMX is quite slow, hence sufficient time must be allowed for attainment of a steady potential after each addition of t i t r a n t . Addition of s e v e r a l d r o p s of thymol blue helps in anticipating the equivalence point. The color change is from yellow through g r e e n to blue. Before the equivalence point, when t i t r a n t is added the color will change i m m e d i a t e l y to blue; this color, however, will gradually change back to yellow. Simultaneously, a slow d e c r e a s e in emf is o b s e r v e d . At the equivalence point the potential b e c o m e s s t e a d i e r and the blue color will not change. In MIBK the potential b r e a k at the equivalence point is g r e a t e r than in DMF (Fig. 1-2). In this solvent, t h e r e f o r e , the t i t r a n t should be added in 0.05-ml i n c r e m e n t s near the equivalence point. RDX and HMX a r e fairly soluble in cyclohexanone and Y~butyrolactone. The l a t t e r solvent cannot be used in nonaqueous t i t r i m e t r y since it r e a c t s with the b a s e , apparently being slowly saponified. RDX can be t i t r a t e d in cyclohexanone, with a potential b r e a k even g r e a t e r than in MIBK. The t i t r a n t should be added in 0.05-ml i n c r e m e n t s n e a r the equivalence point. HMX, although soluble^ could not be d e t e r m i n e d in this solvent. Since the solvent blank for cyclohexanone was fairly l a r g e (0,35 m l / 2 0 ml solvent) an attempt was made to purify this solvent. Redistillation plus ion exchange by the method of Mostalyk, Chatten, and P e r n a r o w s k i reduced the blank to an acceptable level, (Table 1-4.) Table 1-4. Blank t i t r a t i o n of 20 ml cyclohexanone. Titration, ml 0.35 0,25 0.15 0,03

T r e a t m e n t of solvent Reagent g r a d e , as received Redistilled Ion exchange Redistilled + ion exchange

Since the coefficient of expansion of nonaqueous solvents is considerably g r e a t e r than for w a t e r , for p r e c i s e r e s u l t s the t i t r a n t should be kept and used at constant t e m p e r a t u r e . It is believed that the r e s u l t s r e p o r t e d in Tables I - l , 1-2 and 1-3 could be improved by making use of constant t e m p e r a t u r e facilities. The use of a well-ventilated hood is mandatory for this work.

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Appendix 7 Calculation of Equivalence Point The equivalence point is that point w h e r e AE/AV is m a x i m u m . (E = emf, V = volume of titrant.) Equal i n c r e m e n t s of t i t r a n t a r e to be added near the endpoint. Compute the m a x i m u m slope AE/AV at the point where the second derivative A E / A V (slope of AE/AV v e r s u s the V curve
becomes 0. Example: Volume 10 .90 .00 .10 .20 .30 .40 .50
emf. AE/AV A^E/AV^

294
>

6 10 30 90 70 60

+4 +20 +60 -20 -10

300 310 > 340 ^ 430 500 > 560

>

X
>

^endpoint = '''^' + ^'''^^ [zrho]

References 1

= '''^'^

W, Selig, Lawrence Radiation L a b o r a t o r y ( L i v e r m o r e ) Internal

Document GCTN-39 (Feb. 23, 1961). 3 4 S, M. Kaye, Anal, Chem, 27, 292 (1955). R. D, Sarson, Anal. Chem, 30, 932 (1958).

R. H. Cundiff and P. C. Markunas, Anal, Chem. 28, 792 (1956), ^J. S. F r i t z and S, S. Y a m a m u r a , Anal. Chem. 29, 1079 (1957). R, G, Moskalyk, L, G. Chatten, and M. P e r n a r o w s k i , J, P h a r m . Sci. 5_0, 179 (1961). 7 J. J. Lingane, E l e c t r o a n a l y t i c a l C h e m i s t r y (Interscience P u b l i s h e r s , N. Y . , 1958), 2nd ed. , pp. 9 1 - 3 .

 500

-600

-700

>
I

800

00

900

1000

6 ml TITRANT

10

12

GLL-646-1633 Fig. I - l .

T i t r a t i o n of RDX and HMX in D M F .

-100

-200 ~ -300

r
r r
^ ^ MIBK

-400

-500

>

-600

-700

W=

&

_ _

-800 - 9 0 0 -

A
CYCLOHEXANONE 1 ! 3 f 4 f 5 t

DMF\

1000

1
7

1
8 9 GLL--646-1634

m l TITRANT F i g . 1-2.

T i t r a t i o n of RDX in v a r i o u s s o l v e n t s .

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ll.

T H E ANALYSIS O F H M X , P O L Y - 2 , 2 - D I N I T R O P R O P Y L A C R Y L A T E , SILICA, AND E T H Y L - AND M E T H Y L - 4 , 4 - D I N I T R O P E N T A N O A T E IN E X P L O S I V E S * Abstract P r o c e d u r e s f o r t h e a n a l y s i s of e x p l o s i v e s c o n t a i n i n g HMX, p o l y - 2 , 2 - d i n i t r o p r o p y l a c r y l a t e (D^^), m i x t u r e s of e t h y l - and m e t h y l - 4 , 4 - d i n i t r o p e n t a n o a t e (E^Mp), and silica a r e p r e s e n t e d . The dinitropentanoates a r e extracted with carbon tetrachloride. In t h e a b s e n c e of s i l i c a , D i s e x t r a c t e d w i t h e t h y l e n e d i c h l o r i d e l e a v i n g a r e s i d u e of HMX w h i c h m a y b e r e m o v e d by d i m e t h y l s u l f o x i d e (DMSO), N , N - d i m e t h y l f o r m a m i d e ( D M F ) , o r ybutyr olactone. In the p r e s e n c e of s i l i c a , HMX and D^^ a r e e x t r a c t e d w i t h D M F . T h e Dg, i s d e t e r m i n e d p h o t o m e t r i c a l l y in the p r e s e n c e of s o d i u m h y d r o x i d e a t 375 mfx, HMX i s d e t e r m i n e d b y d i f f e r e n c e . T h e m e t h o d s p r e s e n t e d a r e g e n e r a l and m a y b e a p p l i e d o v e r w i d e r a n g e s of c o m p o s i t i o n . T h e y s u p e r s e d e p r o c e d u r e s g i v e n p r e v i o u s l y for s p e c i f i c c o m p o s i t i o n s . Introduction A m e t h o d for t h e a n a l y s i s of an e x t r u s i b l e e x p l o s i v e c o n t a i n i n g

HMX, s i l i c a , p o l y - 2 , 2 - d i n i t r o p r o p y l a c r y l a t e (D ), and a m i x t u r e of e t h y l 1 and m e t h y l - 4 , 4 - d i n i t r o p e n t a n o a t e ( E M ) w a s r e p o r t e d p r e v i o u s l y . This m e t h o d , h o w e v e r , w a s found to b e not a p p l i c a b l e for a s o l i d h i g h - e n e r g y e x p l o s i v e c o n t a i n i n g t h e s a m e i n g r e d i e n t s (with t h e e x c e p t i o n of s i l i c a ) in different proportions. are: Component HMX E^Mp D, Si02 Extrusible Explosive 74% 24% 1% 1% Solid E x p l o s i v e 92% 2% 6% T h e a p p r o x i m a t e c o m p o s i t i o n s of t h e two e x p l o s i v e s

T h i s n o t e d e s c r i b e s m e t h o d s for t h e a n a l y s i s of m i x t u r e s c o n t a i n i n g a n y o r a l l of t h e following i n g r e d i e n t s : d i n i t r o p r o p y l a c r y l a t e (D ). G e n e r a l C h e m i s t r y T e c h n i c a l N o t e N o . 130, d a t e d O c t o b e r 3 , 1963. HMX, SiO^ ( C a b - O - S i l ) , and m i x t u r ) and p o l y - 2 , 2 of m e t h y l - and e t h y l - 4 , 4 - d i n i t r o p e n t a n o a t e ( E M

-11-

Expe r i m e n t a l M a t e r i a l s and Equipment Analytical b a l a n c e , Ainsworth, Type S. Beckman Model DK-2 Spectrophotometer or equivalent i n s t r u m e n t , with 1 cm silica c e l l s . S i n t e r e d - g l a s s c r u c i b l e s , medium porosity, 50 ml capacity. Vacuum oven, 60-70C. Suction filtration equipment ( F i s h e r F i l t r a t o r ) , Volumetric g l a s s w a r e . Carbon t e t r a c h l o r i d e , reagent g r a d e . Acetone. N, N-dimethylformamide (DMF). 1,2-dichloroethane, technical g r a d e . Dimethylsulfoxide (DMSO). y-butyrolactone. Sodium hydroxide, 0.2 M aqueous, HMX. Silica, Cab-O-Sil. P o l y - 2 , 2 - d i n i t r o p r o p y l a c r y l a t e (D ), a E M , consisting of 85% by weight e t h y l - 4 , 4-dinitropentanoate and 15% m e t h y l - 4 , 4-dinitropentanoate. Procedures Determination of HMX, E , M , and SiO.,, If the m a t e r i a l is solid, d p 2 grind it up by a r e m o t e - c o n t r o l m o r t a r and p e s t l e . Weigh 1 to 1.5 g into a t a r e d 100 ml b e a k e r containing a s t i r r i n g rod flattened out at the end into a disc of approximately 5 m m d i a m e t e r . Add 20 ml carbon t e t r a c h l o r i d e , cover with a watch g l a s s , and bring cautiously (danger of bumping) to boil on a hot plate. Remove occasionally from the hot plate and m a c e r a t e any c o n g l o m e r a t e s with the s t i r r i n g rod; this is p a r t i c u l a r l y r e q u i r e d for extrusible e x p l o s i v e s . Let cool to r o o m t e m p e r a t u r e and filter by suction through a tared m e d i u m - p o r o s i t y 50 ml s i n t e r e d - g l a s s c r u c i b l e . Wash b e a k e r and crucible with four 5 ml portions of CCL and filter. Dry b e a k e r and crucible in a vacuum oven at 60-70C for one hour. Cool to r o o m t e m p e r a t u r e and weigh. 1.

-12T r a n s f e r most of the precipitate quantitatively into the previously used 100 ml b e a k e r . Add about 25 ml hot DMSO and w a r m on hot plate until m o s t of the precipitate is dissolved. F i l t e r by suction through the corresponding previously used c r u c i b l e . Rinse b e a k e r and crucible with s e v e r a l portions of w a r m DMSO and filter. Finally, wash b e a k e r and crucible with s e v e r a l portions of acetone and filter. Dry b e a k e r and crucible in a vacuum oven at 60-70C for one hour. Cool to r o o m t e m p e r a t u r e and weigh. C a r r y out all e x t r a c t i o n s in a well-ventilated hood. D i s c a r d the DMSO e x t r a c t in a waste explosives container. Calculations: 1) Weight l o s s after C C l . extraction = amount of E M ' ^ 4 d p 2) Weight loss after DMSO extraction = amount of HMX 3) Residue = amount of SiO Determination of HMX, E , M , and D , D e t e r m i n e the E . M as ___^ d p a_ d p d e s c r i b e d above. T r a n s f e r m o s t of the precipitate quantitatively into the previously used 100 ml b e a k e r . Add 20 ml ethylene d i c h l o r i d e , cover with a watch g l a s s , and cautiously (danger of bumping) bring to boil on a hot plate. Cool to r o o m t e m p e r a t u r e and filter by suction through the previously used s i n t e r e d - g l a s s c r u c i b l e . Wash b e a k e r and crucible with four 5 ml portions of ethylene dichloride and filter. D r y b e a k e r and crucible in a vacuum oven for one hour, cool to r o o m t e m p e r a t u r e , and weigh. If d e s i r e d , the r e s i d u e may be dissolved in DMSO a s d e s c r i b e d above to check the r e s u l t s obtained for HMX by difference. Calculations: 1) Weight l o s s after CCL extraction = amount of E M ' & 4 d p 2) Weight loss after ethylene dichloride extraction = amount of D 3) Residue (or l o s s after DMSO e x t r a c t i o n ) = amount of HMX 3. Determination of HMX, E_M , D , and SiO_,. D e t e r m i n e E_M a s d p a 2_ d p d e s c r i b e d p r e v i o u s l y . T r a n s f e r most of the r e s i d u e quantitatively into the previously used 100 ml b e a k e r , add about 25 ml w a r m DMF, and heat on a hot plate until m o s t of the precipitate is dissolved. filtrate quantitatively in a 100 ml v o l u m e t r i c flask. F i l t e r by suction through the corresponding previously used filter c r u c i b l e , collecting the Wash b e a k e r and 2,

-13-

crucible with s e v e r a l portions of w a r m DMF.

