The physical properties of organic titanates
by Howard M Smith
A THESIS Submitted to the Graduate Faculty in partial fulfillment of the requirements for the degree
of Master of Science in Chemistry
Montana State University
© Copyright by Howard M Smith (1950)
Abstract:
A study has been made of the molar polarizations of titaniumtetra-ethylate at temperatures ranging
from 20°C to -60°Co' The values obtained were practically constant at these temperatures, The values
ranged from 114.6 cc/mole at. 17°C to 112.3 cc/moIe at -60°C.
The associations of titaniumtetrapropylate, titaniumtetrabutylate, and monochloro-triethoxy-titanium,
have been measured in dilute solution in benzene and have been found to be approximately three.
Pure crystals of titaniumtetraethylate were prepared and, identified as being monoclinic. The compound
was optically biaxial and its indices of refraction were: n beta (y) 1.601 more or less, n alpha (x) 1.591
or less, n gamma (z) l.608 or more. The determination of n alpha and n gamma are only approximate. THE PHYSICAL PROPERTIES OF ORGANIC TITANATES
by
HOWARD M. SMITH
v A THESIS
S ubm itted to th e G raduate F a c u lty
in
A
p a r t i a l f u l f i l l m e n t o f th e re q u ire m e n ts
f o r th e d eg ree o f
M aster o f S cien ce i n C hem istry
at
Montana S ta te C o lleg e
Approved:
Head, M ajor D epartm ent
Bozeman, Montana
November, 1^50
S ''n s '
I,
—2 —
y'l
TABLE OF CONTENTS
I.
II.
III.
>
H
v.
VI .
ABSTRACT . . . . . . . . .
...................... . . . . . . . . . .
INTRODUCTION .................................................................................................
J1
LITERATURE
. . . .
5
THEORY AND POSSIBILITIES . . . . . . . . . . . . . . . . .
6
SURVEY . . . . . . . . . .
PREPARATION OF COMPOUNDS USED
......................
. . . . . . . . . . . . . .
11
T i t a n i u m - te tr a e th y la te . . . . . . . . . . . . . . . .
H
T ita n iu m - te tr a p r o p y la te
. . . . . . . . . . . . . . .
U
T i t a n i u m - te tr a b u ty la te . . . . . . . . . . . . . . . .
LI
Mono c h lo r o - t r i e t b o x y - t ita n iu ra
. . . . . . . . . . . .
11
POLARIZATION OF 1 1 ( 0 0 ^ ) ^ AT LOW TEMPERATURES . . . . . .
13
A pparatus used f o r m easurem ents
P o la r i z a tio n s
V II.
............................................
13
. .................. . . . . . . . . . . . . . .
1$
ASSOCIATIONS . . . . . . . . . . . . . . . . . . . . . . .
38
A s s o c ia tio n o f
T ita n iu m - te tr a p r o p y la te . . . . . . . .
A s s o c ia tio n o f T ita n iu m - te tr a b u ty la te
A s s o c ia tio n o f
I4I
. . . . . . . .
M o n o c h lo ro -trie th o x y -tita n iu m . . . . .
PREPARATION OF CRYSTALS OF TITrANITJM=-TETRAETHYLATE
!4$
. . . .
I48
C ry s ta lo g ra p h ic D ata . . . . . . . . . . . . . . . . .
I48
5
V III.
Page
3
DISCUSSION OF EXPERIMENTAL RESULTS . . . . . . . . . . . .
30
X.
SUMMARY. . ........................................ . . . . . . . . . . . . . .
32
XI .
ACKNOWLEDGEMENTS . . . . . . . . . . . . . . . . . . . . .
$3
X II.
LITERATURE CITED AND CONSULTED . . . . . . . . . . . . . .
5k
98375
r 3 I.
ABSTRACT
A s tu d y has been made o f th e m o lar p o la r iz a t io n s o f t i t a n i u m t e t r a e th y la te a t te m p e ra tu re s ra n g in g from 20°C to -SO0 C0 ' The v a lu e s o b ta in e d
were p r a c t i c a l l y c o n s ta n t a t th e s e te m p e ra tu re s „ -The v a lu e s ra n g e d .from
l l l u 6 .cc/m ole at. 17°C t o 112 »3 cc/moIe a t -6 0 °C e
The a s s o c ia tio n s o f tita n iu m te tr a p r o p y la te , t i t a n i u m t e t r a b u t y l a t e ,
and m o n o c h lo ro -trie th o k y -tita n iu m , have been m easured i n d i l u t e s o lu tio n
i n benzene and have been found to be a p p ro x im a te ly t h r e e e
Pure c r y s t a l s o f t i t a n i u m t e t r a e t h y l a t e were p re p a re d and i d e n t i f i e d
a s b e in g m o n o c lin ic . The compound was o p t i c a l l y b i a x i a l and i t s in d ic e s
o f r e f r a c t i o n w ere: n b e ta (y) ^*601 more o r l e s s , ri a lp h a (x) 1*391 o r
l e s s , n gamma.(z) l o608 o r more* The d e te rm in a tio n o f n a lp h a and n gamma
a re o n ly ap p ro x im a te e
“>
Ho
!=
.
,
INTRODUCTION
P h y s ic a l p r o p e r tie d and s t r u c t u r e s o f in o rg a n ic t i t a n a t e s have been
known f o r some tim e b u t v e ry l i t t l e i s known ab o u t th e o rg a n ic d e r iv a tiv e s
o f T iC li f
'
'
■
Some in o rg a n ic t i t a n a t e s p o s s e s s v e ry la r g e d i e l e c t r i c c o n s ta n ts and
a s such a r e e x c e p tio n a l d i e l e c t r i c m a t e r i a l s .
I n view o f t h i s f a c t i t was
d e c id e d to s tu d y o rg a n ic d e r iv a tiv e s o f T i Cl^ i n o rd e r to f i n d o u t more
ab o u t t h e i r d i e l e c t r i c b e h a v io r«
Crowe (I.) succeeded i n showing t h a t th e r e
was n o th in g u n u su a l i n th e d i e l e c t r i c p r o p e r t i e s o f th e s e o rg a n ic compoundsa t oM fn a ry te m p e ra tu re s j however K a tz 8s (2 ) work w ith th e
p o la riz a tio n
o f t i t a n i u m t e t r a e t h y l a t e a t low er te m p e ra tu re s in d ic a te d some i n t e r e s t i n g
s t r u c t u r a l im p lic a tio n s .
Some r e s t r i c t e d r o t a t i o n was in d ic a te d and i t
was th p purp o se o f ..,the p r e s e n t .work to v e r i f y t h i s in fo r m a tio n .
Katz a ls o
succeeded i n p r e p a r in g i r r e g u l a r c r y s t a l s o f t i t a n i u m t e t r a e t h y l a t e which
w ere to be u sed in.. X -ray d i f f r a c t i o n m easurem ents and d e te rm in a tio n o f
c ry s ta l h a b it.
S in c e th is .h a d - n o t been accom plished it- w a s a ls o d e s ir a b le
to p r e p a r e .r e g u la r .. c r y s t a l s i f p o s s ib le to o b ta in t h i s in fo r m a tio n .
