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The addition compound of phosphorous oxide and boron trifluoride

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The addition compound of phosphorous oxide and boron trifluoride

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Content THE ADDITION C O M PO U N D OF PHOSPHOROUS OXIDE
AND BORON TRIFLUGRIDS
A T h e s is
p r e s e n te d to
th e F a c u lty o f th e D epartm ent o f C h em istry
The U n iv e r s it y o f S o u th ern C a lif o r n ia
In P a r t i a l F u lf illm e n t
o f t h e R eq u irem en ts f o r t h e D egree
M aster o f S c ie n c e
by
L o u is R od erick Rapp
F eb ru ary 1944
UMI Number: EP41547
All rights reserved
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UMI EP41547
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under the direction of h%%. Faculty Committee,
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presented to and accepted by the Council on
Graduate Study and Research in partial fulfill
ment of the requirements for the degree of
MASTER OF SCIENCE
D ean
Secretary
Faculty C om m ittee
airman
TABLE O F CONTENTS
CHAPTER PAGE
I . INTRODUCTION .........................................................' . . . . 1
R eview o f th e l i t e r a t u r e ............................................. 1
M o le cu la r s tr u c tu r e . . . . 2
P h o sp h o r ic an h yd rid e .................................................. 2
P h osp horus s u lf o x id e .................................................. 4
H ex a m eth y len etetra m in e ............................................. 4
The p r o b l e m ...................................................................... 5
I I . THE TECHNIQUE INVOLVED IN THE EXPERIMENT . . . 6
The pump sy stem and McLeod Gauge . . . . . . 6
The d ry in g to w er ............................................................ 8
The tu b e o p e n e r .......................................................... .. . 8
The s e a l - o f f t u b e ............................................................ 9
The w e ig h in g b u l b ............................................................ 9
R e a c tio n bulb w ith m agn etic s t i r r e r . . . . 9
The h ig h tem p eratu re e q u ilib r iu m b u lb . . . 10
The U t u b e s ........................................................................... 10
The g a so m eter . ........................... , ...................... 11
C a lib r a tio n o f th e a p p a r a t u s ................................... 12
I I I . PREPARATION O F REAGENTS................................................. 13
P h osp h orou s o x i d e ............................................................ 13
P r e p a r a tio n o f phosp horous o x id e .................... 13
P u r i f i c a t i o n o f p h osp horous o x id e . . . 16
i i i
CHAPTER PAGE
A n a ly s is o f p h osp h orou s o x id e .......................... 17
P h y s ic a l p r o p e r t ie s o f phosp horous o x id e . 18
Boron t r i f l u o r i d e ................................................... 25
P r e p a r a t i o n ............................................................. 25
O ther r e a g e n t s ...................... . .......................................... 27
S u lfu r d io x id e ................................................................. 27
T rim eth y l a m i n e ........................................................ 27
■IV. RESULTS OF INDIVIDUAL EXPERIMENTS................. 28
T rim eth ylam in e and p h osp h orou s o x id e . . . . 28
S u lfu r d io x id e and p h osp h orou s o x id e . . . . 28
Boron f lu o r id e and p h osp horous o x id e . . . . 29
Boron f lu o r id e and ph osp horous o x id e i n
s u lf u r d io x id e s o l v e n t , E xperim ent I . . _ 29
E xperim ent I I ........................................................ 30
P r e s s u r e E xperim ent I .................................... 34
P r e s s u r e E xperim ent I I ....................................... . 35
V. CONCLUSIONS....................................................................... 38
S u m m a r y ............................. 39
BIBLIOGRAPHY.............................................................................................. 41
LIST OF FIGURES
FIGURE RAGS
I . s t r u c t u r a l P a t t e r n s ...................................... 3
I I . The High Vacuum A p p a r a t u s ................ ....... 7
I I I . P hosp horous O xide P r e p a r a tio n A p p aratu s . . . 1 4
IV . T it r a t io n Curve o f P h o sp h o ric A c id . . . . . . 19
V. Vapor T e n sio n Curve o f P h osp horous O xide . . . 21
V I. D e ta c h a b le M a n o m e te r .................. ....................................... 32
LIST OF TABLES
TABLE _ PAGE
I . Vapor P r e s s u r e s o f P h o sp h o ro u s Oxide . . . . . . 22
• I I . M o le c u la r W eight D e te rm in a tio n s o f
P h o sp h o ro u s.O x id e* . . . . . . . . . . . . . . 24
I I I . R e a c tio n o f P4 O 0 w ith BFg i n SOg S o lv e n t
E x p erim en t I . . . . . . . . . . . . . . . . 57
E x p erim en t I I * 37
P r e s s u r e E x p erim en t I . . . . . . . . . . . . 37
P r e s s u r e E x p erim e n t I I • • • • . . . . . . . 37
CHAPTER I
INTRODUCTION
In r e l a t i o n to th e stu d y o f ch em ica l bonding a v a r ie t y
o f m ethods m ight be u s e d . The method ch osen by th e a u th o r
was th a t o f a d d it io n com pounds, t h a t i s , by th e stu d y o f
r e a c t i v i t y o f a compound tow ard s e v e r a l o th e r compounds, in
an e f f o r t to form a d d it io n p r o d u c ts , th e ty p e o f ch em ica l
bond and i t s power o f bon din g may be d e te r m in e d . Among th e
many compounds c o n sid e r e d f o r s tu d y , p h osp h orou s o x id e
app eared to be one o f th e m ost i n t e r e s t i n g , and a lth o u g h i t
i s somewhat t o x i c , i t s v o l a t i l i t y e n a b le s one to h a n d le i t
f a i r l y s a f e l y by m eans o f a h ig h vacuum a p p a r a tu s.
I . REVIEW O F THE LITERATURE
P r e v io u s s t u d i e s o f ph osp h orou s o x id e w ere c e n te r e d
m a in ly around i t s p r e p a r a tio n and th e d e te r m in a tio n o f i t s
m o le c u la r s tr u c tu r e by e le c t r o n d i f f r a c t i o n m ethods and
X -ray a n a l y s i s . The p r e p a r a tiv e c h e m istr y began w ith th e
e x p e r im e n ta l work o f B. G. la S a g e;^ how ever th e lim it e d
com b u stion m ethod u se d by Thorpe and T u tto n 2 in 1 8 9 0 , b u t
1
w M e llo r f s C om prehensive T r e a t is e on In o r g a n ic and
T h e o r e tic a l C h em istr y ,* P h o sp h o ru s, V o l. V III (Longm ans,
G reen and Company, 1 9 2 8 ), p . 8 9 9 .
2
T. E . Thorpe and A. E . T u tto n , J . Chem. S o c ., 5 7 ,
549 (1 8 9 0 ). —
2
f o r a few s l i g h t m o d if ic a t io n s in th e a p p a r a tu s, 3 i s th a t
w hich i s g e n e r a lly u sed to d a y . X -ray a n a l y s is and e le c t r o n
d i f f r a c t i o n 4 m ethods h ave d e f i n i t e l y e s t a b lis h e d th e
m o le c u la r s tr u c tu r e o f ph osphorous o x id e t o ' b e s i m i l i a r t o
th o s e o f p h o sp h o r ic a n h y d r id e , a r se n o u s o x id e , h ex a -
m e th y le n e te tr a m in e , and ph osp horus s u l f o x i d e .
M o le cu la r s t r u c t u r e . S t r u c t u r a lly c o n s id e r e d , t h e s e
f i v e compounds have th e symmetry o f th e p o in t group T^.
They may be d e s c r ib e d a s h a v in g a c r y s t a l l i n e s tr u c tu r e in
p a r a l l e l o r ie n t a t i o n on a body c e n te r e d c u b ic l a t t i c e .
F ig u r e I shows th e s t r u c t u r a l p a tte r n o f fo u r o f th e s e
compounds.
P h o sp h o ric a n h y d r id e . A stu d y o f th e ch em ica l bond
o f p h o sp h o ric o x id e , by th e u se o f a d d itio n compounds, was
3
H. W oolf and H. Schm ager, B e r . 62B , 771 (1 9 2 9 ).
C. C. M il l e r , £ . Chem. S o c . . 1 3 3 . 1847 (1 9 2 8 ).
H. B i l t z and A. G r o ss, B e r . 52B. 762 (1 9 1 9 ).
T . A. K rju k ova, J . G en. Chem, ( U .S .S .R .) , 9 . 577
(1 9 3 9 ) . “
4
M axw ell, H en d rick s and D em ing, J . Chem. P ^y. 5 ,
626 (1 9 3 7 ). ~ “
G. Hampson and A. S t o s i c k , J . Am. Chem. S o c . 6 0 ,
1814 (1 9 3 8 ). " -------- ------ —
5
G. Hampson and A. S t o s i c k , J . Am. Chem. S o c . 6 0 .
1 8 1 5 ; 6 1 , 1130 ( 1 9 3 9 ) . “ -------- ----- —
PHOSPHOROUS OXIDE HEXAMETHYLENETETRAM INE
PHOSPHORIC OXIDE PHOSPHORUS SULFOXIDE
STRUCTURAL PATTERNS
FIGURE I
z *
u n d erta k en by Ingram . I t was fou n d t h a t p h o sp h o ric o x id e
f a i l e d to r e a c t w ith th e g e n e r a l b a s e s , trim eth yliam in e and
p y r id in e , b u t t h a t i t w ould r e a c t w ith a b a s ic r e a g e n t w h ich
p o s s e s s e d an a c id ic hydrogen c a p a b le o f m ig r a tio n , such a s
d im e th y la m in e . I t was found to b 6 i n a c t iv e to w a rd s boron
t r i c h l o r i d e , a f a c t w hich was a t t r ib u t e d to th e fir m b on d in g
power o f th e v a le n c y e le c t r o n s o f o x y g e n .
