The dielectric properties of some esters of titanium tetrachloride containing organic groups
by Robert W Crowe
A THESIS Submitted to the Graduate Committee in partial fulfillment of the requirements for the
degree of Master of Science in Chemistry
Montana State University
© Copyright by Robert W Crowe (1948)
Abstract:
Several derivatives of TiC14 containing organic groups, have been prepared and, the dielectric
properties of some of these studied. The compounds prepared were: titanium tetraethylate,
Ti(OC2H5)4 monochloro-tri- ethoxy-titanium, TiCl(OC2H5)3; trIchloro-phenoxy-tItanium,
TiC13OC6H5; di- chloro-diethoxy-titanium, TiC12(OC2H5)2; and compounds formed by the reaction
of TiC14 with ethylene glycol and hexamethylene glycol.
The dielectric constants of Ti(OC2H5)4, TiCl(OC2H5)3 and Ti13OC6H5. have been measured in
dilute solution in benzene at 25°C and their molar polarizations, calculated by an equation derived from
the Debye-Clausius-Mossotti equation, have been found to be 108, 222 and 250 ml. respectively. The
molar refraction of Ti(OC2H5)4 has been calculated from measurements of its refractive index and
density in the pure state. The value obtained was 64.4 ml. The molar refractions of TiCl(OC2H5)3 and
TiCl3OC6H5 were calculated from measurements of their refractive indices and densities in dilute
solution in benzene. The values obtained here were and 66.6 ml. res— , pectively. The electric
moments for Ti(OC2H5)4, TiCl(OC2H5)3 and TiC13OC6H5 have been found to be 1,4, 2.83 and 2.97
Debye units respectively. Several unsuccessful attempts have been made to purify the other compounds
prepared.
Ti(OC2H5)4 previously reported as a liquid, has been found to exist as a white solid, stable below
34°C. The dielectric constant of this compound has been measured through its melting point to
determine the effect of solidification on the rotation of the molecule.
The apparatus used for all measurements has been described and an attempt made to explain the
experimental results. i
. OHE DIELECTRIC PROPERTIES OF SOME ESTERS OF TITjUJIUM
. .TETRACHLORIDE CONTAINING ORGANIC GROUPS
'
'
'
by
ROBERT V, CROM
-
A THESIS
S u b m itte d to th e G ra d u a te Com m ittee
in
" p a r t i a l f u l f i l l m e n t o f th e r e q u ir e m e n ts
f o r th e d e g re e o f
M a s te r o f S c ie n c e i n C h e m is try
at
M ontana S t a t e C o lle g e
A pproved :
I n C harge o f M ajo r V^lrk
Bozem an9 M ontana
A u g u s t9 1948
c, S K b tb
°°f- 3
.
-
2
H tt1
-
TABLE OF CONTENTS
P age
I.
ABSTRACT ...........................................
3
II.
INTRODUCTION .................................
U
III.
LITERATURE SURVEY........................
5
IV.
THEORY AND POSSIBILITIES . .
7
V.
PREPARATION OF COMPOUNDS USED
T ita n iu m t e t r a e t h y l n t e
14
..................................................................
K o n o c h lo ro -t r i e t h o x y - t i t a n i u m
14
....................................................
15
D i c h l o r o - d i e th o x y - t ita n i u m
.........................................................
16
T r i c h l o r o - p h e n o x y - tita n iu m
.........................................................
18
T ita n iu m T e t r a c h l o r i d e —e th y le n e g l y c o l compound . . .
19
ELECTRIC MOMENT MEASUREMENTS ..............................................................
21
A p p a ra tu s u s e d f o r m easu rem en ts ...............................................
21
M ethod o f c a l c u l a t i o n .......................................................................
26
E l e c t r i c moment o f ti ta n i u m t e f r a e t h y l a t e
........................
28
E l e c t r i c moment o f m o n o c h lo r o - tr ic th o x y - ti ta n iu m . . .
43
E l e c t r i c moment o f T r ic h lo r o - p h e n o x y - tita n iu m . . . .
46
DIELECTRIC CONSTANT OF Ti(OC2H ^)lt, THROUGH TRANSITION POINT
51
V III,
DISCUSSION OF EXPERIMENTAL RESULTS ...............................................
54
IX
SUMMARY.................................................................................................................
56
X
ACKNOWLEDGEMENTS ..........................................................................................
53
XI,
LITERATURE CITED AND CONSULTED .........................................................
59
V I.
V
I
V
Rj
U
'X
X
V II,
I.
ABSTRACT
S e v e r a l d e r i v a t i v e s o f T iC l^ 8 c o n t a in in g o r g a n ic g r o u p s » h av e b e e n
p r e p a r e d and, th e d i e l e c t r i c p r o p e r t i e s o f some o f th e s e s t u d i e d .
pounds p r e p a r e d w e re :
The com­
t i ta n i u m t e t r a e t h y l a t e , Ti(OCgH g)^; m o n o c h lo r o - tr i-
e t h o z y - t i t a n i u m , TiC l(O C gH g)^; tr i c h l o r o - p h e n o x y - t i t a n i u m , TiClgOC^Hg; d i -
^
c h l o r o - d i e t h o x y - t i t a n i u m , TiClg(OOgEg)ZS and compounds fo rm ed b y th e r e a c ­
t i o n o f T iC l^ w ith e t h y le n e g l y c o l and h e x a m e th y le n e g l y c o l .
The d i e l e c t r i c c o n s ta n t s o f Ti(O C gE g)^, TiCl(OCgHg)^ and TiCl^OC^Hg,
h av e b e e n m easu red i n d i l u t e s o l u t i o n i n b e n z e n e a t 25°C and t h e i r m o la r
p o l a r i z a t i o n s , c a l c u l a t e d b y an e q u a tio n d e r iv e d , from th e D e b y e -C la u s iu s M o s s o tti e q u a t io n , h a v e b e e n fo u n d to be 108, 222 and 250 m l. r e s p e c t i v e l y .
The m o la r r e f r a c t i o n o f 'Ti(O C gEg)^ h a s b e e n c a l c u l a t e d fro m m easu rem en ts o f
i t s r e f r a c t i v e in d e x and d e n s i t y i n th e p u re s t a t e .
6 4 .4 m l.
The v a lu e o b ta in e d w as
The m o la r r e f r a c t i o n s o f TiCl(OCgHg)^ an d TiClgOC^Hg w ere c a lc u ­
l a t e d from m easu rem en ts o f t h e i r . r e f r a c t i v e i n d i c e s and d e n s i t i e s in d i l u t e
s o lu tio n in b en ze n e.
p e c tiv e ly .
The v a l u e s o b ta in e d h e r e w ere 5 4 .8 and 6 6 .6 m l. r e s - .
The e l e c t r i c moments f o r T i (O C g H g )T iC l(O C g H g )^ and TiClgOC^Hg
h a v e b e e n fo u n d to - b e 1 , 4 , 2 .8 3 and 2 .9 7 Debye u n i t s r e s p e c t i v e l y . ' S e v e r a l
u n s u c c e s s f u l a t te m p t s h av e b e e n made to p u r i f y th e o t h e r compounds p r e p a r e d .
T i (OCgHg)|j., p r e v i o u s l y r e p o r t e d a s a l i q u i d , h a s b e e n fo u n d to e x i s t a s
a w h ite s o l i d ,
s t a b l e below 34°C .
The d i e l e c t r i c c o n s t a n t o f t h i s compound
h a s b e e n m easu red th ro u g h i t s m e lti n g p o i n t to d e te rm in e th e e f f e c t o f s o l i ­
d i f i c a t i o n on th e r o t a t i o n o f th e m o le c u le .
The a p p a r a tu s u s e d f o r a l l m easu rem en ts h a s b e e n d e s c r ib e d and an a t ­
te m p t made to e x p l a i n th e _ e x p e r im e n ta l r e s u l t s .
I
— ^4- OW
>
Ho
IN T RODUCTION
T ita n iu m d io x id e and s e v e r a l o t h e r in o r g a n i c compounds o f ti t a n i u m
'
'
I
h av e b e e n known f o r some tim e to p o s s e s s an a b n o rm a lly h ig h d i e l e c t r i c
c o n s ta n t*
AS a r e s u l t thoiy hav e b@@n*used q u i t e e x t e n s i v e l y a s d i e l e c t r i c
m a t e r i a l s in e l e c t r i c a l c o n d e n s e r s .
From t h i s f a c t ,
i t seem ed t h a t p e r h a p s
some o rg an o ti t a n i u m compounds m ig h t a l s o e x h i b i t ab n o rm al b e h a v io r , and
t h a t t h e i r o t h e r p r o p e r t i e s m ig h t make them ev en more u s e f u l a.s d i e l e c t r i c s
th a n t i ta n i u m d i o x i d e .
W ith th e s e p o s s i b i l i t i e s i n m ind, i t was d e s i r e d to a tte m p t th e p r e p a r a t i o n and p u r i f i c a t i o n o f some d e r i v a t i v e s o f T iC l^ c o n t a i n i n g o r g a n ic
g r o u p s , and s tu d y t h e i r d i e l e c t r i c p r o p e r t i e s .
I n a d d i t i o n , a s tu d y o f
th e s e p r o p e r t i e s w i l l add v a l u a b le in f o r m a tio n r e g a r d i n g th e n a t u r e and
s t r u c t u r e o f th e compounds and th e b o n d s in v o lv e d .
S e v e r a l p o ly m e r - lik e compounds o f q u e s ti o n a b le s t r u c t u r e and com posi­
t i o n h a v e b e e n p r e p a r e d by th e r e a c t i o n o f T iC l^ w ith p o ly - h y d r o x y a l c o h o l s
su c h a s g l y c o l and g l y c e r o l ,
T hese compounds a lo n e , i f s t a b l e , . s h o u ld make
a v e r y i n t e r e s t i n g s tu d y ,
. . . . .
--Ir f T!'*1, 11*Wn-lWa
iT
'O i ■ "
T
...
.
III.
L IEBBATDKB SURVEY
Many im p o r ta n t a d v an c es h av e r e c e n t l y "been made from d i e l e c t r i c
s t u d i e s c o n c e r n in g th e s t r u c t u r e and c o n f i g u r a t i o n o f m o le c u le s .
In t h i s
c o n n e c tio n , th e e l e c t r i c moment c o n c e p t i s o f c o n s id e r a b le v a l u e , s in c e i t
can be u s e d to d e te r m in e th e e l e c t r i c a l asym m etry o f m o le c u le s .
B o th Debye ( 3 ) and Smyth (1 0 ) h av e g iv e n a co m p re h en siv e t r e a t i s e on
d i e l e c t r i c p r o p e r tie s in g e n e r a l.
A more d e t a i l e d tr e a tm e n t o f a p o r t i o n
o f t h e i r w ork i s g iv e n in th e n e x t s e c t i o n . ' T h e ir w ork and th e w ork o f
num erous o t h e r i n v e s t i g a t o r s i n t h i s f i e l d h a s done a g r e a t d e a l to ad v an c e
o u r know ledge o f p o l a r m o le c u le s an d th e r e l a t i o n o f d i e l e c t r i c c o n s t a n t s
to m o le c u la r s t r u c t u r e .
■ T ita n iu m d io x id e p o s s e s s e s , p e r h a p s , some o f th e m o st u n u s u a l d i e l e c ­
t r i c p ro p e rtie s .
M ost s o l i d s h av e d i e l e c t r i c c o n s t a n t s fro m I to 1 0 , w h ile
t h e r e a r e a few in o r g a n i c s o l i d s w ith d i e l e c t r i c c o n s t a n t s o f 15 to 3 0 *
The m ost common fo rm o f T.102 ( R u t i l e ) , h o w ev er, h a s b e e n fo u n d to h a v e a
mean d i e l e c t r i c c o n s t a n t o f I l h ( l ) w h ich i s e s s e n t i a l l y c o n s ta n t w ith f r e ­
q u e n c y . ."B ecau se o f t h i s a b n o r m a lity , i t h a s r e c e n t l y fo u n d u s e a s a d i ­
e l e c t r i c i n h ig h f r e q u e n c y e l e c t r i c a l c a p a c i t o r s .
The d i e l e c t r i c p r o p e r t i e s o f a few o r g a n o - m e ta l lic compounds h a v e b e e n
s t u d i e d - ( l l ) » b u t v e r y l i t t l e h a s b e e n done w ith su ch compounds c o n t a i n i n g
tita n iu m .
U l i c h 9 H e r t e l and H e s p i t a l (1 2 ) h av e m easu red th e t o t a l p o l a r i ­
z a t i o n s and d ip o l e moments o f a few a d d i t i o n a l compounds o f T iC lifi su ch a s
T iC lifC 2K5CH, T iC ljfa G 2H5CH, T iO ljfC ^ E 5CH, and TiCljif0CgH5HO2 .
I n th e p r e ­
s e n t i n v e s t i g a t i o n , h o w ev er, th e m ain i n t e r e s t was c e n t e r e d aro u n d d e r i v a -
vr-
I-,-.!-,.- ..
■ fcives o f TiClj^ c o n t a in in g o r g a n ic g r o u p s .
S e v e r a l p f th e s e compounds
h a v e b e e n p r e p a r e d p r e v i o u s l y . . Compounds o f th e ty p e , T i(O R )^ , h av e b e e n
p r e p a r e d b y B ls c h o f f and A dkins ( 2 ) .
J e n n in g s , W ardlaw and Way ( ? ) h a v e
a l s o p r e p a r e d s e v e r a l , c h l o r o - e s t e r s o f th e ty p e TiGl(QR)-J and T iO lg C O ^ g .
I n a d d i t i o n , p o ly m e r - lik e compounds o f q u e s ti o n a b le s t r u c t u r e h av e b e e n
p r e p a r e d w ith TiCljij, an d p o ly - h y d r o x y a l c o h o ls su ch a s g l y c o l and g l y c e r o l
(5 ).
As f a r a s can be d e te r m in e d , h o w ev er, no d i e l e c t r i c s t u d i e s h av e
b e e n made o r a tte m p te d on an y o f th e s e com pounds.
.
'
-
I!
'
■ v: ■
IV.
THEOBY AM POSSIBILITIES
When two c h a r g e s o f e l e c t r i c i t y a r e s e p a r a t e d b y a d e f i n i t e d i s t a n c e ,
t h e r e i s a f o r c e a c t i n g b etw ee n th e m .
The m a g n itu d e o f t h i s f o r c e i s
d e te rm in e d b y a p r o p e r t y c a l l e d th e d i e l e c t r i c c o n s t a n t o f th e medium i n
w h ic h - th e c h a r g e s a r e p r e s e n t .