I n a d d itio n .a .stu d y of. the. a s s o c ia ti o n o f s e v e r a l o f t h e s e o rg a n ic
d e r iv a tiv e s would add a v a lu a b le in fo rm a tio n r e g a r d in g .th e n a tu re and
s t r u c t u r e o f th e compounds and th e bonds in v o lv e d .
x
Ill.
LITERATURE SURVEY
A g r e a t advance co ncerning t h e s t r u c t u r e o f
m o lecu les has b een made
d u rin g th e p a s t few y e a rs th ro u g h th e f i e l d o f d ie l e c t r i c s =
The e l e c t r i c a l
symmetry o r asymmetry o f m o lecu les can be d eterm in ed th ro u g h th e s e stu d ie s=
P ro b a b ly th e b e s t in fo rm a tio n o b ta in a b le on t h i s s u b je c t i s Debye8s ltP o la r
M oleculesn (3) and Smyth’ s " D i e l e c t r i c C o n stan t and M o lecu lar S tr u c tu r e "
(U )o There a re some m o d ific a tio n s on th e above t r e a t i s e s such as .O nsagert s( 5>) m o d if ic a tio n o f Debye1s th e o ry j how ever, th e r e i s a la r g e amount o f
work t h a t rem ains to be done i n t h i s f ie ld =
The l i t e r a t u r e h as l i t t l e o r no In fo rm a tio n re g a rd in g th e d i e l e c t r i c
o r o th e r, p h y s ic a l p r o p e r tie s o f o rg a n ic tita n iu m compounds = A th o ro u g h
l i t e r a t u r e s e a rc h on th e p a r t o f Crowe ( I ) and.K atz ( 2) has re v e a le d t h a t
p r a c t i c a l l y n o th in g i s known ab o u t th e o rg a n ic e s t e r s o f T iC l^ 0
. T here i s some in fo rm a tio n on th e p r e p a r a tio n o f th e s e compounds=
The
in fo rm a tio n t h a t has been u se d m ost e x te n s iv e ly i n . t h i s manner i s t h a t of
B is c h b ff and Adkins ( 6 ) and J e n n in g s , Ward low, and Way (7) =
—6 “
' IV .
THEORY MD POSSIBILITIES
O r d in a r ily i t would n o t be p e rm iss a b le t o le a v e o u t a t h e o r e t i c a l
d is c u s s io n on th e r e l a t i o n s h i p betw een d i e l e c t r i c s and m o le c u la r s tr u c ­
tu re .
However3 s in c e t h i s has been a d e q u a te ly d is c u s s e d i n Crow e's th e s i s
( I ) i t a p p ea rs j u s t i f i a b l e to r e f e r th e re a d e r to t h i s work and t o sub­
s t i t u t e i n i t s p la c e a d is c u s s io n ab o u t th e r e l a tio n s h ip betw een d ie le c ­
t r i c s and m o le c u la r a s s o c i a t i o n .
L iq u id s may be c l a s s i f i e d a s norm al o r abnorm al, th e norm al b ein g
th o s e whose p r o p e r tie s conform t o c e r t a i n laws,,, and th e abnorm al bein g
th o s e w h o se ..p ro p e rtie s d e v ia te from t h e i r .law s. , The u se o f f r o n t o n 's
r u l e and th e E otvos-R am say-S hields c o n s ta n t may be m entioned a s p a r tic u ­
l a r l y common m e th o d s .o f.c l a s s i f i c a t i o n .
A bnorm ality i s a t t r i b u t e d to
m o le c u la r a s s o c ia ti o n , a term which im p lie s an a g g re g a tio n o f s in g le mol­
e c u le s in to complexes c o n ta in in g two o r more o f th e s in g le m o le c u le s .
The e x te n t o f th e supposed a s s o c ia ti o n i s m easured by th e a s s o c ia ti o n
f a c t o r which i s th e av erag e number o f s in g le m olecules i n th e a c tu a lly
e x i s t i n g m o le c u les o f th e .s u b s ta n c e .
Thus, i f a l l th e s in g le m o lecu les
have combined t o form double m o le c u le s th e a s s o c ia ti o n f a c t o r i s 2.
If .
a l l th e s in g le m olecules combine to form a g g re g a te s o f t h r e e , th e f a c to r
i s 3 o The d eg ree o f a s s o c ia ti o n i s , o f c o u rs e , th e f r a c t i o n o f th e s in g le
m o lecu les w hich have formed a g g re g a te s .
I t i s custom ary to c a lc u la te th e
a s s o c i a t i o n f a c t o r from th e d e v ia tio n o f th e p ro p e rty u n d er ex am in atio n
from th e sim ple law supposed t o a p p ly to norm al l i q u i d s .
A phenomenon
w hich causes a d e v ia tio n i n one p ro p e r ty is. a p t to cause d e v ia tio n i n
a n o th e r a s w ell? liq u id s w hich a re found abnorm al by one method a re
■ _
7
-
u s u a ll y found abnorm al by o th er's 0
The cause o f m o le c u la r a s s o c ia ti o n i s p ro b a b ly i n th e s tr a y e le c ­
t r i c a l f o r c e s a s s o c ia te d w ith u n s a tu r a te d o r sec o n d a ry v a le n c e s w hich
a r i s e from l o c a l d ip o le s i n th e m o le c u le s, i n th e f o r c e s due to m olec­
u l a r d ip o le s which v a ry in v e r s e ly as th e t h i r d power o f th e d is ta n c e s
from th e c e n te rs o f th e d ip o le s , and from van d e r Vfalls f o r c e s .
However,
th e f o r c e s e x e rte d b y d ip o le s a re much more im p o rta n t th a n th o s e e x e rte d
by van d e r Waals fo rc e s*
The t o t a l p o l a r i z a t i o n P, i s made up o f th r e e p a r t s ; th e e le c tr o n i c
p o la r iz a tio n : Pe , th e atom ic p o l a r i z a t i o n Pa , and t h e p o l a r i z a t i o n due to
th e perm anent moment P »
t o r t i o n p o l a r i z a t i o n , Pe +
I t can be shown (Ij.) t h a t th e
=
induced o r d i s ­
where N .is Avogadro8s Number.
cC0 i s th e moment in d u ced i n a s in g le m olecule by u n it e l e c t r i c f i e l d .
I t can a ls o be shown..that.ec.o = Z e ^ / f , where f i s a p r o p o r t i o n a l i t y c o n sta n t
w hich d e te rm in e s th e r e s t o r i n g f o r c e e x e r te d upon th e charge e when i t i s
,t
d is p la c e d a d is ta n c e x by th e a c tio n o f a. f i e l d . I f th e r e f r a c t i v e in d e x
n , were d e term in e d a t wave le n g th s to o s h o r t f o r o r i e n t a t i o n p o l a r i z a ­
tio n P
t o o c c u r, th e n th e . m olar r e f r a c t i o n would not c o n ta in th e c o tttr i-
b u t i o n .o f th e s h i f t s o f atoms o r r a d i c a l s i n th e f i e l d o f th e l i g h t wave.