Remove the v o l u m e t r i c Dry

flask, and wash b e a k e r and crucible with s e v e r a l portions of acetone.

b e a k e r and crucible in a vacuum oven at 60-70 C for one hour, cool to r o o m t e m p e r a t u r e , and weigh. Dilute the v o l u m e t r i c flask to volume with DMF and mix, Pipet an aliquot not to exceed 0.4 mg D into a 50 ml v o l u m e t r i c flask, add 1.0 ml 0.2 M aqueous sodium hydroxide, and dilute to volume with DMF. D e t e r m i n e the absorbance at 375 m|JL v e r s u s a DMF r e f e r e n c e . At this wavelength the molar absorbance of D is 18,600. The solution is stable for at l e a s t 3 h o u r s . a Calculations: 1) Weight l o s s after CCl, extraction = amount of E , M ' ^ 4 d p 2) Residue after DMF extraction = amount of SiO 3) Spectrophotometric d e t e r m i n a t i o n - amount of D 4) Calculated by difference = amount of HMX Results and D i s c u s s i o n s The method r e p o r t e d previously was i n c r e a s e d from 1 to 6%. for the a n a l y s i s of an extrusible was completely e x t r a c t e d , explosive did not work when the amount of d i n i t r o p r o p y l a c r y l a t e polymer Although the E M the amount of 1, 2-dichloroethane specified (10 mil) w a s insufficient to e x t r a c t the i n c r e a s e d amount of D in a r e a s o n a b l e length of t i m e , a Two methods w e r e investigated in this work. In the f i r s t , i n c r e a s i n g amounts of cold solvent w e r e used to e x t r a c t the p o l y m e r . The r e s u l t s a r e This p r o p r e s e n t e d in Table I I - 1 , and i l l u s t r a t e d in Fig. 11-1. With 60 ml of ethylene dichloride, 98.6% of the polymer is e x t r a c t e d on the a v e r a g e . cedure is limited to a polymer content of 5-8%. be r e d e t e r m i n e d . The second method investigated is that outlined in p r o c e d u r e 2, Rather than extracting the D with s e v e r a l portions of cold solvent, the explosive m i x t u r e is brought to boiling with the solvent, cooled to r o o m t e m p e r a t u r e , filtered, and washed. This p r o c e d u r e is m o r e time consuming because of However, the total solvent r e q u i r e d for additional weighing and the n e c e s s i t y of cooling before filtering (HMX being m o r e soluble in the hot solvent). extraction of D is l e s s , and the p r o c e d u r e is valid over a wide range of D concentrations. It was t r i e d successfully on m i x t u r e s containing up to 28% D If the composition is

changed beyond this range the optimum amount of ethylene dichloride m u s t

-14-

An attempt to substitute ethanol for carbon t e t r a c h l o r i d e in the extraction of E^M p was unsuccessful, d An attempt was made to apply the hot extraction method also to m i x t u r e s containing HMX, E . M , and SiO-, and HMX, E M , D , and " d p 2 d p a SiO-,. This succeeded for the f o r m e r ; for the l a t t e r , however, the extraction of D by dichloroethane was not quantitative. Table II-2 shows that as the amount of Cab-O-Sil i n c r e a s e s in a m i x t u r e the r e c o v e r y of D by extraction ' a ' with ethylene dichloride d e c r e a s e s . In the p r e s e n c e of Cab-O-Sil D m u s t , 3 ^ t h e r e f o r e , be d e t e r m i n e d photometrically in DMF. R e c o v e r i e s of the components of known m i x t u r e s a r e p r e s e n t e d in Tables I I - 3 , II-4, I I - 5 , and II-6. Analyses of some explosives a r e given in Table I I - 7 . Where available, r e s u l t s using the cold extraction technique previously used a r e shown. Adoption of the hot extraction method d e s c r i b e d h e r e is r e c o m m e n d e d for m a t e r i a l s containing two or m o r e of the components d e s c r i b e d . Acknowledgment The w r i t e r is indebted to Guy Lopez for running the e x t r a c t i o n s r e ported in Table I I - 1 .

-15-

Table I I - l . mg taken 139.9 102,0 90.2 104,5 103.1 120.0 178.0 110.2 98.8 105,0 97,7 94.7 90,0

Recovery of D by cold extraction with 1, 2-dichloroethane. mg r e c o v e r e d % recovery ml dichlor

20
11 II

130.1 93.0 92.0 90.2 79.5 88.1 100.2 95.9 96.7 93.8 116.2 96.8 174.0 97.8 99.7 109.9 97.2 98.4 103.0 98.1 96.2 98,5 93.3 98.5 88.6 98.4 Average r e c o v e r y with 60 ml solvent: Standard deviation:

40
11

It
11

60
II II II II II

98,6% 0,56

Table II-2. mg taken 12.9 23,7 11.7 201,9 204.5 195,2 66.8 128,3 62.1

Recovery of D in p r e s e n c e of SiO^ by p r o c e d u r e 2, a ^ mg r e c o v e r e d mi-g SiO p r e s e n t % recovery 12.3 21.6

7,9

190.5 191.0 168.5 63.5 117.8 44.2

95.4 91.1 67.5 94.4 93,4 86.3 95,1 91.8 71.2

11.0 11,2 23.5 11.4 22.6 42.4 21.6 21.4 41.9

_16-

Table I I - 3 . mg taken 127.4 119.2 129.6 110.3 176.5

Recovery of Dg^ by p r o c e d u r e 2. mg r e c o v e r e d 126.5 118.4 132.0 111.1 176.6 % recovery 99.3 99.3 101.9 100.7 100.1 100,3% 1,09

Average r e c o v e r y Standard deviation

Table II-4. mg taken 839,3 800,2 835,9 894.0 840.8 728.0 731.6 755.2

R e c o v e r y of HMX by p r o c e d u r e s 1 and 2, mg r e c o v e r e d 839.1 800,8 832,2 893.2 840.7 727.9 731.8 755.5 Average r e c o v e r y Standard deviation % recovery 100.0 100.1 99.7 99.9 100.0 100.0 100.0 100.0 99.96% 0.14

Table I I - 5 .
m g taken 85.5 140.2 77.9 407.8 201.7 153.2 229.8 220.8 248.5

R e c o v e r y of E^Mp by p r o c e d u r e s 1, 2, and 3,
recovered 86.6 140.4 78.2 408.0 201,7 152.4 229.7 220.9 247,9 % recovery 101,3 100.1 100.4 100.1 100.0 99.5 100.0 100.1 99.8

Average r e c o v e r y Standard deviation

100.14% 0.50

-17-

Table II-6. mg taken

65.,8

R e c o v e r y of silica. % recovery 102.7 101.4 103.7 103.7 103.5 104.1 100.8

99,2

mg r e c o v e r e d

Procedure 2,3. 2,3, 2,3, 2,3. 2.3. 2.3. 2,1, 2.1, 2.1, 103,2% 0,99 100,13% 0.83

76.4
73..7 82,,7

86.5
78..7

24.9
39.,1 82,,3

67.6 77.5 76.4 85.8 89.5 81.9 25,1 38,8 82.6 Average r e c o v e r y p r o c e d u r e Standard deviation Average r e c o v e r y p r o c e d u r e Standard deviation

100.4 3 1

Table II-7, Sample RX-06-AC ( J . O , 1095-1) Average Average

Analysis of explosive compositions. % HMX 68,23 67.75 68.18 68.05 67.87 73.90 73.95 74.22 74.02 73.71 73.93 74.00 74,47 74.13 73,86 69.79 69.66 69.84 69.76 93,23 93.52 % EdMp 29.68 3.0.14 29.69 29.84 30.19 24.49 24,42 24.17 24.36 24.82 24.64 24,55 24.14 24.44 24.63 27.64 27.79 27.55 27,66 0.74 0.69 % Dj
-__ __

% Si02 2.08 2.11 2.13 2,11 1.94 1.61 1.63 1.61 1,62 1.48 1.43 1.45 1.39 1.42 1.51
__ __ __
_

By Ref . 4, RX-06-AF ( J . O . 1115)

__

By Ref. 4, RX-06-AF (43612B)

Average Average

__ __ __

By Ref. 4, RX~06-AA (Sn 1065-2)

Average Average

Average RX-09-AA (5K110)

2.56 2.55 2.61 2.57 6.03 5.79

__

-18-

References G. L. G r o s s m a n and W. Selig, " T h e Analysis of E x t r u s i b l e E x p l o s i v e s . II, The D e t e r m i n a t i o n of Ethyl- and Methyl-4, 4 - d i n i t r o p e n t a n o a t e , P o l y - 2 , 2 - d i n i t r o p r o p y l a c r y l a t e , Silica, and HMX," Lawrence Radiation L a b o r a t o r y ( L i v e r m o r e ) Internal Document GCTN-78 (July 10, 1962). 2 W. Selig, " T h e Spectrophotometric Determination of Ethyl- and Methyl4, 4-Dinitropentanoate Mixtures in an E x t r u s i b l e E x p l o s i v e , " Lawrence Radiation L a b o r a t o r y ( L i v e r m o r e ) Internal Document GCTN-77 (June 18, 1962). 3 W. Selig, " The Spectrophotometric D e t e r m i n a t i o n of Some g e m - D i n i t r o Compounds in N, N - D i m e t h y l f o r m a m i d e , " UCRL-7116 (October 23, 1962), 4 W, Selig and G. L. G r o s s m a n , " T h e Determination of the Components of an E x t r u s i b l e E x p l o s i v e , " Lawrence Radiation L a b o r a t o r y ( L i v e r m o r e ) Internal Document GCTN-75 (May 17, 1962).

19-

100

20

30

40

50

VOLUME OF 1,2-DICHLOROETHANE

60 GLL-646-1635 (ml)

Fig. I I - 1 . Recovery of poly-2, 2 - d i n i t r o p r o p y l a c r y l a t e v e r s u s volume of 1, 2-dichloroethane.

-20-

III.

THE DETERMINATION OF P E T N AND SILICA IN L X - 0 2 - r "

Abstract A method is presented for the a n a l y s i s of an e x t r u s i b l e explosive containing P E T N , silica, butyl r u b b e r , and acetyltributyl c i t r a t e . The r u b b e r and p l a s t i c i z e r a r e extracted with carbon t e t r a c h l o r i d e ; P E T N is extracted with acetone, leaving a residue of silica. Introduction This work d e s c r i b e s the a n a l y s i s of an extrusible explosive of the approximate composition PETN
SiO^

73%
2%

Butyl rubber + acetyltributyl c i t r a t e 25% The p r o c e d u r e given is a modification of one suggested by du Pont. Experimental E x p e r i m e n t and M a t e r i a l s Analytical b a l a n c e , Ainsworth, Type S. Sintered g l a s s c r u c i b l e s , medium p o r o s i t y , 50 ml capacity. Vacuum oven, maintained at r o o m t e m p e r a t u r e . Steam bath. Suction filtration equipment ( F i s h e r F i l t r a t o r ) . Carbon t e t r a c h l o r i d e , reagent g r a d e , saturated with P E T N . Acetone, reagent g r a d e . PETN. Cab-O-Sil (Si02). du Pont 4600-D Adhesive, Lot 12-61, 48.5% in hexane. Citroflex A-4, Pfizer & Company (acetyltributyl c i t r a t e ) . Procedure Weigh approximately 2 g m a t e r i a l into a t a r e d 100 ml b e a k e r containing a glass s t i r r i n g rod. with watch g l a s s . Add 50 ml carbon t e t r a c h l o r i d e and cover Keep on a s t e a m bath for 30-45 minutes and b r e a k up

'General C h e m i s t r y Technical Note No. 88, dated September 20, 1962.

