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Addition compounds of trimethylamine with boron fluoride and its methyl derivatives.
(USC Thesis Other) 

Addition compounds of trimethylamine with boron fluoride and its methyl derivatives.

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Content ADDITION COMPOUNDS OF TRIMETHYL AMINS WITH BORON FLUORIDE AND ITS METHYL DERIVATIVES A T h e s is P r e s e n te d to t h e F a c u lty o f th e D ep artm en t o f C h e m istry The U n i v e r s i t y o f S o u th e rn C a l i f o r n i a I n P a r t i a l F u l f i l l m e n t o f t h e R e q u ire m e n ts f o r t h e D egree M a s te r o f s c i e n c e by S i s t e r Agnes Ann G re en S ep tem b er 1942 UMI Number: EP41543 All rights reserved INFORMATION TO ALL USERS The quality of this reproduction is dependent upon the quality of the copy submitted. In the unlikely event that the author did not send a complete manuscript and there are missing pages, these will be noted. Also, if material had to be removed, a note will indicate the deletion. GttvcrMtOfs Pjfati H ng UMI EP41543 Published by ProQuest LLC (2014). Copyright in the Dissertation held by the Author. Microform Edition © ProQuest LLC. All rights reserved. This work is protected against unauthorized copying under Title 17, United States Code ProQuest LLC. 789 East Eisenhower Parkway P.O. Box 1346 Ann Arbor, Ml 48106- 1346 This thesis, written by s i s t e r a G - k e s ait:: g r een under the direction of hSJCt. Faculty Committee, and approved by all its members, has been presented to and accepted by the Council on Graduate Study and Research in partial fulfill­ ment of the requirements for the degree of SCIENCE RASTER Secretary Date 1942 ., Faculty C om m ittee ^ . Gfhair airman TABLE O F CONTENTS CHAPTER PAGrE I . INTRODUCTION 1 P r e v io u s i n v e s t i g a t i o n s on r e l a t e d s u b j e c t s . . . . ± S ta te m e n t o f th e p ro b lem . • 3 O r g a n iz a tio n o f th e t h e s i s . 4 I I . THE TECHNIQUE USED AND THE MATERIALS PREPARED . . . 5 H igh vacuum a p p a r a tu s 5 The U -tu b e s 6 The h ig h te m p e r a tu re r e a c t i o n b u lb . 9 P r e p a r a t i o n o f m a t e r i a l s 11 Boron f l u o r i d e . . 12 M eth y lb o ro n f l u o r i d e s 14 M e th y lc h lo ro am ines . . . 15 I I I . THE EXPERIMENTS AND THEIR RESULTS . . . . 18 The a d d i t i o n compound o f b o ro n f l u o r i d e and t r i m e t h y l am ine 18 P r e p a r a t i o n - . . 19 V apor t e n s i o n c u rv e 20 M o le c u la r w e ig h t 23 The a d d i t i o n compound o f m eth y lb o ro n d i f l u o r i d e and tr im e th y la m in e 24 i i i CHAPTER PAGE P r e p a r a t i o n . . • 24 V apor t e n s i o n c u rv e ................. 26 The a d d i t i o n compound o f d im e th y lh o ro n f l u o r i d e and t r i m e t h y l amine < . . . - 30 P r e p a r a t i o n - - - 33 C o m p o sitio n . . 34 V apor t e n s i o n cu rv e _ . 37 IV . DISCUSSION AND CONCLUSIONS 45 S u m m a r y ......................... 48 BIBLIOGRAPHY , - 50 LIST or TABLES TABLE PAGE I . P r e s s u r e o f Boron F l u o r i d e T rim e th y la m in e 21 I I * A s s o c ia tio n i n t h e Gas P h a se o f Boron F lu o r id e T rim e th y l am ine 25 I I I . Vapor T e n s io n C urve f o r M eth y lb o ro n D i f l u o r id e T rim e th y l amine ..................... 28 IV . Vapor P h ase D i s s o c i a t i o n o f M eth y lb o ro n D i f l u o r id e T rim e th y la m in e . . . 31 V. V apor P r e s s u r e s o f D im eth y lh o ro n F lu o r i d e T rim e th y l am ine . * . 38 V I. D i s s o c i a t i o n o f D im eth y lh o ro n F l u o r i d e T rim e th y l am ine 43 LIST OF FIGURES FIGURE PAGE 1 . A U n it o f th e High Vacuum A p p a ra tu s 7 2 . High T em p eratu re R e a c tio n B u l h ............................... 10 3 . A p p a ra tu s f o r P r e p a r a t i o n o f Boron F lu o r id e 13 4 . V apor P r e s s u r e Curve f o r Boron F l u o r id e T r i m e t h y l a m i n e .................... 22 5 . V apor P r e s s u r e Curve f o r M e th y lb o ro n D i f l u o r i d e T rim e th y la m in e . . . . 29 6 . V apor P h a se D i s s o c i a t i o n o f M eth y lb o ro n D i f l u o r i d e T rim e th y l sm ine 32 \ V apor T e n s io n C urve f o r D im eth y lh o ro n F l u o r i d e T rim e th y la m in e 39 8 . D i s s o c i a t i o n C o n s ta n ts o f D im eth y lh o ro n F lu o r i d e T rim eth y lam in e . . . 44 LIST O F PICTURES PICTURE PACE The High Vacuum A p p a ra tu s 17 CHAPTER I INTRODUCTION The e x te r n a l b o n d in g pow er o f compounds o f b o ro n i s o f p a r t i c u l a r i n t e r e s t b e ca u se o f th e e l e c t r o n i c s t r u c t u r e o f th e e le m e n t i t s e l f * C o n ta in in g o n ly t h r e e v a le n c e e l e c t r o n s i n i t s o u t e r e n e rg y l e v e l , t h i s atom i s y e t c a p a b le o f e x e r t in g an a p p a re n t v a le n c e , o r a t t r a c t i v e f o r c e , o f f o u r i n many o f i t s compounds* T h is m ig h t be e x p la in e d a s an e f f o r t to make up f o r a d e f i c i t i n i t s in c o m p le te o c t e t o f o u t e r s h e l l e l e c t r o n s . In i l l u s t r a t i n g th e a b i l i t y o f b o ro n to form compounds i n which i t shows a c o o r d i n a ti o n number o f f o u r , th e f l u o b o r a t e s and th e b o ro n h y d r id e s can be r e a d i l y c i t e d . I n a d d i t i o n to t h e s e , t h e i n t e r e s t i n g complex compounds, such a s p h o sp h in e b o ro n f l u o r i d e , PHg • BFjj1 , and b o r in e tr im e th y la m in e , BH3 • N(CH3 ) 32 a ls o d e m o n s tra te t h i s te n d e n c y . I . PREVIOUS INVESTIGATIONS ON RELATED SUBJECTS Many s t u d i e s have b e e n made o f t h e a d d i t i o n compounds w hich th e b o ro n h a l i d e s form w ith ammonia and a m in es. The f i r s t o f th e s e com plexes was BFg* ^ 3 * a co m b in atio n o f two 1 V. E. W iberg and U. Henbaum, A. a n o r g . a lle g e m . Chem ., 2 2 5 :2 7 0 -7 2 , 1935. 2 A. B. Burg and H. S . S c h l e s i n g e r , J . Am. Chem. S o c . , 5 9 :7 8 0 -8 7 , 19 37. 2 g a s e s , d e s c r ib e d by Davy i n 1812 a s a TAhite s o l i d w hich sublim ed unchanged i n a c lo s e d v e s s e l . 3 More r e c e n t l y th e b o ro n f l u o r i d e e th y la m in e compounds, (C gH g^N • BF^, (CgHg) g NH • BFg, and (CgHgjNHg* BF^, have been p re p a re d and c h a r a c t e r i z e d a s d e f i n i t e a d d i t i o n c o m p lex e s. 4 The r e a c t i o n s o f bo ro n f l u o r i d e i n fo rm in g a d d i t i o n compounds w ith more complex o r g a n ic b a s e s such a s t h e p y r i d i n e s , a m id e s, 5 and c y c l i c a m in e s, 6 have b e en i n v e s t i g a t e d and p o s i t i v e r e s u l t s r e p o r t e d . T hat b o ron f l u o r i d e form ed d e f i n i t e s t a b l e compounds w ith ammonia and w ith t h e e th y la m in e s and h i g h e r o rg a n ic b a s e s seemed a v e ry s tr o n g i n d i c a t i o n t h a t i t w ould a c t i n a s i m i l a r m anner w ith th e m e th y la m in e s. Y et a s e a r c h o f c h em ic al l i t e r a t u r e showed t h a t no work had b e e n done to e s t a b l i s h t h e e x i s t e n c e o f a d d i t i o n compounds o f bo ro n f l u o r i d e w ith t h e s e s im p le s t o f th e alley 1 am in es. No g e n e r a l ­ i z a t i o n s on such a s e r i e s o f complex fo rm a tio n s could be 3 J . W. M e llo r , C om prehensive T r e a t i s e on I n o r g a n ic and T h e o r e ti c a l C h e m is try , V o l. V, p. 1 2 3 , c itX n g J . D avy, P h i l . T r a n s . , 1 0 2 :3 6 5 , 1»12• 4 C. A. K ra u s and 1 . H. Brown, J . Am. Chem. S o c ., 5 1 :2 6 9 0 -9 6 , 1929. ~ 5 H. Bowlus and J . A. N ieuw land, J . Am. Chem. S o c ., 5 3 :3 8 3 5 -4 0 , 1 931. ~ 6 L . L . M a r tin , "The B e h a v io r o f H e x a m e th y le n e te tra - m ine to w a rd Boron F l u o r i d e , " ( u n p u b lis h e d M a s te r ’ s t h e s i s , U n i v e r s i t y o f S o u th e rn C a l i f o r n i a , L os A n g e le s , 1 9 4 0 ). 