MASTER

P^V UCRL-7873

University of California

Ernest O. Lawrence Radiation Laboratory

SOME ANALYTICAL METHODS FOR EXPLOSIVES AND EXPLOSIVE SIMULANTS

Livermore, California

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' '• . or usefulness of any Information. nor any of their employees. 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. makes any warranty. or favoring by the United States Government or any agency thereof. or assumes any legal liability or responsibility for the accuracy. manufacturer. The views and opinions of authors expressed herein do not necessarily state or reflect those of the United States Government or any agency thereof. express or implied. Neither the United States Government nor any agency thereof. or otherwise does not necessarily constitute or imply its endorsement. or process disclosed. apparatus. process. completeness. product.' i i ' I UCRL—7873 DE88 004062 UNIVERSITY OF CALIFORNIA Lawrence Radiation L a b o r a t o r y Livernnore. or service by trade name. recommendation. Reference herein to any specific commercial product. or represents that its use would not infringe privately owned rights. I . trademark. California Contract No.

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and IV. IX. 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 . Sections V. solvent extraction methods have been used. some explosive simulants a r e covered in Sections VIII. and VII a r e concerned with p l a s t i c bonded explosives. Where p o s s i b l e . VI.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. III. and X. W. Selig May 1964 -iii- . Analytical methods for extrusible explosives a r e given in Sections II.

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The Determination of Cyanuric Acid. The Analysis of Tungsten and HMX in RX-12 VIII. . . Poly-Z. Silica.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 .0 2 . The Analysis of HMX. . .D i n i t r o p r o p y l a c r y l a t e .and Methyl-4.1 IV. 4-Dinitropentanoate in Explosives . Melamine. An Analytical P r o c e d u r e for RDX in RX-05 VII.1 X.0 4 . The Analysis of a Mock Material for L X . . LX-02-1 V. . II. . The Determination of PETN and Silica in L X .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 . The Spectrophotometric Determination of Acetyltributyl Citrate in an E x t r u s i b l e Explosive. . The Analysis of Mixtures of HMX. and Viton in Mixtures (LM-04-0) . Viton. 2 . . The Analysis of Mock Explosive 90010 IX. . III. . . . and Ethyl. The E s t i m a t i o n of S y m . -V- . . .CONTENTS I. and Oxamide VI.

.m e t h a n o l a s the t i t r a n t and azo violet as the indicator. although the l a t t e r two solvents a r e p r e f e r r e d . California May 1964 I. 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 . 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. RDX may be deternnined in either DMF. titrants. HMX 1 is d e t e r m i n e d in dimethylformamide (DMF). The method. methylisobutyl ketone (MIBK). minations. has a number of disadvantages. 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 . dated November 7. 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 . 65. any reducible i m p u r i t i e s cause high r e s u l t s . 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 . using sodium methoxide in b e n z e n e . 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. I96I. 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). however.-1_ SOME ANALYTICAL METHODS FOR EXPLOSIVES AND EXPLOSIVE SIMULANTS Walter Selig Lawrence Radiation L a b o r a t o r y . or cyclohexanone. University of California Livermore. 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.

Beckman sleeve-type calomel electrode No. When used as t i t r a n t s for acids in nonaqueous media. Buret. . Magnetic s t i r r e r . Also. No. Expe r i m e n t a l Apparatus Beckman g e n e r a l . 1190-80.p u r p o s e g l a s s e l e c t r o d e . 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 . 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. ' They a r e easily p r e p a r e d and quite stable. 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. Titration c e l l s : 200 ml t a l l . kept under nitrogen atmosphere.c a l o m e l electrode s y s t e m . 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.NOH). 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 . 1170-71. 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 . 10 ml Machlett. While satisfactory for RDX. a fairly l a r g e (300 mg) sample is r e q u i r e d for each titration. 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 .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. 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 .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. 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. 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. 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 . Consequently. 5 bases. 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. with 1000 ml r e s e r v o i r .

7 Purification of Cyclohexanone Convert 50 g r a m s of Dowex 1-XlO. If the t e s t is positive. 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 . Coleman and Bell). Add 20 g r a m s finely ground purified silver oxide. Dimethylformamide. 100-200 m e s h .g l a s s funnel. Standardize the t i t r a n t against benzoic acid. then with methanol.m a g n e s i u m perchlorate trap. purified. Cyclohexanone.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. 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 . 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 . and agitate for one hour. Dissolve 0.H e i m a n n Co. Prepurified by running through A s c a r i t e . Reagent grade (Matheson. and stir for s e v e r a l h o u r s . 100-ml isopropyl alcohol. If the t e s t for iodide is negative. Thyraol blue indicator solution. add 500 ml r e d i s t i l l e d cyclohexanone. 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. Nitrogen. stopper the flask. 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. A i r . Methylisobutyl ketone .(4-methyl-2-pentanone) ( B r a u n . P r i m a r y standard (Baker Analyzed Reagent).K n e c h t . 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. .). Decant the cyclohexanone and filter.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.-3- Re agents A 0. Reagent g r a d e . 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. 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. filter the m i x t u r e through a fine porosity s i n t e r e d . 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.d r y the r e s i n . Benzoic acid.

and equivalent weight of RDX and HMX. Add 20 ml of solvent and d i s s o l v e . Maintain the nitrogen a t m o s p h e r e throughout the titration.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 .1. volume of solvent blank. allow sufficient time to r e a c h a steady potential. 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. I. or by calculation (see appendix). 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. Calculations (V % RDX or HMX = where V. P e r f o r m a blank t i t r a t i o n for each batch of solvent. 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. Add the t i t r a n t slowly under rapid agitation. add the t i t r a n t in 0.V )(normality titrant)(100)(74. 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.10-ml i n c r e m e n t s n e a r the equivalence potential. The . 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 ..NOH.4- 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 . 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 . The t i t r a n t was Bu. In the d e t e r m i n a t i o n of RDX in MIBK or cyclohexanone.l ) . ^2 74.043 . 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. In the d e t e r m i n a t i o n of HMX and RDX in DMF. After each addition of t i t r a n t . — mg sample volume of t i t r a n t .043) . however. add the t i t r a n t in 0.

4898 0.1504 0.5578 0.-5- Table m e q RDX 0.5 100. H O L . meq taken 0. formula weight 74. 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 . CH.6201 0.5369 m e q found 0..5457 no. NO.C H N N O ^ .5304 m e q found 0.2851 0.4056 0.N-N' CH„ N-NO_ ' I «2^ O^N-N.4 99.3350 0. RDX -N-NO.3995 I-l. 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.4788 m e q found 0.8 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 .6 0 .6 Taken m e q HMX 0. meq taken 0. N ^^2 O^N-N^ CH. . 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 .8 T a b l e 1-3. . 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 . 0.5185 % recovery 97. O. A n a l y s i s of HMX* p u r i f i e d on J . A n a l y s i s of RDX p l u s HMX in D M F .2 0 4 .8 100. RDX c o n s i s t s of t h r e e .043. As shown a b o v e . and HMX of four s u c h u n i t s . HMX I ' CH^ I ' N-NO.6187 0. c l a s s A. t h e b a s i c u n i t of RDX and HMX i s .3 101.4922 0.4777 % recovery 100.4740 0. 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 ) .4760 0. meq total 0. 3 2 4 % recovery 99.5560 0.1374 T a b l e 1-2. detns.S R .

In this solvent.05-ml i n c r e m e n t s near 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. Titration. Redistillation plus ion exchange by the method of Mostalyk. 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 .03 T r e a t m e n t of solvent Reagent g r a d e .35 m l / 2 0 ml solvent) an attempt was made to purify this solvent. will gradually change back to yellow.35 0. 1-2). apparently being slowly saponified. The color change is from yellow through g r e e n to blue. a slow d e c r e a s e in emf is o b s e r v e d . t h e r e f o r e . and P e r n a r o w s k i reduced the blank to an acceptable level. Chatten. (Table 1-4.25 0. 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. 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. Since the solvent blank for cyclohexanone was fairly l a r g e (0. however. Simultaneously. 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. ml 0. RDX can be t i t r a t e d in cyclohexanone. Blank t i t r a t i o n of 20 ml cyclohexanone. The use of a well-ventilated hood is mandatory for this work. . RDX and HMX a r e fairly soluble in cyclohexanone and Y~butyrolactone.l . this color. with a potential b r e a k even g r e a t e r than in MIBK. Before the equivalence point. although soluble^ could not be d e t e r m i n e d in this solvent.-6- The neutralization reaction of RDX and HMX is quite slow. Addition of s e v e r a l d r o p s of thymol blue helps in anticipating the equivalence point. It is believed that the r e s u l t s r e p o r t e d in Tables I . The t i t r a n t should be added in 0. 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 .05-ml i n c r e m e n t s n e a r the equivalence point. HMX.) Table 1-4.15 0. hence sufficient time must be allowed for attainment of a steady potential after each addition of t i t r a n t . the t i t r a n t should be added in 0. 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 .