-21-

lumps with the s t i r r i n g rod. Let cool to r o o m t e m p e r a t u r e and filter by suction through a t a r e d m e d i u m - p o r o s i t y , 50 m l , s i n t e r e d g l a s s c r u c i b l e . Wash b e a k e r , s t i r r i n g rod, and crucible with t h r e e s u c c e s s i v e 5 ml portions of carbon t e t r a c h l o r i d e . Dry the b e a k e r with s t i r r i n g rod and crucible in a vacuum oven at room t e m p e r a t u r e for one hour and weigh. Dissolve the PETN in the b e a k e r and crucible with successive portions of a total of 50 ml acetone at r o o m t e m p e r a t u r e . Wash with s e v e r a l 5 ml portions of acetone. Discard the filtrate in the explosives waste container. Dry the b e a k e r with s t i r r i n g rod and crucible in a vacuum oven at room t e m p e r a t u r e for one hour and weigh. Calculations 1. 2. 3. Weight l o s s after carbon t e t r a c h l o r i d e extraction Weight l o s s after acetone extraction Residue Results and D i s c u s s i o n The extraction scheme given in the p r o c e d u r e is b a s e d on the solubility of the adhesive (butyl r u b b e r + acetyltributyl c i t r a t e ) , in carbon t e t r a chloride which does not dissolve the PETN and silica. extracted with acetone, leaving a residue of silica. T a b l e s III-1 and III-2 p r e s e n t r e s u l t s obtained with known saraples p r e p a r e d by weighing the components into a b e a k e r . The data w e r e obtained If by the p r o c e d u r e suggested by du Pont, using vacuum drying at 60C. Under these conditions the a v e r a g e r e c o v e r y r a t e for PETN was 99.64%. vacuum drying at r o o m t e m p e r a t u r e , as outlined in the p r o c e d u r e given h e r e , is used, the r e c o v e r y r a t e for P E T N will be c l o s e r to 100%, Table III-3 shows r e s u l t s for some e x t r u s i b l e e x p l o s i v e s . The use of an u l t r a s o n i c g e n e r a t o r is suggested for the carbon t e t r a chloride e x t r a c t i o n . This will probably speed up the d i s i n t e g r a t i o n of the eliminate the use of s t e a m bath. r u b b e r - l i k e sample m a t e r i a l and may The P E T N is then = amount of adhesive = amount of PETN = amount of silica

-22-

Table III-l. mg taken 1506.5 1500.7 1268.5

R e c o v e r y of P E T N f r o m e x t r u s i b l e e x p l o s i v e . mg recovered 1501.6 1496.3 1262.7 Average recovery Average deviation % recovery 99.67 99,71 99.54 99.64% 0.07

Table III-2. mg taken 99.8 103.8 94.9

R e c o v e r y of s i l i c a f r o m e x t r u s i b l e e x p l o s i v e . mg recovered 99.9 103.6 95.4 Average recovery Average deviation % recovery 100.10 99.81 100.53 100.15% 0.26

Table III-3. Sample No. HE 107, A5 HE 107, 0 H E 107, 03 HE 121

A n a l y s i s of e x t r u s i b l e e x p l o s i v e s . % PETN 72.86 72.89 72.96 72.92 72.68 72.75 73.07 73,10 % Si02 1.81 1.84 1.84 1.82 1.51 1.60 2.05 2.05

-23-

IV,

THE SPECTROPHOTOMETRIC DETERMINATION OF ACETYLTRIBUTYL CITRATE IN AN EXTRUSIBLE EXPLOSIVE, L X - 0 2 - 1 * Abstract

A s p e c t r o p h o t o m e t r i c method for the a n a l y s i s of acetyltributyl c i t r a t e (ATBC) in an extrusible explosive (LX-02-1) containing pentaerythritol t e t r a n i t r a t e (PETN), s i l i c a , butyl r u b b e r , and ATBC is p r e s e n t e d . ATBC i s e x t r a c t e d with anhydrous ethanol. The e s t e r is converted to the hydroxamic acid witli b a s i c hydroxylamine and the purple complex developed with f e r r i c ion is d e t e r m i n e d photometrically. (A c o r r e c t i o n for the absorbance of PETN is n e c e s s a r y . ) Introduction The a n a l y s i s of an extrusible explosive, L X - 0 2 - 1 , of the approximate composition PETN 73% Silica 2% Butyl rubber + acetyltributyl c i t r a t e (ATBC) p l a s t i c i z e r 25% is r e p o r t e d in Section HI, leaving a r e s i d u e of silica. The d e t e r m i n a t i o n of the p l a s t i c i z e r , by saponification or by the f e r r i c hydroxamate method, r e q u i r e s the p r e s e n c e of sodium hydroxide. T h e r e f o r e , carbon t e t r a c h l o r i d e , which is attacked by c a u s t i c , is u n s a t i s factory a s an e x t r a c t a n t . of ATBC is available. Many r e c e n t p a p e r s r e p o r t on the p h o t o m e t r i c d e t e r m i n a t i o n of e s t e r s by the f e r r i c hydroxamate method; of t h e s e , the most p r o m i s i n g a r e by 1 2 3 Goddu, LeBlanc, and Wright, P i l z , and Gutnikov and Schenk. Organic e s t e r s form hydroxamic acids by the r u c t i o n shown in Eq, (1), The hydroxamic acid then r e a c t s with f e r r i c ion to form a purple complex [as shown in Eq. (2)] which can be d e t e r m i n e d p h o t o m e t r i c a l l y . General C h e m i s t r y Technical Note No. 127, dated Septerhber 5, 1963. No selective solvent for the differential extraction In this method the rubber and p l a s t i c i z e r a r e extracted with carbon t e t r a c h l o r i d e and P E T N is then extracted with acetone,

-24-

RCOOR' + NH^OH Fe"*"^ + n RCONHOH

OH" O R(!!-NHOH + R'OH (RCONHO) F e ^ ^ " ^ + nH"*"

(1) (2)

The above p r o c e d u r e s w e r e t r i e d for acetyltributyl c i t r a t e and only 3 the method of Gutnikov and Schenk was found applicable with minor modifica tions. This paper p r e s e n t s a p r o c e d u r e for the d e t e r m i n a t i o n of ATBC in LX-02-1 using this method. Expe r imental Reagents and Equipment 1.4 M Hydroxylammonium p e r c h l o r a t e .
' ^

This solution is p r e p a r e d
3

according to the p r o c e d u r e of Gutnikov and Schenk. Dissolve 195 g sodium p e r c h l o r a t e monohydrate in 450 ml absolute methanol with heating. Dissolve 105 g r e a g e n t grade hydroxylamine hydrochloride in 550 ml absolute methanol with heating. room temperature. Add the sodium p e r c h l o r a t e solution slowly to the Add 50 m l benzene and let cool to hydroxylamine solution with s t i r r i n g .

Chill solution and p r e c i p i t a t e for one hour in an ice

bath and filter the sodium chloride on a s i n t e r e d g l a s s filter with suction. Store the hydroxylammonium p e r c h l o r a t e solution in a polyethylene bottle. 2.5 M Sodium hydroxide. absolute methanol. Reflux 100 g sodium hydroxide with 1000 ml Store the solution in a polyethylene bottle.

Stock f e r r i c p e r c h l o r a t e solution. Weigh 3.1534 g iron w i r e into a 150 ml b e a k e r . Add 36 ml 70% p e r c h l o r i c acid and heat at low heat on a hot plate until the iron d i s s o l v e s . (Caution: The i r o n d i s s o l v e s quite rapidly when the acid is hot.) Cool the b e a k e r and t r a n s f e r the contents to a 200 m l v o l u m e t r i c flask with absolute ethanol. Dilute to volume with absolute ethanol, cooling under a tap a s the alcohol is added. F e r r i c p e r c h l o r a t e r e a g e n t . To about 1.5 l i t e r s of absolute ethanol add 100 ml of the f e r r i c p e r c h l o r a t e stock solution. Slowly add 130 ml 70% p e r c h l o r i c acid while cooling under a t a p . Allow to cool and dilute to 2 l i t e r s with absolute ethanol. Ethanol, anhydrous, Rossville Gold Shield. Acetyltributyl c i t r a t e , Pfizer Citroflex A-4.

-25-

Acetyltriethyl c i t r a t e , Pfizer Citroflex A - 2 . Tributyl c i t r a t e , Pfizer Citroflex 4. Triethyl c i t r a t e , Pfizer Citroflex 2. Beckman Model DK-2 r e c o r d i n g spectrophotometer or equivalent i n s t r u m e n t , with 1 c m c e l l s . P r e p a r a t i o n of Calibration Curve Weigh s e v e r a l s a m p l e s of ATBC (or other c i t r a t e e s t e r s ) covering the range of 0.5 to 8 mg into 50 ml volumetric flasks and add 5 ml of anhydrous ethanol, or p r e p a r e stock solutions so that aliquots of 5 ml r e s u l t in the d e s i r e d araounts. Pipet in 3 ml of 1.4 M hydroxylammonium p e r c h l o r a t e and then 10 ml of 2.5 M methanolic sodium hydroxide. Let stand for 20 minutes and add 22 to 23 ml of a f e r r i c p e r c h l o r a t e - a c e t o n e mixture made by mixing, for each s a m p l e , 35 ml f e r r i c p e r c h l o r a t e r e a g e n t and 2.5 ml acetone. Allow to stand for 5 m i n u t e s , then dilute to volume with the same a c e t o n e - f e r r i c p e r c h l o r a t e m i x t u r e . Mix thoroughly, let stand for one hour, and read the absorbance v e r s u s a r e a g e n t blank at 517-522 mfx. Plot absorbance v e r s u s mg ATBC. (The absorbance of a sample containing ATBC may be r e a d up to 4 h o u r s after sample p r e p a r a t i o n . ) PETN Blank P r e p a r a t i o n Weigh approximately 750 mg d r y PETN into a 150 ml b e a k e r , add 50 ml anhydrous ethanol, and heat gently until dissolved. g l a s s and let cool to roona t e m p e r a t u r e . Cover with a watch Wash F i l t e r by suction through a m e d i u m

porosity s i n t e r e d - g l a s s crucible into a 100 m l v o l u m e t r i c flask. ethanol. in LX-02.

crucible and funnel with s e v e r a l portions of ethanol; dilute to m a r k with Use 5 ml of this solution as a blank for the d e t e r m i n a t i o n of ATBC This solution, if well stoppered, m a y b e kept indefinitely.

D e t e r m i n a t i o n of ATBC in LX-02-1 Accurately weigh approximately 500 mg of explosive sample into a 100 ml b e a k e r . Add 25 ml anhydrous ethanol, place on a hot plate at low Let cool to r o o m t e m p e r a t u r e . F i l t e r by suction heat, and let boil gently for 15 to 30 m i n u t e s , s t i r r i n g occasionally to b r e a k up l a r g e a g g l o m e r a t i o n s . flask. through a m e d i u m - p o r o s i t y , s i n t e r e d - g l a s s crucible into a 50 ml v o l u m e t r i c Wash crucible and funnel with s e v e r a l portions of ethanol and dilute

-26-

to m a r k with ethanol.

T r a n s f e r a n a l i q u o t c o n t a i n i n g 2 - 7 m g A T B C into a

50 m l v o l u m e t r i c f l a s k t h e n follow t h e p r o c e d u r e for p r e p a r a t i o n of t h e calibration curve (see above). R e s u l t s and D i s c u s s i o n T h e a b s o r p t i o n s p e c t r u m of t h e f e r r i c h y d r o x a m a t e c o m p l e x of A T B C i s s h o w n in F i g . I V - 1 . M a x i m u m a b s o r p t i o n for t h i s c o m p o u n d a n d t h e o t h e r c i t r a t e e s t e r s i n v e s t i g a t e d o c c u r s b e t w e e n 517 and 522 mfi a s a b r o a d 1, 4 p e a k ( s a m e a s p r e v i o u s l y r e p o r t e d for o t h e r e s t e r s ' ). T h e m o l a r a b s o r b a n c e s for s e v e r a l c i t r a t e e s t e r s a r e g i v e n in T a b l e I V - 1 . in this t a b l e , the a b s o r p t i v i t y per e s t e r g r o u p is c o n s t a n t . Table I V - 1 . Citrate Acetyltributyl Acetyltriethyl Tributyl M o l a r a b s o r b a n c e s for s o m e c i t r a t e e s t e r s a t 5 1 7 - 5 2 2 mfj,. e X 10~ 3.52 3.43 2.54 e X lO" per ester group 0.88 0.86 0.85 0.83 As s h o w n

Triethyl 2.49 ' A v e r a g e of 4 to 7 d e t e r m i n a t i o n s .

