S E C T I ON 4
Fluorine Compounds
w . KWASNIK
Genera l Remark s
In view of t h e s p e c i a l p o s i t i o n o c c u p i e d by f l u o r i n e a m o n g t h e h a l o g e n s in t h e p e r i o d i c s y s t e m , t h e p r e p a r a t i o n of i t s c o m p o u n d s i s s o d i f f e r e n t f r o m t h a t of t h e o t h e r h a l o g e n c o m p o u n d s t h a t it i s fitting to c o n s i d e r t h e f l u o r i n e c o m p o u n d s in a s e p a r a t e s e c t i o n . I n o r g a n i c f l u o r i n e c o m p o u n d s a r e p r e p a r e d chiefly by t h e follow- ing m e t h o d s :
1. T r e a t m e n t of t h e o x i d e s , h y d r o x i d e s o r c a r b o n a t e s w i t h a q u e o u s h y d r o g e n f l u o r i d e . M o s t b i n a r y f l u o r i d e s t h a t do not u n d e r - g o h y d r o l y s i s m a y be p r e p a r e d in t h i s w a y ( e . g . , a l k a l i f l u o r i d e s , a l k a l i h y d r o g e n f l u o r i d e s , a l k a l i n e e a r t h f l u o r i d e s , A 1 F3, S b F3, Z n F2, P b F2, H g F , A g F ) .
2. T r e a t m e n t of t h e a p p r o p r i a t e a n h y d r o u s c h l o r i d e s with a n h y - d r o u s h y d r o g e n f l u o r i d e ( e . g . , T i F4, Z r F4, N b FB, T a FB, V F4, S n F4, S b Fs, P O F3, S O F2) . T h i s r e a c t i o n i s c a p a b l e of m u c h w i d e r a p p l i c a - t i o n t h a n t h a t g i v e n in t h e l i t e r a t u r e until now. T h i s m e t h o d h a s b e c o m e i n c r e a s i n g l y i m p o r t a n t s i n c e a n h y d r o u s h y d r o g e n f l u o r i d e b e c a m e c o m m e r c i a l l y a v a i l a b l e .
3 . T r e a t m e n t of e l e m e n t s , o x i d e s o r h a l i d e s w i t h e l e m e n t a l f l u o r i n e . T h i s m e t h o d i s u s e d chiefly for t h e p r e p a r a t i o n of t h o s e b i n a r y f l u o r i d e s in w h i c h e l e m e n t s r e a c h t h e i r h i g h e s t v a l e n c e ( e . g . , I F7, R e F6, U F6, S F6, B i F5, C F4, C o F3, A g F2) . T h e h a l o g e n f l u o r i d e s m a y often b e u s e d i n s t e a d of e l e m e n t a l f l u o r i n e . H o w e v e r , t h e s e f l u o r i d e s c a n in t u r n b e p r e p a r e d only f r o m e l e m e n t a l f l u o r i n e . T h e r e i s a d r a w b a c k in t h e u s e of h a l o g e n f l u o r i d e s i n s t e a d of e l e m e n t a l f l u o r i n e in that it i s often difficult t o s e p a r a t e t h e f r e e h a l o g e n e v o l v e d in t h e r e a c t i o n f r o m t h e r e a c t i o n p r o d u c t . On t h e o t h e r hand, m o s t h a l o g e n f l u o r i d e s a r e e a s i e r to h a n d l e in t h e l a b o r a t o r y ( s t o r a g e , m e a s u r i n g out) t h a n e l e m e n t a l f l u o r i n e . Halogen f l u o r i d e s a r e definitely to b e p r e f e r r e d w h e n , in addition to f l u o r i n e , one i n t e n d s to add a s e c o n d h a l o g e n to an u n s a t u r a t e d s u b s t a n c e ( e . g . , COC1F, C O B r F , C O I F , S Q , B r F ) . In g e n e r a l , h a l o g e n f l u o r i d e s m a y b e e i t h e r m o r e a c t i v e (C1F3) o r l e s s a c t i v e ( I F5) f l u o r i n a t i n g a g e n t s t h a n t h e e l e m e n t itself.
1 5 0
4. F L U O R I N E C O M P O U N D S 1 5 1
4. S p e c i a l r e a c t i o n s . T h e s e a r e s o different f r o m e a c h o t h e r a n d o c c u r s o s p o r a d i c a l l y t h a t t h e y cannot b e c l a s s i f i e d in any s y s t e m a t i c w a y . F o r e x a m p l e , N F3 m a y be p r e p a r e d by e l e c t r o l y s i s of m o l t e n a m m o n i u m h y d r o g e n f l u o r i d e ; O F2 i s p r o d u c e d by a t t a c k of F2 on 2% s o d i u m h y d r o x i d e s o l u t i o n ; and C^Fg i s f o r m e d f r o m
F2 + Ο 2 in a glow d i s c h a r g e tube cooled with liquid n i t r o g e n . S o m e f l u o r i n e c o m p o u n d s m a y b e p r e p a r e d by any one of s e v e r a l m e t h o d s ( e . g . , N O F f r o m NO + F2 o r f r o m N O B F4 + N a F ) , s o t h a t t h e c h o i c e of a m e t h o d of p r e p a r a t i o n m a y b e b a s e d on t h e a v a i l a b i l i t y of s t a r t i n g m a t e r i a l s o r a p p a r a t u s .
T h e p r e p a r a t i o n of o r g a n i c f l u o r i n e c o m p o u n d s a l s o r e q u i r e s m e t h o d s different f r o m t h o s e u s e d for t h e o t h e r o r g a n i c h a l o g e n c o m p o u n d s . B e c a u s e of t h e high h e a t of f o r m a t i o n of C F4 (231 k c a l . ) and H F (64 k c a l . ) , t h e t r e a t m e n t of o r g a n i c s u b s t a n c e s w i t h f l u o r i n e r e s u l t s m a i n l y in t h e f o r m a t i o n of C F4 and H F , in addition to c h a r r e d and t a r r y s u b s t a n c e s , w h i l e no a p p r e c i a b l e q u a n t i t i e s of n o r m a l s u b s t i t u t i o n p r o d u c t s a r e o b t a i n e d . T h i s m e t h o d , w h i c h i s u s e d in i n d u s t r y for t h e p r o d u c t i o n of p e r f l u o r o c a r b o n s , i s not s u i t a b l e for w o r k on a l a b o r a t o r y s c a l e . O r g a n i c f l u o r i n e c o m p o u n d s a r e p r e p a r e d in r e a s o n a b l e y i e l d s chiefly by t h e following p r o c e d u r e s .
1. Addition of H F to o l e f i n s ( e . g . , e t h y l f l u o r i d e ) .
2. T r e a t m e n t of a c h l o r i n e c o m p o u n d w i t h a n h y d r o u s h y d r o g e n f l u o r i d e ( e . g . , b e n z o t r i f l u o r i d e ) . T h i s m e t h o d i s l i m i t e d t o c o m p o u n d s with t h r e e f l u o r i n e a t o m s on t h e c a r b o n a t o m . Acid f l u o r i d e s c a n a l s o be p r o d u c e d f r o m a c i d c h l o r i d e s , u s i n g a n h y d r o u s h y d r o g e n f l u o r i d e .
3 . T r e a t m e n t of c h l o r i n e c o m p o u n d s with antimony(III) f l u o r i d e ( F . S w a r t s ) . T h i s m e t h o d i s e s p e c i a l l y s u i t e d for c o m p o u n d s with l e s s t h a n t h r e e F a t o m s on t h e c a r b o n a t o m ( e . g . , 2 , 2 - d i f l u o r o p r o p a n e ) .
4 . T r e a t m e n t of c h l o r i n e c o m p o u n d s w i t h a n h y d r o u s h y d r o g e n f l u o r i d e in t h e p r e s e n c e of a n t i m o n y c a t a l y s t s . T h i s m e t h o d i s i n t e r m e d i a t e b e t w e e n t h e two m e n t i o n e d a b o v e and i s v e r y b r o a d l y a p p l i c a b l e ( e . g . , d i c h l o r o d i f l u o r o m e t h a n e ) .
5. T r e a t m e n t of a h a l o g e n c o m p o u n d w i t h a m e t a l f l u o r i d e , s u c h a s A g F , H g F , H g F2 ( e . g . , f l u o r o f o r m ) .
6. D i a z o t i z a t i o n w i t h n i t r i t e in h y d r o f l u o r i c a c i d m e d i u m . T h i s m e t h o d i s u s e d for t h e p r e p a r a t i o n of a r o m a t i c f l u o r i n e c o m p o u n d s ( e . g . , f l u o r o b e n z e n e ) .
7. T h e r m a l d e c o m p o s i t i o n of d i a z o n i u m b o r o f l u o r i d e s (G. Balz and G. S c h i e m a n n ) . T h i s p r o c e d u r e i s a l s o a p p l i c a b l e to a r o m a t i c f l u o r i n e c o m p o u n d s , p a r t i c u l a r l y on t h e l a b o r a t o r y s c a l e (e.g., p - f l u o r o t o l u e n e ) .
T h e l a b o r a t o r y e q u i p m e n t of t h e f l u o r i n e c h e m i s t i s u n u s u a l in t h a t o r d i n a r y c h e m i c a l g l a s s w a r e cannot be u s e d in m o s t c a s e s . A p p a r a t u s m a d e of n i c k e l , i r o n , c o p p e r , l e a d , s i l v e r , p l a t i n u m , f l u o r s p a r o r s i n t e r e d a l u m i n a i s u s e d i n s t e a d . W h e r e t r a n s p a r e n c y i s i n d i s p e n s a b l e , q u a r t z e q u i p m e n t i s u t i l i z e d .