P hosp horus s u l f o x i d e . No work c o n c e r n in g th e
c h em ica l a c t i v i t y o r ch em ical b on d in g o f t h i s compound h a s
b een r e p o r te d . A p p a r e n tly , s in c e i t s d is c o v e r y by Thorpe
and T u tto n ' in 1 8 9 2 , t h e o n ly work on i t h as b een th e
d e te r m in a tio n o f th e s tr u c tu r e by Hampson and S t o s i c k . 8
H ex a m e th y len ete tra m in e . The r e a c t i v i t y o f h e x a -
m e th y le n e te tr a m in e and ph osp h orou s o x id e sh o u ld b e v e r y
s im ila r , f i r s t , b e c a u se o f t h e i r s t r u c t u r e , and, se c o n d ,
b e c a u se b oth compounds have s im ila r e le c t r o n c o n f ig u r a t io n s
on th e n itr o g e n and p h osp h oru s atom s r e s p e c t i v e l y . In th e
c a se o f t h e amine th e r e a r e two u n sh ared v a le n c e e le c t r o n s
6
D. Ingram , "The B eh a v io r o f P h o sp h o ric A nhydride
Towards A c id ic and B a sic R e a g e n ts,* (u n p u b lish e d M a ste r ’ s
t h e s i s , U n iv e r s it y o f C h ic a g o , 1 9 3 9 ).
7
T. E . T horp6 and A. E. T u tto n , Z e i t . A n org. Chem.
1 , 1 ( 1 8 9 2 ) .
“ 8
Hampson and S t o s i c k , o j d. c i t . . 6 1, 1130 (1 9 3 9 ).
5
w hich sh o u ld be f r e e to r e a c t a d d i t iv e ly w ith an e le c t r o n
a c c e p to r such a s boron t r i f l u o r i d e ; and in th e c a s e o f
p h osp horous o x id e th e two u n sh ared v a le n c e e le c t r o n s o f th e
p h osp horus m igh t b6 e q u a lly a v a ila b le to th e e le c t r o n
a c c e p to r b oron t r i f l u o r i d e . M artin 9 in h i s stu d y o f h e x a -
m e th y le n e te tr a m in e con firm ed th e s u p p o s it io n i n th e c a s e o f
th e am ine when he found th a t boron t r i f l u o r i d e w ould r e a c t
a d d i t iv e ly w ith th e amine in t h e r a t i o o f fo u r boron t r i
f lu o r id e m o le c u le s t o one amine m o le c u le .
The p ro b lem . W ith t h e s e f a c t s i n mind th e a u th o r
d eterm in ed t o stu d y t h e b e h a v io r o f ph osp h orou s o x id e w ith
r eg a rd t o i t s a c t i v i t y to w a rd s th e b a s e , tr im e th y la m in e ,
and th e two a c id s , s u lf u r d io x id e and boron t r i f l u o r i d e .
I t s f a i l u r e t o r e a c t a d d it iv e ly w ith tr im e th y la m in e
i n d ic a t e s a la c k o f a c id ic p r o p e r t ie s . I t s r a th e r weak
b a s ic p r o p e r t ie s w ere shown by th e f a c t th a t i t d id r e a c t
w ith boron f l u o r id e b u t f a i l e d to r e a c t w ith th e w eaker
a c id , s u lfu r d io x id e .
9
La Verne M a rtin , ^ B eh avior o f H ex a m eth y len etetra m in e
tow ard s Boron T r iflu o r id e ,* * (u n p u b lish ed M a ste r ’ s t h e s i s ,
The U n iv e r s it y o f S o u th ern C a lif o r n ia , L os A n g e le s , 1 9 4 0 ).
CHAPTER I I
THE TECHNIQUE INVOLVED IN THE EXPERIMENT
The e x p e r im e n ta l te c h n iq u e and a p p a ra tu s u sed f o r t h e
m ain p o r t io n o f th e work was s im ila r to th a t u sed by s t o c k ’ * '
i n h i s work on th e h y d r id e s o f boron and s i l i c o n . The
a p p a ra tu s w as c o n s tr u c te d e n t i r e l y o f p y r e x g l a s s and
d i f f e r e d from S t o c k 's in d e s ig n and in t h e u s e o f tw o -
m illim e t e r sto p c o ck s i n th e p la c e o f m ercury f l o a t v a lv e s .
The s to p c o c k s, thou gh co m m ercia lly made, w ere hand ground
t o in s u r e t h e i r freed om from le a k s a s much a s p o s s i b l e .
The lu b r ic a n t u sed was A p iezo n L g r e a s e . A diagram m atic
v ie w o f t h e a p p a ra tu s i s shown in F ig u r e I I .
The pump sy stem and McLeod g a u g e . The a p p a ra tu s was
e v a c u a te d by m eans o f an apron j e t m ercury d i f f u s i o n pump
backed by a Cenco Hyvac two s t a g e o i l im m ersion m ech a n ica l
pump. By t h i s means a p r e s s u r e a s lo w a s 1 0 “ ^ mm. 0 f
m ercury c o u ld be e s t a b l i s h e d . The McLeod g a u g e , M C L , was
c a lib r a t e d t o read p r e s s u r e s a s lo w a s 1 .7 x 10~^mm. The
pump was c o n n e c te d t o th e system th rou gh sto p cock and
th e McLeod gau ge th rou gh S g . In t h i s manner th e y co u ld b e
opened t o , o r c lo s e d from , th e sy stem a t w i l l .
1
S to c k , B er. 54A, 142 (1 9 2 1 ).
5/2
59
.A,
so so
D T
50
SO
HXEB
KJ
RBM 5
VV
TO
THE HIGH VACUUM APPARATUS
FIGURE H
8
The d r y in g to w e r . A ir , f r e e d from w a te r and carbon
d io x id e by p a s s in g th rou gh th e lo n g d r y in g tu b e , DT, co u ld
be in tr o d u c e d to th e m a n ifo ld th rou gh th e s to p cock S g , and
from th e r e t o any o th e r p a r t o f th e a p p a ra tu s. The tu b e
c o n ta in e d d i s t i n c t la y e r s o f c a lc iu m c h lo r id e , fu s e d
p o ta ssiu m h y d r o x id e , and p h o sp h o r ic an h yd rid e on g l a s s
b e a d s.
The tu b e o p e n e r . The in tr o d u c tio n o f co n d en sa b le
v o l a t i l e m a t e r ia ls was a c co m p lish ed by th e u s e o f th e vacuum
tu b e o p e n e r , TO, s im ila r to th a t d e s c r ib e d by S to c k . The
tu b e o p en er was cem ented to th e system through th e p o r tio n
d e s ig n a te d SO by m eans o f P ic e in w ax, w hich form s a vacuum-
t i g h t c o n n e c tio n .
The su b sta n c e to be in tr o d u c e d i s p la c e d in a c lo s e d
b u lb to w hieh i s s e a le d a drawn-down tu b e to f i t th e tu b e
o p e n e r . The b u lb i s th e n cem en ted , by P i c e i n , in t o th e open
tu b e o f t h e tu b e o p e n e r , and ev a cu a ted th rou gh th e sto p
cock S g . The h a n d le o f th e o p en er i s tu r n e d , b r e a k in g o f f
th e t i p o f th e c em e n te d -in tu b e and p la c in g th e i n t e r i o r o f
th e b u lb i n c o n ta c t w ith th e w hole a p p a r a tu s. The sam ple
co u ld th e n be d i s t i l l e d to any p a r t o f t h e a p p a ra tu s d e s ir e d .
2
S to c k , B er. 51, 985 (1 9 1 8 ).
9
The s e a l - o f f t u b e . The t r a n s f e r o f v o l a t i l e m ater
i a l s from th e a p p a ra tu s in t o s e a le d b u lb s f o r s to r a g e w as
c a r r ie d o u t in t h e p o r tio n o f t h e a p p a ra tu s d e s ig n a te d by
SO. The tu b e in w hich th e m a te r ia l was to be p la c e d was
cem ented t o th e a p p a ra tu s by m eans o f F ic e i n w ax, and
e v a cu a te d th rou gh th e r e s p e c t iv e sto p c o c k , Sg o r $ io « The
sam ple was th en d i s t i l l e d in t o th e tu b e and th e tu b e s e a le d
o f f by m eans o f an oxygen t o r c h .
Through t h i s SO sy stem o th e r tem porary a p p a ra tu s
such a s th e w eig h in g b u lb , s to p -c o c k e d s to r a g e b u lb s , and
rem ovable r e a c t io n t u b e s , c o u ld be a tta c h e d to th e
perm anent a p p a r a tu s.
The w e ig h in g b u lb . The w e ig h in g b u lb c o n s is t e d o f a
12 mm. p y r e x tu D e, 40 mm. in le n g t h , w ith a t e s t tu b e
b o tto m , s e a le d to a 2 mm. s la n t bore p y rex s to p - c o c k . The
b u lb c o u ld be cem ented to t h e a p p a r a tu s, e v a c u a te d , th e
s to p cock c lo s e d , t h e tu b e removed and w e ig h e d . In th e
same manner th e tu b e cou ld be w eigh ed a f t e r th e sam ple had
b een con d en sed in t o th e b u lb .