I t i s a w e ll known p h y s i c a l f a c t t h a t th e
f o r c e a c t i n g b e tw e e n tw o .c h a r g e s i s p r o p o r t i o n a l to th e p r o d u c t o f th e
c h a r g e s d iv i d e d b y th e s q u a re o f th e d i s t a n c e b e tw e e n th em .
.
T h e re fo re , i f
two c h a r g e s , e^ and e g , a r e s e p a r a t e d b y a d i s t a n c e d , th e r e s u l t i n g f o r c e
i s g iv e n b y th e r e l a t i o n s h i p f s e-^ eg /d ^ e, w here E i s c a l l e d th e d i e l e c t r i c
c o n s ta n t.
The d i e l e c t r i c c o n s ta n t i s a l s o f a m i l i a r a s a q u a n t i t y to w h ich th e
c a p a c it a n c e o f a c o n d e n s e r i s p r o p o r t i o n a l .
I n o t h e r w o rd s, C - <e Cq , w h ere
Cq i s th e c a p a c i t y o f th e c o n d e n s e r w ith a vacuum b e tw e e n i t s p l a t e s .
How­
e v e r , when m e a s u rin g by t h i s m eth o d , th e d i e l e c t r i c c o n s ta n t o f s u b s ta n c e s
h a v in g a c o n s ta n t c o n s id e r a b ly g r e a t e r th a n o n e ,, v e r y l i t t l e
e r r o r i s in ­
tro d u c e d b y u s i n g Cq a s th e c a p a c i t y w ith a i r b e tw e e n th e p l a t e s , s in c e i t
h a s a d i e l e c t r i c c o n s t a n t v e r y c l o s e to u n i t y .
H i i s i s th e m ost common
m ethod b y w hich th e - d i e l e c t r i c c o n s t a n t may be d e te r m in e d e x p e r i m e n t a lly .
I n o r d e r to v i s u a l i z e b e t t e r th e c o n c e p t o f d i e l e c t r i c s , i t i s n e c e s ­
s a r y to c o n s id e r a s i n g l e m o le c u le o f a compound o r s u b s ta n c e .
E v e ry m ole­
c u l e , th o u g h e l e c t r i c a l l y n e u t r a l , c o n t a in s b o th p o s i t i v e and n e g a t iv e
e le c tric ity .
In a few ty p e s o f m o le c u le s th e c e n t e r s o f p o s i t i v e an d n e g a ­
t i v e e l e c t r i c i t y c o i n c i d e , w h ile i n m ost m o le c u le s , due to c o n f i g u r a t i o n ,
:- v ..
th e y a r e s e p a r a t e d b y a d e f i n i t e d i s t a n c e .
:
V ''v V
1J
. 'V
M o le c u le s o f t h i s ty p e a r e ’
c a l l e d -p o la r, s in c e th e y " p o s s e s s a p erm a n en t d i p o l e moment, m = e d .
T— V —■»-TTVuI ^ -
H C l. i s
•—
Q
w
a c o n v e n ie n t exam ple o f a p o l a r m olecule-.
S in c e th e c h l o r i n e atom h a s a
g r e a t e r a t t r a c t i o n f o r e l e c t r o n s th a n th e h y d ro g e n ato m , i t te n d s to s h i f t th e c e n t e r o f n e g a t iv e e l e c t r i c i t y i n i t s d i r e c t i o n .
The c e n t e r o f p o s i ­
t i v e e l e c t r i c i t y i s th u s s h i f t e d to w ard th e h y d ro g e n ato m .
I n a m o le c u le
•of C C l^, h o w ev er, i t can he s e e n t h a t any r e s u l t i n g s h i f t o f e l e c t r o n s
to th e c h l o r i n e atom s w ould he c a n c e l l e d , s in c e th e f o u r c a rb o n b o n d s a r e
te tra h e d ra l.
T h is m o le c u le , th e n , i s n o n - p o l a r .
The e l e c t r o n s and n u c l e i i n an y m o le c u le a r e , to some e x t e n t , m o b ile
and so when th e m o le c u le , w h e th e r i t i s p o l a r o r n o n - p o la r ,
i s p la c e d in
an e l e c t r i c f i e l d t h e r e w i l l he a sm a ll d is p la c e m e n t o f th e e l e c t r i c a l
c e n t e r s w ith th e r e s u l t t h a t a d i p o l e , in a d d i t i o n to one w h ich may a l ­
r e a d y he p r e s e n t , w i l l h e in d u c e d i n th e m o le c u le .
Tlie d i e l e c t r i c c o n s t a n t
d ep en d s upon th e e x t e n t o f t h i s d is p la c e m e n t, th e p e rm a n e n t d is p la c e m e n t
and th e num ber o f m o le c u le s p e r u n i t volum e o r d e n s i t y o f th e compound.
I f th e s t r e n g t h o f a u n ifo rm e l e c t r i c f i e l d p ro d u c e d b y two c h a rg e d
p l a t e s i s Bq ;. th e n in a n o n - p o la r medium th e f i e l d s t r e n g t h i s re d u c e d to
B b e c a u s e th e d i p o l e s in d u c e d i n th e m o le c u le s a c t in o p p o s i t i o n to th e ap­
p lie d f ie ld .
The r a t i o Bq /B i s th e d i e l e c t r i c c o n s ta n t o f th e medium.
It
h a s b e e n shown b y e l e c t r o s t a t i c s t h a t Bq » B -f-lj-T? I , w h ere I i s th e in d u c e d
e l e c t r i c moment p e r u n i t v o lum e.
A ssum ing t h a t th e a c t u a l i n t e n s i t y B, a c t i n g u p o n one m o le c u le , c a u s e s
i t to assum e a n e l e c t r i c moment m, th e n m - cCF, w h e re c C is c a l l e d th e p o l a r ­
i z a b i l i t y o f th e m o le c u le .
T h is i n t e n s i t y o r f o r c e i s c a l c u l a t e d b y s u p -
p o s in g a u n i t c h a rg e to be e n c lo s e d in a s m a ll s p h e r i c a l c a v i t y w h ich i s
r e l a t i v e l y l a r g e a s com pared w ith a m o le c u le » b u t s m a ll i n c o m p ariso n w ith
th e d i s t a n c e b e tw e e n th e c h a rg e d p l a t e s , a s shown i n F ig u r e I ,
I t con-
>
~b
/
't
-=>
->
Y-
+
^
------->
Y-
■>
------- >
V-
—>
•
->
-----5>
F ig u r e I
s i s t s o f t h r e e p a r t s , F m F-^Y F g + F^ ( 3 ) .
.
F^ i s th e f o r c e w h ich r e s u l t s
fro m th e e l e c t r i c c h a rg e s on th e two p l a t e s h a v in g a s u r f a c e d e n s i t y c h a rg e
T hus, F]_ —
S0 .
The se c o n d f o r c e F^ i s due to th e p r e s e n c e o f
th e d i e l e c t r i c and c o n s i s t s o f two p a r t s , one c a u s e d b y th e in d u c e d c h a r g e s
bn th e s u r f a c e o f th e d i e l e c t r i c
in c o n t a c t w ith th e p l a t e s , and th e o t h e r
by th e in d u c e d c h a rg e on th e s u r f a c e o f th e s p h e r i c a l c a v i t y w h ich s u n - ■
ro u n d s t h e ' m o le c u le .
T h is f o r c e i s g iv e n by th e e x p r e s s io n , Fg = - 4 TTl-fbTfi/ 3 .
I
10 -
F i n a l l y , th e com ponent i y i s th e c o n t r i b u t i o n to th e f o r c e b y th e atom s
i n s i d e th e s p h e r e .
iia lly z e ro .
I t h a s b e e n shown t h a t in c u b i c a l c r y s t a l s
is a c t-
T h is r e s u l t i s a l s o a p p l i c a b l e i n th e c a s e o f l i q u i d s and
g a s e s w hich a r e noh^BseociiabtStiU
By
Burning
gg 0 th e t o t a l f o r c e
p _ B0 - 4 TTI + 4 r r 1 /3 i s a p p l i c a b l e o n ly to g a s e s and l i q u i d s i n w h ich
th e m o le c u le s move in d e p e n d e n tly o f one a n o t h e r .
T h e r e f o r e , s in c e
Bq - E -h 4T T I, F - E h 4 7 r i / 3 .
S in c e b y d e f i n i t i o n , I I s th e e l e c t r i c moment p e r u n i t volume o f th e
d i e l e c t r i c , I = nm = n<F = n<c(E h 4 r a / 3 ) , w here n i s th e number o f m o le c u l e s p e r u n i t v o lu m e.
U sin g t h i s r e l a t i o n s h i p , and th e fa.cu t h a t E0
th e f o llo w in g e q u a t io n may be d e r i v e d ;
tL = I
"
•
.
■
= & 7/774;
3
an d s in c e n - STd/M, w here M i s th e m o le c u la r w e ig h t, N A v o g ad ro 1s num ber,
and d th e d e n s i t y , th e e q u a t io n r e d u c e s to th e fo rm :
p _
“
"nnl
2
d
^ ^ j f ZyoC
3
The above e q u a t io n i s known a s th e C la u s iu s —M o s s o tti. e q u a t io n w here P i s
th e m o la r p o l a r i z a t i o n .
S in c e i t w as d e r iv e d on th e a s s u m p tio n t h a t t h e r e
i s no i n t e r a c t i o n b etw ee n th e m o le c u le s i n th e d i e l e c t r i c ,
i t is u se fu l
o n ly f o r g a s e s i n w h ich th e m o le c u le s a r e r e l a t i v e l y f a r a p a r t .
A c c o rd in g to M a x w e ll's .L a w , 6 = ^
i s th e in d e x o f r e f r a c t i o n . '
f o r a n o n - p o la r s u b s ta n c e w h ere r
H en ce, . th e f o llo w in g e q u a tio n h o ld s ( 3 ) ;
r ^ - l
rZ if- 2
I
d
& TrHcC
3
A cc o rd in g to th e e q u a tio n d e r iv e d f o r th e m o la r p o l a r i z a t i o n , i t s v a lu e
s h o u ld n o t ch an g e w ith te m p e r a t u r e .
1
T
H ow ever, i t h a s b e e n n o te d t h a t t h i s i s
n o t a l w a y s ,th e c a s e . ■ The p o l a r i z a t i o n f o r p o l a r m o le c u le s d o es change
w ith te m p e r a tu r e .
Dehye ( 3 ) h a s shown m a th e m a tic a lly t h a t th e p o l a r i z a ­
b i l i t y =C9 i s n o t alw ay s c o n s ta n t a s was p r e v i o u s l y t h o u g h t.
oped th e f o llo w in g e q u a t io n f o r t h i s q u a n t i t y ; eC g
/ 3%
He h a s d e v e l­
w here
i s th e p e rm a n e n t e l e c t r i c moment o f th e m o le c u le , k th e B oltzm ann c o n s ta n t
and T th e a b s o lu t e te m p e r a tu r e .
A c c o rd in g to t h i s , cC w i l l be c o n s t a n t
o n ly f o r n o n - p o la r m o le c u le s w ith no p e rm a n e n t e l e c t r i c moment.
By i n t r o ­
d u c in g th e s e r e s u l t s in t o th e o r i g i n a l C la u s i u s - M o s s o tti e q u a tio n , th e f o l ­
lo w in g r e l a t i o n s h i p was o b ta in e d ;
£ ""I
k -f-2
P -
0
M
d
S3
T h is e q u a t io n i s known a s th e Debye f o r m u la f o r t o t a l m o la r p o l a r i z a t i o n .
I t h a s b e e n u s e d e x t e n s i v e l y , s in c e i t s d e r i v a t i o n , f o r d e te r m in in g d ip o l e
moments o f g a s e o u s m o le c u le s .
T h is , h o w ev er, i s so m etim es n o t c o n v e n ie n t,
e s p e c i a l l y w ith compounds w h ich a r e d i f f i c u l t to v a p o r i z e .
C o n s e q u e n tly ,
a s i m i l a r e q u a tio n h a s b e e n d e v e lo p e d f o r c a l c u l a t i n g p o l a r i z a t i o n b y d i s ­
s o lv in g th e compound to be s t u d i e d , i n a non—p o l a r s o l v e n t .
I f th e s o l u t i o n s
a r e d i l u t e enough th e d is s o l v e d p a r t i c l e s w i l l b e f a r a p a r t and th e o n ly
i n t e r a c t i o n o f im p o rta n c e w i l l be b e tw e e n th e p o l a r m o le c u le s an d th e s u r ­
ro u n d in g non—p o l a r m o le c u le s o f th e s o l v e n t .
P o r t h i s m ethod, th e f o llo w ­
in g e q u a tio n h a s b e e n fo u n d to b e a p p l i c a b l e ( 1 0 ) ;
£ 12 - I
e I 2 -f- 2
. CqM1 -if-cgMp
d 12
w here c ■i s th e mole f r a c t i o n .
s o lu te , r e s p e c tiv e ly .
= C1P 1 -*- C2Pa « F 12
The s u b s c r i p t s I and 2 i n d i c a t e ,s o l v e n t and
By d e te r m in in g th e m o la r p o l a r i z a t i o n P 2 a t s e v e r a l
c o n c e n t r a t i o n s an d p l o t t i n g th e s e v a lu e 's a g a i n s t m ole f r a c t i o n s o l u t e 0 2 »
- 12 -
a c u rv e w i l l r e s u l t w h ich may h e e x t r a p o l a t e d to i n f i n i t e d i l u t i o n .
The
e x t r a p o l a t e d v a lu e g iv e s th e p o l a r i z a t i o n o f th e s o l u t e i n a s o l u t i o n o f
i n f i n i t e d i l u t i o n w here t h e r e w ould he no i n t e r a c t i o n b e tw e e n m o le c u le s
o f th e s o l u t e .
.
Two m ethods e x i s t f o r d e te r m in in g th e p e rm a n e n t d i p o l e moment y£4
from th e above e q u a t i o n s .
I t c a n h e s e e n from th e Debye e q u a t io n , d e r iv e d
a b o v e , t h a t i f a m o le c u le h a s a p e rm a n e n t d i p o l e moment i t s m o la r p o l a r i ­
z a t i o n w i l l be a l i n e a r f u n c t i o n o f th e r e c i p r o c a l o f th e a b s o lu t e temp­
e r a t u r e . , By p l o t t i n g p o l a r i z a t i o n s a t i n f i n i t e d i l u t i o n a g a i n s t l / T ,
th e d i p o l e moment may he d e te r m in e d from th e s lo p e b o f th e c u r v e , •
yto. - 0 . 012? x 10” ^
^b"* e l e c t r o s t a t i c u n i t s .