3 made w ith o u t some know ledge o f t h e s e r e a c t i o n s , s i n c e th e f i n d i n g s i n s im p le r c a s e s a r e a p t to be more e a s i l y u n d e r­ sto o d and i n t e r p r e t e d , I I . STATEMENT OF THE PROBLEM The g e n e r a l p u rp o se o f t h i s work was (1) to i n v e s t i ­ g a te th e r e a c t i o n s o f b o ro n f l u o r i d e and t h e m eth y b o ro n f l u o r i d e s w ith a s e r i e s o f m eth y lam in e compounds, and ( 2 ) t o make v a p o r p r e s s u r e m easurem ents on any a d d i t i o n com­ pounds w hich m ig h t be form ed . I n th e p r e s e n t stu d y an a tte m p t was made t o f i l l a gap i n t h e know ledge o f th e r e a c t i o n s o f th e b o ro n f l u o r i d e s w ith th e a m in es, by an i n v e s t i g a t i o n o f th e p o s s i b i l i t i e s o f fo rm in g a d d i t i o n compounds o f BF3 , CH3 BFg and (CH3 ) g BF w ith ( C H ^ N , <CH3) 2N Cl and (CH3) N C lg . W hile p a r t o f t h i s g o a l was s u c c e s s f u l l y r e a l i z e d i n th e work w ith t r i m e t h y l a ­ m in e, p a r t o f i t was abandoned when tim e-co n su m in g d i f f i ­ c u l t i e s w ere e n c o u n te re d due to t h e d e c o m p o sitio n o f th e m e th y lc h io ro a m in e s . I n d i c a t i o n s o f a complex compound w ere o b s e rv e d i n th e r e a c t i o n o f b o ro n f l u o r i d e w ith d im e th y lc h lo ro a m in e , b u t w h e th e r t h i s was a t r u e m o le c u la r a d d i t i o n p ro d u c t o f d im e th y lc h lo ro a m in e , o r o f one o f i t s d e c o m p o sitio n p r o d u c ts , was l e f t f o r l a t e r i n v e s t i g a t i o n . I t was found more p r o f i t a b l e to c o n f in e th e stu d y to th e 4 r e a c t i o n s o f tr im e th y la m in e ((CHgJgN) w ith b o ro n f l u o r i d e (BF3 ) and i t s m eth y l d e r i v a t i e s , m e th y lb o ro n d i f l u o r i d e (CHgBFg) and d im e th y lh o ro n f l u o r i d e ((CH3 ) gBF). I I I . ORGANIZATION OF THE THESIS The o r g a n i z a t i o n o f t h e re m a in d e r o f t h e t h e s i s i s h e re b r i e f l y o u t l i n e d . C h a p te r I I c o n ta in s a d i s c u s s i o n o f t h e l a b o r a t o r y te c h n iq u e , a s w e ll a s a d e s c r i p t i o n o f th e p r e lim in a r y p r e p a r a t i o n o f th e compounds n e c e s s a r y f o r th e e x p e rim e n ts . C h a p te r I I I i s concerned w ith th e e x p e rim e n ta l i n v e s t i g a t i o n s and r e s u l t s . T h a t i s , i t . w i l l c o n ta in d e t a i l s o f th e e x p e rim e n ts i n p r e p a r i n g and i n v e s t i g a t i n g th e new com plex com pounds, t o g e t h e r w ith t h e o b se rv e d d a ta , w hich w i l l be i n t e r p r e t e d b r i e f l y . The l a s t c h a p te r i s a summary o f f i n d i n g s and a s ta te m e n t o f th e c o n c lu s io n s draw n. CHAPTER I I THE TECHNIQUE USED AND THE MATERIALS PREPARED Q u a n t i t a t i v e work w ith g a s e s was made p o s s i b l e by th e u s e o f th e h ig h vacuum te c h n iq u e in tr o d u c e d by S t o c k , 7 and d e v e lo p e d by s c h l e s i n g e r and Burg8 i n t h e i r work w ith th e v o l a t i l e h y d r id e s o f b o ro n . I n g l a s s a p p a r a tu s u n d e r g r e a t l y re d u c e d p r e s s u r e , g a s e s c o u ld be t r a n s f e r r e d , f r a c t i o n a l l y d i s t i l l e d , o r b ro u g h t i n to r e a c t i o n w ith o u t l o s s o f r e a c t a n t s o r p r o d u c t s . A s p e c i a l a d v an tag e was th e f a c i l i t y w ith w hich a h y d r o ly z a b le g a s such a s boro n f l u o r i d e c o u ld be h a n d le d w ith o u t d e c o m p o s itio n . I . THE HIGH VACUUM APPARATUS The a p p a r a tu s c o n s i s t e d o f s e v e r a l u n i t s , e n t i r e l y o f g l a s s , a tta c h e d to a c e n t r a l tu b e th ro u g h s to p c o c k s . The system was e v a c u a te d by two pumps i n s e r i e s , a m e c h a n ic a l (Hyvae) pump w hich was c a p a b le o f p ro d u c in g a vacuum o f a h u n d re d th o f a m i l l i m e t e r , and a m erc u ry d i f f u s i o n pump w hich when a id e d by th e m ec h an ica l pump re d u c e d t h e p r e s s u r e 7 A. S to c k , H y d rid e s o f Boron and S i l i c o n ( I t h a c a , New Y ork: C o r n e ll U n i v e r s i t y P r e s s , 19337^ 8 H. I . S c h l e s in g e r and A. B. B urg, J . Am. Chem. S o c ., 5 3 :4 3 2 1 , 1931; 5 9 :7 8 0 , 1937. « • Q to a p p ro x im a te ly 2 x 10 m i l l i m e t e r s . T hese low p r e s s u r e s were m easured by a McLeod g a g e ^ in w hich th e m ercu ry was r a i s e d by a tm o sp h e ric p r e s s u r e and lo w e re d by a w a te r a s p i r a t o r * I n such a vacuum, c o n d e n s a tio n o f g a s e s t a k e s p la c e q u a n t i t a t i v e l y w h e rev e r th e te m p e ra tu re i s s u f f i c i e n t l y lo w e re d . The r a t e o f c o n d e n s a tio n i s p r a c ­ t i c a l l y th e sp eed o f th e m o le c u le s th e m s e lv e s , s in c e th e i n t e r f e r e n c e o f a i r m o le c u le s i s n e g l i g i b l e . The U -T u b es. A s e r i e s o f U - tu b e s , shown i n F ig u r e 1 , s e p a r a te d from each o t h e r by s to p c o c k s , made up th e w orking u n i t o f th e h ig h vacuum a p p a r a t u s . I n i t s e p a r a t i o n s by means o f f r a c t i o n a l d i s t i l l a t i o n s and c o n d e n s a tio n s w ere e a s i l y c a r r i e d o u t i n th e p r o c e s s o f p u r i f y i n g v o l a t i l e s u b s ta n c e s . Yapor t e n s i o n s o f compounds a t lo w te m p e ra ­ t u r e s w ere m easured e i t h e r i n U -tu b e D o r i n t h e sm a ll b u lb E, b o th o f w hich w ere a tt a c h e d t o th e m anom eter C. B a th s a t d i f f e r e n t low te m p e r a tu re s c o u ld e a s i l y be a p p lie d and m a in ta in e d , s in c e th e U -tu b e s were o f a s i z e to f i t i n to Dewar (th erm o s) v e s s e l s c o n v e n ie n tly . 9 J . S t r o n g , P ro c e d u r e s i n E x p e rim e n ta l P h y s ic s (New Y ork: F r e n t i c e - H a i i , i 9 3 8 f 7 PpV 1 1 1 -2 2 . 10 I b i d . , p p . 1 5 8 -4 3 . r FIGURE 1 A UNIT O F THE HIGH VACUUM APPARATUS 8 The U -tu b e D a tt a c h e d to th e m anom eter was c a l i b r a t e d f o r e x a c t volum e i n o r d e r to have a p la c e f o r m e a su rin g g a s e s by m eans o f t h e i r p r e s s u r e s * T h is was done by u s in g an e a s i l y condensed gas o f known q u a n t i t y i n th e fo llo w in g m anner. A sam ple o f s u lp h u r d i o x id e , w hich m easured 40 c c . i n a g a so m e te r u n d e r a p r e s s u r e o f 403 mm. a t room te m p e r a tu r e , a t 23° C, was c o m p le te ly con­ den sed i n t o th e p r e v i o u s ly e v a c u a te d U -tu b e D by m eans o f a l i q u i d a i r b a th . S to p c o c k s 5 and 7 w ere c lo s e d , and th e te m p e r a tu re o f th e s u lp h u r d io x id e a llo w e d to r i s e t o 23°C. From t h e p r e s s u r e r e g i s t e r e d on th e m anom eter C (201mm.) t h e volume o f U -tu b e D, i n c lu d in g th e b u lb E, was c a l c u l a t e d a c c o rd in g to th e r e l a t i o n s h i p P]_ 7^ * Pg Vg * T h is volum e, a f t e r b e in g c o r r e c t e d t o a r e f e r e n c e l e v e l f o r t h e v a r i a ­ t i o n o f th e m ercu ry i n th e m anom eter, was foun d to be 7&*6 c c . A ll re c o rd e d volum es i n t h e f o llo w in g e x p e rim e n ts w ere c o r r e c t e d f o r th e p o s i t i o n o f t h e m ercury l e v e l . T h is c o r r e c t i o n was e a s i l y made b e c a u se o f t h e u n ifo rm d ia m e te r o f th e m anom eter t u b in g . The volum e o f th e sm a ll b u lb E a lo n e , w ith sto p c o c k 6 / c lo s e d , was d e te rm in e d i n a l i k e m anner and fo u n d t o be 2 6 .8 c c . T h is s m a lle r c a l i b r a t e d b u lb was found v e ry c o n v e n ie n t i n m e a su rin g volume and v a p o r t e n s i o n s o f v e r y sm a ll q u a n t i t i e s o f g a s e s . y G ases u se d i n l a r g e q u a n t i t i e s w ere s t o r e d i n l a r g e b u lb s eq uipp ed w ith s to p c o c k s which were e i t h e r p e rm a n e n tly a tt a c h e d to th e vacuum a p p a r a tu s o r t e m p o r a r i l y s e a le d i n to a n o p e n in g (S to p c o ck 1 i n F ig u r e 1) w ith vacuum cem ent. S m all q u a n t i t i e s o f v o l a t i l e m a t e r i a l w ere s t o r e d i n t u b e s , such a s A i n F ig u r e 1 . The c o n te n ts o f t h e s e tu b e s w ere e a s i l y in tr o d u c e d i n t o th e vacuum sy ste m by means o f th e tu b e - o p e n e r B, a d e v ic e d e s c r ib e d by S t o c k . 11 The s id e aim o f th e tu b e was s e a le d i n t o t h e tu b e - o p e n e r , t h e sp ace e v a c u a te d , and t h e c o n te n ts o f th e tu b e r e l e a s e d by t u r n in g th e h a n d le th ro u g h th e g r o u n d - g la s s J o i n t , w hich knocked th e t i p o f f th e s i d e arm . The h ig h te m p e r a tu r e r e a c t i o n b u l b . F o r t h e m easu re­ ment o f v a p o r p r e s s u r e s a t te m p e ra tu re s h i g h e r th a n room te m p e r a tu r e , th e b u lb shown i n F ig u r e 2 was u s e d . T h is b u lb , d e s ig n e d by Burg and S c h l e s i n g e r , 12 co u ld be co m p lete­ l y imm ersed t o g e t h e r w ith i t s a tta c h m e n ts i n a t w o - l i t e r b e a k e r. Any s u i t a b l e t r a n s p a r e n t l i q u i d c o u ld be u se d t o o b t a i n u n ifo rm te m p e r a tu r e s . The b u lb was a tt a c h e d to th e vacuum system by m eans o f th e lo n g t u b e G. I n o r d e r to 11 A. S to c k , o p . c i t . , A ppendix p . 3 . 12 A. B. Burg and H. I . S c h l e s i n g e r , I . Am. Chem. S o c . , 5 9 :7 8 5 , 1937. 