T h e f e r r i c h y d r o x a m a t e c o m p l e x of A T B C i s s t a b l e u p to f o u r h o u r s a f t e r s a m p l e p r e p a r a t i o n ; t h e c o m p l e x e s of t h e o t h e r c i t r a t e e s t e r s a r e s o m e w h a t l e s s s t a b l e a s s h o w n in T a b l e I V - 2 . recommended. T a b l e I V - 2 . F a d i n g r a t e s in p e r c e n t for f e r r i c h y d r o x a m a t e c o m p l e x e s of s o m e c i t r a t e e s t e r s . Hours after initial^ Citrate Acetyltributyl Acetyltriethyl Triethyl Tributyl 0.5 0.6 2.3 1.1 1.3 2.1 3.4 reading 0^5 P e r c e n t D e c r e a s e in A b s o r b a n c e 1 1.5 2 3 0.6 2.8 3.6 5.3 4 4,1 5.2 T h e r e f o r e , d e t e r m i n a t i o n of the a b s o r b a n c e of t h e c o m p l e x e s one h o u r a f t e r s a m p l e p r e p a r a t i o n i s

-27

B e e r 's Law applies up to 8 mg e s t e r p e r 50 m l . for ATBC is shown in F i g . IV-2. LX-02-1 a r e p r e s e n t e d in Table I V - 3 . Table I V - 3 . Sample No. 1 2 3 4 5 6 7

A calibration curve

The r e s u l t s of sorae a n a l y s e s of ATBC in

P e r c e n t ATBC in L X - 0 2 - 1 . % ATBC added 3.4 5.1 6.8 6.8 6.8 5.6 5.6 % ATBC found 3.4 5.0 7.0 7.0 6.7 5.4 5.6 1 2

A s u m m a r y of the reaction conditions used by Goddu et a l . , P i l z , 3 and Gutnikov and Schenk is given in Table I V - 4 . Goddu's method could not be used for ATBC since the fading r a t e of the complex w a s 5% per hour and the r e s u l t s w e r e not r e p r o d u c i b l e . P i l z ' s p r o c e d u r e applied to ATBC produced a 4% d e c r e a s e in a b s o r b a n c e during the f i r s t hour after the initial r e a d i n g , d e c r e a s i n g t h e r e a f t e r at a slower r a t e ; no reproducible r e s u l t s w e r e obtained. 3 The method of Gutnikov and Schenk was found applicable to ATBC and other c i t r a t e e s t e r s . A slight modification was r e q u i r e d , however. After dilution to volume and mixing, the sample was allowed to r e a c h t h e r m a l equilibrium before the photometric d e t e r m i n a t i o n . This r e q u i r e d a p p r o x i mately one hour. Also, in p r e p a r a t i o n of the f e r r i c p e r c h l o r a t e r e a g e n t , iron w i r e was found s u p e r i o r to anhydrous f e r r i c p e r c h l o r a t e due to the hygroscopicity of the salt. In addition, a PETN blank was r e q u i r e d since the absorbance of a saturated solution of P E T N in ethanol at 25C is 0.022 at 520 mfx. References R. F . Goddu, N. F . LaBlanc, and C. M, Wright, Anal. Chem. 7 , 1251 (1955). ^W. P i l z , Z. Anal. Chem. 162, 81 (1958). 3 G. Gutnikov and G. H, Schenk, Anal. Chem. 34, 1316 (1962). G. Norwitz, Anal. Chem. 3 1 , 2012 (1959).

-28-

Table IV-4. E x p e r i m e n t a l conditions for some methods for e s t e r d e t e r m i n a t i o n in the r e c e n t l i t e r a t u r e . Goddu et al. mg F e / m l Acidity (molar) NH2OH (mmol) NaOH (mmol) 0.27 0.1 2.7 4.7
1

Pilz 5 . 0 5 - :11,.2 0 . 0 0 4 - 0,.04

2.5

Gutnikov and Schenk" 0.51 0 . 0 7 - 0.08

4.2 25

6.25 KNO3 Water

490

Removal of e x c e s s hydroxylannine None Solution Ethanol ^max (-f^) Color stability (hours) 520 - 550 0 to " s e v e r a l "

Acetone Ethanol
524

l/?-4

0- 3

29-

o
<

o
CO

Pi

cq <

450

475

500

550

600 GLL-6^+6-1636

WAVELENGTH (millimicrons) F i g . I V - 1 A b s o r p t i o n s p e c t r u m of the f e r r i c h y d r o x a m a t e c o m p l e x of a c e t y l t r i b u t y l c i t r a t e (3.97 m g A T B C / 5 0 m l ) .

-30-

1.4

6 mg A T B C / 5 0 m l Fig. IV-2.

7 GLL-646-1637

Calibration curve for acetyltributyl c i t r a t e at 520 m^.

-31-

V.

T H E ANALYSIS O F M I X T U R E S O F HMX, V I T O N , AND O X A M I D E *

Abstract A m e t h o d for t h e a n a l y s i s of a p l a s t i c - b o n d e d e x p l o s i v e c o n t a i n ing HMX, V i t o n , and o x a m i d e is p r e s e n t e d , Viton is d e t e r m i n e d b y a n i t r i c a c i d Soxhlet e x t r a c t i o n . HMX p l u s V i t o n i s d e t e r m i n e d by h o t - w a t e r e x t r a c t i o n and t h e o x a m i d e c a l c u l a t e d b y d i f f e r e n c e . The oxamide m a y a l s o be d e t e r m i n e d by -y-butyrola c t o n e e x t r a c t i o n and the HMX c a l c u l a t e d b y d i f f e r e n c e . Introduction T h i s note d e s c r i b e s a m e t h o d for t h e a n a l y s i s of a p l a s t i c - b o n d e d e x p l o s i v e of t h e a p p r o x i m a t e c o m p o s i t i o n : HMX Viton Oxamide 80% 15% 5%

T h e V i t o n i s d e t e r m i n e d by a n i t r i c a c i d Soxhlet e x t r a c t i o n w h i c h i s a l s o u s e d f o r the d e t e r m i n a t i o n of V i t o n in L X - 0 4 . An a t t e m p t to find s p e c i f i c s o l v e n t s for t h e o t h e r c o m p o n e n t s , HMX and o x a m i d e , d i d not s u c c e e d . H e n c e t h e m e t h o d s p r e s e n t e d r e q u i r e c o r r e c t i o n s for p a r t i a l s o l u b i l i t y of t h e c o m p o n e n t s in the s o l v e n t s u s e d . These methods are a hot-water extrcLCtionfor o x a m i d e and a Y ~ h u t y r o l a c t o n e e x t r a c t i o n for H M X . In t h e h o t - w a t e r e x t r a c t i o n o x a m i d e i s r e m o v e d l e a v i n g a r e s i d u e of HMX and V i t o n . T h e HMX u s u a l l y c o n t a i n s a s m a l l a m o u n t of RDX w h i c h i s It i s , t h e r e f o r e , n e c e s s a r y t o e s t a b l i s h a p p r e c i a b l y s o l u b l e in h o t w a t e r .

the w a t e r s o l u b i l i t y of e a c h b a t c h of HMX u s e d in m a k i n g t h e p l a s t i c - b o n d e d e x p l o s i v e , and t o c o r r e c t for it in t h e d e t e r m i n a t i o n of HMX p l u s V i t o n . T h e a l t e r n a t e p r o c e d u r e u s e s y - b u t y r o l a c t o n e to e x t r a c t HMX and V i t o n , l e a v i n g a r e s i d u e of o x a m i d e . S i n c e o x a m i d e i s s o m e w h a t s o l u b l e in b u t y r o l a c t o n e , a c o r r e c t i o n m u s t be applied.

"^General C h e m i s t r y T e c h n i c a l N o t e N o . 108, d a t e d M a r c h 2 0 , 1 9 6 3 .

-32-

Exper imental M a t e r i a l s and Equipraent Analytical b a l a n c e , Ainsworth, Type S. Sintered g l a s s c r u c i b l e s , medium p o r o s i t y , 50 ml capacity. Vacuum oven, at 60-70C. Suction filtration equipment ( F i s h e r F i l t r a t o r ) . Soxhlet extraction a p p a r a t u s consisting of: Soxhlet tube, 70 ml capacity. Round-bottom flask, 250 ml capacity. T a l l - f o r m fritted g l a s s e x t r a c t i o n t h i m b l e , c o a r s e porosity, 25 m m d i a m e t e r , 85 m m high, Condenser, Anti-bump rod. Heating inantle with V a r i a c . Nitric acid, reagent g r a d e . ^ - B u t y r o l a c t o n e , Matheson, Coleman, and Bell. Carbon t e t r a c h l o r i d e , reagent g r a d e . HMX, Lot A134. Oxamide, Matheson, Coleman, and Bell. Viton A. Explosive s a m p l e . Procedures 1. Soxhlet extraction for d e t e r m i n a t i o n of Viton. Weigh a sample of P l a c e the

approximately 1 g r a m a c c u r a t e l y into an e x t r a c t i o n t h i m b l e . thimble into a Soxhlet tube. condenser and a round-bottom 250 m l flask.

Connect the extraction tube to a w a t e r - c o o l e d The l a t t e r contains an a n t i F i l l the

bump rod and is t w o - t h i r d s filled with concentrated n i t r i c acid. acid.

thimble containing the sample about one-half full with concentrated n i t r i c Place a heating m.antle under the flask and heat to refluxing (Variac Allow to reflux for about 4 h o u r s . Wash the Inspect If inclusions Let setting of approximately 110 volts).

the a p p a r a t u s cool and r e m o v e thimble from extraction tube. the Viton r e s i d u e which should be a clear t r a n s l u c e n t film.

thimble with distilled water and filter by suction ( F i s h e r F i l t r a t o r ) .

of HMX a n d / o r oxamide a r e found, b r e a k up the film with a procelain spatula

-33-

and r e - e x t r a c t for s e v e r a l h o u r s . 6 0 - 7 0 C for at l e a s t one h o u r . 2.

D r y t h e t h i m b l e in a v a c u u m o v e n at

Cool t o r o o m t e m p e r a t u r e and w e i g h . Weigh

W a t e r e x t r a c t i o n for the d e t e r m i n a t i o n of HMX and V i t o n .

a g r o u n d s a m p l e of a p p r o x i m a t e l y 1 g r a m a c c u r a t e l y into a t a r e d 100 m^l beaker containing a s t i r r i n g rod. to p r e v e n t s p a t t e r i n g . Add 50 m l hot w a t e r a n d b o i l g e n t l y on a hot p l a t e for a b o u t 10 m i n u t e s , s t i r r i n g m e a n w h i l e to w e t a l l p a r t i c l e s and F i l t e r by suction ( F i s h e r F i l t r a t o r ) while hot t h r o u g h Wash b e a k e r , Dry beaker a t a r e d 50 m l m e d i u m p o r o s i t y s i n t e r e d g l a s s c r u c i b l e .

s t i r r i n g r o d , a n d c r u c i b l e w i t h s e v e r a l p o r t i o n s of hot w a t e r . Cool t o r o o m t e m p e r a t u r e and w e i g h . 3'

w i t h s t i r r i n g r o d and c r u c i b l e in a v a c u u m o v e n at 6 0 - 7 0 C for one h o u r .

B u t y r o l a c t o n e e x t r a c t i o n f o r t h e d e t e r m i n a t i o n of o x a m i d e .

Weigh

a p p r o x i m a t e l y 1 g g r o u n d s a m p l e a c c u r a t e l y into a t a r e d 50 m l m e d i u m porosity sintered g l a s s crucible containing a stirring rod. b u t y r o l a c t o n e and s t i r t h o r o u g h l y to b r e a k up t h e m a t e r i a l . Add 10 m l y The s t i r r i n g

m a y r e q u i r e a b o u t 15 m i n u t e s , and r a a y b e f a c i l i t a t e d b y f i r s t i n t r o d u c i n g t h e c r u c i b l e into a b e a k e r c o n t a i n i n g b u t y r o l a c t o n e s u s p e n d e d in a n u l t r a sonic t r a n s d u c e r unit. F i l t e r b y s u c t i o n and r e p e a t w i t h t h r e e a d d i t i o n a l W a s h c r u c i b l e and s t i r r i n g r o d w i t h two Rinse the 5 m l p o r t i o n s of b u t y r o l a c t o n e .

s u c c e s s i v e 5 m l p o r t i o n s of c a r b o n t e t r a c h l o r i d e a n d f i l t e r . butyrolactone.

b o t t o m of t h e c r u c i b l e w i t h c a r b o n t e t r a c h l o r i d e to r e m o v e a n y r e m a i n i n g D r y t h e c r u c i b l e and s t i r r i n g r o d in a v a c u u m o v e n a t 6 0 - 7 0 C for at l e a s t one h o u r . . Cool to r o o m t e m p e r a t u r e and w e i g h . Calculations T3 J 1 or TT-i P r o c e d u r e 1: % V i t o n m g r e s i d u e ,__ =^ :; 100 mg sample if>^ ^ (ro^g s a m p l e ) , .