The se c o n d m ethod f o r d e te r m in in g th e p erm a n en t d i p o l e moment i s de­
r i v e d from th e f a c t t h a t th e t o t a l p o l a r i z a t i o n c o n s i s t s o f th r e e p a r t s .
' T hese a r e ( l ) t h e ' e l e c t r o n i c p o l a r i z a t i o n Pe , (Z ) th e a to m ic p o l a r i z a t i o n
P , and (3 ) th e o r i e n t a t i o n p o l a r i z a t i o n Pq , w here Pa -^ P 0 - 4 TT-NoQ/^ and
P q - d-Tf$?/6 ? /9 k T .
S in c e th e s q u a re o f th e r e f r a c t i v e in d e x o f a h o n - p o la r
compound i s e s s e n t i a l l y th e same a s th e d i e l e c t r i c c o n s t a n t , P a ^ P 0 may
b e d e te r m in e d from r e f r a c t i v e in d e x and d e n s i t y m e a su re m e n ts.
The t o t a l
p o l a r i z a t i o n P may b e d e te rm in e d fro m d i e l e c t r i c c o n s t a n t and d e n s i t y
d a ta .
The p e rm a n e n t d ip o l e moment, th e n , may b e c a l c u l a t e d from th e r e l a ­
tio n s h ip :
D ip o le moments h av e b e e n v e r y u s e f u l in d e te r m in in g s t r u c t u r e s an d
c o n f i g u r a t i o n s o f many moM c u l e s .
S in c e th e d ip o l e moment i s due to th e
— 13
'd i f f e r e n c e in th e e l e c t r o n e g a t i v i t y o f two atom s c o n n e c te d b y a c h e m ic a l
bond* i f i s e v id e n t t h a t i t s h o u ld be p o s s i b l e to a s s o c i a t e a d i p o l e moment
w ith e v e r y l i n k a g e . ■ The r e s u l t a n t d i p o l e moment o f a m o le c u le i s ,
th e n ,
th e ' v e c t o r sum o f th e i n d i v i d u a l bond moments s in c e e a c h a c t s a lo n g th e
l i n e c o n n e c tin g th e c e n t e r s o f th e atom s fo rm in g th e . b o n d .
T h is view i s .
in harm ony w ith th e f a c t t h a t s y m m e tric a l m o le c u le s l i k e CClif, h av e no
moment ,alth o u g h e a c h c a r b o n - c h l o r in e bond h a s 'a n a p p r e c i a b l e moment.
The
f o u r bond moments- a r e d i r e c t e d t e t r a h e d r a l l y and t h e i r v e c t o r sum i s z e r o .
Many bond moments h a v e b e e n d e te rm in e d b y th e m easurem ent o f v a r i o u s com­
po u n d s.
.By th e v e c t o r a d d i t i o n o f th e s e bond moments th e r e s u l t a n t d ip o l e -
moments o f v a r io u s o t h e r s u b s ta n c e s h a v e b e e n fo u n d to b e i n a g ree m en t
w ith t h e o b s e rv e d v a l u e s .
Bond a n g le s may a l s o be e s ti m a t e d from d ip o le
moment m e a su re m e n ts.
A n o th e r i n t e r e s t i n g a s p e c t o f th e q u e s ti o n o f o r i e n t a t i o n p o l a r i z a ­
t i o n i s t h a t i n th e s o l i d s t a t e . th e m o le c u le s re m a in a lm o s t r i g i d l y f i x e d
i n . t h e sp a c e l a t t i c e
so t h a t no o r i e n t a t i o n in th e d i r e c t i o n o f th e e l e c ­
t r i c f ie ld is p o s s ib le .
U nder t h e s e c o n d i tio n s ev en a- p o l a r m o le c u le w i l l
show no o r i e n t a t i o n p o l a r i z a t i o n .
T h is s h o u ld r e s u l t i n a m arked d i f f e r ­
en ce b e tw e e n th e t o t a l - p o l a r i z a t i o n ' an d d i e l e c t r i c c o n s ta n t i n th e l i q u i d
and s o l i d s t a t e s .
F o r a n o n - p o la r s u b s ta n c e , h o w e v e r, t h e r e i s no o r i e n ­
t a t i o n p o l a r i z a t i o n i n any c a s e , so th e d i f f e r e n c e .i n th e two s t a t e s
s h o u ld b e ' sm a ll°
- I b -
I
V.
PREPARATION OP COMPOUNDS USED
The compounds p r e p a r e d f o r s tu d y h av e a l l been, p r e p a r e d b e f o r e b y
o th e r in v e s tig a to r s .
H owever, l i t t l e
i s known r e g a r d i n g many o f z t h e i r
p ro p e rtie s .
.
' T ita n iu m T e t r a e t h v l a t e - T i (OOoH^)>[;
T h is compound was p r e p a r e d ac­
c o r d in g to B is c h o f f an d A dkins (2 ) b y th e r e a c t i o n ,
.
T i C l ^ + WNaOCgBj
------- =>
T l ( OGgE^) ^ + 4N aC l.
-
'■
7 5 0 ' m l. o f a b s o lu t e e t h y l a lc o h o l w ere p la c e d in a th r e e - n e c k e d , ro u n d 0.
b o tto m f l a s k e q u ip p e d w ith a r e f l u x c o n d e n s e r and a m e c h a n ic a l s t i r r e r .
To t h i s was added $0 gram s o f sodium m e ta l i n r a t h e r l a r g e p i e c e s .
r e a c t i o n was c o o le d b y means o f an i c e - w a t e r b a t h .
The
A f t e r th e r e a c t i o n
h a d s u b s id e d , th e b a t h w as removed and h e a l a p p l i e d s lo w ly u n t i l th e
sodium was e n t i r e l y d i s s o l v e d .
A f t e r th e r e a c t i o n mass h a d c o o le d , 58«,»5 m l. o f T iC l^ w ere ad d ed d r o p w is e b y m eans o f a d ro p p in g f u n n e l o v e r a p e r i o d o f t h r e e h o u r s w ith con­
tin u o u s s t i r r i n g . . A g ain an i c e - w a t e r b a t h w as p la c e d ' aro u n d th e r e a c t i o n
f l a s k s in c e th e r e a c t i o n b e tw e e n -T iC l^ an d sodium e th o x id e i s q u i t e exo­
th e r m ic .
Through th e e n t i r e a d d i t i o n , l a r g e am ounts o f 'smoke w ere p ro d u c e d
i n .th e r e a c t i o n f l a s k , an d th e m ix tu r e assum ed a c h a lk y a p p e a r a n c e .
The m ix tu re was th e n t r a n s f e r r e d to a c e n t r i f u g e in o r d e r to s e p a r a t e
th e sodium c h l o r i d e and o th e r s o l i d s form ed, i n th e r e a c t i o n , from th e
a l c o h o l i c s o l u t i o n c o n t a in in g th e T i ( OCgH^)j^.
The l i q u i d w as d e c a n te d .
from th e c e n t r if u g e - b o t t l e s and t h e e x c e s s - a l c o h o l rem oved b y d i s t i l l ^ . t ^ p h
w ith a w a te r b a t h a t IOO0C.
'
.'The r e s i d u e w h ich was a c l e a r , v is c o u s , y e llo w l i q u i d , was t r a n s f e r r e d
— 15 —
to a s m a ll' C la is e n f l a s k and d i s t i l l e d u n d e r re d u c e d p r e s s u r e .
d i s t i l l e d a t 158°C a t 20 mm. p r e s s u r e .
E ie p r o d u c t
I t was d i s t i l l e d th r e e tim e s to
in s u r e c o m p le te p u r i f i c a t i o n .
' ' 'The f i n a l p r o d u c t was a d o lo rle@ s» v is c o u s l i q u i d which, h y d r o ly z e d
r a p i d l y when ex p o sed to a i r .
I t s g e n e r a l p r o p e r t i e s c h e c k e d c l o s e l y w ith
th o s e r e c o r d e d i n th e l i t e r a t u r e .
A lth o u g h r e p o r t e d a s a c o l o r l e s s l i q u i d ,
i t was fo u n d t h a t t h i s compound a l s o e x i s t s a s a w h ite s o l i d a t room ternI
p e r a t u r e i f c o o le d to c o n s id e r a b ly b elo w z e ro en d g r a d u a l l y w arm ed.
Upon
w a rm in g ,' th e v is c o u s l i q u i d was g r a d u a l l y tr a n s f o r m e d i n t o a w h ite s o l i d ,
s t a b l e i n t h i s s t a t e b elo w J h 0 C.
The s o l i d i f i c a t i o n p r o c e s s r e q u i r e d b e­
tw een t h r e e an d f o u r h o u r s .
I n o r d e r to v e r i f y th e c o m p o s itio n o f th e Ti(OCgB^)Jij, p r e p a r e d , two
a n a l y t i c a l d e t e r m in a tio n s w ere m ade.
A C a riu s h a lo g e n d e t e r m in a tio n show­
ed an a b s e n c e o f c h l o r i n e in th e m o le c u le .
T ita n iu m d e t e r m in a tio n s w ere
made b y h y d r o ly z in g sam p les w ith w a te r an d i g n i t i n g in a p o r c e l a i n c r u c i b l e
o v e r a M eker b u r n e r .
showed:
The r e s id u e w as assum ed to b e T iO g»
2 0 .9 6 , 2 0 .8 8 , 2 1 .0 9 , and 2 1 .0 0 # t i t a n i u m .
i s 2 1 . 05# .
Th8 r e s u l t s
The t h e o r e t i c a l v a lu e
The com pound.was t h e r e f o r e assum ed to be r e a s o n a b ly p u r e .
M onoc h lo r o - tr ie th o x v - tita n iu m
- T iG l( QCqIRl3 :
.T h is compound w as p r e ­
p a re d a c c o r d in g to J e n n in g s , W ardlaw and Way ( ? ) b y th e r e a c t i o n :
Ti(OC2H5 ) 4 -H CH3 COCl ------- >
TiCl(OC2H5 ) 3 -f CH3 COOC2H5 .
.18 gram s o f a c e t y l c h l o r i d e w ere ad d ed d ro p w ise to 52 gram s o f t i t a n i u m
t e t r a e t h y l a . t e , c o o le d b y means o f an i c e —W ater b a t h . '
A f te r th e a d d itio n " ,
th e m ix tu r e was r e f l u x e d f o r two h o u r s an d th e e t h y l a c e t a t e d i s t i l l e d o f f .
The y e llo w , v is c o u s r e s i d u e was th e n d i s t i l l e d u n d e r re d u c e d p r e s s u r e .
'
j
- 16 -
The d i s t i l l a t e , a p a l e y e llo w , e x tre m e ly v is c o u s l i q u i d , "boiled a t 170°C
a t 15 mm. p r e s s u r e .
p u rific a tio n .
The p r o d u c t was r e d i s t i l l e d s e v e r a l tim e s to i n s u r e
S in ce i t h y d r o ly z e s r a p i d l y i n a i r ,
i t was. n e c e s s a r y to
s t o r e i t in a s e a le d f la s k *
.
Di c h i 0 r o - d i e t h o x v - 1 i t a n ium - T iC lg (
‘
J e n n in g s , WardlaW and
Way ( ? ) h a v e i n d i c a t e d two m ethods f o r th e - p r e p a r a t io n o f t h i s com pound.
The f i r s t , m ethod c o n s i s t s i n th e r e a c t i o n o f T lC l^ w ith e t h y l a l c o h o l
a c c o r d in g to th e e q u a tio n :
T iC lil, - t ZC2H5OH —----- >
T iC l2 (OG2H5 ) 2 + 2KC1 .
The seco n d c o n s i s t s o f th e r e a c t i o n o f a c e t y l c h l o r i d e w ith TiCl(OC2H5 ) 5 :
TiCl(O C2H5 ) 3 + CE3 COCl --------- > T iC l2 (OC2H5 ) 2 -h CH3COOC2H5 .
B oth o f th e s e m ethods w ere u s e d , "but s e v e r a l d i f f i c u l t i e s w ere e n c o u n te r e d
i n ea c h • c a s e .
I n th e f i r s t m eth o d , 100 gram s o f T iC l^ w ere ad d ed d ro p w ise to 100
gram s o f a b s o l u t e e t h y l a l c o h o l in a th r e e - n e c k e d ro u n d -b o tto m f l a s k e q u ip ­
p e d w ith a r e f l u x c o n d e n s e r , a m e c h a n ic a l s t i r r e r an d a d ro p p in g f u n n e l .
HCl was e v o lv e d i n th e r e a c t i o n and th e m ix tu re tu r n e d y e llo w an d becam e
q u ite v is c o u s .
A f t e r r e f l u x i n g a t IOO0 C f o r two h o u r s , . th e m ix tu re was
f r a c t i o n a l l y d i s t i l l e d u n d e r re d u c e d p r e s s u r e .
A t 7 0 ° C /l5 mm. a w h ite sub­
lim a te b e g a n to form in th e n eck o f th e d i s t i l l i n g f l a s k .
From IOO0 C to
140°C, a y e llo w l i q u i d d i s t i l l e d o v e r an d s e t to a y e llo w s o l i d im m e d ia te ly
on c o o l i n g .
The y i e l d w as v e r y s m a ll and th e p r o d u c t h a d a s tr o n g o d o r o f.
HCl even a f t e r r e d i s t i l l a t i o n .
s h o u ld b o i l a t 1 4 2 °C/ IS mm.
e q u a l ly p o o r r e s u l t s .
A c c o rd in g to t h e l i t e r a t u r e , T iC l2 (OC2H5 ) 2
The r e a c t i o n was r e p e a te d s e v e r a l tim e s w ith
— 17 —
I
In, th e seco n d method* 3 I gram s o f a c e t y l c h l o r i d e w ere added d ro p w ise
to 84 gram s o f TiCl(O C2H ^ ) and th e m ix tu r e r e f l u x e d f o r two h o u r s .
The
e t h y l a c e t a t e was d i s t i l l e d o f f and th e y e llo w , v is c o u s r e s id u e d i s t i l l e d
u n d e r re d u c e d p r e s s u r e .
H ere a g a in a w h ite s u b lim a te b eg an to form a t ■’
7 0 ° C /l5 mm., and a. p a l e y e llo w l i q u i d w as c o l l e c t e d b etw ee n 100° C end
l4 0 ° C .