R e a c tio n b u lb w ith m a g n e tic s t i r r e r . T h is b u lb ,
RBMS, c o n s is t e d o f a 12 mm. tu b e 20 cm. lo n g on w hich was
s e a le d a ground g l a s s m ale j o i n t . The cap c o n s i s t s o f a
fe m a le j o in t s e a le d t o a 2 mm. s la n t- b o r e sto p c o ck . The
ground g l a s s j o i n t e n a b le s one to open t h e tu b e and remove
10
th e s t i r r e r as t h e o c c a s io n demands. The s to p cock e n a b le s
one to rem ove th e r e a c t io n tu b e from th e a p p a ra tu s w ith o u t
d is tu r b in g i t s c o n t e n t s . The s t i r r e r i t s e l f c o n s i s t s o f a
sm a ll g l a s s - i n c l o s e d ir o n rod a tta c h e d t o a g l a s s rod w ith
a s p ir a l e n d . A g it a t io n i s o b ta in e d by su rrou n d in g th e
u p p er p o r t io n o f th e tu b e w ith a c o i l a tta c h e d to an
o r d in a r y c i r c u i t in t e r r u p t e r . Thus when th e c u rren t i s
o n , t h e m a g n e tic a t t r a c t io n draws th e s t i r r e r up and when
th e c u r r e n t i s stop p ed th e s t i r r e r f a l l s by g r a v it a t io n a l
f o r c e .
The h ig h tem p era tu re e q u ilib r iu m b u lb . The h ig h
tem p era tu re e q u ilib r iu m b u lb , HTEB, u se d in d e te r m in in g th e
m o le c u la r w e ig h t o f ph osp h orou s o x id e and i t s vapor t e n s io n
curve, i s s im ila r t o t h a t d e s c r ib e d by Burg and s c h l e s i n g e r . 3
The U t u b e s . The U tu b e system d e s ig n a te d TJ^, tfg , U3
and T J 4 , i s p erh a p s one o f th e m ost u s e f u l s e c t io n s o f th e
a p p a r a tu s, f o r i t i s h e r e t h a t th e s e p a r a tio n and i s o l a t i o n
o f v o l a t i l e m a t e r ia ls i s c a r r ie d o u t . F r a c t io n a l d i s t i l l a
t i o n s 4 a s w e ll a s f r a c t i o n a l c o n d e n s a tio n s5 a r e u sed f o r
3
A . B . Burg and H. I . S c h le s in g e r , J . Am. Chem. S o c .
5 9 , 780 ( 1 9 3 7 ) . “ ------
4
S t o c k , B e r . 5 0 , 998 (1 9 1 7 ).
5
S to ck and S o m ie sk i, B er. 54B, 746 (1 9 2 1 ).
11
t h e s e s e p a r a t io n s .
The manometer a tta c h e d to U3 i s p a r t i c u la r ly u s e f u l
in d e te r m in in g th e p u r it y o f a m a te r ia l by m easu rin g i t s
vap or t e n s io n . A c o ld h a th o f a s u i t a b l e c o n sta n t
te m p e r a tu r e , b elow room te m p e r a tu r e , i s p la c e d around th e
tu b e and a f t e r a llo w in g enough tim e f o r t h e a tta in m e n t o f
e q u ilib r iu m , th e p r e s s u r e i s rea d by th e a id o f th e mano
m e te r .
B x a ct volum es o f g a s sam p les co u ld be d eterm in ed by
co n d en sin g t h e m a te r ia l in one o f th e U tu b e s and a llo w in g
i t to expand. By r e c o r d in g th e p r e s s u r e , from th e m anom eter,
and th e te m p e r a tu r e , and a p p ly in g th e volum e c a lib r a t io n o f
t h e a p p a r a tu s, th e stan d ard volum e o f g a s can b e c a lc u la t e d
by th e u s e o f th e g a s la w s . I f t h e p r e s s u r e e x c e e d s
a tm o sp h e ric p r e s s u r e , 8 ^ 5 i s opened th u s a llo w in g
a tm o sp h e r ic p r e s s u r e to be in tr o d u c e d in to one arm o f th e
m anom eter; th u s on e can rea d p r e s s u r e s as h ig h a s one and
one h a l f a tm osp h eres s a f e l y .
The g a s o m e te r . A n oth er m ethod o f m easu rin g e x a c t
volum es o f g a s e s was th rou gh th e u s e o f th e g a so m e te r , G.
I t c o n s is t e d o f a lo n g c a lib r a t e d t u b e , one end o f w hich
was a tta c h e d t o th e a p p a ra tu s and t h e o th e r to a m ercury
w e l l , open to t h e a tm osp h ere, t h e n t h e tu b e was e v a c u a te d ,
t h e m ercury c o m p le te ly f i l l e d th e c a lib r a t e d s e c t io n ;
12
how ever when a g a s was In tro d u c ed th e m ercury was fo r c e d
down; th u s from th e p r e s s u r e , te m p e r a tu r e , and th e c o n fin in g
volu m e, th e sta n d a rd volum e o f t h e g a s c o u ld be c a lc u la t e d .
C a lib r a tio n o f th e a p p a r a tu s. The c a lib r a t io n o f
th e U tu b e s e c t io n and th e h ig h tem p era tu re e q u ilib r iu m
bu lb was a cco m p lish ed by th e u s e o f carb on d io x id e . The
carbon d io x id e was in tr o d u c e d in t o th e a p p a r a tu s by m eans
o f a rem ovable U tu b e th rou gh th e SO sy stem and p la c e d in
t h e s to r a g e b u lb , SB . Then by m eans o f th e th r ee -w a y
c o c k s , 8 5 and i t was a llo w e d to expand in t o th e g a so
m eter u n t i l a s u i t a b l e volum e was o b ta in e d . T h is e x a c t
known volum e o f g a s w as th e n condensed in to Ug and a llo w ed
to warm t o room te m p e r a tu r e . From th e p r e s s u r e d e v e lo p ed
and th e tem p era tu re o f t h i s known volum e o f g a s , th e e x a c t
volum e o f th e U tu b e was c a lc u la t e d . In th e same manner
th e v a r io u s p a r t s o f t h e a p p a ra tu s were c a lib r a te d * The
c o r r e c t io n f o r th e v a r ia t io n o f th e m ercury l e v e l s in th e
manometer was made from t h e known in t e r n a l d ia m e te r o f th e
manometer t u b e . The c o r r e c t io n was e x p r e ss e d a s th e
in c r e a s e o f volum e, due to u n it d is t a n c e o f r e c e s s io n o f
t h e m ercu ry, o v e r th e volum e a t zero p r e s s u r e .
CHAPTER I I I
PREPARATION OF REAGENTS
The e x p e rim e n ta l w ork r e s o lv e d i t s e l f i n t o two
p ro b le m s; f i r s t , th e p r e p a r a t i o n o f th e r e a g e n t s i n t h e i r
p u r i f i e d form ; and se c o n d , t h e 'r e a c t i o n - b e t w e e n th e s e
r e a g e n t s , Among th e m o st d i f f i c u l t to p r e p a r e and p u r i f y
was p h o sp h o ro u s o x id e , A r a t h e r i n t e n s i v e stu d y o f i t s
p h y s i c a l p r o p e r t i e s was made i n d e te rm in in g i t s p u r i t y .
I , PHOSPHOROUS OXIDE
P r e p a r a t i o n o f p h o sp h o ro u s o x id e . The m ethod o f
p r e p a r a t i o n was e s s e n t i a l l y t h a t o f Thorpe and T u tto n 1 -
e x c e p t f o r a s l i g h t m o d if i c a t io n o f t h e i r a p p a r a t u s .
I n c h - lo n g p i e c e s o f d r i e d y e llo w p h o sp h o ru s a r e
p la c e d i n th e co m bu stion tu b e , A (s e e F ig u re I I I ) , w hich
i s b e n t i n th e form shown t o p r e v e n t m o lte n p h o sp h o ru s from
e s c a p in g . One end o f th e co m b u stio n tu b e i s open to a d m it
a i r , w hich need n o t be d r i e d ; th e o t h e r i s s e a le d to th e
d e l i v e r y tu b e , B. I n th e f a r t h e r end o f th e d e l i v e r y tu b e ,
a t C, i s p la c e d a p lu g o f g l a s s w ool a b o u t two in c h e s lo n g
to p r e v e n t m ost o f th e p h o sp h o ru s o r th e l e s s v o l a t i l e
o x id e s from e n t e r i n g th e U tu b e t r a p , D. One end o f th e U
1 . . . .
Thorpe and T u tto n , J . Chem. S o c ., 57, 545 (1890) .
PHOSPHOROUS OXIDE PREPARATION APPARATUS
FIGURE 10
15
tu b e tr a p i s a tta c h e d to th e d e liv e r y tu b e , by P ic e i n wax,
and th e o th e r end i s a t ta c h e d , th rou gh a ca lciu m c h lo r id e
d r y in g tu b e , to an a s p ir a t o r , by th e a id o f w hich a i r i s
drawn o v e r th e b u rn in g p h o sp h o ru s. The U tu b e i s
surrounded by a - 7 8 .5 ° C. b ath t o con d en se th e ph osp h orou s
o x id e form ed i n th e r e a c t io n .
W ith th e a s p ir a t o r s e t , th e phosp horus i s ig n i t e d
e it h e r sp o n ta n e o u sly o r w ith th e a id o f a sm a ll fla m e n ear
th e a n t e r io r end o f th e com b ustion tu b e . I t h a s been found
th a t th e y i e l d o f o x id e in c r e a s e s w ith th e r a t e o f draw ing
a i r o v e r th e b u rn in g p h o sp h o r u s. 2
2 f th e a c t io n i s to o l o c a l , th e m ain p ro d u ct may be
p h o sp h o r ic a n h y d r id e . When th e exp erim en t i s g o o d , la r g e
q u a n t i t i e s o f red P40 w i l l form in th e p o r t io n o f th e d e liv e r y
tu b e n e a r e s t th e b u rn in g p h o sp h o ru s. The d e liv e r y tu b e
sh o u ld be warmed g e n t ly d u rin g th e r e a c t io n to in s u r e f a i r l y
com p lete t r a n s f e r o f th e p h osp h orou s o x id e t o th e U tu b e
tr a p . Care m ust be ta k e n , h ow ever, n o t to h e a t th e
d e liv e r y tu b e to o h o t a s th e l e s s v o l a t i l e o x id e s w i l l be
d r iv e n to th e U tu b e th u s c o m p lic a tin g th e p u r i f i c a t i o n
som ew hat.