10 FIG U R E I HIGH TEMPERATURE REACTION BULB Designed lor Complete Immersion 11 open t h e b u lb to th e r e s t o f th e a p p a r a t u s , t h e m ercury was lo w e re d to th e p o i n t E by e v a c u a tin g th e b u lb G and o p e n in g th e g r o u n d - g la s s j o i n t a t D. To c lo s e t h e b u lb , a f t e r th e i n t r o d u c t i o n o f th e sam ple t o be s t u d i e d , t h e m ercu ry was r a i s e d i n th e two tu b e s by o p e n in g th e b u lb C to a tm o sp h e ric p r e s s u r e and a g a in l i f t i n g t h e v a lv e a t D. T hese two colum ns o f m ercu ry a c te d a s a m anom eter in r e g i s ­ t e r i n g t h e p r e s s u r e o f th e m a t e r i a l i n F a s th e te m p e ra tu re was v a rie d * The d i f f e r e n c e o f m ercury l e v e l s was m easured by means o f a c a th e to m e te r . The volume o f t h i s bulb was found to be 172*5 c c . by u s in g a known q u a n t i t y o f s u lp h u r d io x id e a s i n c a l i ­ b r a t i n g th e U -tu b e . M o le c u la r w e ig h t m easu rem en ts were c a r r i e d o u t i n t h i s b u lb on sam ples o f known w e ig h t, s in c e th e volum e, a s w e ll as th e te m p e r a tu re and p r e s s u r e , co u ld be o b s e rv e d . I I . PREPARATION OF MATERIALS Some m a t e r i a l s , such a s trim e th y la m in e , w ere o b ta in e d , a lr e a d y p re p a r e d and p u r i f i e d , due to th e work o f o t h e r r e s e a r c h s t u d e n ts o f t h i s d e p artm e n t who had been u s in g them . Only th o s e w hich w ere p r e p a r e d d u rin g t h i s stu d y w i l l be d is c u s s e d h e r e . Boron f l u o r i d e . Boron f l u o r i d e was p r e p a r e d a c c o rd ­ in g to th e m ethod g iv e n by Booth and W ills o n 13 w ith th e f o llo w in g m o d i f i c a t i o n s . The a p p a r a tu s was s i m p l i f i e d a s shown i n F ig u r e 3 , s in c e th e i n t r o d u c t i o n o f a l i q u i d a i r t r a p e lim in a te d a l l d a n g e r o f i n t e r n a l gas p r e s s u r e . The b o ro n f l u o r i d e was p r e p a re d from ammonium f l u o b o r a t e , b o r ic o x id e , and s u lp h u r ic a c i d , a c c o rd in g to th e e q u a tio n 6J S H 4 BF4 ♦ B20 3 + 6H2S 04------ > 8BF3 ♦ 6N H4 BS04 ♦ 3HgO. The p ro d u c t was c o l l e c t e d a s a s o l i d a t l i q u i d a i r te m p e ra ­ t u r e i n a U - tu b e . T h is tu b e c o u ld be d e ta c h e d from th e g e n e r a t o r and c o n n e c te d to th e vacuum a p p a ra tu s v e ry con­ v e n i e n t l y . A f t e r pumping a t l i q u i d a i r te m p e r a tu re t o remove a i r , th e p ro d u c t was d i s t i l l e d from a U -tu b e a t - 7 8 .6 ° C ( e t h e r c o o le d by s o l i d c a rb o n d i o x i d e ) , to s e p a r a t e i t fro m such i m p u r i t i e s a s s u lp h u r ic a c i d , w a te r, and h y d ro g en f l u o r i d e , and s t o r e d i n a l a r g e b u lb . The p u r i t y o f th e b o ro n f l u o r i d e was checked by i t s v a p o r p r e s s u r e a t a te m p e ra tu re below i t s b o i l i n g p o i n t . A c o n s ta n t lo w te m p e ra tu re o f -1 1 1 .9 ° C was f u r n i s h e d by a b a th o f a s o l i d - l i q u i d m ix tu re o f c a rb o n d i s u l f i d e . At t h i s te m p e r a tu re th e v a p o r p r e s s u r e o f th e d i f f e r e n t f r a c ­ t i o n s o f b o ro n f l u o r i d e v a r i e d from 303 mm. to 305 mm., 13 H. S . Booth and K. S . W ills o n , "Boron F l u o r i d e ," I n o r g a n ic S y n t h e s i s , V o l. 1 (Hew Y ork: M cG raw -H ill t 1 9 3 9 ), pp". 2 1 -2 2 . 'FLUORIDE. PREPARATION O F 14 w hich a g re e d w ith th e e q u a tio n d e te rm in e d by p o h la n d and H a r lo s :^ lo g P ( l i q . ) * - H 7 4 . 4 / T + 1*75 lo g T - 0*01535 T ♦ 8*0536 Boron f l u o r i d e , a g a s a t o r d i n a r y te m p e r a tu r e s , m e l t s a t -1 2 7 ° C and b o i l s betw een -9 9 ° C and -1 0 1 ° C. I n c o n ta c t w ith m o is t a i r i t h y d ro ly z e s r a p i d l y , a c c o rd in g to t h e e q u a tio n BF3 ♦ 3H20 --------- ► H3BO3 * 3HF. The m e th y lb o ro n f l u o r i d e s * M ethyboron d i f l u o r i d e was p r e p a r e d from m e th y b o ric a n h y d rid e , a c c o rd in g to t h e o r i g i n a l m ethod d e s c r io e d by A. B. B u rg , ! 5 t y t h e a d d i t i o n o f a m easured amount o f b o ro n f l u o r i d e . ( 0 1 ^ 3 8 0 ) 3 * 2 B F 3 ^ 3 C H 3 B F 2 + B g 0 3 * The amount o f b o ro n f l u o r i d e u se d was l e s s th a n th e c a l c u l a t e d am ount, and was t h e r e f o r e c o m p le te ly u s e d . In t h e p r e p a r a t i o n 2 4 .7 c c . o f boro n f l u o r i d e and 19 c c . (v a p o r p h a se m easurem ent) o f m e th y lb o ric a n h y d rid e w ere b ro u g h t t o g e t h e r , p ro d u c in g 3 4 .7 c c . o f m e th y lb o ro n d i f l u o r i d e t h e o r e t i c a l y i e l d , (3 7 .1 c c . ) . The p u r i f i c a t i o n o f th e 14 1 . Von P o h la n d and W. H a r lo s , 2. a n o rg . a llg e m . Chem., 2 0 7 :2 4 2 , 1935. 15 A. B. B urg, J . Am. Chem. S o c . , 6 2 :2 2 3 1 -3 4 , 19 40. 15 m e th y lb o ro n d i f l u o r i d e was e a s i l y a cc o m p lish e d by d i s t i l l a ­ t i o n from a tu b e a t - 7 8 .6 ° C. I t s p u r i t y was checked by i t s v a p o r p r e s s u r e w hich was found to s a t i s f y th e r e p o r t e d e q u a t io n :16 lo g p = - 1 2 0 4 .O/T + 1 .7 5 lo g T - 0 .0 0 6 8 4 T + 5.9680 M eth y lb o ro n d i f l u o r i d e h a s a m e ltin g p o i n t o f - 1 3 0 .5 ° C and a b o i l i n g p o i n t o f - 6 2 .3 ° C. A sam ple o f d im e th y lh o ro n f l u o r i d e p r e p a r e d by A. B. B urg17 d u rin g h i s stu d y o f t h e m e th y lb o ro n f l u o r i d e s , was fo u n d on i t s rem o v al from i t s s e a le d tu b e to have u n d e r­ gone some s l i g h t d e c o m p o sitio n o v e r a p e r io d o f two y e a r s . The m ain body o f th e sam ple was o b ta in e d i n a p u re s t a t e a f t e r s e v e r a l f r a c t i o n a l d i s t i l l a t i o n s , rem oving two sm a ll (to p and bottom ) f r a c t i o n s . The m e th y lc h lo ro a m in e s . One o f t h e s e compounds, d im e th y lc h lo ro a m in e , was p r e p a r e d a c c o rd in g to t h e o r i g i n a l m ethod u se d by B erg18 i n 1893. A n e u t r a l s o l u t i o n o f sodium h y p o c h lo r i te 19 was added to a s o l u t i o n o f d im eth y lam in e h y d r o c h lo r id e i n c h e m ic a lly e q u iv a le n t am ounts. 16 L o c. c i t . 17 L o c . c i t . 18 A. B e rg , Compt. r e n d . , 1 1 6 :8 8 7 -8 9 , 1893. A. B e rg , Ann. C hirn., (7) 3 :3 0 8 -3 4 , 1894. 19 P r e p a r e d by w e ig h in g th e amount o f c h l o r i n e ta k e n up by a w eighed sodium h y d ro x id e s o l u t i o n . 16 Upon d i s t i l l i n g th e s o l u t i o n u n d e r re d u c e d p r e s s u r e th e p r o d u c t, d im e th y lc h lo ro a m in e , p a s s e d o v e r f i r s t i n an a lm o st p u re s t a t e . F u r t h e r p u r i f i c a t i o n was a c h ie v e d by d i s t i l l a t i o n from a - 7 8 ,6 ° C b a t h , w hich was p o s s ib l e s in c e d im e th y lc h lo ro a m in e a t t h i s te m p e r a tu re i s s t i l l a l i q u i d w ith a s l i g h t v a p o r p r e s s u r e . However, no v a p o r p r e s s u r e m easu rem en ts o f t h e m e th y lc h lo ro a m in e s have been p u b l is h e d , by w hich f u r t h e r c o m p a riso n s c o u ld be made. A p r e l i m i n a r y e x p e rim e n t showed t h a t t h i s compound r e a c te d w ith m e rc u ry . T h is f a c t p r e v e n te d q u a n t i t a t i v e work w ith t h e d im e th y l c h lo ro amine i n th e vacuum sy ste m , where c o n ta c t w ith m ercu ry i s n e c e s s a r y i n m e a su rin g volume and v a p o r p r e s s u r e . D im eth y lch lo ro am in e was found to be f a i r l y s t a b l e a t low te m p e r a tu re s and was k e p t s e v e r a l weeks a t - 7 8 .5 ° C. At room te m p e r a tu re i t decom posed a f t e r a p e r io d o f h o u r s , fo rm in g one p ro d u c t w hich c o u ld n o t be d i s t i l l e d i n th e vacuum sy ste m . T h is u n s t a b le c h a r a c t e r i s ­ t i c made i t d i f f i c u l t to d e te rm in e th e p r o d u c ts o f i t s r e a c t i o n s w ith boron f l u o r i d e . S in c e m e th y ld ic h lo ro a m in e was known t o be s t i l l l e s s s t a b l e , t h i s p a r t o f th e vx>rk was abando ned . 17 THE HIGH VACUUM APPARATUS CHAPTER I I I THE EXPERIMENTS AND THEIR RESULTS Boron f l u o r i d e and i t s m eth y l d e r i v a t i v e s w ere found t o form d e f i n i t e a d d i t i o n compounds w ith t r i m e t h y l a - m in e. The d e s c r i p t i o n o f th e e x p e rim e n ta l work which d e m o n s tra te d t h i s i s a rra n g e d i n t h r e e s e c t i o n s i n t h i s c h a p t e r . I n t h e f i r s t d i v i s i o n , th e s tu d y o f th e r e a c t i o n o f boron f l u o r i d e w ith trim e th y la m in e i s d is c u s s e d ; i n t h e se co n d , th e r e a c t i o n o f m e th y lb o ro n d i f l u o r i d e w ith t r i m e t h y l am ine; i n th e t h i r d , th e r e a c t i o n o f d im et hy]bor on f l u o r i d e w ith tr im e th y la m in e . I . THE ADDITION COMPOUND OF BORON FLUORIDE AM) TRIMETHYL AMINE T h at b o ro n f l u o r i d e form ed a v e ry s t a b l e compound w ith trim e th y la m in e was re c o g n iz e d from th e f o llo w in g p r e ­ l im i n a r y w ork. A sam ple o f 29 c c . o f boro n f l u o r i d e was in tr o d u c e d i n t o an e v a c u a te d b u lb c o n ta in in g a sam ple w eig h in g 0 .1 5 8 gm. o f th e s o l i d tr im e th y la m in e s u l f u r d io x id e com plex, 20 and th e d is p l a c e d g a s rem oved, m ea su re d , and i d e n t i f i e d a s s u l f u r d i o x id e . T hese r e s u l t s i n d i c a t e d 20 A. B. B u rg, U n p u b lish e d r e s e a r c h a t th e U n i v e r s i t y o f S o u th e rn C a l i f o r n i a . 