Chem. . 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. 7 J. R. 27. 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. and M.30 . Chem. 5_0.50 emf. P e r n a r o w s k i . 28.20 . 179 (1961). 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 .40 . 1958). Kaye. Chem. pp. Chem. 29. S. Anal. 292 (1955). M. 792 (1956). Chatten. 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. N. Anal. S. (E = emf. 23. L. . Y a m a m u r a .) 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.90 . Selig. J.10 . Markunas. R.00 . 932 (1958). 2nd ed. Cundiff and P. D. Sarson. G. Anal. J. Anal. F r i t z and S.3 . G. P h a r m . 30. Sci. V = volume of titrant. ^J. . Lingane. 1961). R. 1079 (1957).-7- 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 . 9 1 . Example: Volume 10 . 3 4 S. H. Moskalyk. C. Y .

• 500 -600 -700 > I • 800 ~ 00 •900 - 1000 2 4 6 ml TITRANT 8 10 12 GLL-646-1633 Fig. T i t r a t i o n of RDX and HMX in D M F .l . . I .

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 .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 . . 1-2.0 — -100 — -200 ~ -300 r r r ^ ^ MIBK -400 -500 > a -600 -700 W= & — — « _ _ -800 .

2 . 2 .d i m e t h y l f o r m a m i d e ( D M F ) . 2 of m e t h y l .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. 4 . 130. HMX. T H E ANALYSIS O F H M X .and e t h y l .4 . 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). P O L Y . 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. In t h e a b s e n c e of s i l i c a . This m e t h o d .d i n i t r o p e n t a n o a t e ( E M . and m i x t u r ) and p o l y . N . HMX and D^^ a r e e x t r a c t e d w i t h D M F . AND E T H Y L .and m e t h y l .2 . 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. 2 .2 . In the p r e s e n c e of s i l i c a . 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 . m i x t u r e s of e t h y l . 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 .AND M E T H Y L .d i n i t r o p r o p y l a c r y l a t e (D ). 2 . s i l i c a .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. o r ybutyr olactone. 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 Dg. p o l y .O . SILICA.D I N I T R O P R O P Y L A C R Y L A T E .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 . 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 . 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 ).4 .-lo- ll. d a t e d O c t o b e r 3 . 1963. and a m i x t u r e of e t h y l 1 and m e t h y l . The dinitropentanoates a r e extracted with carbon tetrachloride. 4 . 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 .4 .S i l ) . SiO^ ( C a b .2 . 4 . h o w e v e r .4 . 4 . and silica a r e p r e s e n t e d . p o l y .d i n i t r o p e n t a n o a t e (E^Mp).d i n i t r o p r o p y l a c r y l a t e (D^^).

p o r o s i t y 50 ml s i n t e r e d . 4-dinitropentanoate. Type S. 1. 4-dinitropentanoate and 15% m e t h y l .-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 .g l a s s c r u c i b l e s . and SiO. 1. consisting of 85% by weight e t h y l . Procedures Determination of HMX. Acetone.2 M aqueous.g l a s s c r u c i b l e . with 1 cm silica c e l l s .d i n i t r o p r o p y l a c r y l a t e (D ). N. Beckman Model DK-2 Spectrophotometer or equivalent i n s t r u m e n t . Cab-O-Sil. Weigh 1 to 1.2 . technical g r a d e . 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 . Silica. Add 20 ml carbon t e t r a c h l o r i d e . Suction filtration equipment ( F i s h e r F i l t r a t o r ) .4 . and bring cautiously (danger of bumping) to boil on a hot plate. HMX. Carbon t e t r a c h l o r i d e . 60-70°C. Wash b e a k e r and crucible with four 5 ml portions of CCL and filter. 50 ml capacity.2-dichloroethane. N-dimethylformamide (DMF). d p 2 grind it up by a r e m o t e . 2 . Cool to r o o m t e m p e r a t u r e and weigh. Vacuum oven. S i n t e r e d . y-butyrolactone. E .c o n t r o l m o r t a r and p e s t l e . P o l y . Volumetric g l a s s w a r e . Dry b e a k e r and crucible in a vacuum oven at 60-70°C for one hour. Dimethylsulfoxide (DMSO). Sodium hydroxide. 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 . a E M .. reagent g r a d e . Ainsworth.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 . . 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.4 .. cover with a watch g l a s s . M . If the m a t e r i a l is solid. 0. medium porosity.

cool to r o o m t e m p e r a t u r e . and D . . Wash b e a k e r and crucible with four 5 ml portions of ethylene dichloride and filter. 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 . E_M . M . Finally. F i l t e r by suction through the corresponding previously used c r u c i b l e . wash b e a k e r and crucible with s e v e r a l portions of acetone and filter. Add about 25 ml hot DMSO and w a r m on hot plate until m o s t of the precipitate is dissolved.g l a s s c r u c i b l e . Calculations: 1) Weight l o s s after C C l .. D i s c a r d the DMSO e x t r a c t in a waste explosives container. collecting the Wash b e a k e r and 2. 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 . and SiO_. add about 25 ml w a r m DMF. C a r r y out all e x t r a c t i o n s in a well-ventilated hood. E . D . 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 . 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. Cool to r o o m t e m p e r a t u r e and weigh. Dry b e a k e r and crucible in a vacuum oven at 60-70°C for one hour. M as ___^ d p a_ d p d e s c r i b e d above. D r y b e a k e r and crucible in a vacuum oven for one hour. and cautiously (danger of bumping) bring to boil on a hot plate. F i l t e r by suction through the corresponding previously used filter c r u c i b l e . Determination of HMX. 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. 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.-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 . filtrate quantitatively in a 100 ml v o l u m e t r i c flask. cover with a watch g l a s s . 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. and heat on a hot plate until m o s t of the precipitate is dissolved. If d e s i r e d . D e t e r m i n e the E . and weigh. 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 20 ml ethylene d i c h l o r i d e .

Pipet an aliquot not to exceed 0. and weigh. extraction of D is l e s s .0 ml 0. At this wavelength the molar absorbance of D is 18. cooled to r o o m t e m p e r a t u r e .600. 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 . This p r o c e d u r e is m o r e time consuming because of However. add 1.2 M aqueous sodium hydroxide. The second method investigated is that outlined in p r o c e d u r e 2. a ° Two methods w e r e investigated in this work.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%. In the f i r s t . 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 . and wash b e a k e r and crucible with s e v e r a l portions of acetone. 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 . Dilute the v o l u m e t r i c flask to volume with DMF and mix. 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 . 98. Remove the v o l u m e t r i c Dry flask. 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 . 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).6% of the polymer is e x t r a c t e d on the a v e r a g e . and i l l u s t r a t e d in Fig. 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 . and the p r o c e d u r e is valid over a wide range of D concentrations. b e a k e r and crucible in a vacuum oven at 60-70° C for one hour. filtered. 11-1.-13- crucible with s e v e r a l portions of w a r m DMF. and washed. cool to r o o m t e m p e r a t u r e . extraction = amount of E .1 . The solution is stable for at l e a s t 3 h o u r s . be r e d e t e r m i n e d . cedure is limited to a polymer content of 5-8%. Rather than extracting the D with s e v e r a l portions of cold solvent. for the a n a l y s i s of an extrusible was completely e x t r a c t e d . the explosive m i x t u r e is brought to boiling with the solvent. a Calculations: 1) Weight l o s s after CCl.4 mg D into a 50 ml v o l u m e t r i c flask. 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. With 60 ml of ethylene dichloride. and dilute to volume with DMF.

for the l a t t e r . D . and " d p 2 d p a SiO-. d An attempt was made to apply the hot extraction method also to m i x t u r e s containing HMX. M . II-4. and II-6. E M . 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 . however. 3 ^ t h e r e f o r e . This succeeded for the f o r m e r . I I .5 . Where available.7 . 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 .3 . be d e t e r m i n e d photometrically in DMF. In the p r e s e n c e of Cab-O-Sil D m u s t . 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 . and HMX. r e s u l t s using the cold extraction technique previously used a r e shown.1 . and SiO-.-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.. 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 . E . . Analyses of some explosives a r e given in Table I I . the extraction of D by dichloroethane was not quantitative.