W . K W A S N 1 K
T o b e a b l e t o p r o d u c e f l u o r i d e s a t any t i m e and avoid lengthy p r e p a r a t i o n s , it i s a d v i s a b l e to h a v e on hand t h e following c o m m o n l y u s e d p i e c e s of e q u i p m e n t :
s e v e r a l n i c k e l , f l u o r s p a r o r s i n t e r e d a l u m i n a b o a t s ; a n i c k e l o r Monel r e a c t i o n t u b e (30 c m . long, 2,5 c m ,
d i a m e t e r ) w i t h g r o u n d j o i n t s a t both e n d s ; a n i r o n r e a c t i o n t u b e ;
s e v e r a l c y l i n d r i c a l i r o n v e s s e l s ;
t h r e e to five q u a r t z t r a p s with a t t a c h e d g r o u n d joint s e a l s ; t h r e e P y r e x g l a s s t r a p s w i t h a t t a c h e d g r o u n d joint s e a l s ; s e v e r a l q u a r t z d r y i n g t u b e s ;
s e v e r a l q u a r t z U t u b e s ; two i r o n c o n d e n s e r s ; a n i r o n t r a p ;
s e v e r a l s t e e l c y l i n d e r s , 0 . 5 - t o 5 - l i t e r c a p a c i t y (for s t o r a g e of g a s e o u s f l u o r i d e s ) .
F o r w o r k with l o w - b o i l i n g f l u o r i d e s it i s u s e f u l to h a v e on hand a p a r t - g l a s s , p a r t - q u a r t z v a c u u m s y s t e m p r o v i d e d with a s p i r a l q u a r t z m a n o m e t e r .
C o n n e c t i o n of t h e v a r i o u s p a r t s of a q u a r t z a p p a r a t u s i s b e s t a c c o m p l i s h e d with n o r m a l , u n g r e a s e d g r o u n d j o i n t s , w h i c h a r e m a d e a i r t i g h t by an e x t e r i o r l a y e r of c e m e n t (picein). M e t a l - t o - q u a r t z g r o u n d joint c o n n e c t i o n s m a y a l s o be m a d e a i r t i g h t with p i c e i n , but t o e n s u r e b e t t e r a d h e s i o n of t h e c e m e n t t h e m e t a l s u r f a c e
should be v e r y hot. S t o p c o c k s should b e g r e a s e d only l i g h t l y , p r e f e r a b l y w i t h v i s c o u s f l u o r o c a r b o n s ; in difficult c a s e s t h e y m a y b e r e p l a c e d by c o p p e r d i a p h r a g m v a l v e s . M e t a l p i e c e s m a y b e c o n n e c t e d w i t h one a n o t h e r by m e a n s of t h r e a d e d j o i n t s , f l a n g e s o r g r o u n d j o i n t s . L e a d r i n g s with a s b e s t o s i n s e r t s o r soft i r o n o r c o p p e r w a s h e r s m a y a l l b e u s e d a s g a s k e t s w h e r e flange c o n n e c - t i o n s a r e u s e d . N e e d l e v a l v e s with a s t e e l s t e m , b r a s s s e a t a n d l e a d - a s b e s t o s p a c k i n g h a v e p r o v e n s u i t a b l e for u s e with s t e e l c y l i n d e r s and a u t o c l a v e s .
F l u o r s p a r a p p a r a t u s i s m a d e by t h e following m e t h o d : f r e s h l y p r e c i p i t a t e d C a F2 i s m i x e d with w a t e r to a t h i c k p a s t e . T o o b t a i n p l a s t i c i t y , h y d r o c h l o r i c a c i d i s a d d e d u n t i l t h e a c i d i t y of t h e p a s t e i s about 0.02N. It i s t h e n p o u r e d into p l a s t e r m o l d s . T w o - p a r t m o l d s a r e u s e d for b o a t s , t h r e e - p a r t m o l d s for t u b i n g . A f t e r r e m o v a l f r o m t h e m o l d s , t h e p i e c e s a r e s c r a p e d s m o o t h with a s p a t u l a if n e c e s s a r y a n d t h e n a i r d r i e d for a few d a y s . Since t h e s t r e n g t h i s low, a l l s u b s e q u e n t handling m u s t b e v e r y c a r e f u l . If t h e f l u o r - s p a r a p p a r a t u s c a n n o t b e f i r e d t o g e t h e r w i t h o r d i n a r y c e r a m i c w a r e in a t u n n e l kiln a t a b o u t 1250°C, then it should be f i r e d in a G l o b a r f u r n a c e . T h e p i e c e s , e m b e d d e d in Z r C ^ , a r e p l a c e d in a p o r c e l a i n t u b e and the oven i s slowly h e a t e d to 1250°C. D u r i n g t h e f i r i n g , d r y n i t r o g e n i s p a s s e d t h r o u g h t h e p r o c e l a i n t u b e t o r e m o v e w a t e r v a p o r a n d c a r b o n d i o x i d e . F l u o r s p a r e q u i p m e n t p r e p a r e d in
4 . F L U O R I N E C O M P O U N D S 1 5 3
t h i s w a y i s n o n p o r o u s and s m o o t h . It c a n b e w o r k e d on a w e t e m e r y w h e e l . In g e n e r a l , h o w e v e r , it i s b r i t t l e a n d m u s t b e h a n d l e d with g r e a t c a r e . A s a r e s u l t of d r y i n g and f i r i n g t h e p i e c e s s h r i n k by a b o u t 1/3 and t h i s s h o u l d b e t a k e n into a c c o u n t in t h e d e s i g n . B o a t s c a n a l w a y s b e m a d e without difficulty, w h e r e a s t u b e s (say, of 1 5 - c m . length, 1 . 5 - c m , I . D . , 2 - m m . w a l l t h i c k n e s s ) s o m e - t i m e s u n d e r g o d e f o r m a t i o n if t h e f u r n a c e t e m p e r a t u r e i s s o m e - w h a t too high. [O. Ruff and A. R i e b e t h , Z . a n o r g . a l l g . C h e m . 1 7 3 , 373 (1928); O. Ruff and J . F i s c h e r , Z . a n o r g . a l l g . C h e m . 179, 166 (1929); O. Ruff a n d W. K w a s n i k , Z . a n o r g . a l l g . C h e m . 209, 113 (1932).]
When q u a r t z o r g l a s s e q u i p m e n t i s u s e d , one m u s t a l w a y s b e a r in m i n d t h a t t h e r e a c t i o n p r o d u c t s m a y b e c o n t a m i n a t e d with f l u r o - s i l i c a t e s o r I ^ S i F6. U n d e r t h e s e c o n d i t i o n s , g a s e o u s f l u o r i d e s often c o n t a i n S i F4.
G a s e o u s f l u o r i d e s c o n d e n s e d by m e a n s of D r y Ice o r liquid o x y g e n * d i s s o l v e a i r in a p p r e c i a b l e q u a n t i t i e s , a s do a l m o s t a l l l o w - b o i l i n g s u b s t a n c e s . C a r e m u s t t h e r e f o r e b e t a k e n to r e m o v e t h e d i s s o l v e d a i r by r e p e a t e d d i s t i l l a t i o n of t h e p r o d u c t u n d e r v a c u u m . T h e a i r d i s s o l v e d in t h e s e l o w - b o i l i n g c o m p o u n d s m a y l o w e r t h e i r m e l t i n g point by a s m u c h a s 20°.
G e n e r a l e q u i p m e n t of a f l u o r i n e l a b o r a t o r y should i n c l u d e l a r g e , h i g h - s u c t i o n h o o d s , r u b b e r g l o v e s , p r o t e c t i v e g o g g l e s , a g a s m a s k , a n d a n H2- 02 t o r c h f o r w o r k w i t h q u a r t z a p p a r a t u s . D r y I c e and liquid oxygen a r e p r a c t i c a l l y i n d i s p e n s a b l e for t h e p r e p a r a t i o n of l o w - b o i l i n g f l u o r i d e s . One should h a v e a b o t t l e of 10% a m m o n i u m c a r b o n a t e s o l u t i o n r e a d y in c a s e of a c c i d e n t . Skin i n j u r i e s c a u s e d by H F o r f l u o r i d e s should b e b a t h e d i m m e d i a t e l y w i t h t h i s s o l u - t i o n o r t r e a t e d with c o m p r e s s e s c o n t a i n i n g t h i s s o l u t i o n . T h i s t r e a t m e n t should be a d m i n i s t e r e d e v e n b e f o r e m e d i c a l a s s i s t a n c e a n d should b e continued for half a n h o u r .
Chlorin e Monofluorid e
C1FCI, + F2 = 2 C1F
70.92 38 108.92
A v e r t i c a l n i c k e l o r Monel c y l i n d e r e n c a s e d in a f u r n a c e (Fig. 107) s e r v e s a s r e a c t i o n v e s s e l . A m e t e r e d s t r e a m of c h l o r i n e g a s i s i n t r o d u c e d t h r o u g h a n o z z l e - t y p e t u b e . F l u o r i n e g a s i s fed
*Caution: liquid oxygen i s d a n g e r o u s in c o n t a c t w i t h o x i d i z a b l e s u b s t a n c e s .
t h r o u g h a s i d e t u b e . T h e l o w e r p a r t of t h e c y l i n d e r s e r v e s a s a s e p a r a t o r for t h e solid f l u o r i d e s ( N i F3, F e F3) f o r m e d by c o r r o s i o n of t h e c o n t a i n e r w a l l s , so t h a t plugging i s a v o i d e d . T h e p r o d u c t g a s e s a r e p a s s e d t h r o u g h a h o r i z o n t a l , t a p w a t e r - c o o l e d i r o n c o n - d e n s e r and t h r o u g h an i r o n t r a p i m m e r s e d in D r y Ice (without a c e - tone!), w h e r e c h l o r i n e and C 1 F3 a r e c o n d e n s e d . T h e g a s e s a r e t h e n d i s c h a r g e d into a s e c o n d i r o n t r a p , i m m e r s e d in liquid n i t r o g e n . T h e r e t h e C1F i s liquefied, while t h e e x c e s s f l u o r i n e e s c a p e s into t h e hood.