A f t e r th e c o m p le tio n o f th e r e a c t io n , th e sto p c o c k s
o f th e U tu b e a r e c lo s e d and th e tu b e f r e e d from th e
2
Thorpe and T u tto n , 0 £ . c i t . , p . 5 4 6 .
d e liv e r y tu b e and a tta c h e d to th e h ig h vacuum a p p a ra tu s
th rou gh th e SG c o n n e c tio n . The ph osp h orou s o x id e i s th e n
in p o s i t i o n to h e d i s t i l l e d in to th e U tu b e sy ste m .
P u r i f i c a t i o n o f ph osp horous o x id e . The i n i t i a l
p u r i f i c a t i o n was c a r r ie d on by t h e f r a c t i o n a l c o n d e n s a tio n
m eth od, d i s t i l l i n g from room tem p era tu re th rou gh a - 1 5 ° C.
b ath to a - 7 8 .5 ° C b a th . The l e s s v o l a t i l e m a t e r ia ls
rem ained b e h in d , th e p h osp horous o x id e was tra p p ed by th e
-1 5 ° C b a th , and th e more v o l a t i l e m a t e r ia ls tra p p ed by th e
-7 8 * 5 ° C b a th . The more v o l a t i l e m a t e r ia ls w ere e a s i l y
removed th rou gh a s e a l - o f f tu b e c o n n e c te d th rou gh th e SO
sy stem ; how ever th e rem oval o f th e l e s s v o l a t i l e m a t e r ia ls
o f f e r e d more d i f f i c u l t y . I t was fou n d t h a t t h e e a s i e s t and
q u ic k e s t method was to r e p la c e th e d ir t y U tu b e a lt o g e t h e r .
R ep eated c o n d e n s a tio n s o f t h i s ty p e r e s u lt e d i n
f a i r l y pu re p h osp horous o x id e , how ever i t was foun d t h a t i f
th e o x id e was a llo w e d to stan d a t room tem p era tu re f o r a
week o r s o , and a su b seq u en t d i s t i l l a t i o n u n d e rta k en , a
y e llo w r e s id u e w as l e f t i n th e U t u b e . T h is r e s id u e w as
e it h e r u n r e a e te d p h o sp h o ru s, w hich had n o t b een se p a r a te d
from th e o x id e , o r th e p ro d u ct o f th e d i s s o c i a t i o n o f th e
p h osp h orou s o x id e in t o n o n - v o l a t i l e m a t e r ia ls such a s ;
17
The l a t t e r a ssu m p tio n i s based on t h e fo llo w in g
e x p e r im e n t. About 4 m l. o f f r e s h l y p rep ared ph osp h orou s
o x id e w as d i s t i l l e d in t o a sm a ll s e a l - o f f tu b e eq u ip p ed w ith -
a drawn-down s id e arm t o f i t th e tu b e o p e n e r . The tu b e was
s e a le d o f f and h e a te d in an o i l b ath f o r a p e r io d o f two
h o u rs a t 200° C. D uring th e c o u r se o f t h e two h o u rs a
m ix tu r e o f a red and w h ite r e s id u e was form ed. TJpon c o o lin g
t h e tu b e to room te m p e r a tu r e , i t was n o tic e d t h a t ab ou t one
q u a r te r o f t h e o r ig i n a l o x id e had d is a p p e a r e d . The tu b e was
opened to th e vacuum sy stem , w ith th e a id o f th e tu b e o p e n e r ,
and th e p h osp h orou s o x id e d i s t i l l e d o u t . No v o l a t i l e
im p u r ity was d e t e c t e d , how ever th e red and w h ite r e s id u e
rem ained b eh in d i n th e tube* T h is r e s id u e was assum ed to be
d e c o m p o sitio n p r o d u c ts such a s t h o s 6 m en tion ed a b o v e.
In an e f f o r t t o p u r if y th e o x id e s t i l l f u r t h e r , i t
was t r e a t e d , f o r a p e r io d o f t h i r t y - s i x h o u r s , w ith u l t r a
v i o l e t l i g h t from a m ercury vap or lam p. T h is w as th e m ethod
em ployed by Hampson and S t o s ic k 3 in p u r ify in g ph osp h orou s
o x id e , and w as u sed t o c o n v e r t v o l a t i l e w h ite phorp horus to
n o n - v o l a t i l e red p h o sp h o ru s.
A n a ly s is o f ph osp h orou s o x id e , ^n o r d e r to a s c e r t a in
th e p u r it y w h ich had b een o b ta in e d by th e above m eth ods o f
p u r i f i c a t i o n a v o lu m e tr ic a n a l y s is o f a f r e s h l y d i s t i l l e d
3
Hampson and S t o s i c k , J . Am. Chem. S o c . , 6 0 , 1814
( 1 9 3 8 ) . ~
18
sam ple o f ph osp horous o x id e was u n d e rta k en .
A known w e ig h t o f th e o x id e was d i s t i l l e d in t o a
la r g e b u lb eq u ip p ed w ith a s to p -c o c k and w hich c o n ta in e d
about 5 c c . o f c o n c e n tr a te d n i t r i c a c id . The s to p -c o c k was
c lo s e d and th e b u lb , u n a ssem b led , a llo w e d to warm to room
te m p e r a tu r e . The r e s u l t was a v ig o r o u s r e a c t io n e v o lv in g
n it r o u s o x id e . The bulb was a llo w e d to sta n d f o r a sh o r t
w h ile t o in s u r e co m p lete r e a c t io n ; th e n a i r w as a d m itte d ,
th e s to p -c o c k broken o f f and th e c o n te n ts o f th e bulb
w ashed in t o a b ea k e r to be a n a ly z ed a s p h o sp h o r ic a c id .
I n d ic a to r m ethods f a i l e d b e c a u se th e f i r s t end p o in t c o lo r
change was to o g ra d u a l f o r a c c u r a te d e te r m in a tio n s . The
a n a ly s is was c o m p leted , h ow ever, w ith th e a id o f a Beckman
pH m e te r .
A sam ple o f P4 O0 w e ig h in g 0 .1 8 0 9 gm. o x id iz e d and
a n a ly z e d in th e manner d e s c r ib e d above r e q u ir e d 2 7 .8 5 c c . o f
0 .1 2 5 6 N NaOH to n e u t r a l iz e t h e seco n d a v a ila b le hyd rogen o f
th e p h o sp h o r ic a c id . The t i t r a t i o n cu rve f o r t h i s sam ple i s
shown i n F ig u r e IY . C a lc u la t io n s showed th e sam ple to con
t a i n 0 .8 9 p e r c e n t p h osp h oru s im p u r ity .
P h y s ic a l p r o p e r t ie s o f ph osp h orou s o x id e . Yapor
t e n s io n m easurem ents o f p h osp h orou s o x id e w ere made th rou gh
th e u s e o f th e h ig h tem p er a tu r e e q u ilib r iu m b u lb , and a
c a th e to m e te r to m easure t h e d if f e r e n c e i n m ercury l e v e l s .
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20
M easurem ents made on a number o f sam p les co v ered a
tem p era tu re ran ge from 2 2 . 8 ° C to 1 5 1 .5 ° C. The f i r s t few
sam p les c o n ta in e d r e l a t i v e l y la r g e am ounts o f im p u r it ie s and
c o n se q u e n tly t h e vapor t e n s io n s w ere lo w . F ig u r e V shows
th e cu rve r e p r e s e n t in g th e vap or t e n s io n s o f th e p u r e s t
sam p les o f th e o x id e o b ta in e d in t h i s w ork.
The vap or p r e s s u r e s o f p h osp h orou s o x id e betw een t h e
tem p e r a tu r e s 2 2 .8 ° C and 1 5 1 .5 ° C a r e l i s t e d in T a b le I . I t
a ls o c o n ta in s th e lo g o f th e e x p e r im e n ta l vapor p r e s s u r e s
and t h o s e c a lc u la t e d from th e e q u a tio n o f th e c u r v e . The
e q u a tio n o f th e cu rv e w as d eterm in ed by th e m ethod o f l e a s t
sq u a r es and w as found t o be lo g F = 7 .9 8 4 - 2 2 7 4 /T . From
t h i s th e h e a t o f v a p o r iz a t io n was d eterm in ed t o be 1 0 ,4 0 0
c a l o r i e s , Troutonns c o n s ta n t to be 2 3 .3 4 , and th e b o ilin g
p o i n t , by e x t r a p o la t io n , to be 4 4 5 . 6 ^ a *
C om parison o f t h e s e v a lu e s w ith t h o s e o f th e l i t e r a
tu r e ^ a r e f a v o r a b le . The b o ilin g p o in t i s h ig h compared to
t h a t o f C .C . M il l e r 5 (3 7 4 ° A), and lo w compared to t h a t o f
4
C. C. M i l l e r , £ . Chem. S o c . , 1 3 4 , 1823 ( 1 9 2 9 ).
S ch e n c k , M ih r, and B a n th ie n , B e r . 3 9 , 1518 (1 9 0 6 ).
Thorpe and T u tto n , £ . Chem. S o c . , 5 7 . 547 (1 8 9 0 ),
Van Doormaal and S c h e f f e r , R ec. T rav. Chim. 5 0 ,
1100 ( 1 9 3 1 ) . —
5
Miller, loc. cit.
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TABLE I
VAPOR PRESSURES O F PHOSPHOROUS OXIDE
22
Temp. C V .P . mm. lo g .V »P• lo g V .P . C a lc . D i f f .