0 110.7 109.5 88.9 96.5 88.5 93.7 93.8 105.8 44. mg taken 139.4 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 98.0 92.6 21.4 91.7 201.2 98.4 103.l .0 90.7 94.3 62.5 63.2 96.0 178.7 11.6 7.2 98.2 66.9 97.4 41.9 102.9 .6 98.2 95.5 191. mg taken 12.1 96.8 99.9 204.1 100.2 98.1 93.0 97.-15- Table I I .2 11.5 195.4 22.5 103.2 79.0 90.7 90.8 174.9 190.8 71.6% 0.2 23.3 98.9 23.5 117.5 94.0 98.2 104.56 Table II-2. mg r e c o v e r e d % recovery ml dichlor 20 11 II 130.0 Recovery of D by cold extraction with 1.0 11.8 116.1 120.1 91.2 95.0 97.5 11.4 21.3 95.0 168.3 21.1 Recovery of D in p r e s e n c e of SiO^ by p r o c e d u r e 2.4 86.4 93.6 42. 2-dichloroethane.1 67. a ^ mg r e c o v e r e d mi-g SiO p r e s e n t % recovery 12.8 128.

2 129.9 731.5 .4 100.09 Average r e c o v e r y Standard deviation Table II-4.2 R e c o v e r y of HMX by p r o c e d u r e s 1 and 2.0 100.0 840. and 3.0 731.0 99.9 894.1 100.6 140.8 755.0 111.50 . m g taken 85.9 407. 2.2 835. mg r e c o v e r e d 839.9 247.1 176.1 800.0 100.7 727. mg taken 839. recovered 86.7 152.0 99.8 220.6 % recovery 99.6 110.7 100.3 99.2 893.5 R e c o v e r y of E^Mp by p r o c e d u r e s 1.4 78.3 101.3% 1._16- Table I I .0 100.1 100.9 100.0 201.3 176.9 100.8 201.8 832.3 100.8 248.8 Average r e c o v e r y Standard deviation 100.96% 0.4 229.4 132.3 .5 140.8 728.7 99. mg taken 127.5 Recovery of Dg^ by p r o c e d u r e 2.1 99.9 % recovery 101. mg r e c o v e r e d 126.2 840.6 755.1 100.0 100.14 Table I I .5 Average r e c o v e r y Standard deviation % recovery 100.2 229.3 800.0 100.5 118.14% 0.2 77.7 153.1 99.5 100.7 220.2 408.4 119.

79 69.6 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. Sample RX-06-AC ( J .95 74.11 1.69 % Dj -__ __ % Si02 2.42 1.2 mg r e c o v e r e d Procedure 2.9 39.84 30.55 2. O .8 89.64 24.66 0.36 24.14 29.3 67.68 3. RX-06-AF ( J .61 1.3.48 1.14 24.87 73.39 1.1 100.7 103. 4. 2. RX~06-AA (Sn 1065-2) Average Average Average RX-09-AA (5K110) 2.5 104. % HMX 68. 4.74 0..79 27.56 2.22 74. 103.00 74.1.69 29.61 1.82 24. RX-06-AF (43612B) Average Average __ __ __ By Ref.43 1.4 85.0.3.64 27.1.45 1.71 73.1.3.99 100.62 1..7 86.6 77.1 38.44 24.-17- Table II-6.42 24. 2.19 24.. 2.5 81.49 24.8 R e c o v e r y of silica. 4.51 __ __ __ _„ By Ref .17 24.47 74. mg taken 65.7 101.83 76.3.7 103. 2.9 25.63 1.7 82.02 73.13 2. 2.8 82.8 99.4 73.90 73..76 93.5 78.5 76.86 69..52 % EdMp 29.63 27.57 6.4 3 1 Table II-7. % recovery 102. 1115) — __ By Ref.84 69.55 27.7 24. O .05 67.75 68.23 67. 2.1 82.23 93.18 68.61 2.93 74. 2.11 2.03 5.3.2% 0.55 24.13% 0.94 1.13 73..08 2. 1095-1) Average Average Analysis of explosive compositions.79 __ . 2.66 69.3.4 103.

.and Methyl-4. 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. Selig. II. 1962). 1962). G r o s s m a n . L. 4 .D i n i t r o Compounds in N. " 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 .d i n i t r o p r o p y l a c r y l a t e . Selig and G. 1962). " UCRL-7116 (October 23. L.2 .D i m e t h y l f o r m a m i d e . The D e t e r m i n a t i o n of Ethyl. 2 ." 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.d i n i t r o p e n t a n o a t e . " T h e Spectrophotometric Determination of Ethyl.and Methyl4. Selig. and HMX. 1962).-18- References G. Silica. " 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. " The Spectrophotometric D e t e r m i n a t i o n of Some g e m . 4 W. P o l y . Selig. " 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 . 3 W. G r o s s m a n and W. N . 2 W.

.2-DICHLOROETHANE 60 GLL-646-1635 (ml) Fig. 2 .19- 100 20 30 40 50 VOLUME OF 1. 2-dichloroethane. I I . Recovery of poly-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 1.1 .

Vacuum oven. saturated with P E T N . 88. reagent g r a d e . dated September 20. Lot 12-61. P E T N is extracted with acetone. leaving a residue of silica. Suction filtration equipment ( F i s h e r F i l t r a t o r ) . Cab-O-Sil (Si02). Pfizer & Company (acetyltributyl c i t r a t e ) . silica. Citroflex A-4.5% in hexane. maintained at r o o m t e m p e r a t u r e . Ainsworth. butyl r u b b e r . 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. medium p o r o s i t y . Type S. 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 . 1962.0 2 . 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 .-20- III. 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. . 50 ml capacity. 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. 48. Steam bath. du Pont 4600-D Adhesive. Carbon t e t r a c h l o r i d e .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 . THE DETERMINATION OF P E T N AND SILICA IN L X . PETN. Sintered g l a s s c r u c i b l e s . reagent g r a d e . with watch g l a s s . and acetyltributyl c i t r a t e . Acetone.

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. 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. Wash b e a k e r . extracted with acetone. 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 . is used. 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 . 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 . 50 m l . vacuum drying at r o o m t e m p e r a t u r e . 2. in carbon t e t r a chloride which does not dissolve the PETN and silica. s i n t e r e d g l a s s c r u c i b l e . Calculations 1.64%. 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. 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 . as outlined in the p r o c e d u r e given h e r e . Discard the filtrate in the explosives waste container. 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 . 3. The data w e r e obtained If by the p r o c e d u r e suggested by du Pont. 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. Wash with s e v e r a l 5 ml portions of acetone. 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%. r u b b e r . leaving a residue of silica.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 . s t i r r i n g rod.-21- lumps with the s t i r r i n g rod.p o r o s i t y . using vacuum drying at 60°C. 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 ) .

6 1496.26 Table III-3.10 99.67 99.75 73.68 72.84 1.07 73.15% 0. Sample No.05 .89 72. HE 107.07 Table III-2. A5 HE 107.6 95.8 94. mg taken 1506.92 72.7 1268. 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 .05 2.-22- Table III-l.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 .53 100.84 1.10 % Si02 1.60 2.4 Average recovery Average deviation % recovery 100.5 1500. mg recovered 99.7 Average recovery Average deviation % recovery 99.8 103.3 1262.9 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 .71 99.64% 0. 0 H E 107.81 100. mg taken 99.54 99. mg recovered 1501.86 72.81 1.9 103. % PETN 72.82 1.51 1.96 72.