~0l thermocouple
F i g . 107. P r e p a r a t i o n of c h l o r i n e m o n o f l u o r i d e .
J to spiral quartz m a n o m e t e r
m e t a l vessel with l i q . N 2
F i g . 108. D i s t i l l a t i o n of c h l o r i n e m o n o f l u o r i d e .
T h e oven i s h e a t e d t o 400°C and F2 i s p e r m i t t e d t o flow t h r o u g h t h e s y s t e m u n t i l it i s d e t e c t e d at t h e outlet of t h e a p p a r a t u s t h r o u g h
4 . F L U O R I N E C O M P O U N D S 1 5 5
ignition of a n o i l - s o a k e d r a g . T h e c h l o r i n e s t r e a m i s t h e n t u r n e d on. F o r a f l u o r i n e c e l l c u r r e n t of 70 a m p , , t h e r a t e should b e 9 l i t e r s of C ^ / h r .
T h e c h l o r i n e m o n o f l u o r i d e , s t i l l c o n t a i n i n g c o n s i d e r a b l e a m o u n t s of C 1 F3 a n d Clg in s o l u t i o n , i s c o l l e c t e d in t h e t r a p c o o l e d with liquid n i t r o g e n .
A f t e r t h e f l u o r i n a t i o n i s e n d e d , t h e C1F i s d i s t i l l e d into a s t e e l c y l i n d e r . T h e a r r a n g e m e n t of t h e d i s t i l l a t i o n a p p a r a t u s i s shown in F i g . 108. T h e D e w a r f l a s k in w h i c h t h e feed v e s s e l i s p l a c e d i s l o w e r e d a w a y f r o m t h e feed v e s s e l a s f a r a s n e c e s s a r y to s t a r t t h e p r o d u c t boiling. T h e s m a l l f o r e r u n , c o n s i s t i n g chiefly of F2, i s r e m o v e d by a w a t e r a s p i r a t o r . T h e n t h e v a l v e of t h e s t e e l c y l i n d e r i s opened and C1F i s c o n d e n s e d a t a r a t e s u c h t h a t t h e p r e s s u r e in t h e s y s t e m i s m a i n t a i n e d a t about 1 a t m . T h e d i s t i l l a - tion i s e n d e d a s soon a s s i z a b l e q u a n t i t i e s of c o n d e n s a t e (Clg , CIF3) a c c u m u l a t e in t h e q u a r t z t r a p . T h e r e s i d u e i s a l s o d r a w n off w i t h t h e w a t e r a s p i r a t o r . Y i e l d 90% m a x i m u m , b a s e d on c h l o r i n e .
PROPERTIES:
F o r m u l a w e i g h t 5 4 . 4 6 . C o l o r l e s s g a s , p a l e y e l l o w liquid, w h i t e s o l i d . V e r y r e a c t i v e , d e s t r o y s g l a s s i m m e d i a t e l y and q u a r t z in t h e p r e s e n c e of t r a c e s of m o i s t u r e . R e a c t s v i g o r o u s l y w i t h o r g a n i c
s u b s t a n c e s , u s u a l l y w i t h ignition. V e r y v i g o r o u s r e a c t i o n w i t h w a t e r . A t t a c k s t h e b r o n c h i v e r y s t r o n g l y .
M . p . - 1 5 5 . 6 ° C , b . p . - 1 0 0 ° C , tc r - 1 4 ° C , d . (liq.) ( - 1 0 8 ° C ) 1 . 6 7 .
REFERENCES:
O. Ruff, E. A s c h e r a n d F . L a a s . Z. a n o r g . a l l g . C h e m . 176, 256 (1928).
W. K w a s n i k ( u n p u b l i s h e d ) .
Chlorin e Trifluorid e
CIF3
Cl2 + 3 F2 = 2 CIF3 70.92 114.0 184.92
C h l o r i n e t r i f l u o r i d e i s p r e p a r e d u s i n g t h e s a m e a p p a r a t u s and p r o c e d u r e a s for C1F (Fig. 107, with t h e following e x c e p t i o n s , 1) T h e s e c o n d l i q u i d - n i t r o g e n - c o o l e d i r o n t r a p m a y b e o m i t t e d (or left in t h e s y s t e m without c o o l a n t ) . 2) T h e f u r n a c e i s h e a t e d to 280°C i n s t e a d of 400°C. 3) T h e c h l o r i n e flow r a t e i s l o w e r . F o r a 7 0 - a m p . c u r r e n t in t h e f l u o r i n e c e l l , a c h l o r i n e flow r a t e of
6.2 l i t e r s / h r . i s a d v i s a b l e . If t h e r a t i o of f l u o r i n e to c h l o r i n e i s too low, C1F will b e t h e m a i n p r o d u c t and t h e C 1 F3 f o r m e d will b e s t r o n g l y c o n t a m i n a t e d w i t h Clg.
A f t e r c o m p l e t i o n of t h e f l u o r i n a t i o n , t h e liquid C 1 F3 i s p o u r e d f r o m t h e D r y I c e - c o o l e d t r a p into a s t e e l c y l i n d e r a g a i n c o o l e d w i t h D r y Ice (without acetone!) ( u s e a good hood, p r o t e c t i v e g o g g l e s and r u b b e r gloves) and a t h r e a d e d shut-off v a l v e i s i m m e d i a t e l y s c r e w e d on. When t h e s t e e l c y l i n d e r h a s w a r m e d u p to r o o m t e m - p e r a t u r e , an i r o n m a n o m e t e r and a n a d d i t i o n a l v a l v e a r e s c r e w e d on a n d t h e c o n t e n t s of t h e c y l i n d e r a r e a l l o w e d t o e s c a p e u n t i l a g a u g e p r e s s u r e of 1.2 a t m . i s r e a c h e d . T h e C1F, C]q a n d F2 a r e t h e r e b y r e m o v e d .
T h e y i e l d i s 60-80%, d e p e n d i n g on the ClgiFg r a t i o ; t h e r e m a i n d e r i s a l w a y s C1F.
V a l v e s u s e d for h a n d l i n g C 1 F3 m u s t b e f r e e of a l l g r e a s e . L e a d a s b e s t o s i s s u i t a b l e a s v a l v e p a c k i n g . W a s h e r s m u s t be of c o p p e r . If liquid C 1 F3 i s i n a d v e r t e n t l y s p i l l e d , Dry I c e s h o u l d b e s p r i n k l e d o v e r it; it a b s o r b s t h e C1F3 and d i l u t e s it s o a s t o r e n d e r it r e l a t i v e l y h a r m l e s s .
PROPERTIES:
F o r m u l a weight 9 2 . 4 6 . C o l o r l e s s g a s , suffocating o d o r ; s t r o n g l y a t t a c k s t h e b r o n c h i . E x t r e m e l y r e a c t i v e , p a r t i c u l a r l y a s a liquid.
I m m e d i a t e l y d e s t r o y s g l a s s and, in p r e s e n c e of t r a c e s of m o i s t u r e , q u a r t z . O r g a n i c s u b s t a n c e s u s u a l l y r e a c t w i t h ignition. T h e r e a c t i o n with w a t e r i s e x p l o s i v e .
M . p . - 8 3 ° C , b . p . 11.3°C, d. (liq.) ( - 7 8 ° C ) 2.026.
REFERENCES:
O. Ruff and H. K r u g . Z . a n o r g . a l l g . C h e m . 190, 270 (1930).
W. K w a s n i k . N a t u r f o r s c h u n g und M e d i z i n in D e u t s c h l a n d 1939—1946 ( F I A T - R e v i e w ) 2 3 , 168.
Bromin e Trifluoride
BrF32 Br + 3 F2 = 2 BrF3
159.82 114 273,82
B r o m i n e t r i f l u o r i d e i s p r e p a r e d by f l u o r i n a t i o n of b r o m i n e at +80°C. At t h i s t e m p e r a t u r e a p p r e c i a b l e q u a n t i t i e s of B r F5 a r e f o r m e d , w h i c h t h e n r e a c t w i t h t h e e x c e s s b r o m i n e a c c o r d i n g t o t h e e q u a t i o n
4 . F L U O R I N E C O M P O U N D S 1 5 7
3 BrF5 + Br2 = 5 BrF3
t h e r e b y affording r a p i d a n d q u a n t i t a t i v e c o n v e r s i o n of t h e b r o m i n e . An i n c l i n e d i r o n c o n d e n s e r (Fig. 109) s e r v e s a s t h e r e a c t i o n c h a m b e r . An i r o n t u b e , to w h i c h a d r o p p i n g funnel i s a t t a c h e d , o p e n s into t h e c o n d e n s e r . T h e l o w e r end of t h e c o n d e n s e r i s joined to a w y e (Y) a d a p t e r , p r e f e r a b l y m a d e of M o n e l . T h e a d a p t e r s u p p o r t s a n i r o n r e f l u x c o n d e n s e r at t h e t o p and i t s l o w e r end i s p r o v i d e d w i t h a g r o u n d joint, t o w h i c h t h e r e c e i v e r ( q u a r t z ) i s c o n n e c t e d . F l u o r i n e i s p a s s e d t h r o u g h t h e a p p a r a t u s ; w a t e r a t +80°C i s fed t o t h e i n c l i n e d c o n d e n s e r a n d cooling b r i n e a t — 18°C to t h e r e f l u x c o n d e n s e r . B r o m i n e i s t h e n a d d e d d r o p w i s e f r o m t h e d r o p p i n g funnel a t s u c h a r a t e t h a t a l m o s t c o l o r l e s s B r F3 i s c o l l e c t e d in t h e r e c e i v i n g f l a s k . T h e r e f l u x c o n d e n s e r p r e v e n t s B r F3 o r B r F5 f r o m e s c a p i n g with t h e f l u o r i n e s t r e a m .