T h e re fo re , th e e l e c t r o n i c p o l a r i z a t i o n Pe = (n ^ -l)M /(n ^ + 2 )d , where M
i s th e m o le c u la r w e ig h t, and d i s th e d e n s it y .
I f t h i s e x p re s s io n could
be e x tr a p o la te d from th e v i s i b l e re g io n t o i n f i n i t e wave le n g th th e n i t
would g iv e a p p ro x im a te ly th e p o l a r i z a t i o n due to th e e le c tr o n s Pe , b u t
w ould n o t g iv e th e p o l a r i z a t i o n Pq o f th e atom s, s in c e atoms v i b r a t e w ith
fr e q u e n c ie s i n th e i n f r a re d re g io n .
T h e re fo re , s in c e Pa i s s m a ll and
- 8 -
e x tr a p o la tio n to i n f i n i t e wave le n g th o n ly d e c re a se s th e r e f r a c t i o n a
s m a ll amount, th e m olar r e f r a c t i o n i n th e v i s i b l e re g io n can be co n sid e re d
a s th e e l e c t r o n i c c o n tr ib u tio n to th e p o l a r i z a t i o n .
From t h i s i t fo llo w s t h a t m o le c u la r a s s o c ia ti o n may have l i t t l e o r
no e f f e c t upon th e v a lu e o f Pg, and a s P& i s s m a ll, upon Pe + Pa .
I t is
now e v id e n t t h a t s tu d ie s o f p o l a r i z a t i o n can be o f l i t t l e a id i n th e un­
d e rs ta n d in g o f m o le c u lar a s s o c ia tio n i f Pm = 0 .
T h e re fo re , i t i s o f
i n t e r e s t now to i n v e s t i g a t e th e r e l a t i o n betw een m o le c u lar a s s o c ia tio n and
Pm, which a c c o rd in g t o D ebye's (3 ) th e o ry i s e q u al to IdTNx2z^ k T , and where
yc( i s th e perm anent e l e c t r i c moment o f th e m o lecu le, k th e Boltzmann con­
s t a n t and T th e a b s o lu te te m p e ra tu re .
The e f f e c t o f m o le c u la r fo rc e f i e l d s upon one a n o th e r must depend
on th e s iz e o f t h e i r d o u b le ts , on th e lo c a t io n o f th e d o u b le ts i n th e
m o lecu le, and th e g e o m e tric a l shape o f th e m o le c u le.
Two sim p le o rie n ­
t a t i o n s i n which two a d ja c e n t m o lecu les m ight be ex p ected t o p o s itio n them s Ie v e s i n r e l a t i o n to each o th e r a re shown i n F ig u re I .
I n F ig u re I ( a ) ,
th e n e g a tiv e end o f one may a t t r a c t a p o s i t i v e end o f a n o th e r w ith th e
r e s u l t a n t e f f e c t o f le n g th e n in g each s e p a r a te d o u b le t and g iv in g a moment
f o r b o th g r e a t e r th a n 2/(.
GCD
g ?
a.
b.
F ig u re I
I f t h i s o c c u rre d , th e n th e number o f m o le c u les in th e l i q u i d would be
c u t i n h a l f , and
N i n th e e x p re s s io n f o r Pm would th e n be N /2, and
would be 2m j
so
t i o n o f d ouble
th a t.
- 1|1T(E/2) ( 2/f) .^/ 9kT..= 8?TN/^/9kT,
T h e re fo re , forma­
m olecules would double o r p erh ap s more th a n double P
s in c e th e d o u b le ts a re le n g th e n e d by a t t r a c t i o n .
I t i s in d e e d much to o
sim ple a p i c t u r e , b ecause th e e x te n t to w hich th e f o r c e s o p e ra te i s no t
known.
However, even i f th e two s in g le m o lecu les were n o t a s s o c ia te d
d e f i n i t e l y to a c t a s one, th e y would a t t r a c t one a n o th e r and o r i e n t w ith
r e s p e c t to each o th e r so t h a t , when a f i e l d was a p p lie d e x t e r n a l l y to
m easure th e d i e l e c t r i c c o n s ta n t, th e o r i e n t a t i o n would be g r e a te r th a n
t h a t c a lc u la te d .
A lso th e shape, o f m o le c u les would p re v e n t an e x a c t l i n ­
in g up o f d o u b le ts and th e axes o f each would p ro b a b ly make an a n g le of
l e s s th a n ..180°o A s.t h i s a n g le d e c re a s e s , th e p o l a r i z a t i o n d e c re a se s and
th e e f f e c t o f .o r ie n ta tio n would be ,to d e c re a se th e p o l a r i z a t i o n in s te a d
o f in c r e a s in g i t .
I f th e angle, betw een th e axes became z e ro and- th e
d o u b le ts were p a r a l l e l a s in . F ig u re I ( b ) , th e moments would c an c e l one
a n o th e r and th e c o n tr ib u tio n P_.w ould become, z e r o .
T h e re fo re , t h i s
p o s i t i o n o f th e d o u b le ts would give a p o l a r i z a t i o n f o r a p o la r su b sta n c e
e q u a l to Pg + Pq ,
I f th e f i r s t ty p e o f o r i e n t a t i o n p r e v a i l s th e n i t i s
p o s s ib le f o r many m olecu les to be a t t r a c t e d to g e th e r and a p o l a r i z a t i o n
could be b u i l t up i n d e f i n i t e l y i n t h i s m anner.
O th er complex o r ie n ta ­
ti o n s can a l s o 'b e v is u a l iz e d which e i t h e r in c re a s e o r d e c re a s e th e p o la r ­
iz a tio n ,
I f th e r e a re p o s s i b i l i t i e s o f d i f f e r e n t o r i e n t a t i o n s , i t ap p ears
p ro b a b le t h a t i f th e r e i s n o t much d if f e r e n c e betw een th e e n e rg ie s o f th e
d i f f e r e n t o r i e n t a t i o n s , one o r i e n t a t i o n may change to th e o th e r as th e
d is ta n c e s betw een th e d ip o le m olecu les change.
T h e re fo re , when a p o la r
l i q u i d i s d is s o lv e d i n a n o n p o la r l i q u i d , th e o r i e n t a t i o n o f p o la r
.
-IO -T
m o lecu les may change from one ty p e t o a n o th e r w ith change' i n c o n c e n tra tio n *
When i n d i l u t e s o lu tio n , p o la r m o lecu les should..assum e random o r ie n ta tio n s
because th e y a r e f a r a p a r t from one a n o th e r , u n le s s th e y f o m some k in d o f
complex m olecule which i s n o t d is s o c ia te d even i n d i l u t e s o lu tio n *
A good
example o f t h i s i s a c e t i c a c id i n benzene so lu tio n * .. Changes i n te m p e ratu re
p ro b a b ly a f f e c t th e ty p e o f o r ie n ta tio n *
In c re a s in g te m p e ra tu re in c re a s e s
th e th e rm a l a g i t a t i o n o f m olecules and opposes, o r i e n t a t i o n , th e re b y de­
c re a s in g th e p o l a r i z a t i o n , re d u c in g th e a b n o rm a litie s o f l i q u i d s , and con­
fo rm a tio n to th e Debye (3) e q u a tio n becomes c lo s e r .