T h is l i q u i d a l s o s e t to a s o l i d a f t e r c o o l in g , and p o s s e s s e d t h e '
same p r o p e r t i e s a s t h a t p r e p a r e d b y th e f i r s t m eth o d .
The y i e l d was a g a in
■low, and th e p r o d u c t gav e o f f HCl when m e lte d .
'
-
I n o r d e r to v e r i f y th e c o m p o s itio n o f t h i s compound, an i g n i t i o n , w a s
ru n to d e te rm in e th e t i t a n i u m c o n t e n t .
The e x p e r im e n ta l v a lu e was 1 9 .8 ^ ,
w h ile th e c a l c u l a t e d v a lu e 'w a s 2 2 .9 7 $ .
From t h i s a n a l y s i s , i t . was con­
c lu d e d t h a t th e compound was p a r t i a l l y decom posed a t th e te m p e r a tu r e n e c ­
e ssa ry f o r d i s t i l l a t i o n .
T h is c o n c lu s io n i s s u p p o r te d b y th e f a c t t h a t th e
compound fum es c o n s id e r a b ly when warmed to IOO0C.
" ■• ' '
J e n n in g s , VIardlaw and Way (7 ) h a v e a l s o fo u n d t h a t , when TiC! 2 ( 002115)2
i s ad d ed to a minimum am ount o f warm e t h y l a l c o h o l , c o l o r l e s s n e e d l e s sep­
a r a t e o u t on c o o l in g .
T h ere h a s "been some c o n tr o v e r s y c o n c e rn in g th e
s t r u c t u r e o f t h i s com pound. A c c o rd in g to J e n n in g s i, W ardlaw and Way, i t h a s
) ■
,
th e f o rm u la T i C ^ ( OCgH^^ 0 C2H^OH. H ow ever, a c c o r d in g to G a rd n e r and
B ie lo u s s ( 5 )» th e compound form ed i s TiClfO C^B^)^ ° H C l.
The fo rm e r s t r u c ­
tu r e seem s to b e th e ' m ost p r o b a b le s in c e TiCl(OC2H ^ ) a l s o ad d s an a l c o h o l '"
o f c r y s t a l l i z a t i o n when d is s o lv e d i n e t h y l a lc o h o l ( 7 ) •
A ti t a n i u m a n a l y s i s
showed 1 8 . 65$ t i ta n i u m w h ile th e r e q u i r e d v a lu e i s 1 8 .8 2 $ .
T h is a t f i r s t ' ''
seemed a good m ethod f o r p u r i f y i n g th e compound, b u t i n o r d e r to remove th e
— 3.8 —
1
'a lc o h o l o f . c r y s t a l l i z a t i o n ,
enough h e a t was r e q u ir e d to c a u se fu m in g , th u s
-
in t r o d u c in g i m p u r i t i e s .
I t w as f i n a l l y d e c id e d to abandon any f u r t h e r a t te m p t s to p u r i f y th e ■
compound,- s in c e a h ig h d e g re e o f p u r i t y i s re q u ire d , f o r d i e l e c t r i c m e asu re­
m e n ts.
T r i c h lo r o - n h e n o x y - tita n iu m - TiCl^OC^H^;
T h is compound was p r e p a r e d
a c c o rd in g to L u ts c h in s k y an d A ltm gnn ( 8 ) by th e r e a c t i o n :
T i C l ^ C 6H5O H - -----^ T i C l 3 OC6H5 -*-HCl.
Two s o l u t i o n s , - one c o n t a in in g 9 .5 gram s o f TiClz4. in a m ix tu re o f d r y p e t r o ­
leum e t h e r and c h lo ro fo rm and th e o t h e r c o n t a in in g 4 .7 gram s o f p h e n o l i n
th e same s o l v e n t , w ere m ixed t o g e t h e r s lo w ly i n th e c o l d ,
.^he m ix tu r e
tu r n e d d a r k r e d im m e d ia te ly w ith th e e v o l u tio n o f HCl g a s .
A f t e r th e r e a c ­
t i o n was c o m p le te , th e s o lv e n t was d i s t i l l e d o f f u n t i l d a r k re d c r y s t a l s
b eg an to s e p a r a t e .
A t t h i s p o i n t th e m ix tu r e was c o o le d w ith i c e an d f i l ­
t e r e d . . The c r y s t a l s w ere w ashed c a r e f u l l y w ith more s o lv e n t and d r i e d i n - a
vacuum d e s s i c a t o r o v e r PgO5 .
g^-ylng g. d eep r e d s o l u t i o n .
The compound d i s s o l v e d i n CCl^ and henzehe,
Vfhen i t w as d is s o lv e d i n e t h y l a l c o h o l , a r e a c ­
t i o n - t o o k p la .c e g iv in g a y e llo w s o l u t i o n .
g iv in g a c o l o r l e s s s o l u t i o n .
I t decom posed I n s t a n t l y i n w a te r
Vfhen ex p o se d to m o is t a i r ,
th e compound gave
o f f HCl s lo w ly and g r a d u a l l y assum ed a l i g h t r e d c d l o r .
I n o r d e r to v e r i f y th e c o m p o s itio n and p u r i t y o f th e compound, a t i t a n ­
ium a n a l y s i s was m ade.
The r e s u l t s showed 1 9 .58 and 19«35? t i t a n i u m .
The
r e q u i r e d v a lu e i s 1 9 .3 7 $ .' From t h i s a n a l y s i s , . i t was assum ed t h a t th e com­
pound w as s u f f i c i e n t l y p u r e f o r d i e l e c t r i c m easu rem en t.
Hi
r "Y
f'V ..... y " ' IrlI '4
I- 6-,i."
I
- 19 Tltm niiim Tetrm c h i p r i d e - e t h y l e n e g l y c o l Compound;
A v e ry i n t e r e s t i n g
compound fo rm ed by th e r e a c t i o n o f T iC l^ w ith, e th y le n e g ly c o l h a s b e e n r e ­
p o r t e d b y G a rd n e r and B ie lo u s s (5)* b u t th e s e i n v e s t i g a t o r s hav e b e e n un­
a b le to v e r i f y any d e f i n i t e e t r u e t u r e f o r i t *
They h a v e , ho w ev er, o f f e r e d
th e f o llo w in g p o s s i b i l i t i e s :
: ' r-.*
Ti
TIClzj. -VaCIi2OHCH2OH
V
hHCl
• • . ,f.
,OCH2CH2OH
//OCH2
Ti-OCH2
xOCH2
/OCH2 +■ 8HC1
Ti-OCH9
\ \ 6CE2
xOCH2CH2OH
B TiCllt. ^ 5CH20HCH20H
F o r th e p r e s e n t w o rk , T i C was ad d ed d ro p w ise to th e g l y c o l .
f a r e became v e r y v is c o u s and e v o lv e d H C l.
The m ix- ■
A f te r th e r e a c t i o n was c o m p le te ,
m ost o f th e e x c e s s g l y c o l was rem oved b y d i s t i l l a t i o n u n d e r re d u c e d p r e s s u r e .
The r e s i d u e re m a in in g was a, t r a n s p a r e n t , v is c o u s , brow n s u b s ta n c e w h ich h a r ­
den ed to a g l a s s y m a t e r i a l on c o o l in g .
in g th e f l a s k .
I t c o u ld b e rem oved o n ly b y b r e a k ­
I t was fo u n d to b e s o l u b l e in e t h y l a l c o h o l and w a te r b u t
n o t in e t h e r o r b e n z e n e .
1 8 .1 4 an d 1 8 . 38$ .
The ti t a n i u m c o n te n t fo u n d b y i g n i t i o n w as 1 7.4 ?»
The l a c k o f a g re e m e n t i n th e s e r e s u l t s was p r o b a b ly due
to th e f a c t t h a t th e s u b s ta n c e was n o t e n t i r e l y hom ogeneous.
, - ' 1V '
*
■■■ ■
A q u a l i t a t i v e t e s t f o r h a lo g e n was n e x t ru n on th e compound b y means
o f sodium f u s i o n , and c h l o r i n e was fo u n d to he p r e s e n t .
■ ■}•
v
A C a riu s h a lo g e n
,-.-.i,.
',..,r
.n
vl 11'.-1P ..JIr j- |
1 yi~ —
I
-
20 -
d e t e r m in a tio n was th e n a tte m p te d , b u t th e C a riu s tu b e e x p lo d e d ea c h tim e .
A sam ple was th e n p la c e d in a s m a ll ro u n d -b o tto m f l a s k e q u ip p e d w ith a, r e ­
f lu x c o n d e n se r.
added.
100 m l. o f e t h y l a l c o h o l and 10 gram s o f sodium m e ta l w ere
"The m ix tu re was a llo w e d to r e f l u x u n t i l a l l o f th e sodium was d i s ­
s o lv e d .
T h is tr e a tm e n t w i l l decom pose many o r g a n ic com pounds.
A bout kO
m l. o f d i s t i l l e d w a te r was added and th e a l c o h o l d i s t i l l e d o f f . The rem ain —
'
in g m ix tu r e was th e n f i l t e r e d , made a c i d w ith
, an d t r e a t e d w ith a s m a ll
.
amount o f AgNCy to p r e c i p i t a t e th e A gO l.
u n t i l th e h a l i d e h a d c o m p le te ly d i s s o l v e d .
c i p i t a t e d o u t a s th e h y d r o x id e .
At t h i s p o in c th e t i t a n i u m p r e ­
The m ix tu re was f i l t e r e d and ma.de a c i d
a g a in w ith ENOo to p r e c i p i t a t e th e A gC l.
Gooch c r u c i b l e .
NH^OH s o l u t i o n was th e n ad d ed
I t was th e n f i l t e r e d th ro u g h a
The p r e c i p i t a t e was d r i e d and w e ig h e d , and th e c h l o r i n e
c o n te n t d e te rm in e d b y c a l c u l a t i o n .
The r e s u l t s showed 11.73» 1 1 .7 1 an d
12.29j> c h l o r i n e in th e compound.
A p u r i f i c a t i o n o f t h i s p o ly m e r - lik e compound w as a tte m p te d by p r e c i p i ­
t a t i o n o f i t s a l c o h o l i c s o l u t i o n w ith d r y e t h e r .
ed a,s soon a s th e e t h e r was a d d e d .
e th y l a lc o h o l.
A w h ite p r e c i p i t a t e a p p e a r­
T h is was f i l t e r e d and r e d i s s o l v e d i n
H ow ever, w h ile w arm ing, a w h ite pow dery p r e c i p i t a t e fo rm ed
w hich w as fo u n d to b e i n s o l u b l e i n a l l o f th e o r g a n ic s o l v e n t s .
I t d id ,
h o w ev er, b u r n oh i g n i t i o n , i n d i c a t i n g t h a t i t was s t i l l o r g a n ic i n n a t u r e .
Even when a llo w e d to s ta n d i n . a d e s s i c a t o r o v e r
f ° r se v e ra l h o u rs,
a f t e r o n ly one p r e c i p i t a t i o n , th e compound was fo u n d to b e i n s o l u b l e i n
e th y l a lc o h o l.
A f t e r s e v e r a l u n s u c c e s s f u l a t te m p t s a t p u r i f i c a t i o n ,
ET’
th e id e a ox ta k —
21 -
in g s n y d i e l e c t r i c m easu rem en ts on i t was abandoned f o r th e p r e s e n t .
A s i m i l a r compound was p r e p a r e d u s i n g h e x a m e th y le n e g l y c o l i n s t e a d o f
e th y le n e g l y c o l .
I t seem ed to hav e p r o p e r t i e s s i m i l a r to th o s e o f th e
e th y le n e g l y c o l compound and was n o t p u r i f i e d .
'
V I.
ELECTPJC MOMEET MEASUREMENTS
The e l e c t r i c moments o f Ti(OCgH^)Z).* TiCl(OCgH^)--J and TiCl^OC^Htj h av e
b e e n d e te r m in e d .
F o r th e s e d e t e r m in a tio n s i t was r e q u i r e d to m easu re th e
d i e l e c t r i c c o n s t a n t s o f s e v e r a l d i l u t e s o l u t i o n s o f th e s e compounds u s in g
a c o n v e n ie n t n o n - p o la r s o l v e n t .
In t h i s c a s e , b e n z e n e was u s e d .
d e n s i t i e s o f th e s e s o l u t i o n s w ere a l s o m e asu re d .
The
Vfith t h i s d a t a i t w as
p o s s i b l e to c a l c u l a t e th e m o la r p o l a r i z a t i o n s o f th e com pounds.
F o r th e m o la r r e f r a c t i o n c a l c u l a t i o n s , i t was n e c e s s a r y to d e te r m in e
e i t h e r th e r e f r a c t i v e in d e x and d e n s i t y o f th e p u re , compounds o r th o s e o f
th e same d i l u t e s o l u t i o n s d e s c r ib e d a b o v e .
fra c tio n ,
From th e p o l a r i z a t i o n and r e ­
i t was p o s s i b l e to c a l c u l a t e th e p erm a n en t e l e c t r i c moments o f
th e m o le c u le s in q u e s t i o n .
A more d e t a i l e d tr e a tm e n t o f th e m a th e m a tic a l
e q u a tio n s u s e d w i l l b e d i s c u s s e d l a t e r in t h i s s e c t i o n .
A p p a ra tu s u s e d f o r M e a su re m e n ts;
The e l e c t r i c a l c i r c u i t u s e d f o r th e
m easu rem en ts o f d i e l e c t r i c c o n s ta n t s Was a m a d e-o v er a i r c r a f t t r a n s m i t t e r ,
Type CBY-52209.
A s c h e m a tic d ia g ra m o f th e c i r c u i t i s shown i n F ig u r e 2 .
I t c o n s i s t s o f an e l e c t r o n c o u p le d o s c i l l a t o r u s in g th e tu b e 1 6 2 6 , an d a
c r y s t a l and d e t e c t i n g d e v i c e .
The f r e q u e n c y o v e r a s m a ll ran g e i s c o n t r o l -
l e d b y a G e n e ra l R adio 722-D s ta n d a r d p r e c i s i o n c o n d e n s e r .
As an i n d i c a t -
. in g d e v i c e , th e s ta n d a r d c r y s t a l end e l e c t r i c eye tu b e 1629 Were u s e d ;
“ 22 "
0 ,0 5
■ ohm
0,0002
. ohm
1626 ■
osoi lln 'to r
150
v o lts
.115 v o l t s
1 1 5 . v o l t s A .C .