At t h e e n d of t h e f l u o r i n a t i o n t h e r e c e i v e r i s h e a t e d for a s h o r t t i m e t o 100°C in o r d e r t o r e m o v e any B r F5 w h i c h m i g h t b e d i s s o l v e d . After c o o l i n g , the B r F3 i s p o u r e d into an i r o n v e s s e l . T h e yield i s q u a n t i t a t i v e , b a s e d on b r o m i n e , and 90%, b a s e d on f l u o r i n e . T h e p u r i t y i s 98% (the r e m a i n d e r b e i n g B r F5) .
F i g . 109. P r e p a r a t i o n of b r o m i n e t r i f l u o r i d e .
PROPERTIES:
F o r m u l a weight 1 3 6 . 9 1 . C o l o r l e s s liquid. V e r y r e a c t i v e ; f u m e s in a i r and s t r o n g l y a t t a c k s t h e s k i n .
M . p . +8.8°C, b . p . + 1 2 7 ° C ; d . (liq.) 2 . 8 4 . C r y s t a l f o r m : long p r i s m s .
REFERENCE:
W. K w a s n i k , N a t u r f o r s c h u n g und M e d i z i n in D e u t s c h l a n d 1939-1946 ( F I A T - R e v i e w ) 2 3 , 168.
Bromin e Pentafluorid e
BrF52Br + 5 F2 = 2BrF5
159,82 190 349,82
An i r o n r e a c t i o n v e s s e l i s p l a c e d in a c r u c i b l e f u r n a c e h e l d a t 200°C (Fig. 110). In addition to t h e inlet tube for F2 and t h e o u t l e t tube for B r F5, the r e a c t i o n v e s s e l i s p r o v i d e d w i t h a t h e r m o m e t e r w e l l and a c e n t r a l wide Τ t u b e a d a p t e r , w h i c h h o l d s a d r o p p i n g funnel and p e r m i t s t h e n i t r o g e n to flow in f r o m t h e s i d e . (The n i t r o g e n flow s e r v e s m e r e l y a s a p u r g e , to k e e p t h e f l u o r i n e p e n e t r a t i n g t h e d r o p p i n g funnel.) T h e g a s e o u s r e a c t i o n p r o d u c t s a r e c o n d e n s e d in an i r o n c o n d e n s e r . T h e liquefied B r F5 c o l l e c t s in an i r o n t r a p , which i s cooled with an i c e - s a l t m i x t u r e .
A s soon a s t h e a p p a r a t u s i s filled w i t h f l u o r i n e , d r o p w i s e input of B r2 into t h e r e a c t i o n v e s s e l i s s t a r t e d . About one d r o p p e r s e c o n d of b r o m i n e i s i n t r o d u c e d a t a f l u o r i n e c e l l c u r r e n t of 150 a m p . C a r e m u s t be t a k e n t o m a i n t a i n a s t e a d y e x c e s s of F3.
T h e c r u d e p r o d u c t c o n s i s t s of 95% B r F5 a n d 5% B r F3. A f t e r t h e f l u o r i n a t i o n i s t e r m i n a t e d , t h e p r o d u c t i s d i s t i l l e d f r o m a n i r o n a p p a r a t u s in a s t r e a m of f l u o r i n e . C o n d e n s e r a n d r e c e i v e r a r e cooled to about —18°C with an i c e - s a l t m i x t u r e . T h e y i e l d i s 87%, b a s e d on b r o m i n e . B r o m i n e p e n t a f l u o r i d e i s s t o r e d in i r o n o r , p r e f e r a b l y , in Monel v e s s e l s .
PROPERTIES:
to vent
F i g . 110. P r e p a r a t i o n of b r o m i n e p e n t a f l u o r i d e .
F o r m u l a weight 1 7 4 . 9 1 . C o l o r l e s s liquid; f u m e s s t r o n g l y in a i r . C o m p l e t e l y s t a b l e up t o 4 6 0 ° C
4 . F L U O R I N E C O M P O U N D S 1 5 9
M . p . - 6 1 . 3 ° C , b . p . 440.5°C; d. (liq.) (0°C) 2 . 5 7 .
V e r y r e a c t i v e ; r e a c t s with n e a r l y a l l e l e m e n t s with ignition.
V i g o r o u s , n e a r l y e x p l o s i v e r e a c t i o n w i t h w a t e r . At r o o m t e m p e r a - t u r e , d r y g l a s s i s a t t a c k e d s l o w l y , q u a r t z g l a s s p r a c t i c a l l y not a t a l l . M e r c u r y b e c o m e s c o a t e d w i t h a b r o w n f i l m .
REFERENCES:
O. Ruff a n d W. M e n z e l , Z. a n o r g . a l l g . C h e m . 202, 49 (1931).
W. K w a s n i k ( u n p u b l i s h e d ) .
Iodin e Pentafluorid e I F5
I2 + 5 F2 = 2 I F5 253.84 190 443.84
An i r o n d r u m ( s e e F i g . I l l ) p r o v i d e d with a c o o l i n g j a c k e t s e r v e s a s r e a c t i o n v e s s e l . It c o n n e c t s t o a n i n c l i n e d i r o n c o n d e n s e r , f o l - lowed by two q u a r t z t r a p s .
to hood
F i g , 1 1 1 . P r e p a r a t i o n of iodine p e n t a f l u o r i d e .
T h e r e a c t i o n v e s s e l i s filled w i t h i o d i n e , and F3 ( p r e f e r a b l y H F - f r e e ) i s p a s s e d t h r o u g h . T h e c o o l a n t r e m o v e s t h e h e a t of r e a c t i o n a n d p r e v e n t s c o n v e r s i o n of t h e I F5 r e m a i n i n g in t h e v e s s e l to I F7. A s soon a s F3 i s d e t e c t e d a t t h e outlet of t h e s y s t e m , t h e r e a c t i o n should b e t e r m i n a t e d . Cooling of t h e r e a c t i o n v e s s e l i s s t o p p e d , h e a t i s a p p l i e d with a g a s b u r n e r s o t h a t t h e j a c k e t s e r v e s a s a w a t e r b a t h , and I F5 i s d i s t i l l e d off in a s t r e a m of f l u o r i n e . At a f l u o r i n e flow r a t e c o r r e s p o n d i n g to a c e l l c u r r e n t of 80 a m p . , 10 h o u r s a r e n e c e s s a r y for t h e c o n v e r s i o n of 250 g. of iodine (including d i s t i l l a t i o n ) . T h e y i e l d i s 90%, b a s e d on i o d i n e .
Iodine p e n t a f l u o r i d e i s s t o r e d in i r o n f l a s k s . It i s w e l l s u i t e d for t h e f l u o r i n a t i o n of o r g a n i c c o m p o u n d s .
PROPERTIES:
F o r m u l a weight 221.92. C o l o r l e s s liquid; f u m e s in a i r , r e a c t s v e r y v i g o r o u s l y with w a t e r .
M . p . +9.6aC,h.v.+98°C;d. (liq.) (15°C) 3 . 2 3 1 , d . (solid) (0°C) 3.75.
REFERENCES:
F . M o i s s a n . B u l l . Soc. c h i m . F r a n c e [3] 29, 6 (1930).
W. K w a s n i k (unpublished).
Iodin e Heptafluorid e
I F7I2 + 7 F2 = 2 I F7
253.84 266 519.84
An i r o n c y l i n d e r p r o v i d e d w i t h a cooling j a c k e t ( s e e F i g . 112) s e r v e s a s t h e r e a c t i o n v e s s e l . T h e inlet opening i s p r o v i d e d w i t h a s t r a i n e r to hold t h e i o d i n e . T h e o u t l e t o p e n i n g h a s a n a p p r . 3 0 - c m . - long a d a p t e r t o w h i c h a n i r o n c o n d e n s e r i s s c r e w e d on. An i r o n
iron
c, quartz quartz
t o hood
F i g . 112. P r e p a r a t i o n of iodine h e p t a f l u o r i d e .
t u b e l e a d s f r o m t h e l a t t e r t o t h e U - s h a p e d c o n d e n s a t i o n t r a p s . T h e s e a r e m a d e of q u a r t z a n d a r e c l o s e d a t t h e t o p with l o o s e l y fitting q u a r t z g r o u n d j o i n t s . T h e f i r s t U tube i s u s e d t o t r a p t h e I F7, a n d
4 . F L U O R I N E C O M P O U N D S 1 6 1
t h e s e c o n d t o e x c l u d e a t m o s p h e r i c m o i s t u r e . Both t u b e s a r e c o o l e d with liquid n i t r o g e n .