- 11 V.
PREPARATION OF COMPOUNDS USED
T ita n iw n te tr a e th y I a te ™ Ti(OCpHg)^g
This, compound has b een p re p a re d
by B is c h o ff and Adkins ( 6 ) a c c o rd in g -to th e r e a c tio n
T iC l^
4-
I4NaOCgHg
^
TifOOgHg),
+
■
,
IiNaCl.
Crowe ( I ) d e s c rib e s th e r e a c tio n s and- p r e p a r a tio n s o f t h i s compound i n de­
ta il*
The p r e p a r a tio n and s te p s were fo llo w e d e x a c tly e x c e p t f o r one mod­
ific a tio n ,
The m a te r ia l c o n ta in e d i n th e r e a c t i o n f l a s k , w hich in c lu d e d
NaCl, Ti(OCgHg) ^ 5 and- C2HgOH, was r e flu x e d f o r a p p ro x im a te ly two to th r e e
hours a f t e r th e re a c tio n *
T his was found to in c re a s e th e y ie ld *
A nalyses
f o r tita n iu m by m eans,o f h y d ro ly s is to Ti(OH)^ and i g n i t i o n to TiO2 , gave
a tita n iu m c o n te n t o f -20*89%, 20*87%, 21*0li%> 20*89%»
The t h e o r e t i c a l
v a lu e i s 21.03%*
T ita n iu m te tr a p r o p y la te ™ Ti(0C^H^)^g
a .method s im ila r t o th at- u sed i n th e
T his coiiihound was p re p a re d by
p r e p a r a tio n o f Ti(OC2Hg)^*
The
r e a c tio n i s
. T iC lli .■+ ItNaOC3H7
-* Ti(OC3H7) li ’+
ItNaCl '
and i s d e s c rib e d i n d e t a i l .in t h e . t h e s i s o f .Katz ( 2 ) .
ium gave v a lu e s of. 16*77%, 16*82%.
The t h e o r e t i c a l v a lu e i s 16*90%*
T ita n iu m te tr a b u ty la te r Ti(OC^H^)^:
th e same manner a s Ti(OC2H g)^.
A n aly ses f o r t i t a n ­
T h is compound was p re p a re d i n
The r e a c t i o n is .
T iC lli ■+. ItNaOGliHg . ■+ TifOC^H, )^
+
A nalyses f o r tita n iu m gave v a lu e s o f 13*93%, l i t *06%»
v a lu e i s l l t . 08%*
ItNaCCl.
The t h e o r e t i c a l
Mono c h lo r o - tr ie th o x y - tita n iu m - TiCl(QC2Hg)^g T h is compound was
p re p a re d p r e v io u s ly by H odgson.( 8) and K atz (2 ) and used i n th e work' de­
s c r ib e d h e r e in .
I t was prepared- a c c o rd in g to th e method d e s c rib e d b y
" 12 "
J e n n in g s 5 Wardlbw and Way (7 ) by th e
T i (OCgH^) ^
+
CH5GOCl ^
r e a c tio n
TiCl(OG2H5 ) 3
The p e rc e n ta g e o f tita n iu m found was 21.77%«
21,97%,
C h lo rin e found;:
16,37%«
+
CH3COOCgH50
The t h e o r e t i c a l v alu e i s
T h e o re tic a l;,
16,22%
“ 13
VIo
POLARIZATION.OF T i( OG2H^ ) ^ AT L 0¥.TEMPERATURES
The m olar p o l a r i z a t i o n
o f Ti(OCgHg)^ has been d eterm in ed a t tempera™
t u r e s . ra n g in g . fr.om_.17°.C...to. --SO0Co
By .m easuring, the., c a p a c ita n c e o f a s e r i e s
o f d i l u t e s o lu tio n s th e 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 may be computed.&
The d e n s i t i e s o f th e s e s o lu tio n s were th e n m easured and w ith th e s e prelim™
in a r y d a ta i t was p o s s ib le t o c a lc u la te t h e m olar p o l a r i z a t i o n s of th e
compounds o - ..
A pparatus used f o r m easurem ents g.
The ap p aratu s' used f o r th e s e d e te r ­
m in a tio n s i s d e s c rib e d in ' Crowe's t h e s i s ( I ) .
A pump was connected,
th ro u g h a s e r i e s o f copper c o i l s , to a s m a ll therm os r e s e r v o ir *
The
r e s e r v o i r and pump were connected d i r e c t l y t o th e w a te r ja c k e t o f th e
c e l l c o n ta in in g th e s o lu tio n s *
T e c h n ic a l aceto n e was pumped th ro u g h
th e copper c o ils w hich were immersed i n a la r g e therm os c o n tain in g , t h e .
c o o lin g s o lu tio n o f a c e to n e and d ry ic e * . The aceto n e co o led i n t h i s
' manner was f r e e o f COg a n d gave a s te a d y flow*
The a c e to n e was th e n
in tr o d u c e d .in to .the r e s e r v o i r , and th e n fo rc e d th ro u g h th e c e ll*
The
purp o se o f th e r e s e r v o ir , was. to, f a c i l i t a t e th e f i l l i n g o f th e 'system
w ith a c e to n e e ...
A chrom el-alum el therm ocouple was u sed f o r th e te m p e ra tu re m easure­
m ent.
One. ju n c tio n was k e p t i n a c o n s ta n t te m p e ra tu re .b a th a t 23°C and
.the. other, .ju n c tio n , was . i n th e s o lu tio n , i n th e c e ll*
The te m p e ra tu re was
ta k e n b y re a d in g th e emf produced on a DfArsOnval ty p e g alv an o m eter manu fa c tu re d by th e S e n s itiv e R esearch C o rp o ra tio n .
D0 C. P o ly r a n g e r,■No* 91362«
I K.V.
The in s tru m e n t was a
The v o lta g e ran g e was from 0 .0 0 $ v o lt to
The emf was p l o t t e d a g a in s t th e te m p e ra tu re and .by means o f
t h i s graph th e te m p e ra tu re could be fo u n d .
The therm ocouple was C a lii=
b r a te d by u s in g th e f r e e z in g p o in ts o f m ercury, chlo ro fo rm , and a t temp­
e r a tu r e s from -IO 0 C to 2£0 C a b u re a u o f s ta n d a rd s m ercury therm om eter
was em ployed.
'
The c e l l used f o r th e s e m easurem ents i n th e b e g in n in g was th e same
one employed b y Crowe ( l ) i n h is .d e te r m in a tio n s , b u t some d i f f i c u l t i e s ,
such as le a k a g e o f th e w a ter ja c k e t, d e v e lo p e d ..in .its use and a new one
was c o n s tru c te d which was e s s e n t i a l l y th e same ex cep t t h a t i t was en­
t i r e l y . o f g la ss , c o n s tr u c tio n .
Copper f o i l was wrapped around th e o u t­
s id e o f th e c e l l and used f o r ground.
re p la c e d b u t caused v e ry l i t t l e
in d ic a te s .