CIRCUIT USED FOR MEASURING DIELECTRIC CONSTANTS OF. SOLUTIONS '
■
TV
V-
^t AVVi-
F ig u re S
— 23
IWhen th e f r e q u e n c y o f th e o s c i l l a t o r i s e x a c t l y t h a t o f th e c r y s t a l * 4 .6
m e g a c y c le s in t h i s c a s e , th e g rid , o f th e e l e c t r i c ey e tu b e i s e s s e n t i a l l y
s h o r te d to g ro u n d c a u s in g th e eye to o p e n .
T h is p ie c e o f a p p a r a tu s p ro v e d to be q u i t e a c c u r a t e and s e n s i t i v e ,
c a p a c ita n c e ch an g es o f O .O ly ^ j/f. b e in g in d i c a t e d b y a n a rro w in g o f th e
e le c tr ic eye.
The l i m i t i n g f a c t o r in th e a c c u r a c y o f th e c i r c u i t i s th e
f a c t t h a t th e c a p a c ita n c e o f th e s ta n d a r d c o n d e n s e r c a n n o t be much g r e a t ­
e r th a n 150 td 200/ y u f *
The p e r c e n ta g e e r r o r was th u s g r e a t e r th a n i n
c i r c u i t s w here l a r g e r s ta n d a r d c a p a c i t o r s can be u s e d .
T h is i s a p r e c i s e
and e a s i l y c o n s t r u c t e d p i e c e o f e q u ip m en t i f such a w a r s u r p lu s t r a n s ­
m itte r is a v a ila b le .
The c e l l c o n s t r u c t e d f o r m e asu re m en ts' was o f th e Smyth ty p e (1 0 )
and i s shown i n F ig u r e 3 .
c o n s tru c te d .
e rs.
T hree c o n c e n t r i c p la tin u m c y l i n d e r s w ere f i r s t
These w ere h e l d r ig id , b y th e i n s e r t i o n o f s m a ll g l a s s sp a c ­
The o u t s i d e an d i n s i d e c y l i n d e r s w ere c o n n e c te d t o g e t h e r and g r o u n -
,
d e d ..
I
The c y l i n d e r s w ere th e n p la c e d i n a g l a s s c e l l o f a b o u t 20 m l. c a p a ,
'
c i t y and th e p la tin u m l e a d s s e a l e d th r o u g h th e b o tto m . A b r a s s j a c k e t
•
was th e n p la c e d a ro u n d th e e n t i r e c e l l f o r u s e a s a te m p e r a tu r e c o n t r o l l i n g
d e v ic e .
W a te r from a r i g i d l y c o n t r o l l e d c o n s ta n t te m p e r a tu r e b a t h was
c i r c u l a t e d th ro u g h t h i s , j a c k e t .
The e x t e r n a l l e a d s w ere r ig id *
te r m in a -
t i n g i n s m a ll " b a n a n a 11 p lu g s so t h a t th e e n t i r e c e l l c o u ld be p lu g g e d
d i r e c t l y i n t o th e p r e c i s i o n c o n d e n s e r .
In t h i s p o s i t i o n i t i s in p a r a l l e l
w ith th e s ta n d a r d c o n d e n s e r a s shown i n F ig u re I .
The c a p a c ita n c e o f th e
I
-2C -
ci: m
;n3KP fo:; vttsmmto d m : • ■■■• r
rN .i7:o-s
Gr o und G l n s s G t o p p o r
. r=s 3S J u "!<et
j In S 3
Plntlnun Cylinders
F ig u re 3
____________________
— 25 “
' c e l l can t h e r e f o r e he m e asu re d h y m e a su rin g th e c a p a c it a n c e o f th e s t a n d a rd c o n d e n s e r 'a lo n e an d th e n w ith th e c e l l in th e c i r c u i t .
'
T h e 'd i f f e r e n c e
in th e two r e a d in g s g iv e s th e t o t a l c e l l c a p a c it a n c e .
C a l i b r a t i o n o f th e c e l l was a c c o m p lis h e d i n th e f o llo w in g m an n er.
The
t o t a l c a p a c it a n c e o f th e c e l l em pty i s e q u a l to th e sum o f th e l e a d c a p a - .
;
'
.
c i t a n c e and th e p r o d u c t o f th e d i e l e c t r i c c o n s ta n t o f a i r and th e c a p a c l - ;
I
ta n c e b e tw e e n th e f i x e d p l a t e s , v i z . Ca = Cq-*- ^ ouC. C i s o f t e n r e f e r r e d
•
to a s th e c e l l c o n s t a n t .
However, i f a l i q u i d o f known d i e l e c t r i c - c o n s t a n t
i s p la c e d in th e c e l l , th e t o t a l c a p a c it a n c e i s e q u a l to th e sum o f th e
le a d c a p a c it a n c e and th e p r o d u c t o f th e d i e l e c t r i c c o n s ta n t o f th e known
l i q u i d and th e c e l l c o n s t a n t .
T hus:
Cx = C0- H y ;.
By s o lv in g th e s e two
e q u a tio n s s im u l ta n e o u s l y , i t w i l l be n o te d t h a t C ~ (C^ — C a)/ ^ x and £
= (C„ - C -t-^ C )/C .
s t a n t o f 2 .2 7 3
shown in T a b le I .
U sin g p u r e b e n z e n e w ith a known d i e l e c t r i c co n -
25°C , th e c e l l c o n s t a n t was c a l c u l a t e d .
The r e s u l t s a r e
T h is c o n s ta n t w as c h e c k e d s e v e r a l tim e s th r o u g h o u t th e
w ork and w as fo u n d to re m a in s e n s i b l y c o n s t a n t .
TABLE I
Cx
,
,
C
T ri a I TTo .
Ua
I
3 4 .0 2
6 7 .7 9
2 6 .5 3
2
3 4 .0 1
6 7 .7 1
2 6 .4 7
3
3 4 .0 0
67 .7 4
2 6 .5 0
4
3 3 .9 8
6 7 .7 2
2 6 .5 0
5
3 3 .9 8
6 7 .7 2
2 6 .5 0
6
■
3 4 .0 2
6 7 .7 7
2 6 .5 1
tli>
Vyr
Nj ^ -y y , t v ' v - 3 i p p k
A verage
2 6 .5 0
- 26 In o r d e r to c h e c k th e c e l l c o n s t a n t , th e d i e l e c t r i c c o n s ta n t o f CCl^
was d e te r m in e d a t 2 5 °C.
The r e s u l t s o f t h i s d e t e r m in a tio n , shown i n T ab le
I I , show good a g ree m en t w ith th e a c c e p te d v a l u e , 2 ,2 2 7 3 •
TABLE I I
C
T r i a l Ho.
Cr
I
,3 4 .0 0
6 6 ,5 9
2 6 .5 0
2 .2 3 0 1
2
3 3 -9 4
6 6 .5 4
2 6 .5 0
2 .2 3 0 2
.3
3 3 -9 9
6 6 .5 2
2 6 .5 0
2 .2 2 7 5
The te m p e r a tu r e c o n t r o l l i n g d e v ic e c o n s is te d s im p ly o f a w a te r h a t h
h e a te d w ith an e l e c t r i c h e a t e r o f a p p r o x im a te ly 200 w a t t s , a com bined mech­
a n i c a l s t i r r e r and pump, and a r e l a y - c o n t r o l l e d m e rc u ry t h e r m o r e g u la to r .
W ater was c i r c u l a t e d th r o u g h th e c e l l j a c k e t a t th e d e s i r e d te m p e r a tu r e ,
u s in g s h o r t r u b b e r c o n n e c tio n s .
The te m p e r a tu r e c o n t r o l was a c c u r a t e to
0 .1 °C .
M ethod o f C a l c u l a t i o n :
A new m ethod f o r . c a l c u l a t i n g p o l a r i z a t i o n s
o f compounds a t i n f i n i t e d i l u t i o n , fro m m easu rem en ts o f d i e l e c t r i c con­
s t a n t an d d e n s i t y i n d i l u t e s o l u t i o n , h a s b e e n d e v e lo p e d b y H a l v e r s t a d t
and K um ler ( 6 ) .
They h av e w orked w ith o v e r 50 compounds and h av e fo u n d ,
i n e v e ry c a s e , t h a t th e d i e l e c t r i c c o n s t a n t o f th e s o l u t i o n i s a l i n e a r
f u n c t i o n o f th e c o n c e n t r a t i o n e x p r e s s e d i n m o l e .f r a c t i o n o f s o l u t e .
They
have a l s o fo u n d t h a t th e s p e c i f i c v o lu m es o f th e s e s o l u t i o n s v a r y l i n e a r l y
w ith c o n c e n t r a t i o n .
lo w in g e q u a t io n s ;
From th e s e f a c t s ,
C 12 s £ 1 ^-A-Cg
th e y Were a b l e to s e t up th e f o l ­
V12 —
beg* th e s u b s c r i p t s I and
2 r e p r e s e n t i n g s o lv e n t an d s o l u t e , r e s p e c t i v e l y .
Cj
A an d B r e p r e s e n t th e
- 27 s lo p e s o f th e r e s p e c t i v e c u r v e s o b ta in e d b y p l o t t i n g i^ 12 a g a i n s t C2 and
lv 12 a g e ,in s t c 2 •
The v a lu e s
and
a r e th e d i e l e c t r i c c o n s ta n t and
s p e c i f i c volum e o f th e p u re s o lv e n t fo u n d by e x t r a p o l a t i o n o f th e s e c u rv e s
to i n f i n i t e d i l u t i o n .
The same p r o c e d u r e
to be v a l i d i n eac h c a s e .
Wa1S
u s e d i n t h i s w ork and fo u n d
U sin g th e above e q u a tio n s an d th e r e l a t i o n ­
s h ip s :
C1M1 -f-Co Mo
(I)
p 12
= C H i£ -
■
G l-I
f p r
(2 )
pi
(3)
Iim P 1 - P00
C2 -B-O
Iim
=
'
•
= ^ 1 + ^ 2
%
^ 1"
Iim V12 - V1
c2- > o
Iim E 12 - € 1
c Z 9"0
C1 - I
C2-B-O
th e f o llo w in g r e l a t i o n s h i p was o b ta in e d :
e-L -l
= £ ^ 2 ~ (M2V1 ^M 1B)
IAvpM1
ts p a p c r
H a l v e r s t a d t and K um ler h av e i n d i c a t e d t h a t th e u s e -o f t h i s m ethod e lim in a ­
te d s o l v e n t p o l a r i z a t i o n e r r o r s s in c e e x t r a p o l a t e d v a l u e s o f d i e l e c t r i c con­
s t a n t and s p e c i f i c volum e a r e u s e d .
■ The o l d e r m ethod f o r c a l c u l a t i n g p o l a r i z a t i o n s a t i n f i n i t e d i l u t i o n
c o n s i s t s i n c a l c u l a t i n g P 2 , u s in g e q u a t io n s I an d 2 above f o r s e v e r a l
s o l u t i o n s , and p l o t t i n g th e s e v a l u e s a g a i n s t th e c o n c e n t r a t i o n .
By e x t r a ­
p o l a t i n g t h i s : c u r v e to i n f i n i t e d i l u t i o n , th e p o l a r i z a t i o n a t i n f i n i t e
d i l u t i o n i s o b ta in e d .
T h is h a s n o t a lw a y s b een a s u c c e s s f u l m ethod f o r
some com pounds, b e c a u s e t h e i r p o l a r i z a t i o n s i n s o l u t i o n do n o t v a r y
l i n e a r l y w ith c o n c e n t r a t i o n .
T h is f a c t makqs e x t r a p o l a t i o n d i f f i c u l t and
I
— 28 —
in a c c u ra te .
Ti(OC2H ^)i,, was t r e a t e d i n t h i s m anner and i t w i l l be s e e n
' l a t e r t h a t th e r e s u l t i n g a c c u ra c y i s v e r y p o o r .
•,
The m o la r r e f r a c t i o n f o r T i(0C 2H ^)^ Was c a l c u l a t e d from th e r e f r a c — t i v e in d e x and d e n s i t y o f th e p u re compound by th e f o llo w in g e q u a t io n :
F o r TiCI (OC2Hcj)^, th e m easu rem en ts w ere made in . d i l u t e s o l u t i o n i n b e n -
;
zene an d th e r e s u l t s c a l c u l a t e d b y th e same e q u a tio n u s e d above f o r th e
■
p o l a r i z a t i o n a t i n f i n i t e d i l u t i o n e x c e p t t h a t th e s q u a r e o f th e r e f r a c ­
t i v e in d e x w as u s e d i n s t e a d o f th e d i e l e c t r i c c o n s t a n t .
The F l e c t r i c Moment o f T i(OC2H^l;, = F o r th e d e t e r m in a tio n o f th e
e l e c t r i c moment o f Ti(OC2H5 ) 4 , s e v e r a l a c c u r a t e l y W eighed d i l u t e s o l u t i o n s
o f th e compound w ere made up u s in g b e n z e n e a s th e s o l v e n t .
u s e d was B a k e r C. P . ( th io p h e n e f r e e ) .
The b e n z e n e
B e fo re b e in g u s e d i t was r e d i s t i l ­
l e d and s t o r e d o v e r P 2O5 i n a d e s s i c a t o r to in s u r e th e ab se n c e o f any
w a te r .
The d i e l e c t r i c c o n s ta n t s o f th e s o l u t i o n s w ere m easu red i n th e
c e l l a t 25°C a s soon a s th e y w ere made u p i n o r d e r to m in im ize t h e e r r o r
due to a b s o r p ti o n o f m o i s t u r e .
T h e ir d e n s i t i e s w ere th e n m easu red w ith
an O stw a ld p y c n o m e te r a t th e same te m p e r a t u r e .
T a b le I I I shows th e r e s u l t s
o f th e s e m e a su re m e n ts.
V-S,1 >J1.*1 ■: '.y
v :;-
1 V jy ,'--’7
r= 11.
Vj 1
r i . . r 1 k w - - i v rfy-rv;:
” 29 ~
TABLE I I I
vI 2
d 12
Mole F r a c t i o n
€ 12
I
0 .0 0 1 9 3 5
2 .2 8 1 8
0 .8 7 3 5
1 .1 4 4 8
2
0 .0 0 3 4 0 6
2 .2 8 6 4
0 .8 7 4 5
1 .1 4 3 5
3
0 .0 0 2 9 9 3
2 .2 8 4 5
0 .8 7 4 3
1 ,1 4 3 7
k
0 . 006591'
2 .2 9 6 6
0 .8 7 6 2
1 .1 4 1 2
.5
0 .0 0 1 2 4 0
2 .2 7 9 6
0 .8 7 3 4
1 .1 4 4 9
S o lu tio n No.