2 2 . 8 1 .9 5 .2900 .2 9 2 - . 0 0 2
3 0 .0 3 .1 5 .4 9 8 3 .4 7 9 ♦ .0 1 9
3 5 .5 4 .2 0 .6 2 3 3 .6 1 3 ♦ . 0 1 0
4 0 .5 5 .5 5 .7 4 4 3 .7 3 1 ♦ .0 1 3
4 4 .0 6 . 1 0 .7 8 5 3 .8 1 1 - .0 2 6
4 5 .0 7 .1 0 .8 5 1 3 .8 3 4 + .0 1 7
5 0 .0 8 .5 2 .9307 .9 4 3 - .0 1 3
5 2 .0 9 .4 0 .9731 .9 8 6 - .0 2 3
5 3 .5 1 0 .2 5 1 .0 1 0 7 1 .0 1 8 - .0 0 8
5 5 .0 1 1 .0 5 1 .0 4 3 4 1 .0 4 9 - .0 0 6
5 5 .2 5 1 1 .5 5 1 .0 6 2 6 1 .0 5 6 ♦ .0 0 6
5 6 .2 5 1 1 .7 5 1 .0 7 0 1 1 .0 7 7 - .0 0 7
5 9 .8 1 3 .9 0 1 .1 4 3 0 1 .1 2 9 ♦ .0 1 4
6 1 .8 1 5 .1 0 1 .1 7 9 0 1 .1 8 8 - .0 0 9
6 6 . 0 1 8 .7 0 1 .2 7 1 8 1 .2 7 5 - .0 0 4
6 7 .7 5 2 0 .3 0 1 .3 0 7 5 1 .3 1 1 - .0 0 4
6 8 . 0 2 0 .8 5 1 .3 1 8 7 1 .3 1 6 ♦ . 0 0 2
7 1 .0 2 3 .1 0 1 .3 6 3 6 1 .3 7 2 - .0 0 9
7 4 .0 2 7 .2 0 1 .4 3 4 6 1 .4 3 3 ♦ . 0 0 1
7 4 .8 2 8 .1 0 1 .4 4 8 7 1 .4 4 5 ♦ .0 0 3
7 6 .0 2 9 .4 0 1 .4 6 8 4 1 .4 6 8 . 0 0 0
8 2 .0 3 7 .9 5 1 .5 7 9 2 1 .5 7 7 ♦ . 0 0 2
8 4 .5 4 2 .9 0 1 .6 3 2 5 1 .6 1 3 + .0 1 9
8 5 .0 4 3 .8 0 1 .6 4 1 4 1 .6 3 2 ♦ .0 0 8
9 S .5 5 7 .9 0 1 .7 6 2 7 1 .7 6 1 + . 0 0 1
9 5 .0 6 3 .5 0 1 .8 0 2 8 1 .8 0 5 - .0 0 3
1 0 0 . 0 7 7 .9 0 1 .8 9 1 4 1 . 8 8 6 + .0 0 5
1 0 5 .0 9 4 .4 0 1 .9 7 5 0 1 .9 6 6 + .0 0 9
1 1 1 . 0 1 1 9 .5 0 2 .0 7 7 4 2 .0 6 2 + .0 1 5
1 1 8 .0 1 5 4 .5 0 2 .1 8 7 9 2 .1 6 6 + . 0 2 1
1 2 0 .5 1 6 1 .0 5 2 .2 0 7 0 2 .2 0 5 + . 0 0 2
1 2 4 .0 1 8 0 .7 5 2 .2 5 7 1 2 .2 5 5 + . 0 0 2
1 2 9 .5 2 1 4 .0 0 2 .3 3 0 4 2 .3 3 4 - .0 0 4
1 3 0 .0 2 2 2 .5 5 2 .3 4 7 4 2 .3 4 1 + .006
1 3 4 .5 2 4 7 .0 0 2 .3 9 2 7 2 .4 0 7 - .0 1 5
1 3 5 .0 2 6 0 .7 5 2 .4 1 6 2 2 .4 1 0 + .0 0 6
1 3 8 .0 2 7 8 .2 0 2 .4 4 4 4 2 .4 5 0 - .0 0 6
i 3 9 .0 29 8 .9 0 2 .4 7 5 5 2 .4 6 4 + . 0 1 1
1 4 2 .0 3 1 3 .5 0 2 .4 9 6 2 2 .5 0 5 - .0 0 9
1 4 5 .0 3 4 1 .1 0 2 .5 3 2 9 2 .5 4 4 - . 0 1 2
1 5 1 5 .5 4 1 6 .6 5 2 .6 1 9 8 2 .6 2 8 - .0 0 9
Thorpe and T u tto n 6 (4 5 8 ° A) . M ille r o f f e r s a s an exp lan a
t i o n f o r th e h ig h b o ilin g p o in t th e p o s s i b i l i t y o f
in a c c u r a c ie s o f vap or t e n s io n m easurem ents ab ove 6 3 ° C due
to i n t e r a c t io n o f p h osp h orou s o x id e w ith w a te r to p rod u ce
p h o sp h in e . T h is e x p la n a tio n how ever w ould not a p p ly t o th e
work o f t h i s ex p erim en t a s i t was c a r r ie d o u t in th e h ig h
vacuum a p p a ra tu s in th e a b sen ce o f even th e s l i g h t e s t tr a c e
o f m o is tu r e .
The b o i l i n g p o in t a s d eterm in ed in t h i s work i s
p ro b a b ly a s l i g h t b i t h ig h due to th e p r e se n c e o f sm a ll
amount o f p h osp h oru s im p u r ity a s was shown i n th e a n a l y s i s ,
how ever i t i s n ot b e lie v e d to be 7 1 . 6 0 to o h ig h a s w ould be
th e c a se w ere M ille r * s v a lu e a c c e p te d a s t r u e . The au th or
f a i l s to f i n d an e x p la n a tio n f o r t h e break in th e cu rve
p r e s e n te d by M il l e r 7 and h en ce th e b o i l i n g p o in t d e r iv e d
th e r e fr o m cannot be a c c e p te d .
M o le cu la r w e ig h t d e te r m in a tio n s w ere made by ta k in g
a known w e ig h t o f m a t e r ia l, v a p o r iz in g i t and a p p ly in g th e
g a s la w s . The d e te r m in a tio n s (T a b le I I ) w ere h ig h , p o s s ib ly
due to a s s o c i a t i o n o f th e m o le c u le ; how ever i t was n o t ic e d
t h a t th e r e was a c o n tin u o u s d e c r e a s e in m o le c u la r w e ig h t a s
6
Thorpe and T u tto n , J . Chem. S o c . 5 7 . 547 ( 1 8 9 0 ) .
7
C. C. M i l l e r , J . Chem. S o c . 1 3 4 , 1828 ( 1 9 2 9 ).
TABLE I I
M OLECULAR WEIGHT DETERMINATION OF PHOSPHOROUS OXIDE
M ethod
R a o u lts m ethod in b en zen e (1)
R a o u lts m ethod in n a p h th a len e (1)
H offm ans m ethod in T o r r i c e l li a n Vacuum (1 )
A c tu a l M.1
227
218
T em perature C.
1 5 2 .0
1 3 1 .0
1 5 9 .0
1 8 4 .0
1 5 8 .0
1 8 3 .5
A c tu a l D e n s ity
7 .6 7
7 .7 5
7 .7 1
7 .6 9
7 .8 1
7 .8 3
T h e o r e tic a l
220
220
M .1
T h e o r e tic a l D e n s ity
7 .6 2
7 .6 2
7 .6 2
7 .6 2
7 .6 2
7 .6 2
P r e s e n t Work T em perature C.
9 1 .0
1 0 7 .0
1 4 0 .0
1 7 0 .0
1 8 7 .0
A c tu a l M.W.
243
238
239
2 3 5 .6
198
T h e o r e t ic a l
220
220
220
220
2 2 0
25
th e tem p era tu re was in c r e a s e d , in d ic a t in g d e c o m p o sitio n .
When th e b u lb was c o o le d to room tem p era tu re a n o n - v o l a t i l e
r e s id u e was fo u n d . T h is c o u p le d 'w ith th e f a c t t h a t , s in c e
t h e s i z e o f th e sam ple was v e r y s m a ll, a s l i g h t amount o f
im p u r ity w ou ld’ r e s u l t i n an a p p r e c ia b le e r r o r in th e
d e te r m in a tio n s , i s p erh ap s t h e e x p la n a tio n f o r th e v a r ia n c e
in v a lu e s o b ta in e d .
A fte r numerous t r i a l s th e au th or co n clu d ed th a t
b e fo r e th e m o le c u la r w e ig h t co u ld be d eterm in ed a c c u r a te ly
by th e vapor d e n s it y method a v ery pu re sam ple m ust be
o b ta in e d and a r a p id method o f v a p o r iz a t io n em p loyed . I t
was b e lie v e d th a t e it h e r t h e im p u r it ie s o r th e d e c o m p o sitio n
p r o d u c ts th e m s e lv e s c a ta ly z e d th e d e c o m p o sitio n a t th e
h ig h e r te m p e r a tu r e s.
As th e m o le c u la r w e ig h t d e te r m in a tio n was o n ly o f
seco n d a ry i n t e r e s t , no fu r t h e r work w as done tow ard t h i s
en d . However i t d oes s u g g e s t a v e r y i n t e r e s t i n g problem o f
p u r i f i c a t i o n and r a t e s o f d e c o m p o sitio n f o r - f u r t h e r s tu d y .
I I . BORON TRIFLTJ0RID1S
P r e p a r a tio n . Boron t r i f l u o r i d e was made by a
m o d if ic a t io n o f th e m ethod o f B ooth and W ills o n . 8 The
8
B ooth and W ills o n , ” Boron F lu o r id e ,” In o r g a n ic
S y n t h e s i s . V o l. I (New York: McGraw H i l l Book Company, 1 9 3 9 ),
p . 2 3 .