0 2 . of t h e s e . 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. 127. T h e r e f o r e . dated Septerhber 5. by saponification or by the f e r r i c hydroxamate method. (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 . 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. and Gutnikov and Schenk. (1). ) Introduction The a n a l y s i s of an extrusible explosive. ATBC i s e x t r a c t e d with anhydrous ethanol. 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. LeBlanc. L X . 1963. (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 . carbon t e t r a c h l o r i d e .1 . 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 . s i l i c a . THE SPECTROPHOTOMETRIC DETERMINATION OF ACETYLTRIBUTYL CITRATE IN AN EXTRUSIBLE EXPLOSIVE. . butyl r u b b e r . General C h e m i s t r y Technical Note No. of ATBC is available. 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. leaving a r e s i d u e of silica. 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.-23- IV. the most p r o m i s i n g a r e by 1 2 3 Goddu. which is attacked by c a u s t i c . r e q u i r e s the p r e s e n c e of sodium hydroxide.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). P i l z . and ATBC is p r e s e n t e d . is u n s a t i s factory a s an e x t r a c t a n t . Organic e s t e r s form hydroxamic acids by the r u c t i o n shown in Eq.0 2 . L X . and Wright.

Expe r imental Reagents and Equipment 1. Dilute to volume with absolute ethanol. Dissolve 105 g r e a g e n t grade hydroxylamine hydrochloride in 550 ml absolute methanol with heating. . Stock f e r r i c p e r c h l o r a t e solution. 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. • •—'—• • —^ 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. Pfizer Citroflex A-4. 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 .-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. room temperature. cooling under a tap a s the alcohol is added. Store the hydroxylammonium p e r c h l o r a t e solution in a polyethylene bottle.4 M Hydroxylammonium p e r c h l o r a t e .) 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. absolute methanol. 2. Reflux 100 g sodium hydroxide with 1000 ml Store the solution in a polyethylene bottle. Weigh 3. (Caution: The i r o n d i s s o l v e s quite rapidly when the acid is hot. F e r r i c p e r c h l o r a t e r e a g e n t . Slowly add 130 ml 70% p e r c h l o r i c acid while cooling under a t a p . 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. Acetyltributyl c i t r a t e . 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.1534 g iron w i r e into a 150 ml b e a k e r . Dissolve 195 g sodium p e r c h l o r a t e monohydrate in 450 ml absolute methanol with heating. 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 . Allow to cool and dilute to 2 l i t e r s with absolute ethanol.5 M Sodium hydroxide. Rossville Gold Shield. anhydrous. Ethanol.

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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

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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

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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 25°C 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).

51 0 .2 0 .:11. 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 .5 Gutnikov and Schenk" 0. Goddu et al.1 2. 0 7 .550 0 to " s e v e r a l " Acetone Ethanol 524 l/?-4 0.7 4.2 25 6.04 2..25 KNO3 Water 490 Removal of e x c e s s hydroxylannine None Solution Ethanol ^max (-f^) Color stability (hours) 520 .08 4.27 0.-28- Table IV-4.7 1 Pilz 5 . mg F e / m l Acidity (molar) NH2OH (mmol) NaOH (mmol) 0.. 0 5 . 0 0 4 .0.3 .0.

29- o < o CO Pi cq < 450 475 500 550 600 GLL-6^+6-1636 WAVELENGTH (millimicrons) F i g . . I V .97 m g A T B C / 5 0 m l ) .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.

IV-2.-30- 1.4 6 mg A T B C / 5 0 m l Fig. . 7 GLL-646-1637 Calibration curve for acetyltributyl c i t r a t e at 520 m^.

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 . 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 . 108. T H E ANALYSIS O F M I X T U R E S O F HMX. 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 . 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 . V I T O N . . 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 . HMX and o x a m i d e .0 4 .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 . 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 . d i d not s u c c e e d . t h e r e f o r e . 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 . V i t o n . a c o r r e c t i o n m u s t be applied. 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 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 .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 .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 . "^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 . 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 .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 . and o x a m i d e is p r e s e n t e d .b o n d e d e x p l o s i v e c o n t a i n ing HMX.-31- V. 1 9 6 3 . In t h e h o t . 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 . d a t e d M a r c h 2 0 . 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 . 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 . 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 .

B u t y r o l a c t o n e .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 . Coleman. Vacuum oven. Round-bottom flask. Nitric acid. Ainsworth. the a p p a r a t u s cool and r e m o v e thimble from extraction tube. 70 ml capacity. Viton A. Sintered g l a s s c r u c i b l e s . thimble into a Soxhlet tube. at 60-70°C.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 . Oxamide. reagent g r a d e . of HMX a n d / o r oxamide a r e found. Carbon t e t r a c h l o r i d e . and Bell. Explosive s a m p l e . Matheson. Suction filtration equipment ( F i s h e r F i l t r a t o r ) . Soxhlet extraction for d e t e r m i n a t i o n of Viton. Connect the extraction tube to a w a t e r . 85 m m high. Matheson. 50 ml capacity. 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 with distilled water and filter by suction ( F i s h e r F i l t r a t o r ) . ^ . and Bell. 25 m m d i a m e t e r . c o a r s e porosity. condenser and a round-bottom 250 m l flask.t h i r d s filled with concentrated n i t r i c acid. b r e a k up the film with a procelain spatula . 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. 250 ml capacity.antle under the flask and heat to refluxing (Variac Allow to reflux for about 4 h o u r s . acid. T a l l . Wash the Inspect If inclusions Let setting of approximately 110 volts). Soxhlet extraction a p p a r a t u s consisting of: Soxhlet tube. Type S. thimble containing the sample about one-half full with concentrated n i t r i c Place a heating m. Coleman. HMX. Anti-bump rod. Procedures 1.-32- Exper imental M a t e r i a l s and Equipraent Analytical b a l a n c e . medium p o r o s i t y . reagent g r a d e . Lot A134. Heating inantle with V a r i a c . Condenser.

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 . 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. 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 . butyrolactone. 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 .7 0 ° C for at l e a s t one h o u r . „„ = •^—° — -^ 100 mg sample = b y d i f f e r e n c e (100 . 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 .% o x a m i d e ) . 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 . to p r e v e n t s p a t t e r i n g .% Viton . 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 . 6 0 . . P r o c e d u r e 2: m g HMX. 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 . s t i r r i n g r o d . 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.7 0 ° C for one h o u r .% Viton . 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 .7 0 ° C for at l e a s t one h o u r . 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 . u n c o r r e c t e d = (mg r e s i d u e ) gf TTTi^rY% oxamide T-. 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 .% 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 ) . 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 . Cool t o r o o m t e m p e r a t u r e and w e i g h . Cool to r o o m t e m p e r a t u r e and w e i g h .— 100 mg sample if>^ ° ^ (ro^g s a m p l e ) .e x t r a c t for s e v e r a l h o u r s .-33- and r e . J o 0/ -J P r o c e d u r e 3: % oxamide % HMX (mg HMX.__ =—^ :. 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. 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 . 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 . 2. 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 . .

but d i s s o l v e s r e a d i l y in hot w a t e r . R e s u l t s for known m i x t u r e s . 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. Table V .3 150. mg Viton taken 103. is not e n t i r e l y satisfactory. t h e r e f o r e .6 99.3 160.-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 .7 99.w a t e r and butyrolactone extraction a r e c o m p a r e d . The most suitable solvent found was "Y-butyrolactone.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.7 160. R e s u l t s for HMX and oxamide obtained by h o t . HMX usually contains some RDX which is appreciably soluble in hot w a t e r . F r o m Lot A134. 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 . however. using s a m p l e s of approximately 700 mg. be established for the batch of HMX used before the analytical p r o c e d u r e can be applied. 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). 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 .9 0.1 . 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.1 . . Recovery of Viton by n i t r i c acid Soxhlet extraction. however. Results for the analysis of a sample explosive a r e shown in Table V-4. A c o r r e c t i o n factor m u s t .7 Average Standard deviation % recovery 100.3%. s m a l l amounts of oxamide w e r e lost.8 mg Viton r e c o v e r e d 104. requiring a solvent for HMX and Viton.w a t e r extraction method. The h o t . The method is based on the oxidation and solution of HMX and oxamide by hot concentrated nitric acid which does not attack Viton.3 99.8% HMX was lost (see Table V-2). 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 .8 151. an a v e r a g e of 2.