19 t h a t a new compound had b een form ed w hich was more s t a b l e th a n trim e th y la m in e s u l f u r d io x id e , and w hich c o n ta in e d th e two com ponents, b o ro n f l u o r i d e and tr im e th y la m in e , i n a o n e -to -o n e r a t i o . However, s in c e th e re c o v e ry o f s u l f u r d io x id e was n o t com plete (27 c c . o u t o f 29 c c . ) , a n o th e r m ethod, t h a t o f d i r e c t c o m b in a tio n o f th e two g a s e s , was u se d i n p r e p a r in g a p u re sam ple f o r v a p o r p r e s s u r e m ea su re ­ m ents and m o le c u la r w e ig h t d e te r m in a tio n . P r e p a r a t i o n o f b o ro n f l u o r i d e tr im e t h y l a m i n e . A sam ple o f boron f l u o r i d e was t r a n s f e r r e d from th e s to r a g e b u lb to th e c a l i b r a t e d U -tu o e in t h e vacuum system by m eans o f a l i q u i d a i r b a th , and a llo w e d to come to room te m p e ra ­ t u r e t o be m e a su re d . From th e te m p e r a tu r e , th e p r e s s u r e , and th e volum e, t h e volume a t s ta n d a r d c o n d it i o n s was known to be 2 1 *8 c c . o r th e e q u iv a le n t o f 0 .9 7 m il l im o l e s o f g a s . T h is was condensed i n to th e h ig h te m p e ra tu re b u lb w ith a l i q u i d a i r b a th to a s s u r e th e q u a n t i t a t i v e t r a n s f e r o f t h e m easured sam ple. I n a s i m i l a r m anner, t h e same amount o f trim e th y la m in e was m easured and b ro u g h t i n t o t h e r e a c t i o n b u lb . R e a c tio n to o k p l a c e a s t h e te m p e ra tu re slo w ly r o s e a f t e r th e rem oval o f th e c o o lin g b a th . The p r o d u c t, a s t a b l e w h ite s o l i d , e x h ib i t e d no v a p o r p r e s s u r e a t room te m p e r a tu r e ; n o r d id i t show any p r e s s u r e u n t i l a f t e r th e te m p e r a tu re had b een r a i s e d above 70° C by a w a te r b a th i n 20 w hich th e e n t i r e b u lb was im m ersed. F o r f u r t h e r stu d y a t h ig h e r te m p e r a tu r e s , t h e w a te r b a th was r e p la c e d by a t r a n s p a r e n t o i l b a th th ro u g h w hich o b s e r v a t i o n s o f p r e s s u r e and b e h a v io r c o u ld be made e a s i l y . Vapor t e n s i o n c u rv e f o r b o ro n f l u o r i d e tr im e th y la m in e . The p r e s s u r e s f o r a s e r i e s of te m p e r a tu re s were m easured by t h e a id o f a c a th e to m e te r whose r e a d in g s w ere a c c u r a te to one d e cim a l p l a c e (0 . 1 mm.) and w hich c o u ld be re a d t o two f a i r l y s a t i s f a c t o r i l y . S in c e t h e e n t i r e h ig h te m p e ra tu re b u lb , F ig u re 5 , was h e a te d i n an o i l b a th , th e sp ace i n t h e b u lb would c o n t a i n m ercu ry v a p o r. I n o r d e r to make p o s s i b l e a c o r r e c t i o n f o r s a t u r a t e d v a p o r, t h e p r e s s u r e r e a d in g s w ere made a t lo w e r and lo w e r te m p e r a tu r e s a f t e r h e a t in g to an i n i t i a l h ig h te m p e ra ­ t u r e . T h is made th e f i r s t re a d in g s l i g h t l y i n c o n s i s t e n t i n each c a s e , due t o u n s a t u r a t i o n a t t h a t p o i n t , b u t t h e rem a in ­ in g r e a d in g s a g re e d v e ry w e ll w ith t h e C la p e y ro n -C la u s iu s e q u a tio n . Each re a d in g was c o r r e c t e d f o r m ercu ry v ap o r p r e s s u r e and m ercury d e n s i t y . T hese p r e s s u r e s a r e g iv e n i n T able I , r e p r e s e n ti n g two s e r i e s o f o b s e r v a t i o n s , one a t h i g h e r te m p e r a tu r e s th a n t h e o t h e r . F ig u r e 4 a ls o r e p r e s e n t s t h e s e o b s e r v a t i o n s i n g ra p h form . T hese v a lu e s d e te rm in e d t h e e q u a tio n lo g p * 1 0 .2 4 0 - 3 ,6 0 0 /T f o r th e v a p o r p r e s s u r e s o f t h e s o l i d , 21 TABLE I PRESSURE OF BORON FLUORIDE TRIMETHYLAMINE Temp. t°C P r e s s u r e (mm.Obsd) P r e s s u r e ( m m .c o rr.) 0° c Vapor p r e s s u r e ( c a lc d ) Log P 1 /T x 104 *240 240.30 1 7 4 .2 2 .2 3 1 9 .4 9 *230 2 3 6 .3 5 1 7 7 .1 2 .2 4 1 9 .8 8 *220 2 2 6 .1 5 1 6 6 .1 2 .2 2 2 0 .2 8 *200 175 .20 1 5 3 .8 2 .1 8 2 1 .1 4 *190 1 6 1.50 1 4 5 .4 2 .1 6 2 1.59 *180 1 4 2 .2 5 1 3 0 .5 2 .1 1 2 2 .0 7 175 1 1 7 .5 5 1 0 8 .0 2 .0 3 22.3 2 *170 113.00 1 0 4 .7 2 .0 2 2 2 .5 7 170 1 1 0 .8 5 1 0 2 .5 2 .01 2 2.57 165 1 0 0 .3 5 9 2 .5 0 9 3 .5 1 .9 7 2 2 .8 3 *160 8 4 .0 0 77.55 78 .1 1 .8 9 2 3.09 160 8 5 .3 5 78.86 78 .1 1 .9 0 2 3 .0 9 155 71.00 6 5 .7 1 6 5 .0 1 .8 2 23.3 6 150 67.60 5 3 .3 5 5 3 .6 1 .7 3 2 3 .6 4 145 4 6 .7 0 4 3 .2 8 4 2 .5 1 .6 4 2 3 .9 2 140 3 5 .6 5 32.9 7 3 3 .4 1 .5 2 24.21 134 2 6 .3 5 2 4 .2 8 2 4 .8 1 .3 9 2 4 .5 7 130 2 1 .1 0 1 9 .4 5 2 0 .3 1 .2 9 2 4 .8 1 120 1 4 .4 5 1 3 .4 2 1 2 .2 1 .1 3 2 5 .4 4 109 7 .2 5 6 .66 6 .6 0 .8 2 2 6 .1 7 100 4 .7 0 4 .3 5 3 .9 0 .6 4 2 6 .8 0 *T hese r e a d in g s w ere made l a t e r when th e o c c u rre n c e o f a s s o c i a t i o n i n th e v a p o r p h a se i n d i c a t e d th e n e c e s s i t y o f m aking m easurem ents a t h i g h e r te m p e r a tu r e s . I n each o f t h e two s e r i e s th e s u c c e s s iv e te m p e r a tu r e s were lo w e r. r m to p a s a B ^ S ta NO. 6311. J ES SE RAY MILLER, LOS ANGELES 2 s — 21 l / T X 104 23 and th e e q u a tio n lo g p * 8 .7 3 5 -2 9 6 3 /T f o r th e v a p o r p r e s s u r e s o f t h e l i q u i d above th e m e ltin g p o i n t , 150° C. The c a l c u l a t e d v a lu e s f o r v a p o r p r e s s u r e s g iv e n i n T ab le I w ere o b ta in e d from t h e s e e q u a tio n s . U sin g th e r e l a t i o n s h i p a H/RT * 2 .3 0 3 A /T, h e a t s o f s u b lim a tio n and v a p o r i z a t i o n w ere c a l c u l a t e d from th e s e C la u s iu s -C la p e y r o n e q u a tio n s w hich a re g iv e n i n th e form loglO P * B - A/T. The h e a t o f s u b lim a tio n was found from th e f i r s t e q u a tio n t o be 1 6 .5 C a l . , th e h e a t o f v a p o r i z a t i o n from th e se co n d to be 1 3 .0 C a l . , and th e h e a t o f f u s i o n ( e s tim a te d from t h e d i f f e r e n c e ) t o be 3 .5 C a l. From th e e q u a tio n lo g p - 8 .7 3 5 - 2963/T th e b o i l i n g p o i n t was fou nd t o be 233° C. The T ro u to n c o n s t a n t , u s in g th e h e a t o f v a p o r i z a t i o n and t h e b o i l i n g p o i n t d e r iv e d above, i s 2 5 .5 . F o r n o n - a s s o c ia t e d l i q u i d s t h i s r a t i o A H /T sh o u ld be a p p ro x im a te ly 2 1 . The m o le c u la r w e ig h t o f b o ro n f l u o r i d e t r im e t h y l a m in e. The f a c t t h a t th e two com ponents had com bined i n c h e m ic a lly e q u iv a le n t am ounts to form a n o n - v o l a t i l e s o l i d su g g e s te d t h e fo rm u la (CH^lgN • BF3 f o r th e com plex. T h is was t e s t e d by t h e m o le c u la r w e ig h t d e te rm in e d from th e fo llo w in g m easurem ents o f th e v a p o riz e d sam ple. At 230° C, th e 0 .1 2 3 5 gm. sam ple showed a p r e s s u r e o f 1 7 7 .1 mm. ( c o r r e c t e d f o r m ercu ry vapor) i n a 1 7 1 .0 c c . volum e. The m o le c u la r w e ig h t 24 t h u s was c a l c u l a t e d to be 1 2 7 .9 , w hich a g r e e s w ith th e t h e o r e t i c a l m o le c u la r w e ig h t o f 1 2 6 .9 3 f o r t h e compound (CHgJgN • BFg. At lo w e r te m p e r a tu re s t h e a p p a re n t m o le c u la r w e ig h ts w ere h i g h e r , i n d i c a t i n g m o le c u la r a s s o c i a t i o n due to some k in d o f a s s o c i a t i o n i n th e gas p h a se n e a r th e co n d en sa­ t i o n p o i n t . T hese c a l c u l a t i o n s a re g iv e n i n T ab le I I . I I . THE ADDITION COM POUND OF METHYLBORON DIFLUORIDE AND TRIMETHYLAMINE The n e x t p ro b lem i n v e s t i g a t e d was th e e f f e c t o f sub­ s t i t u t i n g a m eth y l group f o r one f l u o r i d e io n i n b o ro n t r i - f l u o r i d e on i t s r e a c t i o n w ith trim e th y la m in e . When m eth y l - b o ro n d i f l u o r i d e , CHgBFg, and tr im e th y la m in e , (CH3 ) 3N, w ere b ro u g h t t o g e t h e r i n c h e m ic a lly e q u iv a le n t am ounts, a w h ite s o l i d was form ed a s t h e o n ly p ro d u c t o f th e g a s r e a c t i o n . Vapor p r e s s u r e m easu rem ents p ro v e d t h i s complex to be l e s s s t a b l e th a n boron f l u o r i d e tr im e th y la m in e : i t i s somewhat more v o l a t i l e and shows th e rm a l d i s s o c i a t i o n i n th e v a p o r s t a t e . P r e p a r a t i o n o f m e th y lb o ro n d i f l u o r i d e tr im e th y la m in e . The p r e l i m i n a r y e x p e rim e n t was c a r r i e d o u t i n a r e a c t i o n tu b e which was t e m p o r a r ily a tta c h e d to th e vacuum a p p a r a t u s . S i m i l a r q u a n t i t i e s , m e a su rin g 1 1 .4 cc. a t s ta n d a r d c o n d i t i o n s , o f m e th y lb o ro n d i f l u o r i d e and trim e th y la m in e were condensed 25 TABLE I I ASSOCIATION IN GAS PHASE OF BORON FLUORIDE TRIMETHYLAMINE Temp. t ° C Temp. T°K P r e s s u r e (mm. c o r r .) 0° C Volume C O . * A p p a ren t M ol. Wt. ( c a l c u l a t e d from d a ta ) 170 443 1 0 4 .7 1 7 0 .6 1 9 1 .0 175 448 1 0 8 .0 1 71 .1 1 8 6 .7 180 453 1 3 0 .5 1 7 0 .7 1 5 6 .6 190 463 1 4 5 .4 1 7 0 .7 1 4 3 .6 200 473 1 5 3 .8 1 7 1 .0 1 3 8 .5 220 493 1 6 6 .1 171.1 1 3 3 .6 250 503 1 7 7 .1 1 7 1 .0 1 2 7 .9 240 513 1 7 4 .2 1 7 1 .2 1 3 2 .5 # W eight o f sam ple m easu red - 0 .1 2 3 5 gram s. ♦Volume c o r r e c t e d f o r v a r i a t i o n o f m ercury l e v e l i n th e a d ja c e n t m anom eter. ^ H ig h e s t re a d in g made f i r s t . T h e r e fo r e c o r r e c t i o n f o r s a t u r a t e d m erc u ry v a p o r a t t h i s p o in t i s u n s a t i s f a c t o r y . 