26
r e a c t io n b u lb c o n s is t e d o f a l i t e r rou n d -b ottom f l a s k w ith
a m ale ground g l a s s j o i n t s e a le d t o i t s n e c k . The f l a s k
c o u ld be a tta c h e d to th e vaeuum a p p a ra tu s th rou gh th e SO
sy stem by th e a id o f a cap c o n s is t in g o f a s to p -c o c k s e a le d
to th e c o r r e sp o n d in g fe m a le ground g l a s s j o i n t .
The c a lc u la t e d q u a n t i t i e s o f ammonium f lu o b o r a t e ,
b o r ic a c id , and s u l f u r i c a c id , w ere p la c e d in th e b u lb . A s
th e bu lb was s lo w ly e v a c u a te d , th e boron f l u o r id e was
e v o lv e d (w ith o u t need o f h e a tin g ) and was tra p p ed i n a tu b e
surrounded by l i q u i d a i r . Any w a te r w hich m igh t have been
c a r r ie d o v e r was tra p p ed o u t by p a s s in g th e BF3 ,. through a
- 7 8 .5 ° C b a th . The e q u a tio n o f th e r e a c t io n i s a s f o llo w s ;
6H H 4BF4 + B20 3 + 6HgS04 - » 8BF3 + 6NH4K304 + 3HgO
The p u r it y o f th e boron f l u o r id e was ch eck ed by i t s
vapor p r e s s u r e ta k e n a t - 1 1 1 .9 ° C. The f r a c t io n ; ta k e n
v a r ie d from 303 mm. t o 305 mm, and was in agreem ent w ith th e
e q u a tio n d eterm in ed by P ohland and H a r lo s, 9
lo g P - 1 1 7 4 .4 /T * 1 .7 5 lo g T - .01335T * 8 .0 5 3 6
and h en ce no f u r t h e r p u r i f i c a t i o n was r e q u ir e d .
9
E. P oh lan d and W. H a r lo s . z. A n org. A llg em . Chem.
2 0 7 , 242 (1 9 3 2 ).
I l l . OTHER REAGENTS
27
S u lf u r d io x id e . Com m ercial s u lf u r d io x id e was
p u r i f i e d by p a s s in g i t through a -6 0 ° C b a th . I t s p u r it y
was ch eck ed by a vapor t e n s io n m easurem ent, nam ely 173 mm.
a t -3 9 ° C.
T rim eth y ja m in e. T h is compound had been p rep ared
p r e v io u s ly i n ou r la b o r a t o r ie s and had o n ly to be ch eck ed
f o r i t s p u r it y by a vapor t e n s io n m easurem ent. Vapor
t e n s io n a t 0 ° C i s 680 mm. 1 0
10
A . Sim on and J . H u ter, Z. H e k tr o c h e m . 4 1 , 31
(1 9 3 5 ).
CHAFFER IV
RESULTS O F INDIVIDUAL EXPERIMENTS
T rim eth ylam in e and p h osp horous o x id e . In o r d e r to
d eterm in e how ph osp h orou s o x id e w ould r e a c t tow ard a g e n e r a l
b a s e , such a s tr im e th y la m in e , a 4 4 .1 c c . sa m p le, 1
(d eterm in ed by w e ig h t) was p la c e d in a r e a c t io n tu b e . Upon
t h i s was con d en sed 6 9 .8 5 e e . o f tr im e th y la m in e . The tu b e
was c lo s e d o f f from th e r e s t o f th e a p p a ra tu s and warmed t o
room te m p e r a tu r e . J tfte r sta n d in g f o r th r e e h o u rs th e tu b e
was c o o le d to - 7 8 .5 ° C and th e tr im e th y la m in e d i s t i l l e d o f f .
The t o t a l tr im e th y la m in e r e c o v e r e d was 6 9 .0 0 c c . and no
change in w e ig h t o f th e p h osp h orou s o x id e c o u ld b e d e t e c t e d .
S u lf u r d io x id e and p h osp horous o x id e . T h is exp erim en t
was perform ed in t h e same manner a s th e p r e v io u s o n e . A
4 0 .3 c c . sam ple o f p h osp h orou s o x id e was w eigh ed o u t and
th e n d i s t i l l e d in to th e r e a c t io n tu b e . S u lf u r d io x id e
( 6 0 .0 c c .) was con densed upon i t and th e m ix tu r e a llo w e d to
warm t o room tem p era tu re and sta n d f o r th r e e h o u r s . The
tu b e was c o o le d by a - 7 8 .5 ° C b ath and th e v o l a t i l e m a te r ia l
d i s t i l l e d o f f a t t h i s te m p e r a tu r e . M l o f th e s u lf u r
d io x id e was r e c o v e r e d and no change in w e ig h t o f th e
p h osp h orou s o x id e was d e t e c t e d .
1
M l g a s volum es m en tion ed in t h i s t h e s i s , a re
e x p r e ss e d in c u b ic c e n tim e te r s a t sta n d a rd c o n d it io n s .
29
Boron, f lu o r id e and p h osp horous o x id e . Two e x p e r i
m en ts o f t h i s ty p e w ere c a r r ie d o u t . The p ro ced u re was th e
same a s th a t u sed in th e two p r e v io u s e x p e r im e n ts.
P hosp horous o x id e (10 c c .) and boron f lu o r id e (80 c c .) w ere
u s e d . The boron f l u o r id e was d i s t i l l e d from th e m ix tu re
a t - 7 8 .5 ° C a f t e r sta n d in g a t room tem p era tu re f o r th r e e
h o u r s , le a v in g a w h ite s o l i d r e s id u e ; th e r e c o v e r e d boron
f l u o r id e w as 76 c c . The rem aind er o f th e boron f lu o r id e
was r e c o v e r e d by p r o lo n g e d pumping on th e r e s id u e a t room
te m p e r a tu r e .
The secon d ex p erim en t produced a p p ro x im a te ly th e same
r e s u l t s . The same 10 c c . o f ph osp h orou s o x id e was u sed w ith
70 c c . o f boron f l u o r i d e . T h is m ix tu re was a llo w e d t o sta n d
o v e r n ig h t . S e p a r a tio n o f th e u n r6 a c te d boron f lu o r id e from
th e m ix tu r e w as c a r r ie d o u t a t - 7 8 .5 C and gave 65 c c . o f
boron f l u o r i d e . The rem ain in g boron f l u o r id e was r e c o v e r e d
a s b e f o r e .
T h ese e x p e rim en ts in d ic a t e d t h a t a weak a d d itio n was
p o s s ib le and s u lf u r d io x id e , a s a s o l v e n t , was th e n u sed to
s e e i f more c o n c lu s iv e r e s u l t s c o u ld be o b t a in e d . 2
Boron f l u o r id e and p h osp horous o x id e i n s u lf u r d io x id e
s o l v e n t : E xp erim ent I . A 6 .1 c c . sam ple o f ph osp h orou s
2
T h is s o lv e n t w as u sed s u c c e s s f u ll y by M a rtin ,
" B eh a v io r o f H ex a m eth y len etetra m in e Towards Boron T r if lu o r id e ,*
(M a s te r 's t h e s i s , U n iv e r s it y o f S o u th ern C a lif o r n ia , Los
A n g e le s , 1940) and A rm stron g.
30
o x id e was w eigh ed ou t and th e n d i s t i l l e d in t o th e r e a c t io n
tu b e c o n ta in in g th e m a g n e tic s t i r r e r . An a p p r o x im a te ly 6
m l. sam ple o f s u lfu r - d io x id e was con densed upon th e o x id e .
In to t h i s was d i s t i l l e d 4 0 .8 c c . o f boron f l u o r i d e . The
s to p -e o c k w as c lo s e d and th e tu b e a llo w e d to warm t o - 7 8 .5 °
C a t w hich tem p er a tu r e th e s u lf u r d io x id e was l i q u i d and
d is s o lv e d m ost o f th e p h osp h orou s o x id e . The m a g n etic
s t i r r e r was o p e r a te d t o in s u r e th orou gh m ix in g .
A f t e r one hour th e v o l a t i l e m a t e r ia ls w ere d i s t i l l e d
o f f a t -4 0 ° G and th e b oron f l u o r id e se p a r a te d from t h e
s u lf u r d io x id e by f r a c t i o n a l c o n d e n sa tio n u s in g a -1 4 5 ° C
b a th . The t o t a l boron f lu o r id e r e c o v e r e d was 37 c c .
The boron f l u o r id e and s u lf u r d io x id e w ere r e tu r n e d
to th e r e a c t io n tu b e and th e above tr e a tm e n t r e p e a te d t w ic e ,
w ith in c r e a s in g a b s o r p tio n o f boron f lu o r id e a s in d ic a t e d
i n T ab le I l i a .
E xperim ent I I . N ine and f o r t y - s i x h u n d red th s c c . o f
ph osp h orou s o x id e was w eigh ed o u t and d i s t i l l e d in t o th e
r e a c t io n tu b e .c o n ta in in g th e m a g n etic s t i r r e r . A p proxim ate
l y 1 0 m l. o f s u lfu r d io x id e w as d i s t i l l e d in to th e tu b e f o r
s o lv e n t p u r p o s e s . To t h i s w as ad d ed , in 9 c c . p o r t io n s ,
4 6 .2 5 c c . o f boron f lu o r id e g iv in g a m ole r a t i o o f a p p r o x i
m a te ly 5 BF3 to 1 P ^ g . A f t e r each a d d it io n , th e m ix tu r e
was warmed to - 7 8 .5 0 C, th e n c o o le d w ith l i q u i d a i r and th e
31
n e x t p o r tio n ad d ed . The ap p earan ce o f a w h ite f l o c c u l e n t
p r e c i p i t a t e was n o t ic e d a f t e r th e secon d 9 c c . a d d it io n .