T h is d e te r io r a te d and
had to be
change i n th e c e l l ' c o n s ta n t, a s T able I
Copper f o i l was r e p l a c e d . a f t e r T r i a l number I and 2 .
v a lu e s w ere ..all., ta k e n .a t 25° C.
These
1
TABLE I
T r i a l No.
Ca
Cx
C
I
3 2 .if)
63.76
2ii.61i
. 2
32.55
63,83
2k.58
3
32.62
63.97
2li,61i
Cx i s th e c a p a c ita n c e o f th e c e l l w ith b en zen e, Ga i s .th e c a p a c ita n c e o f
th e c e l l w ith. a i r , , and C i s th e
c e l l c o n s ta n t.
To check' th e c e l l c o n s ta n t, th e d i e l e c t r i c c o n sta n t o f n-hexane was
d e term in e d a t ..2^°C..
T hese v a lu e s a re shown i n Table I I .
lo r . a p e tro le u m f r a c t i o n o f. hexane, i s 1 .885 ( 9 )«
I f e i l i s v alu e
" 15>- "
TABLE I I
T r i a l No,
Ga '
'
C
0X
I
3 2 .Uo
63.76
2
32.22
3
. 32.62
.
2U.6U
1.8819
6 3 .&3
2U.28
1.88U1
63.97
2U.6U
1.8813
The method u sed to c a lc u la te th e s e p o la r iz a t io n s i s d e s c rib e d i n
Crovret S and K a tz i th e s e s ( I ) (2)»
P o la r i z a tio n o f T i ( QCpHcO ^ from 2 0 ° C t o -60°C «,
In o rd e r to d eterm in e th e v a r i a t i o n o f th e c e l l .c o n s ta n t w ith temp*=
e r a tu r e i n th e range from 20°Q to -SO0 Cj i t was found n e c e s s a ry to deter*=
m ine. a c e l l .constant, i n th e tem perature-range...from ...10.^0 to 20oC„
(See
T able VI.).0 T his w as..accom plished by m easuring...the ,c ap a c itan c e o f a i r ,
benzene and.hexane and th e s e te m p e ra tu re s .
(See F ig o 5S 3 , Us 5)»
From
th e s e d a t a .th e d i e l e c t r i c c o n sta n t o f.n rh e x a n e was c a lc u la te d a t th e se
te m p e ra tu re s and th e n e x tr a p o la te d ,
(T ab le V IIs F ig 0 6 ) 0 By u sin g th e
e x tr a p o la te d values., o f th e d i e l e c t r i c c o n s ta n t o f n -h ex an e, th e d ie le c =
t r i e c o n s ta n t o f . a i r , and th e c a p a c ita n c e o f th e c e l l w ith n-hexane and
a i r . i n th e low er te m p e ra tu re re g io n , a c e l l c o n sta n t was c a lc u la te d f o r
th e ran g e from O0C to -^O0C0
(See T able V III, Fig ?)
H e i l i S v a lu es
( 9 ) f o r th e v a r i a t i o n o f th e d i e l e c t r i c c o n s ta n t o f n-hexane w ith temp­
e r a tu r e (T ab le V II) were a ls o , p l o t t e d i n F ig u re 6 f o r p u rp o se s o f com=
p a r is o n .
The v a lu e s , t h a t had been o b ta in e d p r e v io u s ly (S ee T able IT)
f o r th e d i e l e c t r i c c o n s ta n t o f nrHexane a t 2E>0C.ape a ls o p l o t t e d and
16 "
in d ic a te f a i r l y g o o d " re s u lts i n th e e x tr a p o la t io n .
The hexane t h a t H e il
(9) u sed f o r th e d e term in atio n s was a p e tro le u m f r a c t i o n and th e r e f o r e
th e v a lu e s a r e d i f f e r e n t , p ro b a b ly due to th e v a rio u s o th e r components
w hich c o n trib u te d to th e c a p a c ita n c e .
S e v e ra l a c c u r a te ly weighed d i l u t e s o lu tio n s o f TifOCgH^)^ were made
up u s in g p u re n-tiexane a s th e s o lv e n t.
66 p u re g ra d e n -h e x a n e .
The n-hexane u sed was P h i l l i p s
I t was s to r e d o v e r PgO^ and r e d i s t i l l e d immed­
i a t e l y b e fo re u se to in s u re , th e absence o f w a te r .
The c a p a c ita n c e s o f
th e s o lu tio n s were m easured a s soon as th e y were made up to m inim ize
any e r r o r t h a t could p o s s ib ly be in tro d u c e d due to a b s o r p tio n o f w ater
v a p o r.
(See T able IX, F ig , 8 ) .
D e n s itie s o f s o lu tio n s w ere m easured
i n th e w orking te m p e ra tu re range b y a m o d ifie d O stw ald pycnom eter and a
volume c o rre ctio n ..w as a p p lie d .
m e n ts.
Table X shows th e r e s u l t s o f th e s e 'm e a s u re ­
...
The v alu es, o f th e d i e l e c t r i c c o n sta n t and s p e c i f i c volumes o f s o lu ­
ti o n s w ere p l o t t e d a g a in s t mole f r a c t i o n T i ( O C g H ^ ) Si nce th e s e were
s t r a i g h t l i n e s , . .H a lv e r s ta d t’ s a n d .K um ler9s method (lO ) co u ld be a p p lie d
i n o rd e r to d e te rm in e th e s lo p e s and i n t e r c e p t s o f th e s e l i n e s .
10. and F ig u re. 11. show t h a t th e s e l i n e s a r e l i n e a r .
F ig u re
The v a lu e s o b ta in e d
f o r th e s lo p e s and i n t e r c e p t s a re shown i n Table X I I I . ©C. and^
a re th e
s lo p e s o f 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 volume l i n e s r e s p e c tiv e ly ,
and
and Vf a re th e i n t e r c e p t s , o r th e d i e l e c t r i c c o n s ta n t and s p e c if ic
volume o f th e p u re s o lv e n t .
These v a lu e s were th e n in s e r t e d in to H a ly e r-
s t a d t ’s and K um ler9S e q u a tio n 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 .
The v a lu e s o b ta in e d a re shown in T able XIV.
(See F ig . 1 2 ).
" 17.
: ■
I n F ig u re s 2 and 3 ? a l l th e
r
v a lu e s w ere n o t p l o tte d s in c e some
p o in ts w ere v e ry n e a r o r c o in c id e d 'w ith o th e r p o in ts on th e g ra p h »
TABLE I I I
C ap acitan ce o f c e l l w ith a i r a t v a rio u s te m p e ra tu re s
( Tem perature i n C e n tig ra d e , C ap acitan ce i n x ^ f )
T
:
T
Ca
°a
.
T
Ca
+ 1 0 .6 '
32.29
+12.7
32.29
3 2 .3 0
+ Ik . 7
32.29
—8 .1
3 2 .2 8
+ 1 6 .8
32.29
32.19
- 6 .3
32.29
+ 1 8 .8 .
32.29
-2 8 .8
32.21
tk .9
3 2 .2 6
+ 2 0 .9
32.29
- 2 2 .1
3 2 .2 1 .