0 95.1 95.28 Table V .9 Hot-water extraction % HMX* % oxamide 81.-35- Table V . mg oxamide r e c o v e r e d 08.7 96.3 .5 96. mg oxamide taken 113.7 97.6 86.5 80.1 80. Analysis of an explosive sample.63 • 90. mg HMX taken 711.9 714.5 696.8 0.2 93.5 712.39 15.7 80. % Viton 15.4 723.3 97.9 773.6 Table V .7 3.8 80.1 751.8 Avera •ge St and a r d deviati on % recovery 97.7 3.5 693.1 3.3 Recovery of HMX from HMX-oxamide m i x t u r e s by h o t .2 Average Standard deviation % recovery 95.7 3.0 96. Butyrolactone extraction % HMX % oxamide* 80.8 18.6 .4 .5 Recovery of oxamide by "y-butyrolactone extraction.9 80.7 3.w a t e r mg IX r e c o v e r e d 691.7 122.9 4.5 3.1 81.5 97.1 701.9 80.5 3.37 15.9 81.2 .0 3.2 717.38 Average 15.3 97.2 0.38 Corrected.8 3. extraction.9 695.5 97.1 97.

. 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 . 1961).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. 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. Reference Lee Monteith et a l . 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 .-36- On a routine b a s i s the h o t . .

97. 1962. maintained at r o o m t e m p e r a t u r e . Lot A033. P o l y s t y r e n e . dated D e c e m b e r 28. Carbon t e t r a c h l o r i d e . medium p o r o s i t y . 100 ml b e a k e r s . General C h e m i s t r y Technical Note. 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 . Vacuum oven. No. Ultrasonic g e n e r a t o r . Suction filtration equipment ( F i s h e r F i l t r a t o r ) . Sintered g l a s s c r u c i b l e s . 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. reagent g r a d e . Dow Chemical. RDX. 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.90% Polystyrene 8 .-37- VI.12% Dioctylphthalate (DOP) 2 . 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 . PBX s a m p l e s .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^. 50 ml capacity. . followed by shaking with a w r i s t action shaker for 30 m i n u t e s . Dioctylphthalate.

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 .-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 . 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. in Table V I . Calculations 1. 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. which constitutes a health h a z a r d . 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 . 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 . extraction of p o l y s t y r e n e . 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 . with added known amounts of RDX. 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. 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 . 2. This modification. R e s u l t s obtained by this method a r e . still r e q u i r e d the use of hot C C l . however. p e r c e n t RDX r e c o v e r e d .3 . 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^.1 . and speeds up the a n a l y s i s . . thus eliminating the use of a shaker. 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. 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. shown in Table V I .

6 48. b a t c h 1.5 1817.5 223.2 198.4 2037.0 1784. 8 8 5 % RDX i n u n k n o w n .0 Ground sample RDX r e c o v e r e d mg recovered m g calcd.7 1736.94)Avg."'' 1737.8 Amount taken m g s a m p l e + mg RDX mg total 1956.69 100.1 1804. mg total 212.8 1963. RDX.97 Calculation b a s e d on 88.5 167.2 1648. A.1 1999.2 368.2 1668.5 44.7 211.60 100.8 1956.1 99.0 Percent 88. RDX i n s a m p l e Sn 4 0 7 3 .70 100.62 94.''' 1746.7 190.8 1976.96% RDX found in unknown.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 .8 194.90 93. 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 .3 1806.3 1803.885 1782.96 99.5 211.52 100. i n s a m p l e Sn 4 0 7 3 .7 161.2 Big-RDX r e c o v e r e d 1793.85 94.cd.2 1852.98)88. b a t c h 1.2 .1 1803.8 1792.2 mg RDX taken 1784.45 Amount taken img DOP m g polystyrene 164.0 43. Amount taken mg sample + m g RDX m g t o t a l 1963.2 206.6 1819.2 1853. Pellets Percent 88.04 93.6 1832.9 1821.1 Average % recovery 100.2 1959.91 RD5^.5 158.9 1762.78)Avg. 88. r e c o v e r e d m g r e c o v e r e d m g cal.8 229.0 200.64 Table V I .6 1544.86 94.7 1736. 89.8 mg recovered 203.6 1775.1 .8 45.9 166.5 1777.2 310.8 44. .8 1777.0 1569.9 Average % recovery 95.8 1747.70 100. B.01)88.89 99.99 99.9 1762.4 1804.-39- Table V I .3 203.

4080.38 90. O . batch 1. Ground-up sample hot CCI4 90. Ultrasonic g e n e r a t o r p e l l e t s .29 90.28 .27 % RDX in sample J . cold CCI4 90.3 .-40- Table V I .

Centrifuge. 1964.1 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 . 1 cm cells. 1 4 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 . 70°C. 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 .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 . 40 m l c a p a c i t y . with 95. S t i r r e r and Teflon-coated s t i r r i n g b a r s . Beckman DK-2. Experimental R e a g e n t s and E q u i p m e n t Analytical balance. Vacuum oven. Hirsch type. d a t e d J a n u a r y 2 3 . and Viton i s p r e s e n t e d . 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 . H M X . 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 . Condenser. . Volumetric glassware. S i n t e r e d . inner 19/38 joints. C e n t r i f u g e c o n e s .8% 1. Spectrophotometer. s i z e of t u n g s t e n u s e d . w i t h o u t e r 1 9 / 3 8 j o i n t s .4% 2. Water bath. T H E ANALYSIS O F T U N G S T E N AND HMX IN R X . Funnel._41- Vn. or equivalent instrument.g l a s s c r u c i b l e s . with c o a r s e porosity fritted disc. 60-70°C. Vacuum filtration equipment (Fisher Filtrator). m e d i u m p o r o s i t y . Viton i s d e t e r m i n e d by difference. 50 m l c a p a c i t y .

s i n t e r e d . 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 . 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 . cover with a watch g l a s s . Bring the volume to 1 liter with distilled w a t e r . F e r r o u s a m m o n i u m sulfate. E x t r e m e caution is called for in filling the c u v e t t e s . washings in the 250 ml E r l e n m e y e r . 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. and s t i r until the HMX Add 10. ml acetone. stopper.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 . Add with caution 50 m l concentrated sulfuric acid. 5 0 . Acetone. 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 . E r l e n m e y e r flask. 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 90 ml concentrated sulfuric acid. and place it in a water bath at 25 ± 5°C for 45 m i n u t e s . Procedure 1.m l . b e a k e r and crucible with s e v e r a l portions of acetone. collecting the filtrate in a 250 m l of w a r m acetone. 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. crucible in a vacuum oven at 60-70°C for one h o u r .g l a s s c r u c i b l e . t u r e and weigh. but do not place on hot plate (danger of bumping). plate at low heat. I n s e r t a Teflon-covered s t i r r i n g b a r . the flask. F o r tungsten of p a r t i c l e size > 15 irticrons. p r e p a r e d according to Semel. occasionally. against a Plot a b s o r b a n c e v e r s u s concentration of HMX. automatic pipette fillers are recommended. r e a g e n t blank. add 1 g iron filings and allow the evolved hydrogen to e s c a p e . 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 . ACS specifications.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 . i s in solution. ACS specifications. concentrated.-42- Sulfuric acid. . swirl Measure the absorbance of the solutions at 520 mfj.

add 20 ml of acetone. r i n s e down condenser with s e v e r a l ml of acetone. D r y the centrifuge cone in a vacuum oven at 6 0 . 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. and centrifuge for 5 m i n u t e s at high speed. Let reflux for s e v e r a l 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 . As in p r o c e d u r e 1. F o r tungsten of p a r t i c l e size < 15 m i c r o n s .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 no visible white r e s i d u e is obtained. 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. connect with a w a t e r . 2. r e . 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 . If after evaporation of the acetone solution no white r e s i d u e r e m a i n s . 2. Calculations 1. and decantation with four additional 10 m l portions of a c e t o n e . 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. the extraction was c o m p l e t e . 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 . the extraction i s complete. with the following change: After 30 minutes in the water bath. Repeat reflux.7 0 ° C . 3. 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. centrifugation. r e m o v e from w a t e r bath.-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 .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 . r e weigh the tungsten r e s i d u e . To check on the complete r e m o v a l of HMX and Viton from the tungsten. Cool to r o o m t e m p e r a t u r e and weigh.c o o l e d condenser and i m m e r s e in a water bath at about 70°C. 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 . r e . If a white residue r e m a i n s . 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.

80 ± 0. 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 . 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. V n . e. i n d i c a t e s .2 .2 2 2 . 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 .2 g/lOO m l . 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. Lot A .29^ 3. Compound RDX HMX HMX.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 .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 . 2.1 . b y s u c t i o n t h r o u g h a c o a r s e .1 . In t h i s w o r k .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 . T a b l e V I I . 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 . 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 .65^ 3.1 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 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 . for t h i s b a t c h i s s h o w n in F i g . 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 . 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 . V I I . 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 . 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 . 1 3 L a c c e t t i . 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 . M o l a r a b s o r b a n c e s . 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 . photometric determination.. 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 . t h e d e s i r e d d a t a i s Therefore. h o w e v e r . 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.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 . S e m e l . Lot A . 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 . £ X 10-2 5.