T h e s c r e e n - t y p e s t r a i n e r in t h e r e a c t i o n v e s s e l i s filled with i o d i n e , and f l u o r i n e i s p a s s e d t h r o u g h t h e s y s t e m . T h e F2 m u s t be H F - f r e e . T h i s c a n b e s t b e a c h i e v e d e i t h e r by p a s s i n g it t h r o u g h a D r y I c e - c o o l e d i r o n c o i l o r o v e r f r e s h l y d e h y d r a t e d K F . In t h e f i r s t s t a g e of t h e r e a c t i o n t h e iodine b u r n s in t h e r e a c t i o n v e s s e l t o I F5. W h i l e t h e r e a c t i o n i s in p r o g r e s s , a high w a t e r flow r a t e m u s t b e m a i n t a i n e d in t h e c o o l i n g j a c k e t . A s soon a s f l u o r i n e a p p e a r s a t t h e outlet of t h e s y s t e m , t h e flow of w a t e r t h r o u g h t h e j a c k e t i s shut off, a n d t h e j a c k e t i s h e a t e d f r o m t h e o u t s i d e with a g a s f l a m e s o t h a t it a c t s a s a w a t e r b a t h . T h e a d a p t e r above t h e r e a c t i o n v e s s e l i s now e l e c t r i c a l l y h e a t e d to about 300°C. T h e f l u o r i n e s t r e a m c o n v e r t s t h e I F5 into I F7, w h i c h e s c a p e s t h r o u g h t h e v e r t i c a l c o n d e n s e r into t h e q u a r t z t r a p . T h i s c o n d e n s e r m u s t b e v e r y efficient s o a s t o r e t a i n t h e u n c o n v e r t e d I F5. At t h i s s t a g e of t h e r e a c t i o n , f l u o r i n e m u s t b e p r e s e n t in e x c e s s .
T h e solid p r o d u c t c o l l e c t i n g in t h e a r m s of t h e U t u b e s i s m e l t e d down f r o m t i m e to t i m e o r p u s h e d down with a n i r o n w i r e . T o do t h i s , t h e g r o u n d s t o p p e r s m u s t b e r e m o v e d for a few s e c o n d s .
T h e I F7 i s p u r i f i e d by d i s t i l l a t i o n a t a t m o s p h e r i c p r e s s u r e and 440°C and i s c o l l e c t e d in q u a r t z t r a p s at — 1 9 6 ° C T h e s m a l l r e s i - d u e i s I F 5, w h i c h i s r e t u r n e d to t h e r e a c t o r . T h e I F7 i s t h e n d i s - t i l l e d into a s t e e l c y l i n d e r . When t h e filled c y l i n d e r r e a c h e s r o o m t e m p e r a t u r e , t h e v a l v e i s c a r e f u l l y o p e n e d , and t h e g a s (chiefly S i F ^ i s v e n t e d u n t i l a wad of a l c o h o l - s o a k e d c o t t o n wool i s ignited by t h e e s c a p i n g I F7. T h e y i e l d i s 8 3 % , b a s e d on i o d i n e .
G r o u n d joint c o n n e c t i o n s e a s i l y f r e e z e on c o n t a c t w i t h iodine f l u o r i d e s . T h e y should t h e r e f o r e b e m o v e d a l i t t l e f r o m t i m e to t i m e . T h e j o i n t s should not b e g r e a s e d n o r should t h e y be s e a l e d with p i c e i n ; t h e y should o n l y b e l o o s e l y fitting.
PROPERTIES:
F o r m u l a weight 259.84. C o l o r l e s s . In t h e s o l i d s t a t e it a p p e a r s a s a l o o s e p o w d e r , s o m e t i m e s in t h e f o r m of s m a l l c r y s t a l s .
M . p . 5 . 5 ° C , s u b l . p . 4.5°C; d. (liq.) (6°C) 2 . 8 .
V e r y r e a c t i v e . S i m i l a r in p r o p e r t i e s t o C 1 F3, but c o n s i d e r a b l y l e s s r e a c t i v e . W a t e r d i s s o l v e s g a s e o u s I F7 without d e t o n a t i o n . Sodium h y d r o x i d e s o l u t i o n a b s o r b s it w i t h e v o l u t i o n of a l a r g e a m o u n t of h e a t . Sulfuric a c i d f o a m s when I F7 i s bubbled t h r o u g h it.
A t t a c k s g l a s s and q u a r t z . M u s t y , a c i d i c o d o r .
REFERENCES:
O. Ruff a n d R. K e i m . Z . a n o r g . a l l g . C h e m . 1 9 3 , 176 (1930).
W. K w a s n i k (not y e t p u b l i s h e d ) .
Dioxyge n Difluorid e
02F202 + F2 = 02F2
32Ό 38.0 70.0
T h e g a s e s a r e e l e c t r i c a l l y e x c i t e d in a d i s c h a r g e t u b e c o o l e d w i t h liquid n i t r o g e n , and t h e u n s t a b l e OsFa t h u s f o r m e d i s f r o z e n out.
T h e f l u o r i n e i s s t o r e d in a q u a r t z t r a p c o o l e d with liquid n i t r o g e n a n d i s a s p i r a t e d into t h e a p p a r a t u s t h r o u g h a c o p p e r d i a p h r a g m v a l v e . If a v a i l a b l e , a s t e e l c y l i n d e r w i t h f l u o r i n e m a y b e c o n n e c t e d d i r e c t l y . T h e oxygen i s a l s o t a k e n f r o m a s t e e l c y l i n d e r , w h i c h i s c o n n e c t e d to t h e s y s t e m t h r o u g h a n i r o n o r c o p p e r c a p i l l a r y . T h e r e a c t i o n v e s s e l i s a g l a s s f l a s k ( s e e F i g . 113) i m m e r s e d in a D e w a r f l a s k filled with liquid n i t r o g e n ; p r o v i s i o n s a r e m a d e for g e n e r a t i o n of a b r u s h d i s c h a r g e . C o p p e r w i r e s , t i g h t l y c e m e n t e d w i t h p i c e i n into n a r r o w g l a s s t u b e s p r o j e c t i n g about 10 c m . o u t s i d e t h e a p p a r a t u s , s e r v e a s e l e c t r o d e s . T h e g a s d i s c h a r g e i s g e n e r a t e d by a l a r g e induction c o i l w i t h e i t h e r a W e h n e l t i n t e r r u p t e r o r a n a . c . t r a n s f o r m e r , w h o s e s e c o n d a r y s u p p l i e s 0.05 a m p . a t about 5000 v . A w i d e - a r m q u a r t z U t u b e i s a t t a c h e d t o t h e d i s c h a r g e t u b e . A f t e r c o m p l e t i o n of t h e r e a c t i o n it s e r v e s a s d i s t i l l a t i o n r e c e i v e r and s t o r a g e c o n t a i n e r . A q u a r t z t r a p , c o o l e d t o —196nC
glass
l i q . N2 l i q . N2
F i g . 1 1 3 . P r e p a r a t i o n of dioxygen d i f l u o r i d e .
t o p r e v e n t a c c e s s of a t m o s p h e r i c m o i s t u r e , i s a t t a c h e d t o t h e U t u b e . A m e t a l a s p i r a t o r i s b e s t for t h e g e n e r a t i o n of a v a c u u m . A m a n o m e t e r f o r t h e m e a s u r e m e n t of t h e v a c u u m i s not n e c e s s a r y , s i n c e t h e s h a p e of t h e g a s d i s c h a r g e g i v e s a good i n d i c a t i o n of t h e v a c u u m a t t a i n e d . T h e b e s t o p e r a t i n g p r e s s u r e r a n g e i s 1 0 - 2 0 m m . In t h i s r a n g e t h e d i s c h a r g e t a k e s on a b r u s h l i k e s h a p e .
A s soon a s t h e D e w a r f l a s k s h a v e b e e n p l a c e d u n d e r t h e c o r r e sponding p a r t s of t h e a p p a r a t u s a n d t h e a s p i r a t o r h a s b e e n s t a r t e d ,
4 . F L U O R I N E C O M P O U N D S 1 6 3
t h e s p a r k c o i l i s s w i t c h e d on. T h e d i a p h r a g m v a l v e i s t h e n c a r e - fully opened t o a l l o w f l u o r i n e to p a s s into t h e s y s t e m . Only t h e n i s oxygen allowed to flow in, but at a l o w e r t h a n s t o i c h i o m e t r i c r a t e , f o r o t h e r w i s e solid o z o n e (violet t o blue) m a y f o r m in t h e r e c e i v i n g f l a s k . T h e 03F3 s e p a r a t e s out on t h e w a l l s of t h e d i s - c h a r g e t u b e a s a r e d - b r o w n s o l i d . F r o m t i m e t o t i m e t h e e l e c t r i c d i s c h a r g e i s i n t e r r u p t e d for a few m i n u t e s a n d t h e D e w a r f l a s k i s l o w e r e d . T h i s a l l o w s t h e C ^ F2 to m e l t and flow down into t h e l o w e r t u b u l a r e x t e n s i o n of t h e r e a c t i o n v e s s e l . If solid ozone i s p r e s e n t , t h e m e l t i n g should b e done v e r y c a r e f u l l y s i n c e e x p l o s i o n s m a y s o m e t i m e s o c c u r .