The m ix tu r e rem ained a t - 7 8 .5 ° C f o r n in e and one
h a lf h ou rs and w as th e n warmed to - 2 2 ° C and a llo w e d to
sta n d fo r fo u r h o u rs w ith s t i r r i n g . The v o l a t i l e m a te r ia l
was th e n su b lim ed o f f from a - 7 8 .5 ° C b a th and f r a c t io n a t e d
th rou gh a -1 4 5 ° C b a th . The t o t a l b oron f l u o r id e r e c o v e r e d
was 2 9 .6 3 c c . th u s in d ic a t in g th a t a 1 .7 5 to 1 a d d itio n had
b een m ade.
The r e a c t io n b u lb was rem oved from th e a p p a r a tu s,
w ith o u t a d m ittin g a i r nor warming above - 7 8 .5 ° C, and a
d e ta c h a b le manometer was a tta c h e d to th e ap p aratu s by th e
a id o f p i c e i n (F ig u r e V I ) . The tu b e was a tta c h e d to th e
manom eter so t h a t p r e s s u r e d ev elo p m en ts co u ld be ch eck ed .
The tu b e was opened to th e ev a cu a ted m anom eter but showed
no p r e s s u r e a t - 7 8 .5 ° C. The tu b e was warmed to - 4 5 .2 ° C
(m e ltin g p o in t o f C h lorob en zen e) and a f t e r sta n d in g one and
one h a l f h ou rs a p r e s s u r e o f l e s s th a n 1 mm. was d e t e c t e d .
At 0 ° C a 6 mm. p r e s s u r e was o b ta in e d and t h i s rem ained
c o n sta n t f o r abou t s i x h o u r s.
The tu b e was th e n su rroun ded by a 21° C w a te r bath
and a llo w e d to sta n d f o r e ig h t h o u r s . The p r e s s u r e
d e v e lo p e d was 17 ram . The s to p -c o c k on th e r e a c t io n b u lb
was c lo s e d and th e g a s i n th e manometer s e c t i o n w as rem oved.
The bulb was a g a in opened to th e manometer and t h e new ly
T O LINE
s o _
S Y S T E M
PICEIN
JO IN TS'
R B M S
D E T A C H A B L E M A N O M E T E R
F I G U R E 3ZE
33
d e v e lo p ed p r e ssu r e was a g a in c h e ck ed . In t h i s manner
s e v e r a l sm a ll p o r tio n s o f g a s were removed and each tim e
th e r e was a d e c r e a se i n th e p r e ssu r e d e v e lo p e d . The f i n a l
r e a d in g , ta k e n a t room te m p e r a tu r e , w as 7 mm. a f t e r sta n d in g
fo r t h i r t y - s i x h o u r s .
The tu b e was th e n surrounded by an o i l b ath and
warmed t o 1 8 0 ° C. The v o l a t i l e m a te r ia l w as removed
p e r i o d i c a l l y . Th6 r e s id u e was s t i l l a w h ite g r a n u la r
m a te r ia l show ing no s ig n s o f d ark en in g even a t 180 - 19 0 ° c.
The p r e s s u r e d e v e lo p ed v e r y s lo w ly th u s in d ic a t in g a f a i r l y
s t a b le m a t e r ia l.
The tem p era tu re was g r a d u a lly in c r e a s e d to 308° G.
S m a ll oran ge s p o t s w ere th e n n o tic e d in th e r e s id u e . T h is
was assum ed to be th e d e c o m p o sitio n p ro d u ct w hich was
e v id e n t when th e o x id e i t s e l f was h e a te d to such h igh
te m p e r a tu r e s. The t o t a l boron f l u o r id e r e c o v e r e d was
3 5 .6 3 c c . th u s in d ic a t in g th a t a compound o f th e r a t io
P4 0 g * l.S 4 BF3 rem ained even a f t e r h e a tin g in vacuo to
308° C.
Dry a i r was a d m itted t o t h e sam ple w ith no change in
i t s a p p ea ra n ce. The m a te r ia l was h y g r o s c o p ic , and very
s o lu b le i n w a te r . A q u a l i t a t i v e s u l f i t e t e s t p roved to be
n e g a t iv e . The m a te r ia l when h e ld on a s p a tu la , o v e r an
o p 6 n fla m e , d id ap p ear t o m e lt .
34
The r e s u l t s o f t h i s ex p erim en t are sum m arized in
T a b le I I I b .
P r e s s u r e E xperim ent I . The r e s u l t s o f th e p r o c e e d in g
e x p e rim en ts in d ic a t e d t h a t p erh a p s a more c o m p lete r e a c t io n
co u ld be o b ta in e d by a llo w in g t h e m a t e r ia ls to r e a c t a t a
h ig h e r tem p era tu re and a h ig h e r p r e s s u r e . I t was d e c id e d to
run th e r e a c t io n i n a bomb tu b e a t a p r e ssu r e o f a p p ro x im a te
l y t e n a tm osp h eres and a t room te m p er a tu r e.
Th6 bomb tu b e o f about 16 c c . c a p a c it y was made o u t o f
1 2 mm. p y rex tu b in g and was equip ped w ith a drawn-down s id e -
arm to f i t th e tu b e o p e n e r . T h is tu b e was a tta c h e d to th e
a p p a ra tu s th rou gh th e ’ TO* s e c t i o n and 2 2 .3 e c . o f
p h osp h orou s o x id e d i s t i l l e d in to i t . A p p ro x im a tely 4 m l. o f
l iq u i d s u lf u r d io x id e was th e n d i s t i l l e d upon t h e P4 O 3 and
was fo llo w e d by 1 1 8 .8 c c . o f boron f l u o r i d e . The tu b e was
s e a le d o f f and a llo w e d to warm t o room tem p er a tu r e. The
q u a n t i t i e s u sed w ere such t h a t i f o n ly 1 .7 5 m o le s o f boron
f l u o r id e w ould r e a c t , th e t o t a l p r e s s u r e w ould b e about 1 0
a tm osp h eres and t h a t o f th e boron f l u o r id e b etw een 5 and 6
a tm o sp h e re s.
The fo r m a tio n o f a w h ite p r e c i p i t a t e was n o t ic e d
im m ed ia te ly a s th e s u lf u r d io x id e m e lte d . A t no tim e w as
t h e r e a p e r io d o f pu re s o l u t i o n . The r e a c t io n had begun
and p r e c i p i t a t i o n o c cu rr ed b e fo r e a l l th e o x id e had
35
d is s o lv e d . T h is heavy p r e c i p i t a t e s e t t l e d and caked in th e
bottom o f th e tu b e and i t w as fe a r e d th a t some o f th e o x id e
d id n o t have tim e to d i s s o l v e and an in c o m p le te r e a c tio n
m igh t have r e s u l t e d .
A f t e r s ta n d in g a t room tem p eratu re f o r two h o u r s, th e
tu b e was c o o le d f i r s t w ith a - 7 8 .5 ° G b a th and th e n w ith
l i q u i d a i r . I t was a tta c h e d to th e tu b e o p e n e r , w hich in
tu r n was a tta c h e d to th e vacuum system through th e d e ta c h a b le
m anom eter, and opened to th e d i s t i l l a t i o n sy ste m .
The v o l a t i l e m a te r ia l was th e n su b lim ed from a - 7 8 .5 °
C. b a th and f r a c t io n a t e d th rou gh a -1 4 5 ° C b a th . The t o t a l
b oron f lu o r id e was 6 0 .3 3 c c . th u s show ing t h a t a compound
o f th e r a t io F4 0 g * 2 .8 3 BEg had b een form ed and was s t a b le a t
- 7 8 .5 ° C.
The tem p eratu re su rrou n d in g th e tu b e was r a is e d
u s in g c o n sta n t tem p era tu re b a th s , up t o room te m p e r a tu r e .
I t was th e n h e a te d w ith an o i l b ath to 30 0 ° C. A t each
tem p era tu re r e a d in g , t h e g a s was rem oved and i t s p r e s s u r e
and volum e were ta k e n . The r e s u l t s a r e ta b u la te d in T ab le
I I I c . T h ese f i g u r e s a r e b a sed on sa m p les o f pure
p h osp h orou s o x id e . (A n alyzed sa m p le ).
F i s s u r e E xperim ent I I . T h is ex p erim en t was sub
s t a n t i a l l y th e same a s t h e p r e v io u s e x c e p tin g t h a t s m a lle r
q u a n t i t i e s w ere u sed in an e f f o r t to m in im ize th e
36
d i f f i c u l t i e s produced by th e p r e s e n c e o f th e la r g e
p r e c i p i t a t e form ed b e f o r e .
A bomb tu b e o f th e sam6 c a p a c ity a s b e fo r e , but w ith
two s id e arm s, was m ade. In to t h i s was d i s t i l l e d 6 .7 7 0 c c .
o f pu re p h osp h orou s o x id e . To t h i s was added about 4 ml
o f l i q u i d s u lf u r d io x id e . The tu b e was s e a le d o f f and
a llo w e d t o warm t o room tem p er a tu r e. The o x id e d is s o lv e d
c o m p le te ly i n th e l i q u i d s u lf u r d io x id e g iv in g a c le a r
s o l u t i o n .
The tu b e was c o o le d w ith l i q u i d a ir and opened to
th e a p p a ra tu s w ith th e a id o f th e tu b e o p e n e r . I n to i t
th e n was d i s t i l l e d 1 0 4 .9 3 c c . o f boron f l u o r i d e . The tu b e
was s e a le d o f f and a llo w e d to sta n d a t room tem p era tu re f o r
two w eek s. The w h ite p r e c i p i t a t e form ed a s in th e p r e v io u s
e x p e r im e n ts. The tu b e was th e n c o o le d w ith - 7 8 .5 ° C b a th
and th e n w ith l iq u i d a i r , a tta c h e d to th e tu b e o p en er and
opened t o t h e ap p a ra tu s a s b e f o r e . The v o l a t i l e m a te r ia l
was su b lim ed o f f from a - 7 8 .5 ° C b a th u n t i l no p r e ssu r e
d e v e lo p ed a t t h i s te m p e r a tu r e . T h is o p e r a tio n r e q u ir e d
t h r e e d ays s u b lim a tio n . The tem p era tu re o f th e b ath was
in c r e a s e d and p r e s s u r e s and c o m p o sitio n reco rd ed a s in th e
p r e v io u s e x p e r im e n t. The d a ta o f ^ t h is exp erim en t a re
summ arized in T ab le I I I d .