26 i n to th e tu b e a t l i q u i d a i r te m p e ra tu re and a llo w e d to come slo w ly to room te m p e r a tu r e . The p ro d u c t o f th e g a s r e a c t i o n was a f i n d y d iv id e d w h ite s o l i d . A f t e r b e in g h e a te d and c o o le d s lo w ly , th e compound form ed d e f i n i t e c r y s t a l s . I t was a ls o found to be v o l a t i l e enough t o d i s t i l s lo w ly . A p o r t i o n was moved to th e h ig h te m p e ra tu re b u lb f o r v apor p r e s s u r e m easurem ent i n o r d e r t o check i t s p u r i t y . T hese m easurem ents showed th e p ro d u c t to be one compound, and n ot a m ix tu r e . A f t e r th e p r o o f t h a t m e th y lb o ro n d i f l u o r i d e form ed a sim p le a d d i t i o n compound w ith tr im e th y la m in e i n a com plete q u a n t i t a t i v e r e a c t i o n , t h e second p r e p a r a t i o n was c a r r i e d o u t i n th e h ig h te m p e ra tu re b u lb i t s e l f . An e x a c tl y 1 2 .1 c c . sample o f each g a s was condensed i n t o t h e b u lb and t h e r e a c t i o n a llo w e d to p ro c e e d a t -8 0 ° C. T hese sam ples o f d e f i n i t e l y known q u a n t i t i e s made i t p o s s i b l e to c a l c u l a t e t h e w e ig h t o f th e m a t e r i a l i n t h e b u lb t o be 6 6 .6 mg. O b s e r v a tio n s o f p r e s s u r e , te m p e r a tu re , and volum e c o u ld th e n be i n t e r p r e t e d m ore d e f i n i t e l y . Vapor t e n s i o n c u rv e f o r m e th y lb o ro n d i f l u o r i d e t r i - m eth y l am ine. T e m p e r a tu re -p r e s s u re m easu rem en ts w ere made by im m ersing th e h ig h te m p e r a tu re b ulb i n an o i l b a th . P r e s s u r e r e a d in g s w ere o b se rv e d from room te m p e r a tu re to 160° C by u s in g a c a th e to m e te r f o r com paring t h e m erc u ry l e v e l s 27 (F ig u re 2) . The v a lu e s f o r t h e lo w e r te m p e r a tu r e s a re g iv e n i n T a b le I I I and i n t e r p r e t e d a s a g rap h o f lo g iQp a g a i n s t 1 /T i n F ig u r e 5 . From t h i s c u rv e t h e e q u a tio n loglO P * 8 .5 3 1 - 2 6 5 3 .3/T was o b ta in e d to e x p re s s th e v a p o r p r e s s u r e b e h a v io r o f th e compound. The h e a t o f v a p o r i z a t i o n c a l c u l a t e d from t h i s e q u a tio n i s 1 2 ,1 3 6 c a l . , and t h e t h e o r e t i c a l b o i l i n g p o i n t , 1 7 1 .5 ° C. The T ro u to n c o n s t a n t , w hich e x p re s s e s th e r a t i o o f th e h e a t o f v a p o r i z a t i o n t o t h e b o i l i n g p o i n t i s 2 6 .5 . T h is h ig h v a lu e i s to be e x p e c te d f o r a s u b s ta n c e show ing d i s s o c i a t i o n i n t h e v a p o r s t a t e . The p r e s s u r e m easurem en ts made above th e p o i n t o f co m p lete v a p o r i z a t i o n showed t h a t m e th y lb o ro n d i f l u o r i d e trim e th y la m in e underw ent th e rm a l d i s s o c i a t i o n i n th e g a s p h a s e . The p e r c e n ta g e d i s s o c i a t i o n a t each te m p e r a tu re i n t h i s ra n g e was c a l c u l a t e d f o r m easu rem en ts on t h e second sam ple, whose e x a c t q u a n t i t y was known. By assum ing t h a t th e d i s s o c i a t i o n was e x p re s s e d by t h e e q u a tio n CH3BFg «(CH3 ) 3N ^ = f CH3BF2 ♦ (CHg)3N d i s s o c i a t i o n o r e q u ilib r iu m c o n s t a n t s w ere c a l c u l a t e d a t each te m p e r a tu r e a c c o rd in g to th e d e f i n i t i o n K _ P CH„HF x P {CH3 ) 3 N Katm - --------- S L —2------- ,— ® _2_/760 P com plex 28 TABLE I I I VAPOR TENSION CURVE FOR METHYLBORON DIFLUORIDE TRIMETHYLAMINE Temp. t° c Temp. T°K 1/T x 104 P r e s s u r e (mm.Hg) Log P 34.0* 307.0 32.5 7 0 .7 5 - 0 .1 2 5 3 9 .5 3 1 2 .5 32.00 1 .1 0 40.04 1 4 2 .0 315.0 3 1 .7 5 1 .5 0 0 .1 7 6 51 .0 324.0 3 0 .8 6 2 .1 5 0 .3 3 2 6 1 .0 334.0 2 9 .9 4 3 .8 0 0 .5 8 0 70 .0 343.0 2 9 .1 5 6 .2 0 0 .7 9 2 8 0 .5 3 5 3 .5 28.29 1 0 .8 5 1 .0 3 5 8 2 .5 3 5 5 .5 2 8 .1 3 1 1 .7 0 1 .0 6 8 9 2 .0 365.0 27.40 1 8 .4 0 1 .2 6 5 9 9 .0 372.0 2 6 .8 8 2 5 .7 5 1.41 1 1 0 4 .0 377.0 2 6 .5 2 2 9 .6 5 1 .4 7 2 1 1 4 .0 287 .0 2 5 .8 4 3 5 .3 5 1 .5 4 8 2 7 .0 # 3 0 0.0 3 3 .3 3 0 .55 -0 .2 5 9 41 .0 314.0 3 1 .8 2 1 .2 0 4 0 .0 7 9 5 1 .5 3 2 4 .5 3 0 .8 2 2 .1 0 0 .3 2 2 6 1 .5 3 3 4 .5 2 9 .8 9 3 .9 5 0 .5 9 7 7 1 .5 3 4 4 .5 2 9 ,0 3 6 .8 0 0 .8 3 3 73.0 346.0 2 8 .9 0 7 .0 5 0 .8 4 8 8 1 .0 354.0 2 8 .2 5 1 1 .4 0 1 .0 5 7 9 0 .0 363.0 2 7 .5 5 1 8 .2 5 1 .261 1 0 1 .0 374.0 2 6 .7 4 2 9 .9 5 1 .4 7 6 ^M easurem ents on f i r s t p r e p a r a t i o n . ^M easurem ent on seoond sam p le. Lo, i± c E ~Z5 N O . 6 3 11 , J E S S E RAY M I L L E R , L O S A N G E L E S l / T 10 30 T hese v a lu e s a r e l i s t e d i n T ab le IV, show ing th e o b s e rv e d d a t a , t h e a s s u m p tio n s , and t h e c a l c u l a t e d num bers. The c u rv e i n F ig u r e 6 shows t h e v a r i a t i o n o f lo g Kafcm w ith th e r e c i p r o c a l o f t h e te m p e r a tu re , w hich can a l s o b e e x p re ss e d by t h e e q u a tio n lo g iQ Katm = 1 1 .1 5 2 - 5 ,4 0 0 /T T h is r e l a t i o n s h i p o f d i s s o c i a t i o n c o n s ta n ts f o r d i f f e r e n t te m p e r a tu r e s p ro v id e d a m eans o f c a l c u l a t i n g th e h e a t o f form a­ t i o n and t h e f r e e e n erg y o f t h e compound. The v a lu e s o b ta in e d f o r t h e s e therm odynam ic e x p r e s s io n s a re A H - 2 4 ,6 9 8 c a l . , and A F ° * 2 4 .7 - .05T k . c a l . I I I . THE ADDITION COMPOUND OF DIMETHYLB0R0N FLUORIDE TRIMETHYLAMINE The r e a c t i o n betw een e q u iv a le n t am ounts o f t h e two g a s e s , d im e th y lb o ro n f l u o r i d e and tr im e th y la m in e , p ro d u c e an a d d i t i o n compound w hich i s a l i q u i d a t room te m p e r a tu r e . I n t h e p r e lim in a r y e x p e rim e n t t h e r e a c t i o n was a llo w e d t o p ro c e e d a t i t s own r a t e a t room t e m p e r a tu r e . A f t e r t h e fo r m a tio n o f th e l i q u i d , w hich showed a v a p o r p r e s s u r e o f 2 mm. a t 25° C, a m ore v o l a t i l e p r o d u c t was a ls o fo u n d w hich am ounted i n volum e t o a p p ro x im a te ly one e ig h t h o f th e g a s e s u sed i n th e r e a c t i o n . L a t e r m easurem ents p ro v ed t h a t t h e a d d i t i o n compound s u f f e r e d d i s p r o p o r t i o n a t i o n n e a r 150° C. 51 TABLE IV VAPOR PHASE DISSOCIATION OF METHYLBORON DIFLUORIDE TRIMETHYLAMINE ch3b f2 *(ch3 ) 3n ^=± ch3b f2 B + C + <ch3) 3 n t° c (o b sd .) T° P r e s s u r e (imp. o b sd . c o rr e c te d ) Volume ( c c .) I d e a l p r e s s u r e ( c a l c .) P e r c e n t d i s s o c i a ­ t i o n 1 2 9 .0 4 0 2 .0 9 4.87 1 7 0 .6 79.59 1 9 .2 1 3 5 .5 4 0 8 .5 1 00 .00 1 7 0 .8 8 0 .7 8 2 3 .8 1 4 0 .0 4 1 3 .0 1 0 5 .2 5 1 7 1 .0 8 1 .5 7 2 9 .0 1 4 7 .0 4 2 0 .0 112.12 1 7 0 .9 8 3 .0 1 35 .1 1 5 0 .0 4 2 3 .0 1 1 5 .0 4 1 7 1 .0 8 3 .5 5 3 7 .7 1 5 5 .0 4 2 8 .0 1 1 9 .9 2 1 7 1 .0 8 4 .5 4 4 1 .9 1 6 0 .0 4 3 3 .0 1 2 5 .5 6 1 7 1 .2 8 5 .4 3 4 7 .0 P a r t i a l P a r t i a l Katm * PB l P C Los KAtTn 1/ T x 1C>4 PAX 760 a m 64.31 1 5 .2 8 .00478 -2 .3 2 1 2 4 .8 8 6 0 .5 6 1 9 .2 2 .00803 -2 .0 9 6 2 4 .4 8 57.89 2 3 .6 8 .01275 - 1 .8 9 5 2 4 .2 1 53.9 0 2 9 .1 1 .02069 -1 .6 8 4 2 3.8 1 5 2 .0 6 31.4 9 .02506 - 1 .6 0 1 2 3 .6 4 4 9 .1 6 3 5 .3 8 .03350 -1 .4 7 5 2 3 .3 6 45.3 0 4 0 .1 3 .04678 -1 .3 3 0 2 3 .0 9 W eight o f sam ple = 6 6 .6 mg. Assumed m o le c u la r w e ig h t = 1 2 2 .9 6 IT F H + H + ffl -1 ^ !± b ± iz ± N O . 6 3 1 1 . J E S S E RA Y M I L L E R . L O S A N G E L E S l / T X 105 33 T h is f a c t c o u ld a c c o u n t f o r th e v o l a t i l e p r o d u c t, i f th e h e a t o f th e r a p id r e a c t i o n was s u f f i c i e n t to r a i s e th e te m p e r a tu re o f a p a r t o f t h e g a s sa m p le . I n th e n e x t e x p e r i ­ m ent an a tte m p t was made to c a r r y o u t th e r e a c t i o n a t a lo w e r te m p e r a tu re by t h e a id o f a c o o lin g b a th aro u n d t h e b o tto m o f t h e r e a c t i o n b u lb , and i n t h i s c a s e t h e v o l a t i l e f r a c t i o n was much s m a lle r . T h is i n d i c a t e d t h a t , w ith g r e a t e r c a re i n c o n t r o l l i n g t h e te m p e r a tu r e , a c le a n r e a c ­ t i o n betw een s t o i c h i o m e t r i c q u a n t i t i e s o f th e two g a s e s c o u ld e a s i l y be c a r r i e d o u t . P r e p a r a t i o n o f d im e th y lb o ro n f l u o r i d e tr im e th y 1 a m in e. A sam ple o f d im e th y lb o ro n f l u o r i d e , w hich was c a l c u l a t e d to be 1 2 .8 c c . a t s ta n d a r d c o n d i t i o n s , was condensed q u a n t i t a ­ t i v e l y i n t o th e h ig h te m p e ra tu re b u lb by means o f l i q u i d a i r . A s i m i l a r sam ple o f trim e th y la m in e was c a r e f u l l y m easured o u t and condensed w ith th e d im e th y l bo ro n f l u o r i d e . W ith th e m ercu ry v a lv e c lo s e d , t h e b u lb was a llo w e d to warm up t o room t e m p e r a tu r e . A r a p i d g a s r e a c t i o n to o k p l a c e , form ­ in g d ro p s o f l i q u i d w hich c o l l e c t e d i n t h e b o tto m , and l e f t a r e s i d u a l g a s p r e s s u r e o f 15 mm. i n t h e 171 c c . b u lb . A f t e r th e te m p e r a tu re o f th e m ain p r o d u c t was lo w e re d to 0 ° g , t