34 2.49 2. 18.46 95. 2606 w e r e available.85 1. 3 1 . L a c c e t t i .69 2. Table VII-2. M.01 2. Anal. Roth.06 2. O .00 2. 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 . Roth. Semel. T.07 Average 94.83 2.69 2.15 Filtration n filtration b e c o m e s too slow (usually after two u s e s ) .37 95. O .50 95. Control No.87 3.55 95. A. discarded. Semel. Chem. . 3 1 . 1050 (1959). materials p r o c e d u r e 2 m u s t be used.65 1. " P h y s i c a l and Chemical P r o p e r t i e s of RDX and HMX. 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 .19 2. of J . J. R o g e r s . 20-P~26.74 1. A. and M.48 95. 1962." M.. 1049 (1959). and M. The p a r t i c l e size of the tungsten in RX-12(6K-42-2) is 18.78 2.74 2.58 95.79 94. 2606) % tungsten 95.85 1.65 2.86 References 2 S.72 1.48 94. Sample RX-12-AA ( J .99 95.70 2.98 2.5 m i c r o n s .5 m i c r o n 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. S e r i e s B. Anal.96 1. % Viton 1. Ch6m. Holston Defense Corp.-45- Some typical r e s u l t s a r e shown in Table VII-2.11 95.84 2. Laccetti.99 Analysis of RX-12 m a t e r i a l s . % HMX 2.

.7 — 0. VII-l.4 < 0. .-46- 0. 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. Lot A-222.6 — \ o O CO 0.3 0. \ 0.1 1 400 425 1 450 ! . J 475 500 1 550 1 600 700 GLL-646-1638 WAVELENGTH (millimicrons) Fig.2 ™.5 — \ 0.

V I I .1 1 10 20 30 1 40 1 50 1 60 GLL-646-1639 mg HMX/lOOml F i g .2 2 2 a t 520 m[i.5 / / 0.2 .7 ® / 0.3 < / 0. L o t A . 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 .2 y / / 0.-47- 0.6 / . J/ 0. .4 — u < o CO Pi 0.

Experimental Reagents and Equipment Analytical b a l a n c e . 60-70''C. Magnetic s t i r r e r and s t i r r i n g b a r s .0 . 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. 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 .c h l o r o ethylphosphate (CEF) is p r e s e n t e d . 133.0% * 1. The C E F is e x t r a c t e d with methylene chloride or ethyl e t h e r .-48- VTII. THE ANALYSIS OF MOCK EXPLOSIVE 90010'" Abstract An analysis of mock explosive 90010.3% 0. The r e s i d u e . 3. p e n t a e r y t h r i t o l . and the b a r i u n .p . pH m e t e r . 1963. 50 ml capacity. . Machlett b u r e t . Vacuum filtration eqiiipment ( F i s h e r F i l t r a t o r ) . Barium.0% Barium nitrate Pentaerythritol T r i s .3% 2. medimca porosity.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 qualitatively identified. Glycerol or miineral oil . is c h a r a c t e r i z e d by a spot t e s t .8 ± 0. n i t r o c e l l u l o s e . dated October 29. 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.2 ± 0.g l a s s c r u c i b l e s .bath. 25 m l . n i t r o cellulose. and t V i s . Its nominal composition i s : 46 48 ± 1. consisting of b a r i u m n i t r a t e . S i n t e r e d . 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 . Vacuum oven. Ethyl e t h e r .05% This note p r e s e n t s a method for the analysis of 90010 by a comibination In addition.

6 M sodium hydroxide. performed without artificial light. Benzoin. METAB Indicator Tablets. 6 M. add 25 ml distilled water. of hot water and collect the washings. Transfer most of the residue quantitatively into the previously used beaker. glass Wash beaker and crucible with four 5 ml portions of solvent. 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. 1-naphthylamine reagent: 0. and bring to boil on a hot plate. 0. and bring to boil on a hot plate at low Remove from heat. in a vacuum oven at 60-70°C for one hour. Add 20 ml methylene chloride or ethyl ether. Sodium hydroxide. oven at 60-70° C for one hour. macerate any lumps. cover with a watch glass. Dry Cool to room temperature and crucible.3 g per 70 ml water and 30 ml glacial acetic acid.61 g disodium ethylenediaminetetraacetate dihydrate in water and dilute to 1 liter in a volumetric flask. Fisher Scientific Co. medium-porosity.^ ^r A ^ g bariuiH nitrate c T ri Normality of EDTA = |3|i. freshly prepared. and let cool to room temperaFilter by suction through a tared 50 ml.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. EDTA until the color changes from blue to colorless. Dissolve and dilute Titrate with Adjust to pH 12 (using pH meter) with The titration is best Add one METAB tablet and dissolve. •NT Ti x . ture. Ethylenediaminetetraacetic acid (EDTA).05 M: Dissolve 18. Sulfanilic acid reagent: 1 g per 75 ml water and 25 ml glacial acetic acid. 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. weigh.„49- Methylene chloride. a 100 ml volumetric flask. .

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 . 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 .u s e with hot Since only approximately 0.52 = (26l. 3 Ci . Calculations 1. with w a t e r . 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 . e r y t h r i t o l which is d e t e r m i n e d by difference.-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 . 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 . no c o r r e c t i o n is n e c e s s a r y . A red color in an acetic acid solution of sulfanilic acid and 1-naphthylamine constitutes a positive t e s t . amount of r e d dye.5 mg of n i t r i c acid which d e s t r o y s the red dye. 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. 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 . 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. and mix. (ml EDTA)(normality EDTA)( 1045.52)''* = amount of b a r i u r a n i t r a t e . Weight l o s s after ether (or methylene chloride) extraction = amount of C E F . 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 . Residue after w a t e r extraction = amount of nitrocellulose -f red dye. 2. By difference = amount of p e n t a e r y t h r i t o l . a pH of 12. 3. dilute to 100 ml with w a t e r . w h e r e 261. 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 . 4.38)(4). 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 ) . "1045.38 is the m o l e c u l a r weight of Ba(NO ) . The c r u c i b l e s a r e cleaned for r e . I m m e r s e the t e s t tube in an oil bath preheated to 140 °C.

44 46. J.57 Average 3.A n a l y s t 52.26 % pentaerythritol (by differs 47.58 47.68 2.-51- Some typical r e s u l t s a r e shown in the following table. Otto and F r e d e r i c k B.29 3. Van Nostrand Co. pp.30 3. References F . The Analytical Uses of Ethylenediamine T e t r a a c e t i c Acid (D.28 47. N.25 3. 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 . ^ F . 47 (1963).23 46.30 2. 143-4.30 3. Che m i s t . Welcher.71 46.73 % Ba(N03)2 46.34 % nitrocellulose 2.75 47.22 46. 1 . P r i n c e t o n .72 2.10 46.34 46. Analysis of mock explosive 90010. % CEF 3. 1961). F e i g l .37 46.63 Acknowledgment I a m indebted to C h a r l e s H.33 3. . sample A-192. J.

Add 50 mil hot distilled w a t e r . 1963. Sulfuric acid. dated D e c e m b e r 2. Vacuum filtration equipment ( F i s h e r F i l t r a t o r ) . 50 ml capacity. the volume at about 50 m l . 1:10. leaving a r e s i d u e of Viton. 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 . 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 . and bring to gentle boiling on a hot plate. Vacuum oven. b a r i u m n i t r a t e . cover with a watch g l a s s . THE ANALYSIS OF A MOCK MATERIAL FOR LX-04. 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 .g l a s s c r u c i b l e s . cyanuric acid is d e t e r m i n e d by difference. and Viton i s p r e s e n t e d . 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 . 137.-52- IX. p a r t i c l e s a r e imbedded in the Viton. . S i n t e r e d . 60-70°C. 110°C.V"' Abstract An analysis of a mock m a t e r i a l for LX-04-1 consisting of cyanuric acid. 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 . Drying oven. m e d i u m p o r o s i t y . 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. ' G e n e r a l C h e m i s t r y Technical Note No.