I
U sin g th e m ethod d e s c r i b e d a b o v e, th e v a lu e s o f th e d i e l e c t r i c con­
s t a n t and s p e c i f i c volum e w ere p l o t t e d a g a i n s t mole f r a c t i o n Ti(OC2H ^)if,.
The r e s u l t i n g c u r v e s , shown i n F ig u r e s 4 and 5 w ere s t r a i g h t l i n e s a s th e y
s h o u ld b e a c c o r d in g to H a l v e r s t a d t an d K um ler.
U sin g th e m ethod o f l e a s t
s q u a r e s , th e s lo p e s .a n d i n t e r c e p t s w ore d e te rm in e d a s f o llo w s :
B
S 3
- 0 .7 1 9 7 ,
- 2 .2 7 5 5 , an d V1
=
1 .1 4 5 9 5 «
A a 3 . 1862,
Erom th e s e v a lu e s th e p b I a x i -
■
s a t i o n a t i n f i n i t e d i l u t i o n w as fo u n d to be 1 0 8 .0 m l.
I n o r d e r to .ch eck th e r e p r o d u c i b i l i t y o f th e f i r s t r e s u l t s , s e v e r a l
more s o l u t i o n s w ere made up and m e asu re d in th e same w ay.
m ents a r e shown i n T ab le IT .
in g t h i s d a t a w e re :
As
These m e asu re­
The v a l u e s o f th e s lo p e s an d i n t e r c e p t s , u s ­
B — —0.7013*
2 .2 7 5 3 » and V1 — 1 .1 4 6 1 .
The v a lu e o b ta in e d f o r th e p o l a r i z a t i o n a t i n f i n i t e d i l u t i o n was 1 1 2 .3 m l.
S in c e th e v a lu e s f o r th e p o l a r i z a t i o n a t i n f i n i t e d i l u t i o n a g r e e d
q u i t e c l o s e l y , . th e r e s u l t s can be c o n s id e r e d r e p r o d u c i b l e .
At t h i s p o i n t i t seem ed a d v i s a b l e to d e te rm in e th e p o l a r i z a t i o n a t in ­
f i n i t e d i l u t i o n by c a l c u l a t i n g P2 f o r e a c h s o l u t i o n an d p l o t t i n g th e s e
v a lu e s a g a i n s t c o n c e n t r a t i o n .
■
An e x t r a p o l a t i o n o f t h i s c u rv e to i n f i n i t e
"7T"
2. 1 ?
r
E i s l a c t r i c Sanstanta o f S - I ut i ona "'Iaitfd
Vcet
Vole I r e c t i >n T lta n i o- Te' .-iH. v l e t e Br i Ti Il(OCgHg) 3
in Sonzvr.e at 2S* .
3 ,S S
:
2 -s t k
'S
2 .3 5
O
Ti(TT2H5) 1
O
IiG l XI2I1- I 3
W
—
C
I
<1
I
CO.
C
C
8
-V\
C .; .
r-
1 .1 5 3 I
I. HS -
Spf1S i f l c V--I j g s s
• " S c f l u t i o n s P l o t t e j A, - , l a s t
Volo F n :t iun T itan iu - T e tr a eth y lv te t.-A T i l l - OT-H= Ir. ?>rrer. a t 25-T.
I
F ig u r e
CA
£
O
O
~ 32 TABLE IV
>
•Mole F r a c t i o n
^ 12
I
0 .0 0 1 0 6 9
2 .2 7 8 2
0 .8 7 3 2
1 .1 4 5 2
2
0 .0 0 2 9 5 9
2 .2 8 6 5
0 .8 7 4 3
1 .1 4 3 8
3
0 .0 0 4 4 9 1
2 .2 9 0 2
0 .8 7 5 2
1 .1 4 2 6
0 .0 0 1 9 7 2
2 .2 8 2 3
0 .8 7 3 9
1 .1 4 4 3
5
0 .0 0 5 6 1 3
2 .2 9 4 0
0 .8 7 5 7
1 .1 4 1 9
6
0 .0 0 1 3 0 0
2 .2 8 0 4
0 .8 7 3 5
I . 1448
S o lu tio n No.
'4
'?
'
d i l u t i o n s h o u ld g iv e th e d e s i r e d v a l u e .
com bined f o r t h i s p u r p o s e .
o f Pg.
v 12
*12
D a ta from T a b le s I I I and IV w ere
T ab le V shows th e r e s u l t s o f th e c a l c u l a t i o n
The r e s u l t i n g c u rv e i s shown i n F ig u r e 6 .
In th e more c o n c e n tr e ^
TABLE V
Mole F r a c t i o n
S o lu tio n H o.
?2
*'12
\I
0 .0 0 1 9 3 5
2 6 .8 6 8 1
H l .5 2
2
0 .0 0 3 4 0 6
2 6 .9 8 0 5
107.90
3
0 .0 0 2 9 9 3
2 6 .9 3 7 6
1 0 4 .7 5
4
0.006591
27-2418
1 0 8 .3 0
5
0 .0 0 1 2 4 0
. 26.8032
106.69
6
0.001069
26.7799
7
0.002959
26.9652
1 1 5 .1 4
8
0 .0 0 4 4 9 1
2 7 .0 7 0 7
10 8 .4 5
, 9
0 .0 0 1 9 7 2
26.8650
1 0 8 .6 1
10
0.005613
27.1688
1 0 9 .6 0
11
0 .0 0 1 3 0 0
2 6 .8 1 5 0
.1 1 2 .4 4
U1I j ; T 1--V1v - ^ 1^
rL 1-
v y -y iT
r r.y'-.U,-V
r
I-C/!,I
9 8 .2 2 ■
f
j
' / ; f '''- c K '/'/'l'/,-'" -
I" 5
-
•
T i t r a P t i i y I s t e I n Ssnzpr.e J o i n t ! o n a t Z i1K
150 L-
—O--------- O
O
I
F ig u re
M
04
_L .
I
. I«-*
8
8
C
C
g
g
SO
O
Volo F r a o t l on o f S o l u t o
A ___
r»
5
c
CO
8
o,ooo
I
I
— 3^ ~
t e d s o l u t i o n s th e v a lu e s o f Pn w ere r e l a t i v e l y c o n s t a n t , "but a t h ig h d ilu A
. t i o n th e r e w as l i t t l e
c o n s i s t e n c y , m aking i t d i f f i c u l t to e x t r a p o l a t e th e
/
c u rv e in t h i s r e g io n . I n th e more d i l u t e s o l u t i o n s th e c a l c u l a t i o n s r e ­
q u ire , th e d i v i s i o n o f v e r y s m a ll n u m b ers.
T h is f a c t a lo n e d e c r e a s e s th e
a c c u ra c y o f th e c a l c u l a t i o n .
-
•
.
A f t e r e x am in in g th e r e s u l t s o f th e two m ethods o f c a l c u l a t i o n ,
i t was
d e c id e d t h a t th e fo rm e r was more a c c u r a te and c o n v e n ie n t f o r t h i s , p u r p o s e .
F o r c a l c u l a t i o n o f th e m o la r r e f r a c t i o n f o r Ti(OC2^ ) Z 1,, i t s r e f r a c - \
. t i v e in d e x an d d e n s i t y w ere m easu red in th e p u re s t a t e .
A t 2 5 °C, th e den-r
s i t y was fo u n d to b e 1 .1 0 6 6 and th e r e f r a c t i v e • in d e x I . 5 0 6 9 2 .
S u b s titu - j
I
t i n g th e s e v a l u e s in th e e q u a tio n :
S r i
1 I
z k
,
; th e m o la r r e f r a c t i o n w as fo u n d to "be 64*4 m l. '
■ ‘
.
' '
W ith th e v a lu e s o f th e m o la r r e f r a c t i o n and m o la r p o l a r i z a t i o n , i t
\
r
it
I
i s p o ssib le to c a l c u l a t e th e p erm a n en t e l e c t r i c moment from th e e x p r e s s i o n :
» - 0 .0 1 2 ? x 10-18 !/(Poo -R )E
' The v a lu e o b ta in e d h e r e was 1 .4 4 x IQ -18 e l e c t r o s t a t i c u n i t s .
A c c o rd in g to th e Debye e q u a tio n
I
9kT
•
th e p o l a r i z a t i o n a t i n f i n i t e d i l u t i o n s h o u ld be a l i n e a r f u n c t i o n o f th e
r e c i p r o c a l o f th e a b s o lu t e te m p e r a tu r e i f th e m o le c u le h a s a p e rm a n e n t
■e l e c t r i c m om ent.
T3 =
.
In o t h e r w o rd s, P0= a + b /T , w here a, s
and
T h e r e f o r e , b y m e a su rin g th e p o l a r i z a t i o n a t i n f i n i t e d i l u ­
t i o n a t s e v e r a l d i f f e r e n t te m p e r a t u r e s , th e v a lu e o f th e d ip o le m om ent/#,
t
may be c a l c u l a t e d b y ^ f - 0 .0 1 2 ? x IQ -18 l / T e l e c t r o s t a t i c u n i t s .
j
;
't
i
I
- 35 —
I
In o r d e r to ch eck th e v a lu e
of
th e e l e c t r i c moment, th e n , f o r
Ti(OC2H ^)jIli, i t s p o l a r i z a t i o n a t i n f i n i t e d i l u t i o n w as d e te rm in e d a t 1 0 ° ,
35° and 45°C.V I.
The m easu rem en ts a t th e s e te m p e r a tu r e s a r e shown in T a b le
F ig u r e s 7 , 8 , 9 , 1 0 , 11 and 12 show th e c u rv e s o b ta in e d by p l o t t i n g
and V-^2 a g a i n s t c o n c e n t r a t i o n .
H ere a g a in th e r e s u l t s g iv e a s t r a i g h t
TABLE VI
Srvhvhlnn Ho.
Mole F r a c t i o n _ .
■
I
2
3
4 •
5
M easurem ent a t io ° c
2.3230
0.005367
0 . Q02000
2 .3 1 1 3
2 .3 1 8 1
0.004070
2 .3 1 0 1
0 .0 0 1 6 6 1
0 .0 0 7 8 1 5
, 2 .3 3 1 7
0 .8 9 1 3
0 .8 8 9 7
0.8 9 0 7
0 .8 8 9 4
■ 0 .8 9 2 6
1 .1 2 1 9
1 .1 2 4 0
1 .1 2 2 5
1 .1 2 4 4
1 .1 2 0 3
I
2
3
4
5
M easurem ent a t 3 5 °c
2.2 6 3 2
0 .0 0 3 1 0 6
2.2790
0 .0 0 8 3 9 1
2.2689
0 .0 0 5 1 4 3
2 .2 8 2 1
0 .0 0 9 1 4 5
2 .2 5 6 8
0 .0 0 1 1 0 8
0 .8 6 3 9
0 .8 6 6 6
0 .8 6 4 8
0 .8 6 7 0
0 .8 6 3 0
1 .1 5 7 5
1 .1 5 3 9
1 .1 5 6 3
1 .1 5 3 4
1 .1 5 8 7
0 .8 5 3 9
0 .8 5 2 2
O.8 5 3 1
0 .8 5 6 2
0 .8 5 4 5
1 .1 7 1 1
1 .1 7 3 4
' 1 .1 7 2 2
1.1 6 8 0
1 .1 7 0 3
M easurem ent a t .45-lg.
I
2
3
4
5
6
7
8
9
10
11
12
0.002683
0.009317
0 .0 0 5 2 8 4
0 .0 0 1 7 8 2
0 .0 0 3 2 8 2
O.OO5663
0 .0 0 1 1 2 4
0 .0 0 4 6 7 0
0 .0 0 1 1 9 8
0 .0 0 3 2 3 7
0 .0 0 9 4 4 5
0 .0 0 6 4 2 0
'
2 .2 4 4 6
2 .2 6 4 2
2,2518
2 .2 4 2 4
2 .2 4 6 9
2.2537
2 .2 4 1 2
O
At IO0 C Pe0 was 1 1 2 .0 ; a t 3 5 °C, 1 0 9 .1 ; and
S
-P
c3
Iin e .
v 12
d 12
C12
1 0 7 .0 .
T h ese
v a l u e s w ere p l o t t e d a g a i n s t th e r e c i p r o c a l o f th e a b s o lu t e te m p e r a tu r e .
a s shown in F ig u r e 1 3 , and th e e l e c t r i c moment c a l c u l a t e d from th e s lo p e
- J ': J Vijrqr-Jy.
.
2.535
S olu tion
2 .3 3 0
2 .3 2 5
2.320
2 .3 1 5
D i e l i ^ t r l o Constent* of S o lu t io n s P lo t te d
• ; e l r e t Vole F re o tio n T lte n lu n T e tr e e th y la t e Ir
Benzene a t IO3C.
2 .3 1 0
2.305
2 .300
Vole F r a c t i o n of S ol ut e
\
1.124
0 .0 0 7
S p e c I f t i) Volume o f S o lu t io n
S p e o l f l c Vol-tr.es o f S o lu t io n s P lo t t e d X geln st
Yole r r ec tlo r. T ltsn lu n T e t r s e t h y l e t e In
Benzene a t IO3C.
Kole F r a o t l o n of S o l u t e
F ig u re 9
C^netarta o f S o lu t io n s P l ; - •
■■
- -
T i t «.f
3.'r.tor,9 a t 35°' .
.
Z*2S0
vOto Frootirir *f Solute
.
i . if :
S p e s l f l o Vol vyia of S o l J t l ' n . c I o t r e d A g s l n i t
Volo f r a c t i o n T l t a n l ur rS t r a o t lI) I i * ' In
Benzane a t 3£°C.
'ocI f 1-O Volume o f S o l u t i o n
1.160
1.154
1.152
1.150
L
i . lie
8
8
O
S
C
tO
O
O
O
IO
Y clf T r a c t' on o f Goluto
t
I
GD
8
C
8
O
600*0
ro
C4
g
2 .2 6 5
2.260
2 2 .2 5 5
F ig u r e 11
2.250
D ie li c tr lo Constents of Solutions Plotted
■e a l n f t t Vole F r a c t i o n T i t . n l u a T e t r m e t h y l a t e i n
S e n i e n e a t 45°C.
-
2 .240
2 .2 3 5
Hole F r a c t i o n o f S o lu te
1.191
i
S p e o l f i c Volvcr.es of S o l u t i o n s ° l o t t e . i A g s 'n s t
Vole F r s o t i o n T itsniurn T e t r e e t h y l s o e in
Benzene a t 45°C.