P r o c e d u r e 2: m g HMX, u n c o r r e c t e d = (mg r e s i d u e ) gf TTTi^rY% oxamide T-, J o 0/ -J P r o c e d u r e 3: % oxamide % HMX

(mg HMX, u n c o r r e c t e d ) ( 1 + c o r r e c t i o n f a c t o r ) mg sample = b y d i f f e r e n c e (100 - % Viton - % HMX) ("^g r e s i d u e ) ( l + c o r r e c t i o n f a c t o r ) , = ^ -^ 100 mg sample = b y d i f f e r e n c e (100 - % Viton - % o x a m i d e )

-34-

R e s u i t s and D i s c u s s i o n Viton was d e t e r m i n e d by n i t r i c acid Soxhlet e x t r a c t i o n . R e s u l t s for known m i x t u r e s , p r e p a r e d by weighing the components into Soxhlet e x t r a c tion t h i m b l e s a r e shown in Table V - 1 . The method is based on the oxidation and solution of HMX and oxamide by hot concentrated nitric acid which does not attack Viton. Table V - 1 . Recovery of Viton by n i t r i c acid Soxhlet extraction, mg Viton taken 103.7 160.8 151.8 mg Viton r e c o v e r e d 104.3 160.3 150.7 Average Standard deviation % recovery 100.6 99.7 99.3 99.9 0.66

F o r the d e t e r m i n a t i o n of HMX plus Viton an attempt was made to find a specific solvent for oxamide. Oxamide i s quite insoluble in all common solvents at r o o m t e m p e r a t u r e , but d i s s o l v e s r e a d i l y in hot w a t e r . The h o t - w a t e r extraction method, however, is not e n t i r e l y satisfactory. HMX usually contains some RDX which is appreciably soluble in hot w a t e r . A c o r r e c t i o n factor m u s t , t h e r e f o r e , be established for the batch of HMX used before the analytical p r o c e d u r e can be applied. This can be done by using an amount of HMX equal to that expected in the explosive and c a r r y i n g it through the analytical p r o c e d u r e . F r o m Lot A134, using s a m p l e s of approximately 700 mg, an a v e r a g e of 2.8% HMX was lost (see Table V-2). An a l t e r n a t e p r o c e d u r e for the d e t e r m i n a t i o n of oxamide was sought, requiring a solvent for HMX and Viton. The most suitable solvent found was "Y-butyrolactone; however, s m a l l amounts of oxamide w e r e lost. Again a c o r r e c t i o n factor m u s t be d e t e r m i n e d (Table V-3). Results for the analysis of a sample explosive a r e shown in Table V-4. R e s u l t s for HMX and oxamide obtained by h o t - w a t e r and butyrolactone extraction a r e c o m p a r e d . The a v e r a g e s of four r e p l i c a t e s a g r e e within 0.3%.

-35-

Table V - 2 . extraction. mg HMX taken 711.5 712.9 773.9 714.4 723.2 717,3

Recovery of HMX from HMX-oxamide m i x t u r e s by h o t - w a t e r mg IX r e c o v e r e d 691.9 695.1 751.5 696.1 701.5 693.8 Avera ge St and a r d deviati on
% recovery

97.3 97.5 97.1 97.3 97.0 96.7 97.2 0.28

Table V - 3 . mg oxamide taken 113.7 122.5

97.5

Recovery of oxamide by "y-butyrolactone extraction, mg oxamide r e c o v e r e d 08.8 18.2 93.6 86.2 Average Standard deviation % recovery 95.7 96.5 96.0 95.1 95.8 0.63

90.6

Table V - 4 . % Viton 15.37 15.39 15.38 Average 15.38 Corrected.

Analysis of an explosive sample. Butyrolactone extraction % HMX % oxamide* 80.8 80.7 80.5 80.9 80.7
3.8 3.9 4.1 3.7 3.9

Hot-water extraction % HMX* % oxamide 81.1 81.1 80.9 80.9 81.0

3.5 3.5 3.7 3.7 3.6

-36-

On a routine b a s i s the h o t - w a t e r e x t r a c t i o n i s r e c o m m e n d e d since filtration is rapid and the c r u c i b l e s can be used again after cleaning with acetone. In the butyrolactone extraction filtration is slow and the c r u c i b l e s should be d i s c a r d e d after u s e . Acknowledgment The w r i t e r i s indebted to Milton Finger for suggesting the hot w a t e r extraction method for the d e t e r m i n a t i o n of o x a m i d e . Reference Lee Monteith et a l . , Lawrence Radiation L a b o r a t o r y ( L i v e r m o r e ) Internal Document GCTN-49 (March 10, 1961).

-37-

VI.

AN ANALYTICAL PROCEDURE FOR RDX IN RX-05* Abstract

A p r o c e d u r e for determining the amount of RDX in RX-05 through carbon t e t r a c h l o r i d e extraction of the binding m a t e r i a l is d e s cribed. By using an u l t r a s o n i c g e n e r a t o r the use of hot CCl^ is eliminated and the time of a n a l y s i s reduced. Introduction This work d e s c r i b e s an analytical p r o c e d u r e for RDX in p l a s t i c bonded explosives of the approximate composition: RDX 80 - 90% Polystyrene 8 - 12% Dioctylphthalate (DOP) 2 - 3% The p r o c e d u r e i s a modification of one developed at LASL which r e q u i r e d heating the sample to boiling with CCl^, followed by shaking with a w r i s t action shaker for 30 m i n u t e s . Expe r i m e n t a l Equipment and M a t e r i a l s Analytical b a l a n c e . Ultrasonic g e n e r a t o r . Sintered g l a s s c r u c i b l e s , medium p o r o s i t y , 50 ml capacity. Vacuum oven, maintained at r o o m t e m p e r a t u r e . Suction filtration equipment ( F i s h e r F i l t r a t o r ) . 100 ml b e a k e r s . Carbon t e t r a c h l o r i d e , reagent g r a d e . P o l y s t y r e n e , Dow Chemical. Dioctylphthalate. RDX, Lot A033. PBX s a m p l e s .

General C h e m i s t r y Technical Note. No. 97, dated D e c e m b e r 28, 1962.

-38-

Procedure Weigh approximately 2 g m a t e r i a l into a t a r e d 100 ml b e a k e r . Add 30 ml carbon t e t r a c h l o r i d e and place in u l t r a s o n i c g e n e r a t o r for 10 minutes or until all lumps a r e b r o k e n up. F i l t e r by suction through a t a r e d 50 ml medium porosity s i n t e r e d g l a s s crucible and wash b e a k e r and crucible with t h r e e s u c c e s s i v e 5 ml portions of carbon t e t r a c h l o r i d e . Dry b e a k e r and crucible in a vacuum oven at r o o m t e m p e r a t u r e for one hour and weigh. Calculations 1. 2. Weight l o s s on carbon t e t r a c h l o r i d e extraction = amount of DOP + polystyrene Residue = amount of RDX Results and D i s c u s s i o n A f i r s t modification to the LASL method consisted of grinding up the m a t e r i a l with a mechanical m o r t a r and p e s t l e , thus eliminating the use of a shaker. This modification, however, still r e q u i r e d the use of hot C C l . which constitutes a health h a z a r d . Known s a m p l e s p r e p a r e d by weighing the components into s i n t e r e d g l a s s c r u c i b l e s w e r e e x t r a c t e d with 50 ml hot C C l . . in Table V I - 1 . extraction of p o l y s t y r e n e . The r e s u l t s a r e given The r e c o v e r i e s for RDX w e r e high indicating incomplete This was probably due to the difficulty of dissolving As a check on the efficiency of the

unplasticized polystyrene pellets in CCl^. with added known amounts of RDX. p e r c e n t RDX r e c o v e r e d .

method a n a l y s e s w e r e p e r f o r m e d on an unknown m a t e r i a l , a s r e c e i v e d and The r e s u l t s a r e p r e s e n t e d in Table VI-2. The advantage of grinding up the s a m p l e s is seen from the r e s u l t s for the Finally, the p r o c e d u r e d e s c r i b e d under E x p e r i m e n t a l was adopted. It e l i m i n a t e s e n t i r e l y the use of hot carbon t e t r a c h l o r i d e and grinding up s a m p l e s , and speeds up the a n a l y s i s . shown in Table V I - 3 . R e s u l t s obtained by this method a r e

-39-

Table V I - 1 .

R e c o v e r y of RDX and p l a s t i c from synthetic s a m p l e . mg total 212.5 211.3 203.2 206.7 211.8 mg recovered 203.2 198.7 190.8 194.0 200.9 Average % recovery 95.62 94.04 93.90 93,86 94.85 94,45

Amount taken img DOP m g polystyrene 164.5 167.5 158.7 161,9 166.6 48.0 43.8 44.5 44.8 45.2

mg RDX taken 1784.3 1806,8 1792.1 1804.9 1821,2

Big-RDX r e c o v e r e d 1793.6 1819.4 1804.5 1817.6 1832,1 Average

% recovery 100.52 100,70 100.69 100.70 100,60 100.64

Table V I - 2 .

RDX; i n s a m p l e Sn 4 0 7 3 , b a t c h 1. A, Pellets Percent 88.78)Avg. 89.01)88.885 1782.2 1852.1 99.89 99.91 RD5^; r e c o v e r e d m g r e c o v e r e d m g cal.cd."'' 1737.0 1569.0 1784,2 1853.8

Amount taken m g s a m p l e + mg RDX mg total 1956.9 1762,8 1747,2 1668.8 229.2 368.8 1956.9 1762.8 1976.4 2037.6

C a l c u l a t i o n b a s e d on a v e r a g e 8 8 . 8 8 5 % RDX i n u n k n o w n . RDX i n s a m p l e Sn 4 0 7 3 , b a t c h 1. B. Amount taken mg sample + m g RDX m g t o t a l 1963.7 1736.2 1648.6 1775.2 310.5 223.8 1963.7 1736.2 1959.1 1999.0 Ground sample RDX r e c o v e r e d mg recovered m g calcd.''' 1746.6 1544.8 1777.3 1803.5 1777.1 1803.0 Percent 88.94)Avg. 88.98)88.96 99.99 99.97

Calculation b a s e d on 88.96% RDX found in unknown.

-40-

Table V I - 3 . Ground-up sample hot CCI4

90,38 90.27

% RDX in sample J . O . 4080, batch 1. Ultrasonic g e n e r a t o r p e l l e t s , cold CCI4

90.29 90.28

_41-

Vn.

T H E ANALYSIS O F T U N G S T E N AND HMX IN R X - 1 2 "

Abstract An a n a l y s i s of a m a t e r i a l c o n s i s t i n g of t u n g s t e n , H M X , and Viton i s p r e s e n t e d . An a c e t o n e e x t r a c t i o n r e m o v e s HMX a n d V i t o n f r o m t u n g s t e n . T h e a c e t o n e i s e v a p o r a t e d a n d t h e HMX i n the r e s i d u e is d e t e r m i n e d p h o t o m e t r i c a l l y . Viton i s d e t e r m i n e d by difference. Introduction T h e n o m i n a l c o m p o s i t i o n of R X - 1 2 i s Tungsten HMX Viton and p h o t o m e t r i c m e t h o d s . s i z e of t u n g s t e n u s e d . Experimental R e a g e n t s and E q u i p m e n t Analytical balance. Spectrophotometer, Beckman DK-2, or equivalent instrument, 1 cm cells. S i n t e r e d - g l a s s c r u c i b l e s , m e d i u m p o r o s i t y , 50 m l c a p a c i t y . Vacuum oven, Centrifuge. Water bath, 70C. Funnel, Hirsch type, with c o a r s e porosity fritted disc. C e n t r i f u g e c o n e s , 40 m l c a p a c i t y , w i t h o u t e r 1 9 / 3 8 j o i n t s . Condenser, inner 19/38 joints. Volumetric glassware. S t i r r e r and Teflon-coated s t i r r i n g b a r s . 60-70C. Vacuum filtration equipment (Fisher Filtrator). with 95.4% 2.8% 1.8% T h e m e t h o d of e x t r a c t i o n d e p e n d s on t h e p a r t i c l e

T h i s n o t e p r e s e n t s a m e t h o d for i t s a n a l y s i s b y a c o m b i n a t i o n of e x t r a c t i o n

G e n e r a l C h e m i s t r y T e c h n i c a l N o t e N o . 1 4 1 , d a t e d J a n u a r y 2 3 , 1964.