Heat the filtrate to n e a r boiling on a hot plate. collecting the filtrate quantitatively in a 250 ml b e a k e r . Residue after water extraction ( B a r i u m sulfate)( 1. 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 . 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 . r e d .-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 . (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. and weigh. and weigh. cool to r o o m t e m p e r a t u r e . 2. Dry the crucible in an oven at 1 10''C for one hour.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 . appeared at a pH of about 7 . titration. 3. and keep n e a r boiling for at l e a s t 15 m i n u t e s . in cold w a t e r (0-25 g per 100 ml water at 17°C).d y e d Viton.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. Calculations 1.8 .g l a s s c r u c i b l e .) After filtration r i n s e the bottom of the crucible and the funnel with hot w a t e r . add 10 ml 1:10 sulfuric acid. Dry the crucible in a vacuum oven at 60-70°C for one hour. collecting all the washings in the 250 ml b e a k e r . F i l t e r through a t a r e d m e d i u m . 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 . cool to r o o m t e m p e r a t u r e . 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 . 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).

27 13.53 13.02 13.53 15.60 71.22 15.73 72.58 70.13 15.89 13.66 15.06 % cyanuric acid 71.02 12. This p r o c e d u r e w a s adopted.44 71.23 71.-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 .14 15.18 15.87 15.46 71.46 % Ba(N03)2 Ba(N03)2 13.1.78 12.73 12.66 15.21 15. Some typical r e s u l t s a r e shown in Table IX. Table I X .92 13.26 12.64 15.27 15.10 12.07 12.1 .14 15.62 15.27 15.41 12.16 15. Cyanuric acid is d e t e r m i n e d by difference.64 12.09 15.02 72.75 71.87 71.27 Average .27 13.24 Average RM-04-BC 15.16 15.1 .53 12. Results of a n a l y s e s of mock m a t e r i a l s for L X .46 15.38 72.26 15.00 15.84 13.30 15.12 15.31 15.77 Average RM-04-BB 13.46 71.70 15.0 4 . Sample RM-04-BA % Viton 15.07 71.68 71.03 72.

r a y powder p a t t e r n s . gr. ''"General C h e m i s t r y Technical Note No.42.0 : cyanuric acid. nitric acid extraction. maintained at 60-70°C. 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 . 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. THE DETERMINATION OF CYANURIC ACID. Analytical b a l a n c e .0 4 . Vacuum oven. 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 . 67. m e l a m i n e . Viton is then d e t e r m i n e d by n i t r i c acid extraction. MELAMINE. 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 . 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 . by using a l a r g e r s a m p l e . . Steam bath or hot plate. with s t i r r i n g r o d s . S i n t e r e d . 1.g l a s s c r u c i b l e s . 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. dated March 6. 150 m l .-55- X. mediumi porosity. sp. reagent g r a d e .0 .0 4 . 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 . Experimental M a t e r i a l s and Equipment Nitric acid. 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 . 1962. and Viton. 35 ml capacity. 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 . 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 .

Cool to r o o m t e m p e r a t u r e and weigh. pouring the contents of the b e a k e r into the c r u c i b l e . 3. and filter crucible with s e v e r a l portions of distilled w a t e r . Calculations 1. Procedure Weigh 0.49422) Sample . Cool to r o o m t e m p e r a t u r e and weigh. Dry b e a k e r . then thoroughly with distilled w a t e r to r e m o v e all the acid. with p r o p e r p r e c a u t i o n s . and place in the suction a p p a r a t u s . s i n t e r e d g l a s s c r u c i b l e . taking c a r e not to lose any m a t e r i a l .p o r o s i t y . . F i l t e r . and the filter crucible in a vacuum oven at 60-70° C for at l e a s t one hour. Place the crucible inside the b e a k e r . B r e a k up any lumps with the s t i r r i n g rod. Introduce about 15 ml concentrated n i t r i c acid into the b e a k e r . 5. Remove the crucible from the b e a k e r by m e a n s of platinum-tipped tongs. maintained at r o o m t e m p e r a t u r e .''^ Dry the b e a k e r plus s t i r r i n g rod. Wash b e a k e r . 4. s t i r r i n g rod. Add 50 inl distilled w a t e r . D i s c a r d the filtrate. Residue after water extraction By difference (Melamine cyanurate)(0. and filter crucible in a vacuum oven at 60-70°C for at l e a s t one hour.(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 . Stir the contents of the crucible occasionally to facilitate solution. Digest for about 15 m i n u t e s .-56- Vacuum oven. and wash the sides of the b e a k e r down occasionally with w a t e r . s t i r r i n g rod.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. 2. and a like amount into the c r u c i b l e . 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. Rinse b e a k e r and crucible with s e v e r a l portions of concentrated nitric acid. 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. and bring to boiling on a hot plate. Platinum-tipped t o n g s . 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 . cover with a watch g l a s s . F i l t e r by suction through a t a r e d 35 ml m e d i u m . stir occasionally. Suction filtration equipment.

24 49-40 3.49422 is derived as follows: cyanuric acid _ 129. In melamine cyanurate the ratio i mQ-aon . excess cyanuric acid is removed by filtration. X-2.023389x f and .n Ar^A-yyx mg melamme = — = ? n?338q ~ ' " ^ ^ melamme cyanurate)(0. The factor 0.1. mg melainine cyanurate . This compound precipitates as a very fine powder when aqueous solutions of the components are mixed. the amount of free cyanuric acid is mg cyanuric acid = (normality base) (ml titration) (129. .0_H N . Table X.-57- If a titration is carried out on the water extract.55 Found 27. ^ . C.1. X-3.32 3. in which 3 the components are present in a 1:1 ratio. X-1.49422). X-ray diffraction patterns and infrared spectra of the complex and its components are shown in Figs. The From the weights of the dry salt the amount of melamine in the original mixture is mg melamine = (mg melamine cyanurate) (0. Its melting point is near 390°C. and X-4.08). Results and Discussion Melamine and cyanuric acid are moderately soluble in hot water. then mg rcielamine cyanurate = x . Theoretical 28. is given in Table X-1.023389x = 2. An elemental analysis of melamine cyanurate. a very insoluble salt. Element % carbon % nitrogen % hydrogen Elemental analysis of melamine cyanurate.69 49. melamine cyanurate.45 The materials investigated have a large excess of cyanuric acid hence all the melamine is converted to the cyanurate by digestion in water. \ \.08 melamme 126. however.13 Let X = mg melamine. They form.49422).

1961). M. 3. N. Smolin and L. p. the m a t e r i a l is not of uniform p a r t i c l e size. 3 E. but not in m e l a m i n e or cyanuric acid. 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. Monteith.r a y powder p a t t e r n s . 1959). some m e l a m i n e a n d / o r cyanuric acid miay be encapsulated by the Viton.0 4 . and may t h e r e f o r e show segregation. melamine and cyanuric acid a r e blended with a solution of Viton in methylethyl ketone methylisobutyl ketone. . and X-4 show r e s u l t s obtained with known s a m p l e s . 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 . p.5 . Y. Absorption peaks found in the c y a n u r a t e . or from the infrared s p e c t r u m of the solid in K B r . As Table X-6 shows. 29. 1961). The solvent is then r e m o v e d by application of heat and vacuum. 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 . UCRL-6639 (April 30.03 m i c r o n s .95.4 .2 .3 . . In s a m p l e s of L M . 326.85.74. satisfactory r e s u l t s a r e obtained when determining the cyanuric acid by difference. Rapoport. Colman. this step is not n e c e s s a r y . occur at the following wavelengths: 3. G. Lopez. s . ^W. the n i t r i c acid extraction method is p r e f e r a b l e . Selig and D. As seen from Table X . X . Also. 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 . References L. G r o s s m a n . 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 . and 13. however. n-butyl a c e t a t e . G. 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. 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 . Tables X . when the a n a l y s i s of Viton only is r e q u i r e d .0 . 10. If. 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 . or a s i m i l a r solvent. M.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 . Alternatively.-58- If d e s i r e d . 9-23. 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 .