A s soon a s enough C ^ F2 h a s a c c u m u l a t e d in t h e b o t t o m t i p of t h e d i s c h a r g e t u b e , t h e s p a r k c o i l i s d i s c o n n e c t e d and t h e oxygen a n d f l u o r i n e s t r e a m s a r e t u r n e d off. T h e U - s h a p e d s t o r a g e v e s s e l i s c o o l e d w i t h liquid n i t r o g e n and t h e D e w a r f l a s k i s r e m o v e d f r o m b e n e a t h t h e d i s c h a r g e t u b e . T h e O^Fs d i s t i l l s o v e r (at about 15 m m . ) w i t h p a r t i a l d e c o m p o s i t i o n . T o m i n i m i z e d e c o m p o s i t i o n , c a r e should b e t a k e n not t o l e t t h e Q , F3 t e m p e r a t u r e e x c e e d — 60°C for m o r e t h a n a s h o r t t i m e d u r i n g t h e d i s t i l l a t i o n . T h e 03F3 m a y b e r e d i s - t i l l e d s e v e r a l t i m e s in t h i s m a n n e r t o e n s u r e p u r i t y . T h e f i r s t c u t s a r e m a i n l y o z o n e a n d S i F4. Since t h e d i s t i l l a t i o n a l w a y s r e - s u l t s in a c c u m u l a t i o n of Os and F3, t h e a s p i r a t o r should be k e p t c o n t i n u o u s l y in o p e r a t i o n . F o r t h e s a m e r e a s o n , difficulties a r e e n c o u n t e r e d in t h e d i s t i l l a t i o n of OsF3 into a m p o u l e s .
A f t e r d i s t i l l a t i o n i s c o m p l e t e d , t h e U - s h a p e d s t o r a g e v e s s e l i s m e l t - s e a l e d a t t h e b o t t o m s e c t i o n s of t h e a r m s . Dioxygen d i f l u o r i d e c a n b e s t o r e d only in liquid n i t r o g e n . In e m e r g e n c i e s , D r y Ice m a y b e u s e d .
PROPERTIES:
B r o w n g a s , c h e r r y - r e d l i q u i d , a n d o r a n g e s o l i d .
M . p . - 1 6 3 . 5 ° C , b . p . - 5 7 ° C ; d ( l i q . ) ( - 5 7 ° C ) 1 . 4 5 , d ( s o l i d ) ( - 1 6 ^ 0 ) 1.912.
REFERENCES:
O. Ruff and W, M e n z e l . Z. a n o r g . a l l g . C h e m . 2 1 1 , 204 (1933).
O. Ruff a n d W. M e n z e l . Z . a n o r g . a l l g . C h e m . 217, 85 (1934).
Oxyge n Difluorid e
O F22 F2 + 2 NaOH = O F2 + 2 N a F + H20 76 80.0 54 83.99 18,01
F l u o r i n e g a s i s bubbled a t a r a t e of 1 to 3 l i t e r s / h o u r f r o m a p l a t i n u m t u b e of a p p r . 2 m m . IeD . into a 2% s o l u t i o n of NaOH
1 6 4
c o n t a i n e d in a g l a s s r e a c t i o n v e s s e l . T h e NaOH solution flows t h r o u g h t h e r e a c t i o n v e s s e l a t a r a t e of 1 l i t e r / h o u r f r o m a n e l e - v a t e d s t o r a g e c o n t a i n e r . T h e p l a t i n u m t u b e d i p s about 2 c m . into t h e s o d i u m h y d r o x i d e solution ( F i g . 114).
T h e output g a s m i x t u r e flows t h r o u g h w a s h b o t t l e filled with w a t e r , w h i c h a b s o r b s t h e u n r e a c t e d f l u o r i n e . T h e O F2 i s t h e n c o n - d e n s e d in two g l a s s t r a p s i m m e r s e d in liquid n i t r o g e n .
A f t e r c o m p l e t i o n of t h e r e a c t i o n , t h e c r u d e p r o d u c t , c o n d e n s e d at —196°C in t h e t r a p s , i s e v a c u a t e d with a w a t e r a s p i r a t o r to a p r e s s u r e of 20 m m . , w h i c h r e m o v e s t h e m a j o r p o r t i o n of t h e oxygen d i s s o l v e d in t h e O F2. T o p r e v e n t s i m u l t a n e o u s e s c a p e of t h e O F8 into t h e a t m o s p h e r e , a w a s h b o t t l e c o n t a i n i n g KI s o l u t i o n i s i n s e r t e d b e f o r e t h e a s p i r a t o r . T h e O F2 i s t h e n f r a c t i o n a t e d , with oxygen c o m i n g o v e r f i r s t . T h e f i r s t d i s t i l l a t i o n g i v e s a 98.5% p u r e p r o d u c t . T h e y i e l d i s 4 5 % , b a s e d on f l u o r i n e .
Oxygen d i f l u o r i d e i s s t o r e d in g l a s s f l a s k s o r s t e e l c y l i n d e r s .
Pt tube
- 1 8 3 ° - 1 8 3 °
F i g . 114. P r e p a r a t i o n of oxygen d i f l u o r i d e .
PROPERTIES:
C o l o r l e s s g a s ; y e l l o w , b r o w n i s h - t i n g e d liquid.
M . p . - 2 2 3 . 8 ° C , b . p . - 1 4 4 . 8 ° C ; tQ r - 5 8 . 0 ° C , p c r 48.0 a b s . a t m , cc r 97.6 m l . / m o l e ; d (liq.) (—223.8°C) 1.90, ( - 1 4 5 . 3 ° C ) 1.521; £ H ( f o r m a t i o n ) — 1 1 k c a l . Solubility in w a t e r at 0°C: 6.8 m l . of g a s e o u s O Fg/ 1 0 0 m l .
C h a r a c t e r i s t i c o d o r . I n h a l a t i o n c a u s e s s e v e r e b r e a t h i n g dif- f i c u l t i e s , w h i c h often do not b e g i n u n t i l s e v e r a l h o u r s a f t e r i n - h a l a t i o n and p e r s i s t for h o u r s . D o e s not a t t a c k g l a s s . R e a c t i o n w i t h w a t e r i s h a r d l y n o t i c e a b l e . A t t a c k s m e r c u r y .
Stable t o light, h e a t a n d e l e c t r i c a l ignition. R e m a r k a b l y u n - r e a c t i v e c o m p a r e d t o ClgO. L i k e a l l l o w - b o i l i n g f l u o r i d e s , t h e liquid d i s s o l v e s a p p r e c i a b l e q u a n t i t i e s of a i r .
4 . F L U O R I N E C O M P O U N D S 1 6 5
REFERENCES:
P . L e b e a u and A. D a m i e n s . C o m p t . R e n d . Hebd. S e a n c e s A c a d . S c i . 188, 1253 (1938).
O . Ruff a n d W, M e n z e l . Z . a n o r g . a l l g . C h e m . 190, 257 (1930).
Chlorin e Dioxid e Fluorid e
C102F2C102 + F2 = 2C102F
134.92 38 172.92
T h e a p p a r a t u s , w h i c h m u s t b e m a d e e n t i r e l y of q u a r t z , i s s e t u p a s in F i g . 1 1 5 . F l u o r i n e flows a t a r a t e of 500 m l . / h r . into t h e f i r s t t r a p , in w h i c h a few m i l l i l i t e r s of liquid CICt, a t —50 t o —55°C h a v e b e e n p l a c e d . T h e i n l e t t u b e d i p s a few m i l l i m e t e r s into t h e liquid C 1 03, T h e r e a c t i o n p r o g r e s s e s s m o o t h l y and s t e a d i l y ; m o s t of t h e C 1 02F f o r m e d in t h e r e a c t o r r e m a i n s t h e r e a n d only a s m a l l p o r t i o n r e a c h e s t h e s e c o n d t r a p . When t h e c o l o r of t h e liquid in t h e f i r s t t r a p b e c o m e s v e r y faint, t h e r e a c t o r i s a l l o w e d t o w a r m a n d t h e C 1 02F i s d i s t i l l e d into t h e s e c o n d t r a p in a s t r e a m of f l u o r i n e , w i t h g r a d u a l l y r i s i n g t e m p e r a t u r e . It c o l l e c t s a s a p u r e , c o l o r l e s s s u b s t a n c e r e q u i r i n g no f u r t h e r p u r i f i c a t i o n .
A c c o r d i n g t o M. S c h m e i s s e r , t h e p r o c e d u r e m a y b e a d v a n t a g e o u s l y a l t e r e d in t h e following w a y : C 1 02 i s d i s s o l v e d in C C 13F at —78°C and f l u o r i n a t e d . T h e C 1 02F f o r m e d s e p - a r a t e s a s a d e n s e r liquid p h a s e when s a t u r a t i o n i s r e a c h e d . T h e m i x t u r e i s t h e n c o o l e d to —110°C a n d t h e l e s s d e n s e liquid p h a s e i s r a p i d l y r e - m o v e d by v a c u u m t h r o u g h a c a p i l - l a r y . T h e r e a c t i o n m a y b e p e r f o r m e d in P y r e x g l a s s a p p a r a t u s . If a b s o - l u t e l y p u r e C 1 02F i s r e q u i r e d , w o r k - ing in q u a r t z a p p a r a t u s without e x c e s s a n e c e s s i t y and e n t a i l s r e p e a t e d r e c t i f i c a t i o n of F i g . 1 1 5 .
c h l o r i n e
P r e p a r a t i o n of d i o x i d e f l u o - r i d e .
ClOg b e c o m e s t h e p r o d u c t .
SYNONYM:
C h l o r y l f l u o r i d e .
W . K W A S N I K
PROPERTIES:
F o r m u l a weight 8 6 . 4 6 . C o l o r l e s s , v e r y s e n s i t i v e t o m o i s t u r e , i m m e d i a t e l y f o r m s a fog in m o i s t a i r . T h e r m a l l y m u c h m o r e s t a b l e t h a n C 1 03.