-42-

Sulfuric acid, concentrated, ACS specifications. Acetone, ACS specifications. F e r r o u s a m m o n i u m sulfate, p r e p a r e d according to Semel, Laccetti and Roth : Weigh 100 g f e r r o u s a m m o n i u m sulfate hexahydrate into a 1 liter P y r e x v o l u m e t r i c flask and dissolve in about 500 ml distilled w a t e r . Add with caution 50 m l concentrated sulfuric acid. After the solution has r e a c h e d r o o m t e m p e r a t u r e , add 1 g iron filings and allow the evolved hydrogen to e s c a p e . Bring the volume to 1 liter with distilled w a t e r . P r e p a r a t i o n of Calibration Curve for HMX Weigh s e v e r a l s a m p l e s of HMX covering the range of 5 to 50 mg into 250 ml g l a s s - s t o p p e r e d E r l e n m e y e r f l a s k s . i s in solution. occasionally. r e a g e n t blank. I n s e r t a Teflon-covered s t i r r i n g b a r , add 90 ml concentrated sulfuric acid, stopper, and s t i r until the HMX Add 10.0 ml of the f e r r o u s a m m o n i u m sulfate r e a g e n t , swirl Measure the absorbance of the solutions at 520 mfj, against a Plot a b s o r b a n c e v e r s u s concentration of HMX. the flask, and place it in a water bath at 25 5C for 45 m i n u t e s , swirling

This calibration curve m u s t be p r e p a r e d for each batch of HMX used in the m a t e r i a l to be analyzed. E x t r e m e caution is called for in filling the c u v e t t e s ; automatic pipette fillers are recommended. Procedure 1. F o r tungsten of p a r t i c l e size > 15 irticrons. Weigh about 1 g Add 20

sample a c c u r a t e l y into a 100 ml b e a k e r containing a s t i r r i n g rod. plate at low heat. E r l e n m e y e r flask.

ml acetone, cover with a watch g l a s s , and bring to near boiling on a hot F i l t e r by suction while hot through a t a r e d m e d i u m E x t r a c t the m a t e r i a l with t h r e e additional 10 ml portions Wash p o r o s i t y , 5 0 - m l , s i n t e r e d - g l a s s c r u c i b l e , collecting the filtrate in a 250 m l of w a r m acetone, but do not place on hot plate (danger of bumping). washings in the 250 ml E r l e n m e y e r .

b e a k e r and crucible with s e v e r a l portions of acetone, collecting all the F i l t r a t i o n is facilitated by t r a n s f e r r i n g D r y b e a k e r and Cool to r o o m t e m p e r a a s little as possible of the tungsten onto the filter c r u c i b l e . crucible in a vacuum oven at 60-70C for one h o u r . t u r e and weigh.

-43-

Evaporate the acetone solution in the E r l e n m e y e r to d r y n e s s under a s t r e a m of a i r . I n s e r t a Teflon-covered s t i r r i n g b a r and proceed with the photometric d e t e r m i n a t i o n of HMX a s d e s c r i b e d above, with the following change: After 30 minutes in the water bath, filter the contents of the flask by suction through a c o a r s e porosity H i r s c h funnel into a 250 ml E r l e n m e y e r flask. P l a c e the filtrate in the w a t e r bath for another 15 m i n u t e s , then proceed with the photometric d e t e r m i n a t i o n . To check on the complete r e m o v a l of HMX and Viton from the tungsten, r e - e x t r a c t the r e s i d u e with s e v e r a l 10 ml portions of w a r m acetone and again evaporate the acetone solution to d r y n e s s . If no visible white r e s i d u e is obtained, the extraction i s complete. 2. F o r tungsten of p a r t i c l e size < 15 m i c r o n s . Weigh a p p r o x i m a t e l y 1 g sample a c c u r a t e l y into a 40 ml centrifuge cone provided with a ground joint for accommodation of a c o n d e n s e r , add 20 ml of acetone, connect with a w a t e r - c o o l e d condenser and i m m e r s e in a water bath at about 70C. Let reflux for s e v e r a l m i n u t e s , r e m o v e from w a t e r bath, r i n s e down condenser with s e v e r a l ml of acetone, and centrifuge for 5 m i n u t e s at high speed. Decant the supernatant acetone into a 250 ml E r l e n m e y e r flask taking c a r e not to t r a n s f e r any tungsten. Repeat reflux, centrifugation, and decantation with four additional 10 m l portions of a c e t o n e . D r y the centrifuge cone in a vacuum oven at 6 0 - 7 0 C . Cool to r o o m t e m p e r a t u r e and weigh. E v a p o r a t e the acetone solution in the E r l e n m e y e r flask to d r y n e s s under a s t r e a m of air and proceed with the d e t e r m i n a t i o n of HMX as above. As in p r o c e d u r e 1, r e - e x t r a c t the r e s i d u e with s e v e r a l portions of acetone to check on complete r e m o v a l of HMX and Viton from the tungsten. If after evaporation of the acetone solution no white r e s i d u e r e m a i n s , the extraction was c o m p l e t e . If a white residue r e m a i n s , r e p e a t the photom e t r i c d e t e r m i n a t i o n of HMX and c o r r e c t the initial r e s u l t s . Also, r e weigh the tungsten r e s i d u e . Calculations 1. 2. 3. Residue after acetone e x t r a c t i o n = amount of tungsten Photometric determination Calculated by difference = amount of HMX = amount of Viton

.44-

R e s u l t s and D i s c u s s i o n V i t o n and HMX a r e s o l u b l e in a c e t o n e ; t h i s i s t h e b a s i s of t h e i r s e p a r a t i o n fromi t u n g s t e n . 2.2 g/lOO m l , T h e s o l u b i l i t y of HMX in a c e t o n e a t 3 0 " C i s h e n c e t h e a m o u n t of s o l v e n t u s e d in t h e e x t r a c t i o n p r o c e d u r e s

i n s u r e s c o m p l e t e r e m o v a l of HMX and V i t o n . 1 3 L a c c e t t i , S e m e l , and R o t h ' ' m o d i f i e d t h e c o l o r i m e t r i c f e r r o u s s u l f a t e m e t h o d for t h e d e t e r m i n a t i o n of o r g a n i c n i t r a t e s t o i n c l u d e a l i p h a t i c and c y c l i c n i t r a m i n e s . T h e y w e r e a b l e to d e t e r m i n e m i x t u r e s of HMX and RDX b y t h i s m e t h o d , s i n c e p l o t s of a b s o r b a n c e a g a i n s t c o n c e n t r a t i o n for t h e s e c o m p o u n d s give s t r a i g h t l i n e s w h i c h h a v e d i f f e r e n t s l o p e s b u t i n t e r s e c t at the o r i g i n . T h e m o l a r a b s o r b a n c e s for t h e f e r r o u s n i t r o s y l c o m p l e x e s of RDX a n d HMX a r e g i v e n in T a b l e V I I - 1 . T a b l e V I I - 1 . M o l a r a b s o r b a n c e s , e, for f e r r o u s n i t r o s y l c o m p l e x e s of RDX and HMX. Compound RDX HMX HMX, Lot A - 2 2 2 A v e r a g e of 6 r u n S j 9 5 % c o n f i d e n c e l e v e l . C o m m e r c i a l HMX u s u a l l y c o n t a i n s s o m e RDX a n d p o s s i b l y o t h e r nitramines as contaminants. In t h i s w o r k , h o w e v e r , t h e d e s i r e d d a t a i s Therefore, the a m o u n t of a p a r t i c u l a r b a t c h of HMX in a f o r m u l a t i o n . X 10-2 5,29^ 3.65^ 3.80 0.06*

c a l i b r a t i o n c u r v e s m u s t be p r e p a r e d f o r e v e r y b a t c h of HMX t o b e a n a l y z e d . T a b l e VII-1 s h o w s the m o l a r a b s o r b a n c e of t h e f e r r o u s n i t r o s y l c o m p l e x of HMX, Lot A - 2 2 2 . C o m p a r i s o n w i t h t h e d a t a of L a c c e t t i et a l . i n d i c a t e s , The a b s o r p t i o n s p e c t r u m a s e x p e c t e d , t h e p r e s e n c e of i m p u r i t i e s in t h i s l o t . B e e r ' s L a w a p p l i e s u p to 45 m g / l O O m l . V i t o n i s i n s o l u b l e in c o n c e n t r a t e d s u l f u r i c a c i d . In t h e p r o c e d u r e for Filtration the p h o t o m e t r i c d e t e r m i n a t i o n of HMX i t t e n d s t o a g g l o m e r a t e . photometric determination.

for t h i s b a t c h i s s h o w n in F i g . V I I - 1 and i t s c a l i b r a t i o n c u r v e in F i g . V n - 2 .

b y s u c t i o n t h r o u g h a c o a r s e - p o r o s i t y H i r s c h funnel i s s u g g e s t e d b e f o r e the

-45-

Some typical r e s u l t s a r e shown in Table VII-2. of J . O . 2606 w e r e available. 18.5 m i c r o n s .

The p a r t i c l e size of

the tungsten in RX-12(6K-42-2) is 18.5 m i c r o n s ; no data on the particle size The speed of filtration of this m a t e r i a l indicated that the p a r t i c l e size of the tungsten was probably g r e a t e r than The nominal pore size of mediumi porosity filter c r u c i b l e s is If tungsten of a p a r t i c l e size < 15 m i c r o n s is used in a When 10 to 15 m i c r o n s .

materials p r o c e d u r e 2 m u s t be used. Tungsten cannot e a s i l y be removed f r o m the filter c r u c i b l e s . discarded. Table VII-2. Sample RX-12-AA ( J . O . 2606) % tungsten 95.46 95.48 95.55 95,50 95.58 95,37 95.48 94.79 94.99 95.11 95.07 Average 94.99 Analysis of RX-12 m a t e r i a l s . % HMX 2.69 2.78 2.49 2.65 2.70 2.98 2.84 2.87 3.00 2.83 2.74 2.86 References 2 S. Semel, M. A. Laccetti, and M. Roth, Anal. Chem. 3 1 , 1050 (1959). J, T. R o g e r s , " P h y s i c a l and Chemical P r o p e r t i e s of RDX and HMX," M, A, L a c c e t t i , S. Semel, and M. Roth, Anal, Ch6m, 3 1 , 1049 (1959). % Viton 1.85 1.74 1.96 1.85 1.72 1.65 1,69 2.34 2.01 2.06 2.19 2.15 Filtration
n

filtration b e c o m e s too slow (usually after two u s e s ) , the c r u c i b l e s must be

Method Filtration
II II

(1)

Average

Centrifugation
II

Average RX-12 (6K-42-2)

(1)

Aug. 1962, Holston Defense Corp., Control No, 20-P~26, S e r i e s B.

-46-

0.7

0.6

o
O
CO

0.5

\
0.4

< 0.3

0.2

\
0.1

1
400 425

1
450

! .. J
475 500

1
550

1
600 700 GLL-646-1638

WAVELENGTH (millimicrons) Fig. VII-l. Lot A-222.

A b s o r p t i o n s p e c t r u m of f e r r o u s n i t r o s y l c o m p l e x of HMX,

-47-

0.7

/
0.6

J/
0.5

/
/
0.4

u
<

o
CO

Pi
0.3

<

0.2

y
/

0.1

1
10
20

30

40

50

60

GLL-646-1639 mg HMX/lOOml

F i g . V I I - 2 . C a l i b r a t i o n c u r v e for f e r r o u s n i t r o s y l c o m p l e x of H M X , L o t A - 2 2 2 a t 520 m[i.

-48-

VTII.

THE ANALYSIS OF MOCK EXPLOSIVE 90010'" Abstract

An analysis of mock explosive 90010, consisting of b a r i u m n i t r a t e , p e n t a e r y t h r i t o l , n i t r o c e l l u l o s e , and t V i s - p - c h l o r o ethylphosphate (CEF) is p r e s e n t e d . The C E F is e x t r a c t e d with methylene chloride or ethyl e t h e r . Barium, n i t r a t e and p e n t a e r y t h r i t o l a r e e x t r a c t e d with w a t e r , and the b a r i u n , n i t r a t e i s d e t e r m i n e d by EDTA t i t r a t i o n . The r e s i d u e , n i t r o cellulose, is qualitatively identified. Introduction Mock explosive 90010 i s an i n e r t m a t e r i a l simulating the physical p r o p e r t i e s of PBX 9404. Its nominal composition i s : 46 48 1.0% * 1.0% Barium nitrate Pentaerythritol T r i s - 0 - c h l o r o e t h y l p h o s p h a t e (CEF) Nitrocellulose Red dye of solvent extraction and t i t r a t i o n m e t h o d s . is c h a r a c t e r i z e d by a spot t e s t . Experimental Reagents and Equipment Analytical b a l a n c e . pH m e t e r . Machlett b u r e t , 25 m l . Magnetic s t i r r e r and s t i r r i n g b a r s . Vacuum filtration eqiiipment ( F i s h e r F i l t r a t o r ) . S i n t e r e d - g l a s s c r u c i b l e s , medimca porosity, 50 ml capacity. Vacuum oven, 60-70''C. Glycerol or miineral oil .bath. Ethyl e t h e r .