B 100.0 208.0 .2 196.8 98.7 127.0 93.7 99.1 Average % r e c o v e r y 95% confidence l i m i t s ± 99.2 100.4 100.3 A v e ] rage % r e c o v e r y 95% confidence l i m i t s ± 100.3 109.8 mg taken 91.8 107. 14 % recovery mg taken 86.1 Table X .2 .1 127.9 100.91 0.1 96.2 100.5 97.6 88.3 125.6 196.5 99.0 259.7 92.4 106.8 99.4 100.6 99.1 198. mg r e c o v e r e d 91.2 163. 1 2 3 4 5 6 7 8 9 10 Recovery of m e l a m i n e from L M .0 100.0 100.5 101.8 96.7 163.6 92-2 93. Sample No. mg r e c o v e r e d 86.5 245.8 87.3 101.0 4 .3 100.0 209-9 100.-59- Table X .9 109.5 99.5 125.3 125.1 100. 1 2 3 4 5 6 7 8 9 10 Recovery of Viton from L M .3 102.0 .5 100.2 199.2 99.0 4 .2 259.5 245. 24 0. Sample No.4 .7 124.5 102.3 .9 100.21 % recovery 99.

46 0.32 0. New method 15.19 0.43 23.1 460.72 59.48 0.9 215.56 15.0 4 .49 16.56 23. D e v i a t i o n H E 115 15.4 609-1 99-94 0-10 % recovery 100.06 59.11 0 16. No.0 199.98 15. A n a l y s i s of s o r a e L M .49 0.87 59.0 4 .6 255.81 23.06 23.6 219. Deviation HE 101.8 215.08 % melamine 24.7 215.9 100.03 Average Avg.74 59.7 99. mg taken 207.16 60.35 60.11 60.3 199.35 59-46 59.8 99.6 208.0 .48 16.4 255.17 60.06 Average Avg.0 s a m p l e s .8 220.51 0.1 100.54 16.36 16.20 17. b y d i f f e r e n c e .11 % cyanuric acid 60.4 208.6 215.4 610. aple N o . No.06 Sample HE 101.08 59.4 313.2 459.42 15.1 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 207.01 16. 1 Viton HNO3 extraction 14. D e v i a t i o n .09 23.07 17.40 16.27 24.1 100.76 0.3 313.54 15. 2 Average Avg.74 23.50 24.41 0.20 0.-60- Table X-4.0 99.39 15.83 59.45 16.11 17. 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 .54 23.0 100.61 16.53 16.91 23.1 99-9 99.79 0.11 17.30 24.02 0.22 24.18 17.06 17.8 Table X-5.

4 % recovery 99-5 99.5 .4 195.-61- 9 Table X-6.4 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 226.5 196. mg taken 227. extraction.

X .1 .MELAMINE CYANURATE I OS tSJ I CYANURIC ACID ^ * 'a^iiiH^'Sid' GLB-646-3108 IVLELAMINE F i g . and melam. X . cyanuric acid.ine cyanurate.r a y powder p a t t e r n s of m e l a m i n e . .

-^.:. ^ j PBffl^fflffl^ 4^----.g =:-- \ 1 C-OH T T l 1 4=t -fTTtE 4. X .tl .4%t:-.. .? ..4 ...: "1 t m i r .-^. .__.p .--^•-V_ff_. f j .' i _ " 1---L '-^ lijt.= = E t - Mi^ffBi^M^ 3 : ^—1^ ..I 4 "4E_EECir' flfflMfflPiiWiBM™ =P=iE=iiyii Ift frffl#HfflmffimW^ q f f l S a ^ ^ WWmj^ml^^^m WnW\' H ' 4 ] ^ 4p f ^STOft^^^WfMniit^^l ht rtt444 = E E S _ 4 4 f t 4 i i i M^ -^CK-:^'r --Z iiliipElilillM.__ 20 10 0 [y[|[[l f[]|^^mmTOf|ro .=-r....==--""-ITE:---^!!: '^"t .-.¥ _ E .-- )H mm¥ H N NH ._ i GLL-622-I59O6A Fig.E .E=ll!:iiii=ili.' T = =: = 4^ _.^^7^ SO S:=~-:^.X 4^:E?p t i 4 4 .= = = = :~= SOURCE CYANAMID 70 60 50 40 30 -. ^ j ..= ¥ = .{ ' • •' -" ^ -.= . r . 4 t. t — _ — .. j ._=.. ^ 1 ^...4._-.= = = = RECRYSTALLIZED FROM WATER .= E..^-"-i. _ .^ | : r = -=-p^=^-r:^=Err..tf^- o=c 7 c=o. .._-..-. 1 "=E:"4p}.. RffitimlTulTl^^I |J^-EEEE|E=-:--= == ^= |-E= . ^ ^ ± ._. = = . — .J.^ PHASE SOLID KBr ==^^-^ = . ^—.E r ..=p|iliilll|ll^ ^K4 '4. _..-- 1= : = -.^---:..~ J .:=___.|:^___.^ = ..^ \ ^ .J -3E ^ - .M -^ ..—Et=-E 41 f-b ^..3-=_J r""^"^^ —i—IT J^_ . = _ = = = == = = J E. ___jj£_„. c — i _ — _ | _ :^^—^+4= sH----••••\ -:j^--^. • . 4 _.r z:_ iii#iwW8^^#MM | P i ^ p i t f f ^ i | i i | ^ t|"^3 ^--.j _ . _i r ------- -H^ -• .«<| %i^ ^W^^^p { SmfSjIttf^^ r _ip.T E # .. 47-.I-J .ili^ EL. .-._^ j .^ • .-..5000 too 1500 1400 1300 = = = = = ^ = = = = = = = CYANURIC ACID CgOgNgHg = = = = = = = = = == = = S 90 = = = = = = = = ._.. „ . 1.= "^Jl-•*t-""jlLr ._. Infrared s p e c t r u m of cyanuric acid.-:-• • ^ -^ -r^-j_-:-t ... H M-^itM ----1 OS UO I * 3 E .2 .-_.r 1 2 ^ * ?>itt::::-|i|#| M' ^ W I ^ B fiiiiii^iiiii=i^^:iiiEijiMi^=iii^iPaj -"".—-. .

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 2500 1500 1400 1300 1200 I 3 4 Gli- -I59O5A Fig.

.&=T TE ^*i.:-^-TE-q ll i 1 E j| 1 12 i ^ i .b' tt 4 4 :t ce 0 3 H9 H9 i\DDITrON COMPOUND '-^ i i il EE ^ S EE E ^1 1 1 E 1 ? i \z i EE EE El 1: 1 =E E= PJ ^ .E i == = _t 1 r _ iE .S --/ 4 " ^ .n 1 1 i 4- tB m 1 E =J =E OS . ' .ss [ ^^ -M -^ -= ^ ^ .^^ 1^ 1E .r r =r= ii : "? ^= : .' • | ! l i ~. E . X . E ^^ -E 4^ E^ E =4 ^= ^ 4 4 ~ = f E~ 41 =E — E: -l-t-^T i | 1 i E =-== = -t* T. .| - 1 -t '^f ii • — : • 1 ^ P 45 _ • „ j _ f 1 = 74 J.~. 4 .=--==-= 1 ^i '_ 5 1 1 = 1 + -= = ==-^- 1 -.z: s i fE -^ _tE .=1+ =E E EE^ E ^ = 1' E4=EJE]E^ rt 1 1 1= l[ ± P i L-- 1 ^ . 1 =! = =-= E 1 ~ .. 1= u i5 1 1 11 J 1 E td 11 E= = = E E 3 = •^ = E=r.E ^ = = 3 11 E : .___-1 \> ^ t e» O __ P f t :^ H H=:a „ 1 |-J-. 4fr -! . J = EZ_±_ ! E5 ~ 1 30 20 E 11E | = =P 11 El = = ' =i =f «- i — i —1 ' ~ : . i ' ^ IttP H .. ^-i h -E : E E ^ .^ .•fs E F4k = ^ .f 4^ :zz 4 _ E E 4 t s E4~ "E =h r ^ 4f E .=M: 4*1 -E T-t t 1 14E^ ._ . ..r P E E = ii 4 l}^- H GLL-622-15904A Fig X-4.-^ r :z -_ ' r > . i P ll i 'J 4:^ 1 =^ TT" ~ tt.=f .E E z = \ E 1 4 -t « # 1 .3000 100 90 = di j j b=h fe i E 2500 = 1500 1400 i 1300 1200 'E* it ^ .i: .:=-=Ej ..^ i E 41 E=1E.d E3 E = E = F 1 =! = = llil 10 r 0 II il il J E 1EE p m ^ .EEE= --.= = 1 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 .. --.

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