4-6.6
32.29
- 1 9 .8
3 2 . 2k
+ 8 .6
3 2 .3 0
-1 3 .2
3 2 .2 6
3 2.13
-1 3 .0
.3 2 .2 3
- 3 9 .9
32.18
- 10.8
- 3 7 .7
32.18
- 30.9
-U9o9-
3 2 .1 3
-U 2.0
‘
-
'
C apacitan ce o f th e c e l l w ith a i r as th e d i e l e c t r i c p lo tte d
a g a in s t th e te m p e ra tu re .
in u f aouBffoedeo
F ig u re 2
O-----O -O -O O O -O —
- I? .TABLE IV
C ap acitan ce o f c e l l w ith n-hexane a t v a rio u s te m p e ra tu re s ,
(T em perature i n C e n tig ra d e <, C apacitance in)
T
°h
T
ch
T
Ch
“ 5 7 .8
. 56.92
-25.3
55.75
+10.6
55.55
-55.2
56.83
“ 2 2 .1
55.68
+12.7
55.58
“ 51.2
5 6 ,68
-19.8
5 5 .6 1
+ 15.7
5 5 .5o
“ 5 8 .6
56.58
-17.5
'5 5 .5 1
+ 16.8
55.33 '
“ 56.7
5 6 .5 1
“ 13.0
55.39
+18 08
55.25
-5 2 .0
56.35
- 8.5
55.25
+20.9
55.20
-3 7 .7
56.19
+ 5.9
55.76
+21^7
55.15
-3 3 .2
5 6 .0 5
+ 6 .6
5 5 .6 9 .
+22,9
5 5 .li
-2 8 .3
55.88
+ 8 .6
55.62
C ap acitan ce o f th e c e l l w ith hexane as th e
d i e l e c t r i c p lo tte d a g a in s t th e te m p e ra tu re
Tem perature i n C entigrade
— 21 “
TABLE V
C ap acitan ce o f c e l l w ith benzene a t v a rio u s te m p e ra tu re s
(T em perature i n C e n tig ra d e , C ap acitan ce i n ^ ^ f )
Cb
+ 8 ,6 ■
61.22
+ 8 .6
6ii.k6
611.38
+ 10.6
6 k .37
6I1. 29,
+12,7.
6 k . 2S
6k . 18
+Hu 7
6 k .13.
+16 o8
6 k. 07
+ 16.8
6 k .05
+ 1 8 .8
63*98
+18 id
63.93
+ 20.9
63*88
+ 20.9
63,83
:
+ 1 0 .6
+12 o.7
+Ilu 7
.
.
T
tf 9 J n 3 fi
C ap acitan ce in
C ap acitan ce o f th e c e l l w ith benzene as th e
d i e l e c t r i c p lo tte d a g a in s t th e te m p e ra tu re .
.0
+20
T em perature i n C en tig rad e
™ 23 "
TABLE VI
V a r ia tio n o f c e l l c o n sta n t w ith te m p e ra tu re
(T em p eratu re■i n C e n tig ra d e )
T
C
Blu 6,6
2 li. 6 &
’ +10
+15
+20
■
,
21.63
TABLE V II
V a r ia tio n o f d i e l e c t r i c c o n sta n t
o f n-hexane w ith te m p e ra tu re
(te m p e ra tu re i n C en tig ra d e)
T
+10
+15'
+20
1.9030
1.8966
Lo 8900
H ie l1s v a lu e s o f v a r i a t i o n o f d i e l e c t r i c
c o n sta n t o f n-hexane w ith te m p e ra tu re
(T em perature i n C en tig ra d e)
T
-60
—50
-IiO
—30
-20
-10
0
+10
+20
2.0100
1.9950
,
1.9800
1.9660
■ 1.9520
1.9370
1.9230
1.9080
1.8930
V a r ia tio n o f th e d i e l e c t r i c c o n sta n t o f n-hexane w ith te m p eratu re
H e l l 's v a lu e s
A u th o r's v a lu es
V alues o b ta in e d p re v io u s ly
—20
Tem perature i n C en tig rad e
- 2S TABLE V IIl
V a r ia tio n o f c e l l c o n s ta n t w ith te m p e ratu re
( T em perature i n C en tig ra d e)
T
C
-50
.
21.95
-H O
' .
2jj..90
-3 0 ■
'21. .86
-20
2k . 82
-10
2 k .7 k
0
2k.69
+10
+20
'
2k.66
2 k .63
9 a a n S ti
C e ll C o n stan t
V a ria tio n o f th e c e l l c o n sta n t w ith te m p e ra tu re
Tem perature i n C en tig rad e
- 27 TABLE TX
C ap acitan ce o f s o lu tio n s a t 'v a r i o u s te m p e ra tu re s
(T em perature i n C e n tig ra d e , C ap acitan ce
T
S o lu tio n
number
I
-57.8
5 7 .2 1
57:06
~53.it
-lt 9 .o
-itit.it
S o lu tio n
number .
2.
57.52-
57.30
5 6 .#
57.15
56.70
, 56,96
-39.9
56.53.
56.79
56.61
-3 5 .it
56.39
56. 22, .
-30 .,9
56 . ItS ■
56.30
—26 ©5 ■ 56.07
-2 2 ,1
5 6 .lit ■
55.93
-1 7 .5
-1 3 .0
- 8 .5
+ it.5
+ 8.6
+ 12.7 '
+ 16,8
+ 18.8
55.76
55.97
55.86
55.63
55.19
5 5 ,7 1
5 it .80
55.20
. ' 55.05
5it.6it
5ito5o
. 5 1 .9 1
- 5 1 .7 6
54.67
S o lu tio n
number
3
S o lu tio n
number'
4
57.66
57.44
57.80
58.08
57.57
5 7 .8 6
57.41
57.2-4
57.66
57.51
57.33
57.17
56.99
56.80
56 *69
56.54
56.38
56.23
55.68
55.54
55.38
55.25
57.08
56.91
56.75
56.59
- 56.43
56.28
56.14
55.99
55.84
5 5 .3 4
55.16
55.01
5 4.85
•
'
57.11
56.97
56.82
56 .69
56.54
56.4o
'
56.25
56.10
55.56
55.41
55.27
5 5 .l i
S o lu tio n
number
5
C apacitance o f th e s o lu tio n s p l o tte d a g a in s t th e te m p e ratu re
6
S o lu tio n number 5
I
PO
CD
0
T em perature i n C en tig rad e
+20
— 29 ~
TABLE X
S p e c if ic volumes o f s o lu tio n s a t v a rio u s te m p e ra tu re s
(T em perature i n C en tig ra d e)
T
Solution
number
I
Solution
number
Solu tion. Solution
numbAr
. number
2
3
U
Solution
number
5
a60
-5o
1 .3 7 H
1 o3 6 6 I|.
1.36UO
1.3622
1.3337
1.3873
1.3800
-Uo
“ 30
” 20
—10 .