37
TABLE I I I
(a) R e a c tio n o f w ith BFg in 3 0 g s o l v e n t . E xperim ent 1 .
I n i t i a l Q u a n t it ie s : 6 .1 e e . P4 O5 , 4 0 .8 c c . BFg.
No. Time H rs. c c • BF g R a tio c c . BF3 M ole R a tio
-
r e c o v e r e d to c c . P .0 A
i ! t ? 6
: BFS
1 1 3 7 .0 3 .8 : 6 .1 : 1 . 0 0
2 2 3 6 .2 4 .6 : 6 .1 1 . 3 3 : 1 . 0 0
3 24 3 3 .0 7 .8 : 6 .1 1 . 0 0 : 1 .2 8
(h) E xperim ent 2 .
I n i t i a l Q u a n t it ie s : 9 .4 6 c c . P4 OA, 4 6 .2 5 c c . BFg.
Temp. C BF3 R ecovered EF3 R ea cted M ole R a tio
c c . c c . P .0 fi : BF*
- 7 8 .5 2 9 .6 3 1 6 .6 2 1 .0 0 : 1 .7 5
3 0 8 .0 3 5 .6 3 1 1 .6 2 1 .0 0 : 1 .2 4
( 0 ) P r e s s u r e E xperim ent 1 .
I n i t i a l Q u a n t it ie s ; 2 2 .1 0 c c . o f pu re F^O
Temp. C
- 7 8 .5
- 4 5 .2
- 1 9 .0
2 3 .0
3 0 0 .0
BFg R ecovered
c c .
6 0 .3 0
0 .3 1
1 .9 0
2 .3 9
1 0 .5 0
BFg Reac'
c c .
5 8 .5 0
5 8 .2 9
5 6 .3 9
5 4 .0 0
4 3 .5 0
led
1 1 8 .8
Mole
P4O6
1.00
1.00
1.00
1.00
1.00
c c . BF,
R a tio c
BFg
2 .6 5
2 .6 4
2 .5 5
2 .4 4
1 .9 6
(d) P r e s s u r e E xperim ent 2 .
I n i t i a l Q u a n t it ie s ; 6 .7 7 c o . ~ < 3 f pure P4 O5 , 1 0 4 .9 3 c c . BFg
Temp. G BFg R ecovered ' BFg R ea cted Mole R a tio
c c . c c .
*4°6
BFg
- 7 8 .5 7 9 .8 7 2 5 .0 6 1 . 0 0 3 .7 0
0 . 0 2 .7 1 2 2 .3 5 1 . 0 0 3 .3 0
2 3 .0 1 .5 7 2 0 .7 8 1 . 0 0 3 .0 7
2 8 0 .0 3 .2 5 1 7 .5 3 1 . 0 0 2 .5 7
CHAPTER V
CONCLUSIONS
The e x p e r im e n ta l r e s u l t s have shown th a t boron
f lu o r id e adds t o ph osp h orou s o x id e ; t h e h ig h e s t o b serv ed
m ole r a t io o f boron f lu o r id e to p h osp h orou s o x id e was 3 .7 0 .
The manner i n w h ich boron f l u o r id e was g iv e n o f f from th e
compound i n d ic a t e s a m ix tu r e o f compounds from t h e one to
one r a t i o to t h e on e t o fo u r r a t i o . S tu d y o f t h 6 d ecom p osi
t i o n o f t h e s e compounds by p r e ssu r e m easurem ents i s
ren d ered d i f f i c u l t b e c a u se o f s o l i d s o l u t i o n e f f e c t s .
When t h i s problem was f i r s t u n d erta k en i t was hoped
t h a t d e f i n i t e c o n c lu s io n s ,' a s to J u st w here th e boron
f lu o r id e would ad d , c o u ld be drawn. For exam p le, i f a fo u r
to one a d d itio n had o c cu rr ed and no m ore, we co u ld sa y
p o s i t i v e l y t h a t th e a d d it io n was made th rou gh th e
ph osp horus and n o t th e o x y g e n . On t h e o th e r hand i f a
la r g e r a d d it io n had o c cu rr ed th e oxy g en atom s would
p ro b a b ly be th e e le c t r o n d o n o r s.
However d i f f i c u l t i e s in o b ta in in g v e r y pure
p h osp horous o x id e and th e f a i l u r e to o b ta in a d e f i n i t e fo u r
and one a d d it io n compound make th e c o n c lu s io n s l e s s p o s i t i v e .
None th e l e s s , th e a d d it io n through th e p h osp h orou s atom s i s
th e m ost p r o b a b le . I n th e stu d y o f th e s t r u c t u r e o f
39
p h osp h orou s oxide*' i t h a s been shewn th a t th e v a lu e s o f t h e
P - 0 d i s t a n c e s , 1 .6 7 ‘ 1 i n d ic a t e a la r g e amount o f d ou b le
bond c h a r a c te r , a s do th e v a lu e s o f 1 26° o b ser v ed f o r th e
P - 0 - P bond a n g le . T h is d o u b le bond e f f e c t sh o u ld
ren d er th e oxygen much l e s s a p t to o f f e r i t s e l f f o r th e
a d d it io n o f th e boron f l u o r i d e m o le c u le .
The 3 p e le c t r o n s o f th e p h o sp h o ru s, h ow ever, are
much more a v a ila b le f o r t h i s a d d it io n , and a lth o u g h i t i s
w ith r e lu c t a n c e th a t th e p h osp h oru s sh a r e s two o f t h e s e
e le c t r o n s w ith th e boron f l u o r i d e , a s shown by th e d i f f i
c u lt y i n form in g th e a d d it io n , t h e compound w hich i s form ed
i s s u r p r is in g ly s t a b l e , decom p osing o n ly s lo w ly even a t
te m p e r a tu r e s o f 280 - 300° c e n tig r a d e .
I . SUM M A R Y
P h osp h orou s o x id e was p rep ared and p u r if ie d by means
o f th e h ig h vacuum a p p a r a tu s. I t s p u r it y was check ed by
m easurem ent o f i t s vap or t e n s io n and by a n a ly s is f o r
p h o sp h o ru s. The d a ta on vapor t e n s io n w ere compared w ith
l i t e r a t u r e v a l u e s .
P hosp horous o x id e e v id e n t ly h a s l i t t l e g e n e r a l a c id
c h a r a c te r f o r i t f a i l s t o r e a c t w ith tr im e th y la m in e . On th e
1
L in u s P a u lin g , The N atu re o f th e C hem ical Bond
( I t h a c a , N6 W York: C o r n e ll U n iv e r s it y P r e s s , 1 9 4 0 ) , p . 2 4 7 .
40
o th e r han d, i t s b a se c h a r a c te r i s in d ic a t e d by i t s
d i f f i c u l t l y - r e v e r s i b l e a d d it io n o f boron f l u o r i d e , a
r e a c t io n w h ich p r o c e e d s b e s t i f an a c id ic s o l v e n t , such a s
l i q u i d s u lf u r d io x id e , i s em ployed. S u lf u r d io x id e i t s e l f
d o e s n ot r e a c t w ith p h osp horous o x id e , b u t by i t s u s e i t
was p o s s i b l e to form a m a te r ia l h a v in g th e c o m p o sitio n
P4<)g*3.70 BF3 ( a t h ig h p r e s s u r e s o f boron f l u o r i d e ) . The
rem oval o f boron f lu o r id e from such m a te r ia l i s d i f f i c u l t ,
and d e f i n i t e s t e p s c o u ld not be r e c o g n iz e d .
BIBLIOGRAPHY
BIBLIOGRAPHY
A rm stron g, D ., ^ S tu d ie s in th e C h em istry o f s u l f u r N it r id e ,*
U n p u b lish ed D o c to r ’ s d i s s e r t a t i o n , The U n iv e r s it y o f
S o u th e rn C a l i f o r n ia , Los A n g e le s , 1 9 4 2 .
B i l t z , H. and A. G r o s s, B e r . 52B, 762 (1919) .
B ooth and W illia m s , "Boron F lu o r id e ,* In o r g a n ic S y n t h e s i s .
New Y ork; McGraw H i l l Book Company, 1 9 3 9 .
B urg, A. B, and H. I . S c h le s in g e r , J . Am. Chem. S o c . 5 9 .
7 80, ( 1 9 3 7 ) .
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Hampson, G. and A. S t o s i c k , £ . Am. Chem. S o c . 6 0 , 1814 (1 9 3 7 ).
Ingram , D, "The B eh a v io r o f P h o sp h o ric A nhydride Towards
A c id ic and B a s ic R e a g e n ts.* U n p u b lish ed M a ster ’ s
t h e s i s , U n iv e r s it y o f C h ica g o , 1 9 3 9 .
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P h y. 5 , 626 ( 1 9 3 7 ) . ”
" M ellor’ s C om prehensive T r e a t is e on In o r g a n ic and T h e o r e tic a l
C h e m istr y ,” P h o sp h o r u s, V o l. V I I I . Longmans, G reen
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1823 (1 9 2 9 )”
P a u lin g , L ., The N ature o f th e C hem ical Bond. New York;
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P o h la n d , E . and H a r lo s , Z. A norg. A llg em . Chem. 2 0 7 , 242
(1 9 3 2 ). ~
S e h e n c k , R, F . M ih r, and H. B a n th ie n , B e r . 3 9 , 1518 (1 9 0 6 ) .
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Creator Rapp, L. R (author)

Core Title The addition compound of phosphorous oxide and boron trifluoride

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