M . p . - 1 1 5 ° C , b . p . - 6 ° C .
REFERENCES:
H. S c h m i t z and H. J . S c h u m a c h e r . Z . a n o r g . a l l g , C h e m . 249, 242 (1942).
J . E . S i c r e and H. J . S c h u m a c h e r . Z . a n o r g . a l l g . C h e m . 286, 232 (1956).
M. S c h m e i s s e r a n d F . L . E b e n h o c h . Angew. C h e m . 66, 230 (1954).
Chlorin e Trioxid e Fluorid e
C!03FKC104 + HSO3F = CIO3F + KHSO4 138.56 100.07 102.46 136,17
T e n g r a m s of KC10>4 a r e d i s s o l v e d in 100 g. of H S OaF in a r o u n d - b o t t o m g l a s s f l a s k p r o v i d e d w i t h s t i r r e r and r e f l u x c o n d e n s e r . T h e r e a c t i o n s t a r t s a t 50°C and i s c o m p l e t e a t 85°C. T h e r e a c t i o n g a s e s a r e a l l o w e d t o p a s s o v e r a 10% s o d i u m h y d r o x i d e s o l u t i o n c o n t a i n i n g 5% NagSgOg and a r e t h e n bubbled t h r o u g h a s i m i l a r s o l u - t i o n . T h e g a s i s d r i e d with s o l i d KOH a n d t h e n c o n d e n s e d in a t r a p c o o l e d w i t h liquid n i t r o g e n . D u r i n g t h e r e a c t i o n a s t r e a m of d r y n i t r o g e n i s bubbled t h r o u g h t h e r e a c t i o n m i x t u r e . T h e p r o d u c t c o n t a i n s 1% a i r and 0.4% C 02. T h i s p r o c e d u r e i s a l s o s u i t e d t o t h e p r o d u c t i o n of C 1 03F in k i l o g r a m q u a n t i t i e s .
SYNONYM:
C h l o r y l o x y f l u o r i d e .
PROPERTIES:
C o l o r l e s s g a s , with a c h a r a c t e r i s t i c o d o r r e m i n i s c e n t of O F2. M . p . —152.2°C, b . p . — 48.1°C. F a i r l y s t a b l e t h e r m a l l y . May b e h e a t e d in g l a s s n e a r l y t o t h e softening point. S o m e w h a t s o l u b l e in w a t e r . R e a c t s quite slowly with d i l u t e a q u e o u s a l k a l i .
REFERENCES:
G. B a r t h - W e h r e n a l p . J . I n o r g . Nucl. C h e m . 2, 266 (1956).
4 . F L U O R I N E C O M P O U N D S 1 6 7
Chlorin e Tetroxid e Fluorid e
CIO4F
HCIO4 + F2 = CIO4F + H F 100.46 38.0 118.46 20,0
T h e a p p a r a t u s ( s e e F i g . 116) i s b e s t m a d e of q u a r t z . It c o n s i s t s of a c y l i n d r i c a l r e a c t i o n t u b e a p p r . 50 c m . h i g h , filled with q u a r t z R a s c h i g r i n g s . T h e t u b e i s s u r r o u n d e d by a c o o l i n g j a c k e t fed w i t h flowing w a t e r . T h e f l u o r i n e i s i n t r o d u c e d t h r o u g h a q u a r t z t u b e r e a c h i n g n e a r l y t o t h e b o t t o m of t h e v e s s e l , and 70% H C 1 04 i s a d d e d f r o m a d r o p p i n g funnel. T h e liquid i s d r a i n e d t h r o u g h a siphon, w h i l e t h e g a s e o u s r e a c t i o n p r o d u c t s a r e d r a w n off by s u c t i o n f r o m t h e t o p of t h e r e a c t i o n t u b e into a q u a r t z t r a p i m m e r s e d in liquid n i t r o g e n . T h e s y s t e m e n d s with a d r y i n g t u b e filled with a n h y d r o u s K F .
F i g . 116. P r e p a r a t i o n of c h l o r i n e t e t r o x i d e f l u o r i d e .
T h e HC10>4 input i s one d r o p p e r s e c o n d , u n t i l t h e liquid b e g i n s t o flow t h r o u g h t h e siphon. F l u o r i n e i s t h e n i n t r o d u c e d a t a r a t e of 2.5 l i t e r s / h o u r . In a d d i t i o n t o O Fa, Clg and S i F4, s o l i d C 1 04F c o l l e c t s on t h e w a l l s of t h e c o n d e n s i n g t r a p . B e c a u s e of t h e high e x p l o s i o n h a z a r d , C 1 04F should n e v e r b e m a d e in q u a n t i t i e s l a r g e r t h a n 4 g.
T h e p r o d u c t i s p u r i f i e d by f r a c t i o n a l v a c u u m d i s t i l l a t i o n . It i s s t o r e d in q u a r t z a m p o u l e s c o o l e d w i t h liquid n i t r o g e n . E x p l o s i o n s m a y e a s i l y o c c u r when C 1 04F i s m e l t e d and solidified. T h e y i e l d i s a b o u t 60%.
T h e h i g h e s t y i e l d s ( o v e r 90%) a r e o b t a i n e d w i t h a p l a t i n u m r e - a c t i o n v e s s e l . G l a s s m a y b e u s e d a s t h e a p p a r a t u s m a t e r i a l if o t h e r m a t e r i a l i s u n a v a i l a b l e , but t h e p r o d u c t i s t h e n q u i t e i m p u r e
and o b t a i n e d in low y i e l d . C a r b o n c a n n o t b e u s e d a s t h e c o n s t r u c - t i o n m a t e r i a l , s i n c e it c a t a l y t i c a l l y d e c o m p o s e s C 1 04F .
PROPERTIES:
C o l o r l e s s g a s , v e r y e x p l o s i v e ; often e x p l o d e s d u r i n g m e l t i n g o r c o n d e n s a t i o n . G a s e o u s C 1 04F e x p l o d e s in a m a n n e r s i m i l a r to N OaF , t h r o u g h m e r e c o n t a c t with d u s t , g r e a s e , r u b b e r o r 2N KI s o l u t i o n . In a n open b e a k e r , g a s e o u s C 1 04F e x p l o d e s upon c o n t a c t w i t h a f l a m e o r s p a r k . It h a s a s t r o n g l y a c r i d o d o r , i r r i t a t e s t h e t h r o a t a n d l u n g s , a n d c a u s e s p e r s i s t e n t r e s p i r a t o r y t r o u b l e .
M . p . - 1 6 7 . 2 ° C , b . p . - 1 5 . 9 ° C .
REFERENCES:
G. H. R o h r b a c k and G. H. C a d y . J . A m e r . C h e m . Soc. 69, 677 (1948).
Sulfu r Tetrafluorid e
SF44 C o F3 + S = S F4 + 4 C o F2
463.76 32,06 108.06 387.86
I. Sulfur (17 g.) i s i n t r o d u c e d into a q u a r t z f l a s k and c o v e r e d with a l a y e r of d r y c a l c i u m f l u o r i d e p o w d e r (40 g . , 0.025 t o 0.05 m m . d i a m e t e r g r a i n s ) , and 270 g. of C o F3 i s p l a c e d on t o p . T h e f l a s k i s c o n n e c t e d with a s h o r t p i e c e of tubing t o a t r a p i m m e r s e d in liquid n i t r o g e n . T h i s in t u r n i s c o n n e c t e d t o a v a c u u m s y s t e m . T h e a p p a r a - t u s i s now e v a c u a t e d and t h e q u a r t z f l a s k i s s h a k e n s o t h a t t h e two r a w m a t e r i a l s a n d t h e c a l c i u m f l u o r i d e a r e m i x e d t o g e t h e r . R e - a c t i o n b e g i n s d u r i n g t h e m i x i n g , with evolution of g a s . T h e t e m p e r a - t u r e i s g r a d u a l l y r a i s e d t o 130°C by m e a n s of an oil b a t h a n d m a i n t a i n e d for two h o u r s . A c o l o r l e s s p r o d u c t c o n d e n s e s in t h e t r a p d u r i n g t h e r u n . T h i s i s s u b s e q u e n t l y f r a c t i o n a t e d , u s i n g a q u a r t z s p i r a l m a n o m e t e r t o p e r m i t c o n t r o l a t z e r o m m . g a g e . Sulfur h e x a f l u o r i d e (up to 6% of t h e t o t a l quantity) c o m e s o v e r in t h e f i r s t c u t . T h e m a i n cut i s S F4, w h i c h c o n t a i n s s m a l l q u a n t i t i e s of l o w e r sulfur f l u o r i d e s ( S F2, SgF3). In o r d e r t o o b t a i n a b s o l u t e l y p u r e S F4, it i s s h a k e n with m e r c u r y in a p l a t i n u m (not q u a r t z ) f l a s k ; t h i s r e m o v e s t h e l o w e r sulfur f l u o r i d e s . T h e d e g r e e of p u r i t y i s a s c e r t a i n e d by d e t e r m i n i n g t h e m o l e c u l a r w e i g h t by t h e v a p o r d e n s i t y m e t h o d . T h e boiling point i s not d e c i s i v e for e s t i m a t i n g t h e d e g r e e of p u r i t y of S F4.
II. S F4 m a y b e o b t a i n e d in s m a l l e r y i e l d s (40%), a c c o r d i n g t o F . B r o w n and P . L . R o b i n s o n , by c a r e f u l f l u o r i n a t i o n of sulfur with f l u o r i n e at —70°C ( Fs : N3 = 1 : 3).