0
+10
+17
1.U037
1 .U 206
1.U376
1.3823
1.3986
1.3781
1.39U3
I . U no
1.U279
1.UU32
1 .U632
1 .U81U
1 .U9US
1.3713
1.3873
1 . UoUi
1 .U208
1.U380
. . l.U # 3
1.U73U
1.U918
.1 .5 0 5 1 .
i . Ui^U
. 1.U32U
1.UU99
1.U680
1.U863
1.U99U
1.3962
. . 1.U130
1.U300
1.UU73
1.1632
1.U836
■
1.U967
1.U336
1.U736
■ 1.U863
S p e c if ic volumes o f s o lu tio n s p l o t t e d a g a in s t th e te m p e ra tu re
9 a-m Sfi
S p e c if ic Volumes
!•1+9 —
Tem perature i n C entigrade
TABLE XI
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 v e rs u s mole f r a c t i o n o f TifOCgH^)^
S o lu tio n
number =
I
Mole
fra c tio n
Ti(OC2H5 ) lt= 0«002909
2
3
0.006676
0 .d o 8852
2.0225
2.0086
1.9955
1.9806
1.9667
1.9528
~60°C
~5o
-i|.0
2.0071'
1 ,9 9 3 k
1.9795
2.0169
2 .0031
1.9892
-30
1.9657
1.9751:.
-2 0
-IQ
0
+10 .
+17
1.9519
1.9381
l ,9 2 k k
1.910-6
1.9009
1.9616
1.9579
1.9351
1.9205
■ 1.9107
.
.
.
5
0.010353
2.0302
2.0166
. ■ 2.0029
1.9892
■
;.9 7 5 5
1,9618
1.9389
1.9581
1.9250
1.9355
1.9250
T.9 1 5 3
'
.
5
0.015726
2.0395
2,0252
2.0110
1.9968
1.9826
1.9685
1.9555
1.9502
1.9305
6
D i e l e c t r i c C onstant
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 p l o tte d a g a in s t
mole f r a c t i o n T i ta n iu m - te tr a e th y la te
S o lu tio n
S o lu tio n
S o lu tio n
S o lu tio n
S o lu tio n
11
12
13
Ili
15
number
number
number
number
number
5
L
3
2
I
- .3 3 TABLE X II
S p e c if ic volumes o f s o lu tio n s v e rsu s mole f r a c t i o n o f T i( OCgH^)^
S o lu tio n
number =
I
Mole
fra c tio n .
Ti(OC2H^)i = 0.003176
-6 0 QC
“=5o
-h o . .
-3 0
-20.
-1 0
0
+10
+17
1.3711
1.3873- .
.1.1*037 . .
1 . 1*206.
1.1*376
1.1*553.
1.1*731* •
. 1.1*9.18
. 165.051 -
'
■ 2'
. 0.006676
1.3661* .
1.3823
-1.3986..
1.1*151*
1.1*321*
1.1*1*99.
1.1*680
. 1.1*863
1.1*991*
. 3
■ V ;
5
0.008852
0.01031*3
0 . 011*726
1.361*0 ,
1.3800
1.3962
1.1*130
1.1*30.0.
. 1.1*1*73
1.1*652
1.1*8361.1*967 .
.
1.3622
1.3781 •
1.391*3
1.1*110
1.1*279
1.1*1*52
1.1*632
1.1*811*
1.1*91*5
1.3557
1.3715
1.3875
1.1*01*1
1 . 1*208
1.1*380
1.1*556
1.1*736
1.1*865
S p e c if ic volumes o f s o lu tio n s p l o t t e d a g a in s t
mole f r a c t i o n ti t a n i u m - t e t r a e t h y l a t e
Q S o lu tio n number f>
O
S o lu tio n number U
"O S o lu tio n number
O - S o lu tio n number
O S o lu tio n number
. -
1 50
1 . 1(2 —
12
Mole F r a c tio n x IO^
13
” 3$ "■
TABLE X III
S lopes and I n t e r c e p t s
T 0C
“ 60
-£o
-W
-30
-20
“ 10
0
+10
+17
vI
1.99880
1.98531 ..
1.97151
1.95789
1 .9 W 7
■1.93068
1.91706
1.9031+5
1.89383
1.37551+
1.39171
1.1+0817
1.1+2521+
1.1+1+233
1.1)6019
1.1+781+1
1.1+9705
1.51039
,
■
■
,
. 2.80850
2.76536
2.71+767
2.71719
2.68502
2.65663
2.63381+
2.60675
2.60073
-1.32611+
-1.31+962
-1 .3 8 1 1 6
-1.1+1628
-1.13379
-1.1+81+39
-1.52189
-1.56038
-1.58806
~ 36 ”
TABLE XIV
P o la r i z a tio n a t i n f i n i t e d i lu tio n ' o f T i(OGgH^)^
v e rsu s, l / a b s o lu te te m p e ra tu re
l/T x IO3
P o la r i z a tio n
lte69 .
112„29
112 o,38
112„88
LliB
i|»28
L u
3.9b
3.79
3.66
3.S3
3 . Uh
'
113.06
113=53
. H 3 oL
113=86
l i l t =12
iilt=6L
P o la r i z a tio n a t i n f i n i t e d i l u t i o n o f
Ti(OCpHr), p l o tte d a g a in s t l/T
- 38 - .
V II.
DEGREES OF ASSOCIATION
A s tu d y has been made o f th e d e g re e s o f a s s o c ia tio n o f p ro p y l and
b u ty l o r t h o - t i t a n a t e s and m o n o c h lo ro -trie th o x y -tita n iu m i n benzene s o lu ­
tio n .
The benzene, used f o r th e d e te rm in a tio n s was Mercks C .P. benzenej
th io p h e n e f r e e .
The benzene was k e p t o v e r sodium and th e n d i s t i l l e d im­
m e d ia te ly b e fo re u s e .
T horoughly d r ie d g la s s s to p p e re d f l a s k s were u sed
i n making up th e s o l u t i o n s .
The s o lu tio n s were th e n used im m ediately;
f o r th e d e te r m in a tio n s .. F a i r l y good r e s u l t s could be o b ta in e d f o r th e
p ro p y l and b u ty l o r t h o - t i t a n t e s j how ever, good r e s u l t s could n o t be ob­
ta in e d f o r th e mono c h lo r o - tr ie t h o x y - tita n iu m . . B e tte r r e s u l t s were f i n ­
a l l y o b ta in e d by d i s t i l l i n g b o th s o lu te .a n d s o lv e n t d i r e c t l y in to ' th e ■
a p p a ra tu s, used, f o r th e d e te r m in a tio n s .
Both s o lu te and s o lv e n t were
weighed im m ed iately a f t e r c o lle c tio n w ith o u t acc e ss to w a ter v ap o r i n
th e a i r .
cases.
The Beckman f r e e z in g p o in t lo w erin g method was u s e d i n a l l
I n o rd e r to f a c i l i t a t e t h e .p l a c i n g of. th e Beckman therm om eter
.and s t i r r e r i n th e r e c e i v e r s , a d ry box was used i n which phosphorous
p e n to x id e and s u l f u r i c a c id reduced th e m o is tu r e . content, to a minimum.
Neoprene s to p p e r s .a n d tu b e s were used around th e therm om eter and s t i r r e r
i n o rd e r to p re v e n t w a te r v ap o r from e n te r in g t h e ■a p p a ra tu s and contam­
i n a t i o n o f th e b en zen e.