h i s g a s was d i s t i l l e d o f f and m easured a s 3 .1 c c . a t s ta n d a r d c o n d i t i o n s . The p u r i t y o f th e re m a in in g p ro d u c t was ch eck ed by t h e c o n s ta n t v a p o r p r e s s u r e o f i t s v a r io u s 34 f r a c t i o n s as i t was d i s t i l l e d a t 50° C, and by i t s v ap o r t e n s i o n c u rv e . T h is c u rv e i s i l l u s t r a t e d by t h e g ra p h i n F ig u r e 5 . I n th e second p r e p a r a t i o n o f d im e th y lb o ro n f l u o r i d e trim e th y la m in e , 8 .5 c c . q u a n t i t i e s o f b o th g a s e s , c a l c u l a t e d a t s ta n d a rd c o n d i t i o n s , w ere u s e d . D u rin g t h i s r e a c t i o n t h e lo w e r p o r t i o n o f th e r e a c t i o n b u lb was im m ersed i n a c o o lin g b a th o f a p p ro x im a te ly -8 0 ° C. The v o l a t i l e f r a c t i o n removed a f t e r t h i s r e a c t i o n was m easured a s 1 .1 c c . , o r o n ly a b o u t one s i x t e e n t h o f th e e n t i r e volume o f g a s u s e d . The c o m p o s itio n o f t h e d im e th y lb o ro n f l u o r i d e t r i ­ m e th y la m in e . The r e l a t i v e am ounts o f th e two r e a c t a n t s i n d i c a t e d a sim p le a d d i t i o n o f d im e th y lb o ro n f l u o r i d e and trim e th y la m in e i n c h e m ic a lly e q u iv a le n t am oun ts. However, on a c c o u n t o f t h e sm a ll s id e r e a c t i o n s , no v e ry d e p e n d a b le e s tim a te c o u ld be made o f th e c o m p o sitio n o f th e m ain p r o ­ d u c t. I f no d i s s o c i a t i o n o c c u r r e d , t h e m o le c u la r w e ig h t was e x p e c te d to be t h e sum o f t h a t o f (CH3 ) gBF, 5 9 .8 7 , and t h a t o f (CH3 ) 3N, 5 9 .1 1 , o r 1 1 8 .9 8 t h e o r e t i c a l l y . I n a tte m p tin g to c a l c u l a t e th e m o le c u la r w e ig h t from th e t e m p e r a t u r e - p r e s s u r e m easurem en ts made on t h e whole p ro d u c t o f th e f i r s t p r e p a r a t i o n a c c o rd in g t o th e i d e a l g a s equa­ t i o n pv * m/M RT, t h e r e s u l t s were found t o v a ry from 1 0 3 .3 a t 103° C to 7 8.8 5 a t 155° C. T hese v a lu e s w ere su ch as 35 m ig h t be e x p e c te d i f th e rm a l d i s s o c i a t i o n o c c u r r e d , f o r th e y c o u ld v a ry t h e o r e t i c a l l y betw een 1 1 8 .9 8 and 5 9 .5 9 , t h e a v e ra g e m o le c u la r w e ig h t o f t h e two com ponents. I n o r d e r to e s t a b l i s h d e f i n i t e l y t h e c o m p o s itio n o f t h e com plex a n o th e r m ethod was t r i e d . T h at t h e b o ro n - n i t r o g e n l i n k o f th e compound c o u ld be broken v e ry sim p ly and t h e o r i g i n a l com ponents r e g a in e d and i d e n t i f i e d , was su g g e s te d by t h e u s e o f h y d ro g en c h l o r i d e on a s i m i l a r com­ pound (CH3 ) 3B • N(CH3 ) 3 a c c o rd in g to t h e e q u a tio n 21 (CH3 ) 3B • N(CH3 ) 3 + HC1 > (CH3 ) 3B * HN(CHg)3C l. However, b o ro n f l u o r i d e was p r e f e r r e d f o r su ch a p u rp o se b e c a u se i t s g r e a t e r v o l a t i l i t y would a llo w e a s i e r s e p a r a t i o n o f th e e x c e s s r e a g e n t , and b e c a u se i t seemed l e s s l i k e l y t o r e a c t f u r t h e r w ith th e p r o d u c t. The e x p e c te d r e a c t i o n th u s was ( ch3 ) 2b f • ( ch3 ) 3 n + b f3 — M ch3 ) 2 bf + b f 3 ( ch3 ) 3 h . I n o r d e r to i d e n t i f y t h e com ponents o f t h e compound, a sam ple w e ig h in g 3 0 .2 mg. was d i s t i l l e d i n to t h e w e ig h in g b u lb . The amount o f BF3 n e c e s s a r y to r e a c t w ith t h i s q u a n t i t y was c a l ­ c u la te d to be 5 .7 c c . a t s ta n d a r d c o n d i t i o n s . S e p a r a t io n o f t h e p r o d u c ts would have been e a s i e r i f a s l i g h t l y d e f i c i e n t 21 H. I . S c h l e s i n g e r , N. W. F l o d i n , and A. B. B urg, J . t o . Chem. S o c . . 6 1 :1 0 7 8 -8 3 , 1939. 36 amount o f BFg had been u s e d , b u t by an u n f o r t u n a t e a c c id e n t a s l i g h t e x c e s s , e s tim a te d to be l e s s th a n 1 c c . , was con­ d en sed i n t o th e w e ig h in g b u l b . A lth o u g h th e r e a c t i o n seemed to be i n s t a n t a n e o u s , th e b u lb was l e f t c lo s e d a b o u t tw e n ty f o u r h o u r s . The g a s r e g a in e d was m easured a s a volume o f 6 .5 c c . a t s ta n d a r d c o n d i t i o n s . I t showed a v a p o r p r e s s u r e o f 120 mm. a t - 7 8 .6 ° C. S in c e th e v ap o r p r e s s u r e o f p u re d im e th y lb o ro n f l u o r i d e a t t h i s te m p e r a tu re i s 93 m m .,22 t h i s h ig h e r p r e s s u r e i n d i c a t e d t h e p re s e n c e o f a more v o l a t i l e s u b s ta n c e . I t was found t h a t , by lo w e rin g th e te m p e r a tu re to a p p ro x im a te ly -1 3 0 ° C and d i s t i l l i n g o f f a sm a ll t6 p f r a c ­ t i o n , a l a r g e r e s i d u a l f r a c t i o n o f 5 .6 c c . was o b ta in e d w hich showed t h e c o r r e c t v a p o r p r e s s u r e s o f d im e th y lb o ro n f l u o r i d e . T h is l e f t a 0 .9 c c . e x c e s s w hich was b e lie v e d to be m o s tly BF^ whose v a p o r p r e s s u r e a t -1 3 0 ° c i s a b o u t 50 m m .,23 a m easurem ent w hich would have been d i f f i c u l t to check on so sm all a q u a n t i t y . T h at i t was p o s s i b l e to r e g a i n 5 .6 c c . o f d im e th y lb o ro n f l u o r i d e o u t o f a p o s s i b l e 5 .7 c c . , i n d i c a t e d t h a t t h e c o m p o s itio n o f th e o r i g i n a l com plex was a t r u e o n e -to - o n e m o le c u la r a d d i t i o n i n w hich no d is p r o p o r tio n s - t i o n had ta k e n p l a c e . 22 &. B. B urg, " Vapor t e n s i o n s o f (CH2 ) 2BF d e te rm in e t h e e q u a tio n lo g p « 7 .7 3 7 -1 1 2 1 .4 ," J . Am. Chem. S o c .. 61: 1078 , 1939. T ~ ------- ------ 23 V. E. P o h la n d and W. H a r lo s , 2. a . a . Chem ., 207: 242, 1 935. “ ~ The r e s i d u e i n t h e w e ig h in g b u lb am ounted to 3 2 .2 m g ., i n ag reem ent w ith th e p r e d i c t e d q u a n t i t y o f bo ro n f l u o r i d e tr im e th y la m in e . The e x p e c te d w e ig h t, 32*29 m g ., was b ased upon t h e amount o f b o ro n f l u o r i d e n e c e s s a r y to r e a c t w ith 5 .7 c c . o f t h e com plex a c c o rd in g to t h e e q u a tio n BF3 * (CH3 ) 2BF • N(CH3 ) 3 >BF3 • N(CH3 ) 3 + ( CH3 )gBF V apor t e n s i o n cu rv e f o r d im e th y lb o ro n f l u o r i d e t r i ­ m e th y la m in e . T h ese m easurem ents w ere made p r e v io u s t o th e i n v e s t i g a t i o n o f t h e c o m p o s itio n , b u t t h e y c o u ld n o t b e f u l l y i n t e r p r e t e d u n t i l t h i s had been d e te r m in e d . Vapor p r e s s u r e m easurem ents w ere made i n t h e h ig h te m p e ra tu re b u lb on th e two sam ples a t two d i f f e r e n t s e r i e s o f te m p e ra ­ t u r e s . The f i r s t s e r i e s was a rra n g e d from room te m p e r a tu re to 100° C o b ta in e d by im m ersing th e e n t i r e h ig h te m p e ra tu re b u lb , F ig u r e 3 , i n a w a te r b a t h . The v a lu e s o b ta in e d from t h e s e r e a d i e s a r e g iv e n i n T ab le I I I and a g re e w ith th e C la p e y ro n -C la u s iu s e q u a tio n lo g iQ P - 9*68 - 2 ,8 0 0 /T T h is e q u a tio n i n d i c a t e s a h e a t o f v a p o r i z a t i o n o f 1 2,800 c a l . , a " t h e o r e t i c a l b o i l i n g p o i n t ” o f 152° C. T h is e q u a tio n r e p r e s e n t s t h r e e o u t o f f o u r s e t s o f m easu re m e n ts, two made on each sa m p le . I n m aking th e f i r s t r e a d in g s on th e f i r s t sample th e te m p e r a tu re was r a i s e d to 100° C. The second s e t o f r e a d in g s on t h i s same sam ple, 38 TABLE V VAPOR PRESSURES OF DIMETHYLBORON FLUORIDE TRIMETHYLAMINE Temp. t°C Temp, T°K 1 /T x 104 P r e s s u r e (mm.Hg) L ogioP 25* 298 3 3 .5 5 1 .9 0 .2 7 9 31 304 32.89 3 .0 0 .4 7 7 35 308 32.46 3 .8 0 .5 8 0 40 313 3 1 .9 5 5 .7 0 .7 5 6 45 318 3 1 .4 5 7 .7 0 .8 8 6 50 323 3 0 .9 6 1 0 .4 1 .0 1 7 55 328 30.49 1 4 .7 1 .1 6 7 60 333 3 0 .0 3 1 8 .8 1 .2 4 7 65 338 2 9 .5 8 2 4 .8 1 .3 9 5 25# 298 3 3 .5 5 2 .7 0 0 .4 3 1 30 303 33.0 0 3 .3 0 0 .5 1 8 35 308 32.4 6 4 .2 5 0 .6 2 8 40 313 3 1.9 5 6 .1 0 0 .7 8 5 45 318 3 1 .4 5 7 .8 5 0 .8 9 5 50 323 30.9 6 9 .3 5 0 .9 7 1 55 328 3 0 .4 9 1 4 .5 0 1 .1 6 1 60 333 3 0 .0 3 1 9 .1 0 1 .2 8 1 65 338 2 9 .5 8 24.80 1 .3 9 5 70 343 2 9 .1 5 31.40 1 .4 9 7 * F i r s t m easurem ents made on secon d p r e p a r a t i o n , ^M easurem ents made on same sam ple a f t e r two d i s t i l l a t i o n s . N O . 