3.2 0.3% 2.8 0.3% 0.05%

This note p r e s e n t s a method for the analysis of 90010 by a comibination In addition, the n i t r o c e l l u l o s e

General C h e m i s t r y Technical Note No. 133, dated October 29, 1963.

49-

Methylene chloride. Sulfanilic acid reagent: 1 g per 75 ml water and 25 ml glacial acetic acid. 1-naphthylamine reagent: 0.3 g per 70 ml water and 30 ml glacial acetic acid. Ethylenediaminetetraacetic acid (EDTA), 0.05 M: Dissolve 18.61 g disodium ethylenediaminetetraacetate dihydrate in water and dilute to 1 liter in a volumetric flask. Benzoin. Sodium hydroxide, 6 M, freshly prepared. METAB Indicator Tablets, Fisher Scientific Co. Standardization of EDTA Solution I

Weigh accurately 120 to 250 mg bariumi nitrate into a 250 ml beaker or use an aliquot of a standard barium nitrate solution. to about 100 ml with distilled water. 6 M sodium hydroxide. Dissolve and dilute Titrate with Adjust to pH 12 (using pH meter) with The titration is best

Add one METAB tablet and dissolve.

EDTA until the color changes from blue to colorless. performed without artificial light. NT Ti x - ^ ^r A ^ g bariuiH nitrate c T ri Normality of EDTA = |3|i.38)(^i E D T A ) Procedure

Weigh approximately 1 g of material accurately into a tared 100 ml beaker containing a glass stirring rodheat. ture. Add 20 ml methylene chloride or ethyl ether, cover with a watch glass, and bring to boil on a hot plate at low Remove from heat, macerate any lumps, and let cool to room temperaFilter by suction through a tared 50 ml, medium-porosity, glass Wash beaker and crucible with four 5 ml portions of solvent. Dry Cool to room temperature and

crucible. weigh.

in a vacuum oven at 60-70C for one hour.

Transfer most of the residue quantitatively into the previously used beaker, add 25 ml distilled water, and bring to boil on a hot plate. a 100 ml volumetric flask. Filter through the previously used crucible collecting the filtrate quantitatively in Wash beaker and crucible with several portions Dry beaker and crucible in a vacuum Cool to room temperature and weigh. of hot water and collect the washings. oven at 60-70 C for one hour.

-50-

Cool the filtrate in the v o l u m e t r i c flask to room t e m p e r a t u r e , dilute to 100 ml with w a t e r , and mix. T r a n s f e r an aliquot of 25 m l into a 250 mil b e a k e r and do the EDTA titration as d e s c r i b e d for the standarization of EDTA.

2 P e r f o r m a qualitative t e s t for nitrocellulose on the residue as follows : Place a pinch of the sample ( s e v e r a l mg) into a 3-inch t e s t tube and add

about 100 mg benzoin. I m m e r s e the t e s t tube in an oil bath preheated to 140 C, Cover the mouth of the t e s t tube with filter paper moistened with G r i e s s r e a g e n t , p r e p a r e d by mixing equal volumes of the sulfanilic acid r e a g e n t and the 1-naphthylamine r e a g e n t , A positive t e s t for nitrous acid is shown by the appearance of a red a r e a on the filter p a p e r . Calculations 1, 2, 3, 4, Weight l o s s after ether (or methylene chloride) extraction = amount of C E F , Residue after w a t e r extraction = amount of nitrocellulose -f red dye, (ml EDTA)(normality EDTA)( 1045,52)''* = amount of b a r i u r a n i t r a t e , By difference = amount of p e n t a e r y t h r i t o l . R e s u l t s and D i s c u s s i o n C E F may be extracted with methylene dichloride or ethyl ether (the f o r m e r is l e s s h a z a r d o u s ) . with w a t e r . a pH of 12, P e n t a e r y t h r i t o l and b a r i u m n i t r a t e a r e extracted The b a r i u m n i t r a t e i s t i t r a t e d with standard EDTA solution at The 6 M NaOH used to adjust the pH to 12 m u s t be free of CO F o r standardization of the EDTA solution No i n t e r f e r e n c e is caused by the penta-

otherwise BaCO_ p r e c i p i t a t e s . b a r i u m n i t r a t e is r e c o m m e n d e d .

e r y t h r i t o l which is d e t e r m i n e d by difference. The r e s i d u e from the w a t e r extraction i s n i t r o c e l l u l o s e and a s m a l l The p r e s e n c e of the n i t r a t e group is verified by fusion 2 with benzoin and detection of evolved n i t r o u s acid by the G r i e s s r e a c t i o n , A red color in an acetic acid solution of sulfanilic acid and 1-naphthylamine constitutes a positive t e s t . The c r u c i b l e s a r e cleaned for r e - u s e with hot Since only approximately 0.5 mg of n i t r i c acid which d e s t r o y s the red dye. amount of r e d dye.

red dye is p r e s e n t in the n i t r o c e l l u l o s e r e s i d u e , no c o r r e c t i o n is n e c e s s a r y .

"1045.52 = (26l.38)(4), w h e r e 261,38 is the m o l e c u l a r weight of Ba(NO ) ,

3 Ci

-51-

Some typical r e s u l t s a r e shown in the following table. Analysis of mock explosive 90010, sample A-192. % CEF
3,30 3,29 3,33 3.25 3.30 3.34

% nitrocellulose 2.72 2,68 2.73

% Ba(N03)2 46,23 46,44 46,37 46.10 46.34 46.22 46.26

% pentaerythritol (by differs 47.75 47,58 47,57

Average 3,30

2,71

46,28

47,63

Acknowledgment I a m indebted to C h a r l e s H, Otto and F r e d e r i c k B, Stephens for help with the EDTA t i t r a t i o n of b a r i u m n i t r a t e . References F . J. Welcher, The Analytical Uses of Ethylenediamine T e t r a a c e t i c Acid (D, Van Nostrand Co, , P r i n c e t o n , N. J. 1961), pp. 143-4. ^ F , F e i g l , Che m i s t - A n a l y s t 52, 47 (1963),
1

-52-

IX,

THE ANALYSIS OF A MOCK MATERIAL FOR LX-04- V"' Abstract

An analysis of a mock m a t e r i a l for LX-04-1 consisting of cyanuric acid, b a r i u m n i t r a t e , and Viton i s p r e s e n t e d . B a r i u m n i t r a t e and cyanuric acid a r e e x t r a c t e d with w a t e r , leaving a r e s i d u e of Viton, B a r i u m n i t r a t e is converted to the sulfate and d e t e r m i n e d as such; cyanuric acid is d e t e r m i n e d by difference. Introduction This note p r e s e n t s a method for the a n a l y s i s of a mock m a t e r i a l for LX-04-1 having a nominal composition of: Viton 15% Cyanuric acid Barium nitrate 72% 13% Experimental Reagents and Equipment Analytical b a l a n c e . Vacuum filtration equipment ( F i s h e r F i l t r a t o r ) . Vacuum oven, 60-70C, Drying oven, 110C. S i n t e r e d - g l a s s c r u c i b l e s , m e d i u m p o r o s i t y , 50 ml capacity. Sulfuric acid, Procedure Weigh approximately 1 g of m a t e r i a l a c c u r a t e l y into a 100 ml b e a k e r . Add 50 mil hot distilled w a t e r , cover with a watch g l a s s , and bring to gentle boiling on a hot plate. Remove the b e a k e r periodically from the hot plate Add distilled water to keep and m a c e r a t e the m a t e r i a l with a g l a s s s t i r r i n g rod flattened out at one end into a disc of approximately 5 m m d i a m e t e r . the volume at about 50 m l . p a r t i c l e s a r e imbedded in the Viton. The extraction is complete when no m o r e white This r e q u i r e s at l e a s t 2 h o u r s . 1:10.

' G e n e r a l C h e m i s t r y Technical Note No. 137, dated D e c e m b e r 2, 1963,

-53-

F i l t e r the hot solution by suction through a t a r e d 50 ml m e d i u m porosity s i n t e r e d - g l a s s c r u c i b l e , collecting the filtrate quantitatively in a 250 ml b e a k e r . Rinse b e a k e r and crucible with enough hot w a t e r so that only the Viton r e s i d u e r e m a i n s , (Cyanuric acid may p r e c i p i t a t e in the b e a k e r or funnel on cooling,) After filtration r i n s e the bottom of the crucible and the funnel with hot w a t e r , collecting all the washings in the 250 ml b e a k e r . Dry the crucible in a vacuum oven at 60-70C for one hour, cool to r o o m t e m p e r a t u r e , and weigh. Heat the filtrate to n e a r boiling on a hot plate, add 10 ml 1:10 sulfuric acid, and keep n e a r boiling for at l e a s t 15 m i n u t e s . F i l t e r through a t a r e d m e d i u m - p o r o s i t y g l a s s crucible and wash b e a k e r and crucible thoroughly with hot w a t e r . Dry the crucible in an oven at 1 10''C for one hour, cool to r o o m t e m p e r a t u r e , and weigh. Calculations 1, 2, 3, Residue after water extraction ( B a r i u m sulfate)( 1,11974) By difference = amount of Viton = amount of b a r i u m n i t r a t e = amount of cyanuric acid

R e s u l t s and D i s c u s s i o n The extraction of cyanuric acid and b a r i u m n i t r a t e by water from the m a t r i x of Viton r e q u i r e s r e p e a t e d m a c e r a t i o n and boiling. r e d - d y e d Viton. The extraction is complete when inspection r e v e a l s no m o r e white m a t e r i a l imbedded in the F o r a 1 g sample a m i n i m u m extraction time of 2 hours i s The filtration must be r e q u i r e d with m a c e r a t i o n s at 15-minute i n t e r v a l s . in cold w a t e r (0-25 g per 100 ml water at 17C). B a r i u m n i t r a t e could not be d e t e r m i n e d in the p r e s e n c e of cyanuric acid by EDTA t i t r a t i o n at pH 10 as in 90010 (see Section VIII). appeared at a pH of about 7 - 8 . Cyanuric acid could not be d e t e r m i n e d by t i t r a t i o n with standard b a s e in the p r e s e n c e of b a r i u m n i t r a t e . titration. Again a white precipitate (probably b a r i u m cyanurate) formed at a pH of about 7-8 which interfered with the During adjustment of the pH by m e a n s of sodium hydroxide a white p r e c i p i t a t e

done while the solution is hot since cyanuric acid is only sparingly soluble

-54-

P r e l i m i n a r y e x p e r i m e n t s indicated that b a r i u m ion could be quantitatively removed from m i x t u r e s with cyanuric acid as the sulfate and d e t e r m i n e d g r a v i m e t r i c a l l y . This p r o c e d u r e w a s adopted. Cyanuric acid is d e t e r m i n e d by difference. Some typical r e s u l t s a r e shown in Table IX- 1. Table I X - 1 . Results of a n a l y s e s of mock m a t e r i a l s for L X - 0 4 - 1 . Sample RM-04-BA % Viton 15.27 15.30 15.14 15.12 15.14 15.18 15.26 15.31 15.22 15.09 15.00 15.13 15.21 15.24 Average RM-04-BC 15.27 15.16 15.16 15.66 15.66 15.46 15.62 15.53 15.87 15.70 15.64 15.64 12.53 12.53 13.27 13.27 13.10 12.78 12.89 13.26 12.84 13.02 13.02 72.23 71.07 71.44 71.60 71.58 70.87 71.46 71.46 % Ba(N03)2 Ba(N03)2 13.07 12.92 13.06 % cyanuric acid 71.75 71.68 71.77

Average RM-04-BB

13.02 12.41 12.73 12.46

71.73 72.38 72.03 72.27

Average

-55-

X.