1.177
I
I
135
P o larization a t In f in ite T llutlnn Plotted
A g a i n s t 1/T f o r T l t a n l ' z r , T - ' t r a e t h y l a t e
C
i
O
E
H*
120
C
0
1
O
O
C-
ICC
I
o
to
8
8
eO
8
u>
to
fO
8
8
1/7
O
C
CO
#0
8
*
Oi
to
8
0040
in5
0032
3
C
C
i
I
.
.
■
.■
,
j
o f th e r e s u l t i n g c u r v e .
I
u n its .
.
The v a lu e o b ta in e d was 1 .4 1 x 10
- 1
8
e le c tro s ta tic
T h is i s i n v e r y good a g ree m en t w ith th e v a lu e 1 .4 4 o b ta in e d p r e ­
v io u s ly .
I t w as, t h e r e f o r e , c o n c lu d e d t h a t th e e l e c t r i c moment f o r
T l ( 0 0 2 % )4 i d a p p r o x im a te ly 1 . 4 x 10“ ^
e le c tro s ta tic u n its .
The E l e c t r i c lMoment o f TiCl(OC2H g )^ :
'th e same way a s Ti(OC2Hg)J4,.
1
T h is compound w as m e asu re d i n
S e v e r a l d i l u t e s o l u t i o n s i n b en ze n e w ere made
u p , and t h e i r d i e l e c t r i c c o n s t a n t s and d e n s i t i e s m e asu re d a t 2 5 °C.
V II shows th e r e s u l t s o f th e s e m e a su re m e n ts.
T a b le
H ere, a g a i n , C 12 and v 12 w ere
TABIE V II
v 12
R n ln ti on No.
Mole F r a c t i o n
C12
d 12
I
0 .0 0 2 5 4 1
2 .3 0 1 0
0 .8 7 4 6
, 1 .1 4 3 4
2
O.OO7656
2 .3 6 3 4
0 .8 7 8 5
1 .1 3 8 3
0 .0 0 2 6 2 5
2 .3 0 2 9
0 .8 7 4 9
1 .1 4 3 0
4
0 .0 0 7 1 9 4
2 .3 5 1 0
0 .8 7 8 3
1 .1 3 8 6
5
0 .0 0 4 0 9 3
2 .3 1 7 1
0 .8 7 6 3
1 .1 4 1 2
,
3
s
p l o t t e d a g a i n s t mole f r a c t i o n s o l u t e and th e r e s u l t i n g c u r v e s shown in
j
•
i
i
V
j
!■
j
■
-
F ig u r e s 4 and 5 w ere s t r a i g h t l i n e s . T h is made i t p o s s i b l e to c a l c u l a t e -•
■ ■ .
th e p o l a r i z a t i o n b y th e same e q u a tio n u s e d i n th e c a l c u l a t i o n f o r
'
' Ti(OO2Hg)J4. The V alu es f o r th e s lo p e s A and B o f th e c u r v e s w ere fo u n d to
' -be 1 1 .5 3 9 8 and - 0 .9 6 4 5 , r e s p e c t i v e l y , and th e i n t e r c e p t s C 1 and
V1 ,
2 .2 7 1 8
and 1 .1 4 5 6 , r e s p e c t i v e l y . ' U sin g th e s e v a l u e s th e p o l a r i z a t i o n a t i n f i n i t e
d i l u t i o n was fo u n d to be 2 2 1 .9 m l.
]
'
'
•
B eca u se o f th e e x tre m e ly h ig h v i s c o s i t y and i n s t a b i l i t y o f T iC l(0 C 2Hg)g
i t was d e c id e d to d e te rm in e t h e m o la r r e f r a c t i o n b y m e a s u r in g 'th e r e f r a c -
' T
f V-Vfi);
■-'rv 1 •
W r- iu' V"
T f* "I* '
—
*»
t i v e In d e x and d e n s i t y o f s e v e r a l b e n z e n e s o l u t i o n s o f th e compound.
It
.
seem s r e a s o n a b le t h a t , i f th e s q u a re o f th e r e f r a c t i v e in d e x i s a l i n e a r
f u n c t i o n o f th e mole f r a c t i o n , th e m o la r r e f r a c t i o n c o u ld be c a l c u l a t e d by
th e same e q u a tio n u s e d f o r m o la r p o l a r i z a t i o n c a l c u l a t i o n s , u s in g th e r e ­
f r a c t i v e in d e x s q u a re d i n s t e a d o f th e d i e l e c t r i c c o n s t a n t .
The r e s u l t s
o f r e f r a c t i v e in d e x m easu rem en ts a r e shown i n T ab le T i l l .
The d e n s i t i e s
u s e d w ere ta k e n from th e r e s u l t s o f T a b le T H .
.
The s q u a r e o f th e r e f r a o -
TABLE V III
r 12
Mole F r a c t i o n
1.49843
2 .2 4 5 2 9
0 .0 3 3 7 3 8
1750006
2 .2 5 0 1 8
0 .0 0 5 3 8 0
1 .4 9 7 7 5
2 .2 4 3 2 6
4
0 .0 1 7 9 0 9
1,49879
2 ,2 4 6 3 7
. 5
0.009678
1 .49814
2 .2 4 4 4 2
I
• 0 .0 1 3 1 3 8
2
•3
.
■
t i v e in d e x f o r e a c h s o l u t i o n was p l o t t e d a g a i n s t i t s r e s p e c t i v e m ole f r a c ­
t i o n and th e r e s u l t i n g c u r v e , shown i n F ig u r e l b , g av e th e d e s i r e d
s tra ig h t lin e .
A g ain , u s i n g th e m ethod o f l e a s t s q u a r e s , ^
b e 2 .2 4 2 0 4 an d th e s lo p e - 0 .2 4 1 9 ? .
c a l c u l a t e d an d fo u n d to be
was fo u n d to
From t h i s th e m o la r r e f r a c t i o n was
m l.
The e l e c t r i c moment f o r TiOl(OO2^ ) 5 , u s in g th e v a l u e s f o r t h e m o la r
p o l a r i z a t i o n a n a m o la r r e f r a c t i o n , w as fo u n d ’ to be 2 ,8 3 x 10
s ta tic u n its .
e le c tro -"
T h is V alu e seem s q u i t e r e a s o n a b l e , ' s in c e th e m o le c u le s o f
t h i s compound a r e more u n s y m m e tric a l th a n th o s e o f T i (OC2H5 ) /4,» due to th e
p r e s e n c e o f th e c h l o r i n e ato m .
2 .2 6 5
S q u a r e o f R a f r a c t i v o I nd e x ^ l o t t e d A g a i n s t Vole F r a c t i o n
T i C l ( OC g H j ) J In Fe n z e n e S o l u t i o n a t 2 S0C.
2.255
R a frB ^ tlv o
Index
2 .2 6 0
I
-6.
Cn
S q u a to
of
I
2 .2 3 0
iO
o
d
8
O
O
O
O
O
O
ia
CM
o
o
8
C
Vola Fraction of Soluta
„Lin
g
o
O
O
0 .0 4 6
2.235
The E l e c t r i c Moment o f T iC lo OCgH ^:
The m o lar p o l a r i z a t i o n s n d m o la r ■
r e f r a c t i o n f o r t h i s compound w ere d e te r m in e d i n th e same way a s f o r
TiCl(OC2Hcj)^ from th e m easu rem en ts o f d i e l e c t r i c c o n s t a n t , r e f r a c t i v e in ­
d e x and d e n s i t y i n d i l u t e s o l u t i o n i n "benzene.
T ab le IX shows th e r e s u l t s
o f th e s e m easu rem en ts and F ig u r e s 15» 16 and I ? th e c u r v e s o b ta in e d by
p l o t t i n g 6 1 2 » v 1 2 » and r | 2 a g a i n s t c o n c e n t r a t i o n i n m ole f r a c t i o n .
The
s lo p e s o f th e c u r v e s w ere fo u n d to be 1 3 •6577» - 1 . 5 1 8 6 , and 1 . 2 3 0 5 » and
TABLE IX
2
r 12
S o lu tio n
No.
Mole
F ra c tio n
«12
d 12
V12
I
0 .0 0 1 3 9 2
2 .2 8 7 4
0 .8 7 4 5
1 .1 4 3 5
2
0 .0 0 0 5 7 2
2 .2 7 7 6
0 .8 7 3 5
1 .1 4 4 8
3
0 .0 0 2 3 7 0
2 .3 0 1 7
0 .8 7 5 6
1 .1 4 2 1
4
0 .0 0 0 5 3 5
2 .2 7 6 1
0 .8 7 3 4
1 .1 4 4 9
5
0 .0 0 1 0 1 8
2 ,2 8 2 4
0 .8 7 4 0
1 .1 4 4 1
6
0 .0 0 0 8 1 1
I .49822
2 .2 4 4 6 6
7
0 .0 0 2 9 7 1
1 .4 9 9 0 5
2 .2 4 7 1 5
8 '
0 .0 0 2 0 3 9
1 .4 9858
2 .2 4 5 7 4
9
O.OO363O
1 .4 9 9 4 5
2 .2 4 8 3 5
10
0 .0 0 8 7 4 0
1 .5 0 1 4 2
2 .2 5 4 2 6
rI2
t h e i r i n t e r c e p t s 2.2690» 1 .1 4 5 7 , and 2.2436» r e s p e c t i v e l y .
From th e s e
v a lu e s th e m o la r p o l a r i z a t i o n a t i n f i n i t e d i l u t i o n was fo u n d to be 2 5 0 . 2 ,
and th e m o la r r e f r a c t i o n 6 6 . 6 2 . . The e l e c t r i c moment c a l c u l a t e d w as
2 .9 7 x 10“ I® e l e c t r o s t a t i c u n i t s .
3
2 .2 9 5
F ig u r e 15
2 .2 9 5
D i e l e c t r i c Constants of S o lu t io n s P lo tte d
A gainst Vole F ra c tio n TiCljCCtiHf
in Be nr ere at ZS0C
2 .2 5 0 -
2 .2 7 5
2 .2 7 0
o
Mole F rac tion o f S o lu te
1.147
-
1.146
S p e c i f i c Vulunes c f S o l u t i c r s P l o t te d Arai r st
K:le Frs : t i c r TiCljOCgHij in Benzene
F ig u r e 16
1.140
§
O
O
O
O
O
O
Vo l e F r a c t i o n c f S o l u t e
0 .0 0 3
1.141
2 . 26 5
Square o f F efra o tiv e Index p lo t t e d Against liole F raction
TiClgOCgHg in Benzene S o lu t i m a t 25°C.
2.260
F ig u r e 17
2 .2 3 5
I
O
I
c-
O
C
§
O
Vole ? r e c t i on of Sclu^e
C
C
O
O
O
600*0
2 .2 3 0 L
I
-
50 -
I
S e v e r a l d i f f i c u l t i e s w ere e n c o u n te r e d i n m e a su rin g th e r e f r a c t i v e .
in d e x o f s o l u t i o n s o f t h i s com pound.
v
An a tte m p t w as f i r s t made to m easu re
them in th e cup p r o v id e d w ith th e d ip p in g r e f r a c t o m e t e r .
However, i t w as
fo u n d t h a t th e y r e a c t e d im m e d ia te ly w ith th e m e ta l o f th e in s tr u m e n t,
c a u s in g a r e d d is h p r e c i p i t a t e to a p p e a r .
N e x t, m easu rem en ts w ere a tte m ­
p te d "by p l a c i n g th e s o l u t i o n s i n th e s m a ll g l a s s c u p s p r o v id e d .
T h is , o f
c o u r s e , a llo w e d th e s o l u t i o n s to come in c o n t a c t w ith th e m o is tu re i n th e
a ir.
By th e tim e th e s o l u t i o n s c o u ld r e a c h te m p e r a tu r e e q u i lib r i u m and .
r e a d in g s c o u ld h e ta k e n , enough w a te r h ad b e e n a b s o rb e d to make th e r e a d ­
in g s i n a c c u r a t e and ev en to c a u s e h y d r o l y s i s o f t h e •compound i n s o l u t i o n .
F i n a l l y , a g l a s s cup was c o n s t r u c t e d w h ich w ould f i t t i g h t l y to a r u b b e r
r i n g p la c e d a ro u n d th e in s tr u m e n t j u s t above th e d ip p in g p r is m .
The s o lu ­
t i o n s c o u ld th u s b e p la c e d d i r e c t l y in t o th e c o n s t a n t te m p e r a tu r e b a t h and
r e a d in g s c o u ld b e ta k e n u n d e r an h y d ro u s c o n d i t i o n s . . A lth o u g h th e s o l u t i o n s
w ere h i g h l y c o lo r e d , a w h ite l i g h t s o u rc e was s u f f i c i e n t f o r ta k i n g r e a d ­
in g s u n d e r th e s e c o n d i t i o n s .
1VL I U, -- V • 7
-"I
1" "
•
~
t
—
V II.
D IE IiE C T R IC CONSTANT OE
**
Tl(O C JKg),
THROUG-H
ITS
T R A N S IT IO N P O IN T
I t w as m en tio n ed ' p r e v i o u s l y t h a t Ti(O C gEg)^ c o u ld e x i s t a s a s o l i d a t
room t e m p e r a t u r e .
I t seem ed o f i n t e r e s t to m easure t h e d i e l e c t r i c con­
s t a n t o f t h i s compound i n th e l i q u i d an d s o l i d s t a t e s o v e r a te m p e r a tu r e
and f re q u e n c y r a n g e .
A f l a s k c o n t a in in g th e p u r e , r e d i s t i l l e d Ti(OC2H ^)jIi, was p la c e d i n a
-
"beaker c o n t a i n i n g d ry ic e an d a c e to n e . A f t e r a p e r i o d o f JO m in u te s th e
'
.
, l i q u i d compound h a d become e x tre m e ly v i s c o u s , b u t no c r y s t a l l i z a t i o n h a d
*
;
'
ta k e n p l a c e .
The f l a s k was th e n rem oved from th e b a t h an d a llo w e d to come
i s lo w ly to room te m p e r a tu r e .
A f t e r a p p r o x im a te ly one h o u r f i n e l y d i v i d e d .
:
\
w h ite c r y s t a l s b e g a n to a p p e a r . The compound was th e n t r a n s f e r r e d to th e J
•'
•
■.