63 1 1 . JESSE RAY M IL L E R , LOS A N G E L E S : i - l 1 - M 7! '- ,~ ; - r h n i ~ M# #1 H + n r r t H - J t e , m m :l ,:L |: H: i=|i ■ ^ h j J T L i . t t U i± L b - HH-t-1 i? '#SSj± w pM I±!S i - 1 l i l l l f e f t gtm^r m 40 when g ra p h e d , p ro d u ced a c u rv e w ith a s l i g h t l y lo w e r s lo p e , showing t h a t some change had o c c u r r e d . In m aking t h e s e same m easu rem en ts on a second sam p le, c a r e was ta k e n n o t t o r a i s e th e te m p e r a tu re above 70° C betw een th e two r u n s . These r e a d i n g s , g iv e n i n T a b le I I I , p ro d u ce d th e same c u rv e when r e p r e s e n te d g r a p h i c a l l y . (F ig u re 5) The s lo p e o f t h i s l i n e a ls o a g re e d w ith t h a t o f t h e f i r s t p r e s s u r e m easurem ents on th e f i r s t sam ple. T h a t t h i s s lo p e m ig h t i t s e l f De s l i g h t l y d i f f e r e n t from t h e t r u e o n e , i s s u g g e s te d by t h e fo llo w in g c o n s id e r a ­ t i o n . A f t e r th e r e a c t i o n b etw een d im e th y lb o ro n f l u o r i d e and tr im e th y la m in e , a v o l a t i l e p ro d u c t w as fo u n d w h ich c o u ld e a s i l y be rem oved. I f t h i s r e p r e s e n te d some d i s p r o p o r t i o n a - t i o n r a t h e r th a n an im p u rity i n one o f t h e r e a c t a n t s , th e n a n o th e r s u b s ta n c e o f lo w e r v o l a t i l i t y , n o t so e a s i l y s e p a r a te d by d i s t i l l a t i o n , m ig h t a ls o have b e en fo rm ed . Such an im p u r ity would lo w e r th e s lo p e o f th e v a p o r t e n s io n c u rv e s l i g h t l y . O r, i f t r a c e s o f tr im e th y lb o r o n were p r e ­ s e n t , i t s compound w ith trim e th y la m in e would be v ery d i f f i ­ c u l t to s e p a r a te from th e d im e th y lb o ro n f l u o r i d e com plex. S in c e i t s v a p o r p r e s s u r e c u rv e h a s been r e p o r t e d 24 i t s e f f e c t on th e p r e s e n t m easurem ents c o u ld be e x p e c te d to 24 H. I . S c h l e s i n g e r , N. W. F l o d i n , and A. B. B urg, £ . Am. Chem. S o c . , 6 1 :1 0 7 8 -8 3 , 193 9 . 41 i n c r e a s e th e slo p e s l i g h t l y . I n e i t h e r c a s e , how ever, t h e v a r i a t i o n w ould n o t he enough to make th e e r r o r i n t h e s e m easu rem en ts amount to more th a n two o r t h r e e m i l l i m e t e r s i n t h e u p p e r p a r t o f th e vapor t e n s i o n c u rv e , n o r would i t i n any c a s e i n v a l i d a t e t h e q u a l i t a t i v e r e s u l t s o f t h e e x p e r i ­ m e n ts. The secon d s e r i e s o f te m p e r a tu r e s , o b ta in e d by u s in g a c o t t o n se e d o i l b a th , ra n g e d from 90° C t o 155° C. The p r e s s u r e s a t t h e s e h ig h e r te m p e r a tu re s w ere m easured i n an u n s u c c e s s f u l a tte m p t to f i n d a c o n s t a n t v a lu e f o r t h e r a t i o PV/T. Not o n ly d id th e am ine com plex show d i s s o c i a t i o n i n t h e v a p o r s t a t e , b u t a ls o d i s p r o p o r t i o n a t i o n . T h is was shown by th e f a c t t h a t t h e lo w e r ra n g e o f p r e s s u r e -te m p e r a ­ t u r e r e a d in g s were n o t th e same a f t e r h e a tin g t h e compound t o 155° C. How ever, th e sam ple was n o t c o m p le te ly decomposed by t e n m in u te s h e a t in g a t 155° C, b e c a u s e a p u re f r a c t i o n , am ounting to one h a l f th e o r i g i n a l p ro d u c t by w e ig h t, was re g a in e d a f t e r f r a c t i o n a l d i s t i l l a t i o n . The i m p u r i t i e s were o b se rv e d to be a s t a b l e s o l i d and a s u b s ta n c e m ore v o l a t i l e th a n t h e d im e th y lb o ro n f l u o r i d e trim e th y la m in e ; b u t t h e s e w ere n o t i d e n t i f i e d . S in c e h e a tin g above 100° C c a u se d d i s p r o p o r t i o n a t i o n , a q u a n t i t y o f a f r e s h p r e p a r a t i o n , w hich was sm a ll enough to be v a p o riz e d a t a r e l a t i v e l y low te m p e r a tu r e , was s t u d i e d to i n v e s t i g a t e th e d i s s o c i a t i o n o f th e p ro d u c t i n th e v a p o r 42 p h a s e . F o r t h i s p u rp o s e a sam ple was slo w ly d i s t i l l e d i n t o th e h ig h te m p e r a tu re b u lh from th e w e ig h in g b u lb , u n t i l a q u a n ti t y was o b ta in e d which was c a l c u l a t e d fro m i t s w e ig h t o f 1 9 .7 mg. to be 3 .7 c c .* i n t h e g as p h a s e . T e m p e ra tu re - p r e s s u r e m easu rem en ts showed t h a t t h i s sam ple w as c o m p le te ly v a p o riz e d a t 75° C. The d e g re e o f d i s s o c i a t i o n and th e d i s s o c i a t i o n c o n s t a n t , c a l c u l a t e d a c c o rd in g to th e e q u a tio n (CH3 ) 2BF • (CH3)5N^=±(CH3 )aBF + (CH3 ) 3N w ere found f o r e ac h t e m p e r a tu r e - p r e s s u r e re a d in g b etw een 74° C and 92° C, and a rra n g e d i n T a b le IV . From t h e s e v a lu e s a c u rv e was p l o t t e d f o r th e lo g Kd^ s v a r i a t i o n w ith th e te m p e r a tu r e , F ig u r e 5 . From t h e g ra p h th e e q u a tio n 10610 Katm = 1 1.376 - 4 ,3 8 3 .8 /T was d e te rm in e d . From t h i s e q u a tio n th e f o llo w in g v a lu e s were c a l c u l a t e d : A H * 20 C a l. and A F° = 20 C a l. - .052T. The d e v i a t i o n s o f t h e o b se rv e d v a lu e s f o r K from v a lu e s c a l ­ c u la te d from th e e q u a tio n a re g iv e n i n t h e f o llo w in g t a b l e . Temp. 74 77 80 8 2 .5 86 91 92 Ka tm (o b s v d - ) .042 .061 .091 .127 .1 5 3 .216 .242 .055 .071 .091 .1 1 2 .147 .216 .233 D e v ia tio n + .01 3 o o • -0 - .0 1 5 -.0 0 6 0 - .0 0 9 * T h is f i g u r e i s t h e c a l c u l a t e d g a s volume a t s ta n d a r d c o n d i t i o n s , a t w hich te m p e r a tu re and p r e s s u r e d im e th y lb o ro n f l u o r i d e tr im e th y la m in e i s o f c o u rs e n o t a g a s . 43 TABLE VI DISSOCIATION O F D METHYL BORON FLUORIDE TRB1ETHYLAMIN1 (CH3 ) 2BF • (CH3 ) 5 N ^ = ± ( C H 3 )gBF + (C H ^ N A ^ * B ♦ C T em p era tu re t°C T°K Volume ( c e .) P r e s s u r e (m m .obsd.) D i s s o c i a t i o n p e r c e n t P r e s s u r e ( c a l c u l a t e d ) i d e a l 74 347 1 7 0 .3 3 5 .4 0 6 8 .6 5 20.99 77 350 1 7 0 .4 37 .00 7 4 .4 5 2 1 .2 1 80 353 1 7 0 .5 3 8 .50 8 0 .0 7 2 1 .3 8 8 2 .5 355 .5 1 7 0 .5 3965 8 4 .1 6 2 1 .5 3 86 359 1 7 0 .6 4 0 .4 5 8 6 .1 5 2 1 .7 3 91 364 1 7 0 .6 4 1.70 8 9 .9 2 2 2 .0 3 9 2 .5 3 6 5 .5 1 7 0 .7 4 2.00 9 0 .2 2 2 2 .0 8 P a r t i a l P a r t i a l PB 9 5 3?C PB X Pc Log Katm 1/T x 10* " -tl - - - 760 6 .5 8 1 4 .4 1 0 .0 4 1 5 -1 .3 8 2 2 8 .8 2 5 .4 2 1 5 .7 9 0 .0 6 0 5 -1 .2 1 8 28.5 7 4 .2 6 1 7 .1 2 0 .0 9 0 5 -1 .0 4 3 2 8 .3 2 3 .4 1 1 8 .1 2 0 .1 2 6 7 -0 .8 9 7 2 8 .1 3 3.0 1 1 8 .7 2 0 .1 5 3 2 -0 .8 1 5 2 7 .8 5 2 .3 6 1 9 .6 7 0 .2 1 5 7 -0 .6 6 6 2 7 .4 7 2 .16 1 9 .9 2 0 .2 4 1 7 -0 .6 1 7 2 7 .3 6 W eight o f sam ple u se d = 1 9 .7 mg. T H T 44 Lo, Y 9 5 N O . 6 3 1 1 , J E S S E RA Y M I L L E R . L O S A N G E L E S CHAPTER 17 DISCUSSION A M D CONCLUSIONS A r e l a t e d s e r i e s o f a d d i t i o n compounds h a s b e e n com p leted d u rin g t h i s s tu d y . Boron f l u o r i d e and i t s two m eth y l d e r i v a t i v e s w ere com bined w ith tr im e th y la m in e to form compounds c o n ta in in g m onom olecular p r o p o r t i o n s o f t h e two c o n s t i t u e n t s . I n th e o r d e r o f i n c r e a s i n g number o f m eth y l g ro u p s , t h e s e newly p re p a re d compounds a re (1) boron t r i f l u o r i d e tr im e th y la m in e , BFg • N(CHg)3 , (2) m e th y lb o ro n d i f l u o r i d e tr im e th y la m in e , CH^BFg* N(CHg)g, (3) d im e th y lb o ro n f l u o r i d e tr im e th y la m in e , (CH3 ) gEF • N(CH3 ) 3 , The seq u en ce o f t h e s e t h r e e compounds i n c lu d e s a s a f o u r t h member t r i m e t h y l b o r i n e tr im e th y la m in e , (CHg)gB * N(CH3 ) 3 , w hich h a s been s t u d i e d as a m e th y l d e r i v a t i v e of b o r in e t r i ­ m e th y la m in e ,25 b u t w h ic h , i n c h a r a c t e r and s t a b i l i t y , c a n be c o n s id e re d a m eth y l d e r i v a t i v e o f b o ro n f l u o r i d e t r i m e t h y l a ­ m in e. By th e p r e p a r a t i o n and c h a r a c t e r i z a t i o n o f b o ro n f l u o r i d e trim e th y la m in e a m is s in g member h a s been s u p p lie d to a n o th e r s e r i e s . T h is group b eg an w ith th e compound BFg•NHg p r e p a r e d by Davy i n 1812 and a lr e a d y c o n ta in e d t h e a d d i t i o n compounds o f b o ro n f l u o r i d e w ith t r i e t h y l a m i n e and 25 H. I . S c h l e s i n g e r , N. W. F l o d i n , and A. B. B urg, £ . Am. Chem. g o c . , 6 1 :1 0 7 8 -8 3 , 1939. 