THE DETERMINATION OF CYANURIC ACID, MELAMINE, AND VITON IN MIXTURES (LM-04-0)* Abstract A method is d e s c r i b e d for the analysis of L M - 0 4 - 0 . Melamine and cyanuric acid a r e d e t e r m i n e d as the m e l a m i n e c y a n u r a t e . Viton is d e t e r m i n e d by n i t r i c acid e x t r a c t i o n . The p r e s e n c e of melamine cyanurate in p r e s s e d pellets may be a s c e r t a i n e d from x - r a y powder p a t t e r n s . Introduction

A p r o c e d u r e was r e q u i r e d for the d e t e r m i n a t i o n of the components of L M - 0 4 - 0 : cyanuric acid, m e l a m i n e , and Viton. This work d e s c r i b e s a g r a v i m e t r i c method for the d e t e r m i n a t i o n of melamine and cyanuric acid by formation of m e l a m i n e c y a n u r a t e . Viton is then d e t e r m i n e d by n i t r i c acid extraction. The approximate composition of the m i x t u r e s for a n a l y s i s is Cyanuric acid 60% Melamine 23% Viton 17% P r i o r to this work only the analysis of Viton was r e q u i r e d .

Although Viton

can be d e t e r m i n e d by a m i c r o m e t h o d using the Schoniger combustion 2 technique, by using a l a r g e r s a m p l e , e r r o r s due to s e g r e g a t i o n of the material m a y b e minimized. nitric acid extraction. Experimental M a t e r i a l s and Equipment Nitric acid, reagent g r a d e , sp. gr. 1.42, F o r this r e a s o n , Viton was d e t e r m i n e d by

B e a k e r s , 150 m l , with s t i r r i n g r o d s . S i n t e r e d - g l a s s c r u c i b l e s , 35 ml capacity, mediumi porosity. Analytical b a l a n c e . Steam bath or hot plate. Vacuum oven, maintained at 60-70C. ''"General C h e m i s t r y Technical Note No, 67, dated March 6, 1962,

-56-

Vacuum oven, maintained at r o o m t e m p e r a t u r e . Suction filtration equipment. Platinum-tipped t o n g s . Procedure Weigh 0.5 to 1 g of m a t e r i a l into a t a r e d 150 ml b e a k e r containing a s t i r r i n g rod. Add 50 inl distilled w a t e r , cover with a watch g l a s s , and bring to boiling on a hot plate. B r e a k up any lumps with the s t i r r i n g rod, stir occasionally, and wash the sides of the b e a k e r down occasionally with w a t e r . Digest for about 15 m i n u t e s , taking c a r e not to lose any m a t e r i a l . F i l t e r by suction through a t a r e d 35 ml m e d i u m - p o r o s i t y , s i n t e r e d g l a s s c r u c i b l e . Wash b e a k e r , s t i r r i n g rod, and filter crucible with s e v e r a l portions of distilled w a t e r . D i s c a r d the filtrate.''^ Dry the b e a k e r plus s t i r r i n g rod, and the filter crucible in a vacuum oven at 60-70 C for at l e a s t one hour. Cool to r o o m t e m p e r a t u r e and weigh. Place the crucible inside the b e a k e r . Introduce about 15 ml concentrated n i t r i c acid into the b e a k e r , and a like amount into the c r u c i b l e , rinsing down the sides of both. Put the b e a k e r on a hot plate and boil until only the Viton is left in the c r u c i b l e . Stir the contents of the crucible occasionally to facilitate solution. Remove the crucible from the b e a k e r by m e a n s of platinum-tipped tongs, and place in the suction a p p a r a t u s . F i l t e r , pouring the contents of the b e a k e r into the c r u c i b l e . Rinse b e a k e r and crucible with s e v e r a l portions of concentrated nitric acid, then thoroughly with distilled w a t e r to r e m o v e all the acid. Dry b e a k e r , s t i r r i n g rod, and filter crucible in a vacuum oven at 60-70C for at l e a s t one hour. Cool to r o o m t e m p e r a t u r e and weigh. All operations with concentrated n i t r i c acid a r e to be c a r r i e d out in a hood, with p r o p e r p r e c a u t i o n s . Calculations 1. 2. 3. 4. 5. Residue after water extraction By difference (Melamine cyanurate)(0.49422) Sample - (Viton + melamine) = amount of Viton -f m e l a m i n e cyanurate = amount of m e l a m i n e cyanurate = amount of m e l a m i n e = amount of cyanuric acid

Residue after n i t r i c acid extraction = amount of Viton

''^If d e s i r e d , the aqueous filtrate may be collected and t i t r a t e d with standard b a s e to the phenolphthalein endpoint.

-57-

If a titration is carried out on the water extract, the amount of free cyanuric acid is mg cyanuric acid = (normality base) (ml titration) (129.08). Results and Discussion Melamine and cyanuric acid are moderately soluble in hot water. They form, however, a very insoluble salt, melamine cyanurate, in which 3 the components are present in a 1:1 ratio. This compound precipitates as a very fine powder when aqueous solutions of the components are mixed. An elemental analysis of melamine cyanurate, C,0_H N , is given in Table X-1. Its melting point is near 390C. X-ray diffraction patterns and

infrared spectra of the complex and its components are shown in Figs. X-1, X-2, X-3, and X-4, Table X- 1. Element % carbon % nitrogen % hydrogen Elemental analysis of melamine cyanurate. Theoretical 28.24 49-40 3.55 Found 27.69 49.32 3.45

The materials investigated have a large excess of cyanuric acid hence all the melamine is converted to the cyanurate by digestion in water. excess cyanuric acid is removed by filtration. The

From the weights of the dry

salt the amount of melamine in the original mixture is mg melamine = (mg melamine cyanurate) (0.49422), The factor 0.49422 is derived as follows: cyanuric acid _ 129.08 melamme 126.13 Let X = mg melamine, then mg rcielamine cyanurate = x - 1.023389x = 2.023389x f and , . mg melainine cyanurate , ^ . \ \,n Ar^A-yyx mg melamme = = ? n?338q ~ ' " ^ ^ melamme cyanurate)(0.49422), In melamine cyanurate the ratio

i mQ-aon

-58-

If d e s i r e d , the e x c e s s cyanuric acid can be collected and t i t r a t e d with standard sodium hydroxide to the phenolphthalein endpoint. As seen from Table X - 4 , this step is not n e c e s s a r y ; satisfactory r e s u l t s a r e obtained when determining the cyanuric acid by difference. Tables X - 2 , X - 3 , and X-4 show r e s u l t s obtained with known s a m p l e s , p r e p a r e d by mixing the d r y i n g r e d i e n t s . In s a m p l e s of L M - 0 4 - 0 , melamine and cyanuric acid a r e blended with a solution of Viton in methylethyl ketone methylisobutyl ketone, n-butyl a c e t a t e , or a s i m i l a r solvent. The solvent is then r e m o v e d by application of heat and vacuum. Due to this p r o c e s s i n g the a n a l y s i s of LM-04-0 is m o r e difficult than that of the known m i x t u r e s ; some m e l a m i n e a n d / o r cyanuric acid miay be encapsulated by the Viton, Also, the m a t e r i a l is not of uniform p a r t i c l e size, and may t h e r e f o r e show segregation. The r e s u l t s for some LM-04-0 s a m p l e s a r e given in Table X - 5 . As Table X-6 shows, when the a n a l y s i s of Viton only is r e q u i r e d , the n i t r i c acid extraction method is p r e f e r a b l e . If, however, the a n a l y s i s of m e l a m i n e and cyanuric acid is also r e q u i r e d , the p r o c e d u r e given h e r e is r e c o m m e n d e d . Alternatively, a check on the Viton a n a l y s i s may be p e r formed on a s e p a r a t e s a m p l e . The p r e s e n c e of m e l a m i n e cyanurate in p r e s s e d pellets may be a s c e r t a i n e d from x - r a y powder p a t t e r n s , or from the infrared s p e c t r u m of the solid in K B r . Absorption peaks found in the c y a n u r a t e , but not in m e l a m i n e or cyanuric acid, occur at the following wavelengths: 3.74, 3.95, 9-23, 10.85, and 13.03 m i c r o n s . References L. Monteith, G. G r o s s m a n , G, Lopez, Lawrence Radiation L a b o r a t o r y ( L i v e r m o r e ) Internal Document GCTN-49 (March 10, 1961), ^W. Selig and D, M. Colman, UCRL-6639 (April 30, 1961), p. 29. 3 E. M. Smolin and L. Rapoport, s - T r i a z i n e s and D e r i v a t i v e s (Interscience P u b l i s h e r s , N. Y, , 1959), p. 326.

-59-

Table X - 2 . Sample No.

1 2 3 4 5 6 7 8 9 10

Recovery of Viton from L M - 0 4 - 0 . mg r e c o v e r e d 91.3 102.5 97.9 109.6 88.1 127.7 124.6 196.0 259.5 245.5 99.91 0.21 % recovery
99.8 99.7 99.6 99.8

mg taken 91.5 102.8 98.3 109.8 87.7 127.5 125.2 196.2 259.5 245.3 A v e ] rage % r e c o v e r y 95% confidence l i m i t s

100.5 100.2
99.5 99.9

100.0 100,1

Table X - 3 . Sample No.

1 2 3 4 5 6 7 8 9 10

Recovery of m e l a m i n e from L M - 0 4 - 0 . mg r e c o v e r e d 86.6 92-2 93.5 101.8 107.1 96.3 125.7 163.2 199.0 209-9 100. 24
0. 14 % recovery

mg taken 86.7 92.0 93.3 101.4 106.8 96.3 125.2 163.1 198.0 208.1 Average % r e c o v e r y 95% confidence l i m i t s

99.9 100.2 100.2 100.4 100.3 100.0 100.4 100.1 100.B 100.4

-60-

Table X-4. aple N o . 1 2 3 4 5 6 7 8 9 10

R e c o v e r y of c y a n u r i c a c i d f r o m L M - 0 4 - 0 , b y d i f f e r e n c e . mg taken 207.6 215.7 215.4 208.8 220.0 199.6 255.3 313.1 460.4 610.1 Average % recovery 95% c o n f i d e n c e l i m i t s mg r e c o v e r e d 207.9 215.8 215.6 208.6 219.3 199.4 255.4 313.2 459.4 609-1 99-94 0-10 % recovery 100.1 100.1 100.1 99-9 99.7 99.9 100.0 100.0 99.8 99.8

Table X-5.

A n a l y s i s of s o r a e L M - 0 4 - 0 s a m p l e s . New method 15.42 15.56 15.54 15.39 15.48 0.07 17.11 17.11 17.11 0 16.45 16.36 16.61 16.40 16.46 0.08 % melamine 24.22 24.27 24.30 24.50 24.32 0.09 23.54 23.43 23.49 0.06 23.81 23.91 23.56 23.74 23.76 0.11 % cyanuric acid 60.35 60.17 60.16 60.11 60.20 0.08 59.35 59-46 59.41 0.06 59.74 59.72 59.83 59.87 59.79 0.06

Sample HE 101, No. 1

Viton HNO3 extraction 14.98 15.06

Average Avg. Deviation HE 101, No. 2 Average Avg. D e v i a t i o n H E 115

15.02 0.06 17.20 17.18 17.19 0.01 16.53 16.48 16.54 16.49 16.51 0.03

Average Avg. D e v i a t i o n

-61-

9
Table X-6. extraction. mg taken
227.5 196.4

Recovery of Viton from known m i x t u r e s by n i t r i c acid mg r e c o v e r e d

226.4 195.4

% recovery
99-5 99.5

MELAMINE CYANURATE

I OS tSJ I

CYANURIC ACID

* 'a^iiiH^'Sid'

GLB-646-3108 IVLELAMINE F i g . X - 1 . X - r a y powder p a t t e r n s of m e l a m i n e , cyanuric acid, and melam.ine cyanurate.

5000 too

1500

1400

1300

= = = = = ^ = = = = = = = CYANURIC ACID CgOgNgHg = = = = = = = = = == = = S 90 = = = = = = = = - = = = = RECRYSTALLIZED FROM WATER . = = ; = _ = = = == = = J E- = - E - - - ^ = ; - ^ PHASE SOLID KBr ==^^-^ = - p ; .-.^^7^ SO S:=~-:^- = = = = :~= SOURCE CYANAMID
70 60 50 40 30 -.__ 20 10 0

[y[|[[l f[]|^^mmTOf|ro
._.,<| %i^

^W^^^p {
SmfSjIttf^^
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GLL-622-I59O6A

Fig. X - 2 . Infrared s p e c t r u m of cyanuric acid.

3000

2500

1500

1400

1300

1200

Gli-

-I59O5A Fig. X-3 I n f r a r e d s p e c t r u m of m e l a m i n e

3000 100 90 = di
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1400
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1300

1200
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1 =! = =

llil

10
r

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GLL-622-15904A Fig X-4.

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1=

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1
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1 11
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i

I n f r a r e d s p e c t r u m of m e l a m i n e c y a n u r a t e .