I
d i e l e c t r i c c e l l , d e s c r ib e d p r e v i o u s l y , and a llo w e d to s o l i d i f y c o m p le te ly :
j
;
/
:a t about
2 0 °C. T h is p r o c e s s r e q u i r e d a b o u t t h r e e h o u r s .
r
■ A f te r c o m p le te s o l i d i f i c a t i o n th e d i e l e c t r i c c o n s ta n t o f th e s o l i d
was m easu red o v e r a f r e q u e n c y range- fro m I to 30 m e g a c y c le s and o v e r a
te m p e r a tu r e ra n g e from O0 C to 35°C .
F o r th e s e m easu rem en ts a G e n e ra l R adio
Type 8 2 1 -A Tw in-T im pedance m e a su rin g c i r c u i t was u s e d i n c o n j u n c tio n w ith
a H ick o k c r y s t a l c o n t r o l l e d m i c r o v o lt f r e q u e n c y g e n e r a t o r .
A Hamm arlund
HG-129-X a m a te u r co m m u n icatio n s r e c e i v e r was u s e d a s a d e t e c t i n g d e v i c e .
The te m p e r a tu r e was c o n t r o l l e d b y th e w a te r b a th d e s c r i b e d p r e v i o u s l y .
T ab le X shows th e r e s u l t s o f th e d i e l e c t r i c c o n s t a n t m easu rem en ts a t :
a f re q u e n c y o f two m e g a c y c le s .
The lo w e r c u rv e in F ig u r e 18 shows th e r e ­
s u l t o f p l o t t i n g th e s e " v a l u e s a g a i n s t th e te m p e r a tu r e .
The d i e l e c t r i c
c o n s t a n t b e g a n "to r i s e a b o u t 5° belo w th e m a c ro sc o p ic m e ltin g p o i n t .
At I
I
— j)2 —
135°C th e compound in. th e c e l l was c o m p le te ly m e lte d .
T h ere a p p e a re d to he
no s i g n i f i c a n t change in th e d i e l e c t r i c c o n s ta n t w ith fr e q u e n c y so th e
o t h e r r e a d in g s h av e b e e n d i s r e g a r d e d .
TABLE X
D i e l e c t r i c C o n s ta n t
F reo u en cv
Termo. i n C e n tig r a d e
2 meg.
0 .0
3 .1 0 8
I'
1 0 .0
3 .0 7 5
U
1 5 .0
3 .0 4 1
ti
2 0 .0
3 .0 2 2
n
2 5 .0
3 .0 3 7
I!
3 0 .0
3 .2 6 1
'll
3 2 .0
3 .5 6 3
3 5 .0
3 .6 3 8
1«
A f t e r c o m p le te m e ltin g th e te m p e r a tu r e was g r a d u a l l y lo w ered a g a in to
O0 C and th e d i e l e c t r i c c o n s ta n t d e te rm in e d a t v a r io u s p o i n t s i n t h i s i n - .
te rv a l.
T ab le XI shows th e r e s u l t s o f th e s e m e a su re m e n ts.
The u p p e r
c u rv e i n F ig u r e 18 shows th e r e s u l t o f th e .c o r r e s p o n d in g d i e l e c t r i c c o n TABLE XI
F reo u en cv
Temn. in C e n tig ra d e
D i e l e c t r i c C o n s ta n t
2 5 .0
3 .6 8 0
w . ■
.2 0 .0
3 .7 1 0
it
1 5 .0
3 .7 4 0
it
■ 1 0 .0
2 meg.
11
. O-O '
3 .7 7 0 . 3 .8 2 0
-
.
53
-
Irnrh Shnwinr1 Chmnr" Sr C i I
rj - ConsMnt
With Tenrernt Urw o f fur • T i t n ' Jm T rtru cl kVlute in Bcth Liquid - n>i S niM !Imses
Lt a F r o q u e n n y o f 2
cyn Ie ■
3 .5
3. ; ■
',!e l'V ’ t r l c
a
w
3 .4
s i.P O
3 .C
S Uci
. . rI
3.r-L
I
15
_L _
20
26
Tempi*:-ii urn Ir. Cent I,-
*»
F ig u r e 18
.....
■
................—
- ----------------------------------- -----
I
— 5^ ~
s t s n t , te m p e r a tu r e p l o t .
I
The compound d id n o t s o l i d i f y d u r in g th e s e
o
m easu rem en ts ev e n a t 0 G.
The d i e l e c t r i c c o n s ta n t showed a n o rm al in ­
c r e a s e i n v a lu e w ith d e c r e a s i n g te m p e r a t u r e .
H ere a g a i n , th e r e w as no
s i g n i f i c a n t ch an g e in th e d i e l e c t r i c c o n s t a n t w ith f r e q u e n c y .
V III.
DISCUSSION OT EXPERIMENTAL RESULTS
Q u a l i t a t i v e l y i t i s to he e x p e c te d t h a t a p e rm a n e n t e l e c t r i c moment
w ould e x i s t f o r TiClCOCgH^)^ and TiCl-^OCgH,-.
The p r e s e n c e o f th e h i g h l y
n e g a t iv e c h l o r i n e atom s w o u ld te n d to make th e m o le c u le s q u i t e e l e c t r i ­
c a l l y u n s y m m e tr ic a l.
S in c e no bond, moments f o r th e T i- C l bond a r e known
t h e o r e t i c a l c a l c u l a t i o n s o f th e e l e c t r i c moments a r e im p o s s ib le .
The
-
v a l u e s 2 .8 3 and 2 .9 7 Debye u n i t s , d e te rm in e d e x p e r i m e n t a lly seem q u i t e
-
re a s o n a b le f o r th e s e m o le c u le s .
The p r e s e n c e o f th e e l e c t r i c moment 1 .4 f o r Ti(OC2H5)l|.* c o n s i d e r i n g
i t s a p p a r e n tly s y m m e tric a l s t r u c t u r e ,
i s o f c o n s id e r a b le i n t e r e s t . .
In
t h i s c o n n e c tio n th e c a rb o n a n a lo g u e o f t h i s com pound'C(OCgH^)If. m ig h t b e
c o n s id e r e d .
■
E b e r t , E i s e n s c h i t z and v o n H a r t e l (4 ) fo u n d th e e l e c t r i c
moment o f t h i s compound to be 1 .1 Debye u n i t s .
They a l s o fo u n d th e p r e -
'
' se n c e o f an e l e c t r i c moment i n o t h e r s u b s t i t u t e d m e th an es su ch a s C(OCHg)^,
■C(COOCH3 ) 4 , C(COOCgHj))^. e t c .
In o r d e r to e x p l a in th e p r e s e n c e o f t h e s e
moments th e y assum ed t h a t th e f o u r v a le n c e s o f th e c e n t r a l c a rb o n atom a r e
d i r e c t e d from th e ap ex to w ard th e c o r n e r s o f a r e g u l a r p y ra m id .
' r e a d ily seen th a t,
I t c a n be
i f th e c a rb o n atom may assum e t h i s form and th e f o u r
v a le n c e s a r e s a t i s f i e d b y l i k e g ro u p s , a m o le c u le p o s s e s s in g a d i p o l e
moment m ust r e s u l t .
T h is means t h a t i f OClff and CHff assum e t h i s s t r u c t u r e .
- 55
I
I
th e y s h o u ld a l s o p o s s e s s a moment, w hich i s n o t th e c a s e .
r e a s o n , t h i s th e o r y h a s h e e n d i s r e g a r d e d .
c o n s id e r e d to b e t e t r a h e d r a l .
For th is
The c e n t r a l c a rb o n a.tom i s now-
In t h i s c a s e COl^ and CH^ s h o u ld be q u i t e
s y m m e tric a l and h a v e no r e s u l t a n t moment.
I t s h o u ld be n o te d t h a t th e s u b s t i t u t e d m eth an es p o s s e s s in g p e rm a n e n t .
moments a l l c o n t a i n oxygen atom s in th e g ro u p s s u rr o u n d in g th e c e n t r a l c a r ­
bon atom , a t t a c h e d d i r e c t l y t o , o r v e r y c l o s e to i t .
I f th e two v a l e n c e s
o f th e oxygen a r e alw ay s i n c l i n e d a t a b o u t 105 » 8S th e y a r e in m ost m ole­
c u l e s , th e n th e moments o f th e s e g ro u p s do n o t a c t a lo n g th e l i n e j o i n i n g
them to th e c e n t r a l atom ,
!There w ould b e o n ly a l i m i t e d num ber o f p o s i ­
t r o n s o f th e s e g ro u p s i n w h ich th e t o t a l moment w ould b e c a n c e l l e d .
Even
f r e e r o t a t i o n o f th e g r o u p s , th e n , w ould g iv e a r e s u l t a n t moment f o r th e
m o le c u le .
The ti t a n i u m atom , l i k e c a rb o n , i s a ls o c o n s id e r e d a s a t e t r a h e d r a l
ato m .
T h e r e f o re th e v a lu e 1 . 4 f o r th e moment o f TiCOCgH^)^, in c o m p a r is o n ■;
to 1 .1 f o r C(C)CgEc;)^, i s n o t s u r p r i s i n g .
The f a c t t h a t th e d i e l e c t r i c
c o n s ta n t o f p u re Ti(G)CgHc;)^ i s ' c o n s id e r a b ly l e s s i n th e s o l i d s t a t e th a n i n
th e l i q u i d s t a t e a l s o s u p p o r ts th e p r e s e n c e o f a moment' in th e m o le c u le . " .
.1
I
—
IX.
56
—
'I
SUMHAHY
-
1 . 'T i t s n i T i m t e t r a e t h y l a t e , monoc h l o r o - 1 r I e t h o x y - t i t an iu m , and t r i c h l o r o ~
p h enoxy—t i t a n i u m a r e e a s i l y p r e p a r e d f o r d i e l e c t r i c m easu rem en t, h u t
h y d r o ly z e r a p i d l y In a i r .
I n a d d i t i o n , I n t e r e s t i n g p o ly m e r - lik e com­
pounds may he p r e p a r e d h y th e r e a c t i o n o f ti t a n i u m t e t r a c h l o r i d e w ith
p o ly -h y d ro x y a l c o h o l s .
2.
A sim p le e l e c t r i c a l a p p a r a tu s , c o n s t r u c t e d from a made—o v e r a i r c r a f t
t r a n s m i t t e r , h a s p ro v e n to h e q u i t e a c c u r a te f o r th e d e t e r m in a tio n o f
d i e l e c t r i c c o n s ta n ts o f s o lu tio n s .
A c e l l o f th e Smyth ty p e may he
u s e d w ith t h i s a p p a r a tu s .
3.
An e q u a t io n , d e r iv e d hy H a l v e r s t a d t and K um ler6 h a s "been fo u n d to he
a p p l i c a b l e f o r c a l c u l a t i n g th e e l e c t r i c moments o f ti ta n i u m t e t r a , e t h y l a t e , mono c h lo r o - 1r i e th o x y - t i t an iu m , and t r i c h lo r o - p h e n o x y t Ita n iu m .
4.
The e l e c t r i c moment o f t i t a n i u m t e t r a e t h y l a t e was fo u n d to h e 1 . 4 Debye
u n its .
B a is v a l u e , o b ta in e d h y two d i f f e r e n t m e th o d s, a g r e e s a p p r o x i­
m a te ly w ith th e v a lu e o f 1 .1 d e te rm in e d by E h e r t 9- E i s e n s c h i t s , an d
von H a r t e l f o r th e c a rb o n a n a lo g u e C( O C g H ^ ) i n d i c a t i n g t h a t i t h a s
a s im ila r s tr u c tu r e .
5.
T ita n iu m t e t r a e t h y l a t e h a s b e e n fo u n d to e x i s t b o th a s a s o l i d and a"
l i q u i d a t th e same te m p e r a tu r e .
A s i g n i f i c a n t r i s e i n th e d i e l e c t r i c
c o n s ta n t o f t h i s compound when i t i s m e lte d ,- s u p p o r ts th e p r e s e n c e o f
a p e rm a n e n t e l e c t r i c moment.
6.
The e l e c t r i c moment o f m o n o c h lo ro -t r i e t h o x y - t i t a n i u m and t r i c h l o r p -
■I
( -IIj-X -.,,-, ,1.
■TVK-1
Wu,I,1J M 'tp W A - J T T i J - I 1-MV.1, W ' ' T
. ''" / f '
0
Ie
- 57 p h en o x y - t i t a n inm a r e 2 .8 3 end 2 .9 7 Debye u n i t s , r e s p e c t i v e l y .
,
I t is
e x p e c te d th s .t th e s e compounds w ould p o s s e s s l a r g e r moments th a n t i t a n ­
ium t e t r a e t h y l a t e b e c a u s e o f th e p r e s e n c e o f th e h i g h l y n e g a tiv e
;
'
c h l o r i n e atom s in t h e i r m o le c u le s*
,
7.
T h is i n v e s t i g a t i o n h a s ad d ed to th e know ledge o f th e e l e c t r i c moments
o f t i t a n i u m com pounds.
F u r t h e r i n v e s t i g a t i o n s h o u ld e v e n t u a l l y b e ■
s i g n i f i c a n t i n th e e x p l a n a ti o n o f th e u n u s u a l d i e l e c t r i c p r o p e r t i e s
I
I.
i
i
o f TiOo and o t h e r in o r g a n ic compounds o f t h i s e le m e n t.
,
-
-.ii
H
rA-' itT1
I
— 58 —
I.
ACMOtfLEiDG-EMBSTS
The a u t h o r w is h e s to ta k e t h i s o p p o rtu n ity - to e x p r e s s h i s s i n c e r e
a p p r e c i a t i o n and th a n k s to D r. C h a r le s N. C aughlan f o r h i s p e r s o n a l ■
g u id a n c e and i n s p i r a t i o n d u r in g t h i s r e s e a r c h , and to D r. D. 0 . B in d e r ,
J r . and D r. A. McB. S m ith f o r t h e i r many h e l p f u l s u g g e s tio n s .
He a l s o
w is h e s to th a n k th e R e s e a rc h C o r p o r a tio n o f Hew Y ork f o r m aking t h i s
i n v e s t i g a t i o n p o s s i b l e th ro u g h a g r a n t .
V.'1Sy"!/1' "
1
T.,'' --I —
'v" - n
- ' - . - i ' ' 1f
T
iVTWItiV5’.■'
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- 59 X I, LITERATUKS CITED AED CONSULTED
(1 )
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(2 )
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3 1762
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B)78
c886d
co p . 3
Crowe, R obert VJ.
The d i e l e c t r i c p r o p e r t i e s o f
some e s t e r s o f t i t a n i u m . . .