4 . F L U O R I N E C O M P O U N D S 1 6 9
Sulfur t e t r a f l u o r i d e i s s t o r e d in s e a l e d q u a r t z a m p o u l e s .
PROPERTIES:
C o l o r l e s s g a s , t h e r m a l l y s t a b l e u p t o — 6 0 0 ° C ; r e a c t s v i g o r o u s l y w i t h w a t e r . D e c o m p o s e d e x o t h e r m a l l y by c o n c e n t r a t e d HsS 04. . A t t a c k s g l a s s but not q u a r t z o r m e r c u r y .
M . p . - 1 2 1 . 0 ° C , b . p . - 4 0 . 4 ° C ; d ( l i q . ) ( - 7 8 ° C ) 1.95, (solid) (—183°C) 2.349. R e a d i l y s o l u b l e in b e n z e n e .
REFERENCES:
I. W . L u c h s i n g e r , T h e s i s , T e c h n . H o c h s c h u l e , B r e s l a u , 1936, p . 2 3 . II. F . B r o w n and P . L . R o b i n s o n . J . C h e m . Soc. (London) 1 9 5 5 ,
3147.
Sulfu r Hexafluorid e
S F6
I. S + 3 F2 = SF6
32.06 114.0 146,06
T h e r e a c t o r i s a n i c k e l t u b e 300 m m . long and 25 m m . I.D. ( F i g . 117) c o n t a i n i n g a n i c k e l b o a t filled w i t h s u l f u r . T h e g r o u n d j o i n t s of t h e r e a c t i o n t u b e and of t h e q u a r t z t r a p a r e b e s t left u n g r e a s e d and u n c e m e n t e d but only t i g h t l y c o m p r e s s e d . T h e i r o n d r y i n g t u b e c o n - t a i n i n g f r e s h l y d e h y d r a t e d K F i s for e x c l u s i o n of m o i s t u r e . T h e q u a r t z t r a p i s c o o l e d w i t h liquid n i t r o g e n .
T h i s a p p a r a t u s i s s u i t a b l e for m o s t f l u o r i n a t i o n s in w h i c h a s o l i d r a w m a t e r i a l f o r m s a g a s e o u s f l u o r i d e ( S e F6, T e Fe, A s F5, C F4, G e F4, M o Fe, W F6) . In t h e s p e c i a l c a s e of S Fe t h e a p p a r a t u s m a y b e m a d e e n t i r e l y of g l a s s .
T h e s u l f u r b u r n s with a b l u i s h f l a m e in t h e f l u o r i n e s t r e a m . T h e p r o d u c t c o l l e c t s in t h e c o n d e n s a t i o n t r a p and i s t h e n p a s s e d
F i g . 117. P r e p a r a t i o n of sulfur h e x a f l u o r i d e .
t h r o u g h f r i t t e d w a s h b o t t l e s c o n t a i n i n g hot 10% KOH (not NaOH) in o r d e r t o r e m o v e i m p u r i t i e s ( H F , S F3, S F4, S O F2, SL>F10). F i n a l l y , t h e g a s i s d r i e d in a P205 t u b e a n d i s p a s s e d at r o o m t e m p e r a t u r e o v e r a c t i v a t e d c h a r c o a l t o r e m o v e SgF1 0. T h e y i e l d i s 87%.
Π. S 02 + 3 F2 = SF6 + 02
118.97 40 86.06 72.92
Sulfur dioxide i s b u r n e d w i t h a n e x c e s s of f l u o r i n e t o S Fe in t h e a p p a r a t u s d e s c r i b e d for t h e p r e p a r a t i o n of C O F3 ( p . 206 f).
T h e t e m p e r a t u r e should b e a s high a s p o s s i b l e , p r e f e r a b l y a b o u t 650°C. T h e chief i m p u r i t y in t h e c r u d e S F6 a c c u m u l a t i n g in t h e c o n d e n s a t i o n t r a p i s S OsF3. T h e S Fe i s p a s s e d t h r o u g h s e v e r a l f r i t t e d w a s h b o t t l e s filled with w a t e r and hot 10% KOH, and t h e n d r i e d o v e r P2Os. T h e y i e l d i s 70%, b a s e d on S Os.
Sulftir h e x a f l u o r i d e m a y b e s t o r e d in a g a s o m e t e r o v e r w a t e r , in a g l a s s f l a s k p r o v i d e d w i t h a s t o p c o c k , o r , u n d e r p r e s s u r e , in a s t e e l c y l i n d e r .
PROPERTIES:
C o l o r l e s s , o d o r l e s s ; t h e r m a l l y a n d c h e m i c a l l y v e r y s t a b l e . M . p . —50.8°C ( u n d e r p r e s s u r e ) , s u b l . p . —63.8°C, tc r +45.55°C, pc r 38.33 a b s . a t m ; d (liq.) (—50.8°C) 1.88.
V e r y s p a r i n g l y s o l u b l e in w a t e r , s l i g h t l y s o l u b l e in a l c o h o l .
REFERENCES:
I. W. K l e m m and P . H e n k e l . Z . a n o r g . a l l g . C h e m . 207, 73 (1932).
II. G e r m a n P a t e n t A p p l i c a t i o n I. 72173 IV b / 1 2 i, May 4 , 1942;
W. K w a s n i k , not y e t p u b l i s h e d .
Thiony l Fluorid e
SOF2SOCl2 + 2 HF = SOF2 + 2 HC1
118.97 40 86.06 72.92
An i r o n b o t t l e ( F i g . 118) with a g a s i n l e t t u b e s e r v e s a s t h e r e a c t i o n v e s s e l . A s e c o n d b o t t l e i s c o n n e c t e d t o t h e f i r s t , to r e t a i n t h e u n r e a c t e d H F . T h i s i s j o i n e d t o a g l a s s g a s t r a p i m m e r s e d in liquid n i t r o g e n o r a Dry I c e - a c e t o n e b a t h . A d r y i n g t u b e filled w i t h K F i s a t t a c h e d t o e x c l u d e a t m o s p h e r i c m o i s t u r e .
T h e r e a c t i o n v e s s e l i s filled with 500 g. of SOCL, and 50 g. of SbClg ( c a t a l y s t ) , and a n h y d r o u s g a s e o u s H F i s i n t r o d u c e d t h r o u g h
4 . F L U O R I N E C O M P O U N D S 1 7 1
F i g . 118, P r e p a r a t i o n of thionyl f l u o r i d e .
t h e i n l e t t u b e . T h e H F i s t h o r o u g h l y a b s o r b e d , c a u s i n g a m i x t u r e of S O Fs and HC1 t o b e e v o l v e d , w h i c h t h e n i s c o l l e c t e d in t h e c o n d e n s a t i o n t r a p . T h e r e a c t i o n i s s o e n d o t h e r m i c t h a t t h e o u t s i d e of t h e r e a c t i o n v e s s e l g r a d u a l l y b e c o m e s c o v e r e d with i c e . When a l l t h e S O C ls h a s b e e n c o n s u m e d , m o r e m a y b e a d d e d without f u r t h e r a d d i t i o n of SbClg,
S e p a r a t i o n of t h e S O Fs f r o m t h e HC1 m a y b e a c h i e v e d e i t h e r by d i s t i l l a t i o n o r by r a p i d bubbling of t h e g a s m i x t u r e t h r o u g h i c e - c o l d w a t e r , in w h i c h HC1 i s c o m p l e t e l y a b s o r b e d , w h i l e t h e S O F3 p a s s e s t h r o u g h w i t h a l m o s t no d e c o m p o s i t i o n . T h e g a s i s t h e n d r i e d o v e r c o n c e n t r a t e d HgS04 o r o v e r P30 ^ .
T h i o n y l f l u o r i d e i s s t o r e d u n d e r p r e s s u r e in s t e e l c y l i n d e r s .
PROPERTIES:
C o l o r l e s s g a s , t h e r m a l l y s t a b l e u p t o r e d h e a t . D o e s not c o r r o d e F e , N i , C o , H g , S i , M n , B , M g , Al o r Zn below 125°C. D o e s not a t t a c k g l a s s . Suffocating o d o r . H y d r o l y z e d v e r y s l o w l y in i c e - c o l d w a t e r .
M . p . - 1 1 0 . 5 ° C , b . p . - 4 3 . 7 ° C , tc r 4S8°C; d . ( l i q . ) ( - 1 0 0 ° C ) 1.780, d. (solid) ( - 1 8 3 ° C ) 2 . 0 9 5 .
REFERENCES:
G e r m a n P a t e n t A p p l i c a t i o n I. 53743 IV b / l 2 i.
J . Soil a n d W. K w a s n i k . N a t u r f o r s c h u n g und M e d i z i n in D e u t s c h l a n d 1 9 3 9 - 1 9 4 6 ( F I A T - R e v i e w ) 2 3 , 192.
H. S. Booth and F . C. M e r c i o l a . J . A m e r . C h e m . Soc. 62, 6 4 0 ( 1 9 4 0 ) . U. W a n n a g a t a n d G . M e n n i c k e n . Z . a n o r g . a l l g . C h e m . 2 7 8 , 3 1 0 (1955).
Thiony l Tetrafluorid e
SOF4SOF2 + F2 = S O F4
86.06 38 124.06
T h e a p p a r a t u s ( F i g , 119) i s equipped with a n i c k e l Τ t u b e for g a s m i x i n g . T h e Τ t u b e o p e n s into a l a r g e r n i c k e l t u b e , w h i c h i s h e a t e d