46 many h i g h e r am ine b a s e s . B oron f l u o r i d e tr im e th y la m in e i s a s t a b l e w h ite s o l i d , s u f f i c i e n t l y v o l a t i l e a t te m p e ra tu re s above 100° C to be s t u d i e d i n th e vacuum sy ste m . Vapor p r e s s u r e m ea su re ­ m ents w ere made and have been r e p r e s e n te d i n t a b l e and i n g ra p h form . A C la p e y ro n - C la u s iu s e q u a tio n was d e te rm in e d to e x p re s s th e o b se rv e d change o f v a p o r p r e s s u r e w ith th e te m p e r a tu re (170° C ). Some 50 p e r c e n t o f a s s o c i a t i o n i n th e g a s p h a se was o b s e rv e d n e a r th e c o n d e n s a tio n p o i n t . T h is d e v i a t i o n from th e i d e a l g a s la w d e c re a s e d a s th e te m p e r a tu re was i n c r e a s e d , u n t i l m o le c u la r w e ig h t m easu rem en ts were found t o b e norm al above 230° C. M eth y lb o ro n d i f l u o r i d e trim e th y la m in e i s a much more v o l a t i l e w h ite s o l i d . I t s v a p o r t e n s i o n c u rv e and i t s C la p e y ro n - C la u s iu s e q u a tio n have been d e te rm in e d . In th e v a p o r p h a se t h i s compound showed d i s s o c i a t i o n w hich in c r e a s e d w ith th e t e m p e r a tu r e . D i s s o c i a t i o n c o n s t a n t s w ere c a l c u l a t e d and a v a n 't H o ff e q u a tio n d e te rm in e d t o show t h e i r change w ith th e te m p e r a tu r e . From t h i s e q u a tio n t h e h e a t o f r e a c ­ t i o n and th e f r e e e n e rg y o f f o r m a tio n o f m e th y lb o ro n d i f l u o r i d e trim e th y la m in e w ere c a l c u l a t e d . D im eth y lb o ro n f l u o r i d e tr im e th y la m in e i s a l i q u i d a t room te m p e r a tu r e . I t s v a p o r p r e s s u r e m easurem ents had t o be made a t r e l a t i v e l y low te m p e r a tu re s b e ca u se o f i t s i n s t a b i l ­ i t y n e a r 100° C, above w hich te m p e ra tu re i t showed some 47 d i s p r o p o r t i o n a t i o n a s w e ll as a v e ry h ig h d e g re e o f d i s s o c i a ­ t i o n . F o r t h i s r e a s o n th e e q u a tio n s d e te rm in e d f o r th e te m p e r a t u r e - p r e s s u r e m easurem ents c a n n o t he a s a c c u r a te a s th o s e f o r th e o t h e r two compounds. The im p o r ta n t c o n c lu s io n o f t h i s s tu d y i s t h a t th e s t a b i l i t y o f t h e a d d i t i o n compounds o f b o ro n f l u o r i d e and i t s m eth y l d e r i v a t i v e s w ith tr im e th y la m in e d e c r e a s e s w ith t h e i n c r e a s e o f th e number o f m eth y l g r o u p s . Boron f l u o r i d e trim e th y la m in e b e g in s th e s e r i e s as a v e ry s t a b l e complex show ing no v a p o r p r e s s u r e below 70° c and no d i s s o c i a t i o n i n th e v a p o r p h a se w i t h in th e te m p e ra tu re ra n g e m easu red . S t i l l q u i t e s t a b l e , b u t much more v o l a t i l e , i s m eth y lb o ro n d i f l u o r i d e , t h e n e x t o f th e s e r i e s . T h is compound b e g in s to show v a p o r p r e s s u r e a t room te m p e r a tu re , and u n d e r f a v o r ­ a b le c o n d it i o n s i t s v a p o r p h a se d i s s o c i a t i o n can be s tu d ie d above 125° C. The d im e th y lb o ro n f l u o r i d e complex shows a h ig h d e g re e o f d i s s o c i a t i o n a t r e l a t i v e l y low te m p e r a tu r e s , and i s i t s e l f u n s t a b l e a t te m p e r a tu r e s above 100° C. The e v id e n c e s o f t h e s e e x p e rim e n ts i s p a r a l l e l to th e f i n d i n g s i n th e s tu d y o f b o r in e tr im e th y la m in e and i t s m eth y l d e r i v a t i v e s . 26 The i n f l u e n c e o f i n c r e a s in g th e m eth yl g ro u p s on th e s t a b i l i t y o f th e b o r in e s e r i e s o f a d d i t i o n compounds i s s i m i l a r t o t h a t o b se rv e d i n th e b o ro n f l u o r i d e s e r i e s . 26 L oc. c i t . SUM MARY 48 T hree a d d i t i o n compounds (1) b oron f l u o r i d e f l u o r i d e tr im e th y la m in e , BF3 • N(CH3 ) 3 , (2) m e th y lb o ro n d i f l u o r i d e tr im e th y la m in e , CH3 BF2 • N(CH3 ) 3 , and (3) d im e th y l boro n tr im e th y la m in e , (CH3 ) 2BF • N(CH3 ) 3 , have been p r e p a r e d . The s t a b i l i t y o f t h i s s e r i e s h a s been s tu d ie d th ro u g h v a p o r p r e s s u r e m easurem ents and h a s been found to d e c re a s e w ith th e i n c r e a s e o f s u b s t i t u t e d m eth y l groups* Boron f l u o r i d e trim e th y la m in e (m ,p . 150° C) i s a s t a b l e compound w hich shows a s s o c i a t i o n i n th e vapor p h a se below 230° C* The e q u a tio n s lo g p » 10.240 - 3 ,6 0 0 /T f o r th e s o l i d and lo g p * 8 .7 3 5 - 2963/T f o r th e l i q u i d w ere d e te rm in e d from i t s v a p o r p r e s s u r e m ea su re m e n ts. Vapor p r e s s u r e s o f m e th y lb o ro n d i f l u o r i d e t r i m e t h y l a ­ m ine (m .p . 35° 0) d e te rm in e d th e e q u a tio n lo g p * 8 .4 6 3 - 2 6 3 1 .6 /T . M easurem ents i n th e v a p o r p h a se showed th e rm a l d i s s o c i a t i o n w hich i s e x p re s s e d by th e e q u a tio n lo g Katm * 14.080 - 5 ,5 0 0 /T . T h is i n d i c a t e d t h a t A F° = 2 5 ,1 5 5 - 6.4 T f o r t h e v a p o r-p h a s e r e a c t i o n CH3BF2 • N(CH3 ) 3 * = i CH3BF2 - (CH3 ) 3N At te m p e r a tu r e s b elo w 100° C t h e vapor p r e s s u r e s o f d im e th y lb o ro n f l u o r i d e tr im e th y la m in e (m .p. 15° C) fo llo w e d th e e q u a tio n lo g p = 9 .6 8 - 2 ,8 0 0 /T . Above t h i s te m p e ra tu re t h e compound showed some d i s p r o p o r t i o n a t i o n a s w e ll as a 49 liig h d e g re e o f d i s s o c i a t i o n . The d i s s o c i a t i o n c o n s t a n t s a r e r e p r e s e n te d by t h e e q u a tio n lo g Ka<tm ® 1 1 .3 7 6 - 4384/T . From t h i s e q u a tio n th e r e l a t i o n s h i p a F° * 20 - .052T C a l . i s d e r i v e d . BIBLIOGRAPHY BIBLIOGRAPHY A. BOOKS B o o th , H* S . and K. S . W ills o n , "B oron T r i f l u o r i d e , " I n o r g a n ic S y n t h e s i s , V o l. 1 . New Y ork: M cG raw -H ill Book Company, 193$. M e llo r , J . W. , C om prehensive T r e a t i s e on I n o r g a n ic and T h e o r e t i c a l C h e m is tr y , V o l. 5. ToncCbn: Longman’ s G reen and Company, 2 4 . P a u l in g , L . , The N a tu re o f th e Chem ical Bond. R e v ise d e d i t i o n ; I t h a c a , New Y ork: C o rn e ll U n i v e r s i ty P r e s s , 194 0 . S to c k , A . , H y d rid e s o f Boron and S i l i c o n . I t h a c a , New Y ork: C o m e l l U n i v e r s i t y P r e s s , 193^1 S tr o n g , J . , P ro c e d u re s i n E x p e rim e n ta l P h y s i c s . 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H . , "The R e a c tio n s o f A lk y lc h lo ro a m in e s W ith G rig n a rd R e a g e n ts ," £ . t o . Chem. S o c . , 5 5 :3 0 0 1 -0 5 , 1933. H a n tz s c h , A. and W. G r a f , " A d d itiv e Compounds o f th e T e r t i a r y A m ines," B e r i c h t e , 3 8 :2 1 5 4 -6 1 , 1905. K o h le r, H . , "A C o n t r ib u t i o n o f th e Knowledge o f t h e S u b s t i ­ t u t e d N itro g e n C h l o r id e s ," B e r ic h te , 1 2 :7 7 0 -7 2 , 1879. K ra u s, C. A. and I . H. Brown, " S tu d ie s R e la ti n g t o Boron I . R e a c tio n s o f Boron F lu o r id e w ith Ammonia and th e A k y la m in e s," J . t o . Chem. S o c . , 5 1 :2 6 9 0 -9 6 , 1929. K ra u se , E. and H. P o la c k , " P r e p a r a t i o n o f P u re Sodium T rip h e n y lb o ro n and th e Compounds o f Boron T rip h e n y l w ith O th e r A l k a l i M e ta ls ," B e r i c h t e , 5 9 :7 7 7 -8 5 , 1929. K ra u s e , E. , "A S e r i e s o f R em arkably S t a b l e S e c o n d a ry V alence Compounds o f B oron T r ip h e n y l; a C o n t r ib u t i o n to th e V alen ce P ro b lem o f B o ro n ," B e r i c h t e , 5 7 :8 1 3 -1 8 , 1924. M e ise n h e im e r, I . , "A bout th e A c tio n o f H y p o ch lo ro u s A cid on T e r t i a r y A m ines," B e r i c h t e , 4 6 :1 1 4 8 -6 1 , 1913. P o h la n d , E. Von and W. H a r lo s , "Vapor P r e s s u r e o f Boron F l u o r i d e ," £ Z . a n o rg . a llg e m . Chem. , 2 0 7 :2 4 2 -4 3 , 1932. S c h l e s i n g e r , H. I . , and A. B. B urg, "H y d rid e s of Boron I . An E f f i c i e n t NeW M ethod o f P r e p a r in g D ib o ra n e ," J . t o . Chem. S o c . , 5 3 :4 3 2 1 -3 2 , 1931. 53 S c h l e s i n g e r , H. I . , N. W. F l o d i n , and A. B. B urg, " H y d rid e s o f Boron X I I . S y m m etrica l D im e th y ld ib o ra n e and t h e M ethyl D e r i v a t i v e s o f B o rin e T rim e th y la m in e ," J . Am. Chem. s o c . , 6 1 :1 0 7 8 -8 3 , 1939. S te v e n s o n , D. P . and 7 . Schom aker, " M o le c u la r S t r u c t u r e s o f D im e th y lc h lo ro a m in e and M ethyl D ic h lo ro a m in e ," J . Am. Chem. S o c . , 6 8 :1 9 1 3 -1 6 , 194 0. S to c k , A. and F . Z e i d l e r , " I n f o r m a tio n on t h e M ethyl Borons and th e E th y l B o ro n s," B e r i c h t e , 5 4 :5 3 1 -4 1 , 1981. W iberg, V. E. and W. S u t t e r l i n , "The V apor P r e s s u r e s and M e ltin g P o i n t s o f D im e th y l- and T rim e th y la m in e ," Z . g l& tro ch e m . , 4 1 :1 5 1 -5 3 , 1 93 5 . W iberg, V. E. and U. Henbaum, "The R e a c tio n o f p h o sp h in e w ith B oron F l u o r i d e ," Z. Anorg. A llgem . Chem., 8 8 5 :8 7 0 -7 8 , 1935. C. UNFUBLISHED MATERIAL T a y lo r , J . C . , "P h o sp h o ru s C h l o r n i t r i d e s and T h e ir R e a c tio n s w ith T rim e th y la m in e ." 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Creator Green, A.A. (author) 
Core Title Addition compounds of trimethylamine with boron fluoride and its methyl derivatives. 
Degree Master of Science 
Publisher University of Southern California (original), University of Southern California. Libraries (digital) 
Tag Chemistry, organic,OAI-PMH Harvest 
Language English
Contributor Digitized by ProQuest (provenance) 
Advisor Burg, Anton B. (committee chair), [illegible] (committee member), Copeland, C.S. (committee member) 
Permanent Link (DOI) https://doi.org/10.25549/usctheses-c17-789592 
Unique identifier UC11348169 
Identifier EP41543.pdf (filename),usctheses-c17-789592 (legacy record id) 
Legacy Identifier EP41543.pdf 
Dmrecord 789592 
Document Type Thesis 
Rights Green, A. A. 
Type texts
Source University of Southern California (contributing entity), University of Southern California Dissertations and Theses (collection) 
Access Conditions The author retains rights to his/her dissertation, thesis or other graduate work according to U.S. copyright law. Electronic access is being provided by the USC Libraries in agreement with the au... 
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