I n a l l cases th e a s s o c ia ti o n f a c t o r was a p p ro x im a te ly 3 .
The r e ­
s u l t s a re in d ic a te d i n F ig u re s 12, 13, lU , i n which a s s o c i a t i o n number
i s p l o t t e d a g a in s t mole f r a c t i o n s o l u t e .
F ig u re I!? i n d i c a t e s th e e f f e c t
o f s m a ll amounts o f w a te r upon th e a s s o c ia ti o n o f m o n o -c h lo ro -trie th o x y tita n iu m ..
The a d d itio n o f w a te r was accom plished by ad ding drops o f
“ 39 "
benzene s a tu r a te d w ith w a te re
The amount o f w a ter added can o n ly be con­
s id e r e d approxim ate s in c e i t was c a lc u la te d from th e s o l u b i l i t y o f w ater
i n b e n ze n e „
0 o057 g r./lO O g r . b e n zen e,
7»6 x 10"^ g r , w # te r/d ro p .
*■ 1*0 ■TABLE XV
A s s o c ia tio n o f Ti(OC^Hr7)^
Mole f r a c t i o n
0.0020b
0 . 0090b
0.0133b
0.01773
0.02150
0.02855
0.03790
. M o lecu lar w eight
278
690
831
802
792
76b
708
A s s o c ia tio n number
0 .9 7 8
2.b27
2.923
2 .8 2 1
■ 2.786
2.687
2 .b 9 0
31 a a n 3 fi
A s s o c ia tio n Number
A s s o c ia tio n number p l o t t e d a g a in s t mole f r a c t i o n Ti(OCjH^)^
0 .0 2
Mole F r a c tio n Ti(OC^Hy)^
-IlETABLE. XVI
A s s o c ia tio n o f Ti(OCjjHp)^'
Mole f r a c t i o n
0 «002975
0 . 001*790
0„008670
0„011680
0.021990
0.022600
M olecu lar w eig h t
31*1
' 1*1*0
1021*
1033
986
965
A s s o c ia tio n number
1.002
1.295
3.010
3.037
2.897
2.835
Cl
A s s o c ia tio n Number
A s s o c ia tio n number p l o t t e d a g a in s t mole f r a c t i o n Ti(OC^H^)^
Mole F r a c tio n
TABLE XVII
A s s o c ia tio n o f TiClfOGgH^)^
Mole f r a c t i o n
M o lecu lar w eig h t
F i r s t ru n
O0001*2 2U
0.007396
0.011*11+7
1+67
667
61*2
Second ru n
0.0061*6
0.00.8.95
O0OllhO.
352 .
51*2
639.
A s s o c ia tio n number
2.136
3.052
2.937
.
.
1.610
2 . 1*80
26923
T h ird ru n
0.001*95
0.00816
0.01171*.
F o u rth ru n
0.001*782
0.007901*
0.010596
. ,
..
'
509
677
558
2.329
3.097
2.553
1*92
627
667
2 .251
2.869
3.052
tji ajn3%j
A s s o c ia tio n Number
A s s o c ia tio n number p l o tte d a g a in s t mole f r a c t i o n TiClfOCgH^)^
F o u rth ru n
T h ird ru n
Second ru n
F i r s t ru n
Mole F ra c tio n
" lt6 ■=
TABLE XVIII
E ffe c t o f water on a s s o c ia tio n , o f TiClfOGgH^)^
O rig in a l, c o n c e n tra tio n TiCl(OCpHU), = 0*007396
A pparent m o le c u la r-w e ig h t = 667
O r ig in a l a s s o c ia ti o n number - 3*0^2
W eight o f w ater
added i n grams
7 .638
15.276
2 2 .9 lit
30.552
38,190
x 10~6
x 10“ °
x 10” 6
x 10“ °
x .10"°.
M o lec u la r
w eight
A s s o c ia tio n
number
762
610
593
517
262
3 . It86
2.791
2.713
2*502
2*571
A s s o c ia tio n number p l o t t e d a g a in s t th e w eight o f
w a ter added to a s o lu tio n o f Tid(C)CgH^) ^ i n
n-hexane
Grams o f w ater x 10
V III.
PREPARATION OF CRYSTALS OF T i(OC2H^)^
Pure c r y s t a l s o f T i( OC2H ^ were p re p a re d by d i s t i l l i n g l i q u id
Ti(OC2Hcj)^ in to a s e r i e s o f sm all (6 mm i . d . ) g la s s tu b e s a t a p re s s u re
o f 1-2 mm.
The tu b e s c o n ta in e d a f i n e g la s s w ire ru n n in g th ro u g h th e
c e n te r and s e a le d a t one end o f th e tu b e .
Each o f th e tu b e s was f i l l e d
a p p ro x im a te ly o n e - th ir d f u l l , and s e a le d o ff u n d er vacuum.
They were
allo w ed to s ta n d f o r a p e rio d o f two to s i x weeks and a t th e end o f two
w eeks, v e ry sm a ll
c r y s t a l s could be d e te c te d on th e g la s s w ire and on
th e s id e s o f th e tu b e s , b o th above and below th e l i q u id s u r f a c e .
F ig u re
16 i s a diagram o f th e tu b e .
ZN
US,
F ig u re 16
At th e end o f a month th e c r y s t a l s had th e appearance o f n e e d le s and were
a p p ro x im a te ly 1-2 mm i n le n g th .
The tu b e s were ta k e n to D r. Forbes
R o b ertso n , c r y s ta lo g r a p h e r , a t Montana School o f Mines i n B u tte , Montana,
who i d e n t i f i e d th e c r y s t a l s .
The fo llo w in g i s a summary o f h is r e p o r t;
O p tic a l p r o p e r tie s o f Ti(OC2Hjj)^
The s u b sta n c e i s p ro b a b ly m o n o c lin ic .
There a re two s e t s o f c lea v a g es which develop*
a n g le s t o each o t h e r .
They a re n o t a t r i g h t
Two m easurem ents in d ic a te i n c l i n a t i o n o f about
" lj.9 ™
1 9 ° <i E x tin c tio n p a r a l l e l to one s e t , and no t to th e o th e r .
The compound
i s o p t i c a l l y b i a x i a l , n e g a tiv e 2V 80° tq 8 5 °e
In d ic e s o f r e f r a c t i o n , -
'
n b e ta (y ) 1 ,6 0 1 more o r l e s s .
D e te rm in a tio n o f o th e r in d ic e s o n ly a p p ro x im a te ,
n a lp h a (x).. 1 ,5 9 1 o r l e s s ,
.
n. gamma (z ) .1,608 o r m ore,.;
B ire frin g e n c e e s tim a te on g r a in , 0,020 or.more.,, thus. .the. above in d ic e s a re
not
necessarily..m axim um .and.m inim um .v a lu e s o. D is p e rs io n , t e n t a t i v e r
g r e a te r , th a n .v,, ..Twinning n o te d on. a' few grains.,, .one d i r e c t i o n o n ly , op­
t i c a l . r e l a t i o n s .not. d e te r m in e d ,. The m a te r ia l was c le a r tr a n s p a r e n t when
-. f i r s t removed from .the. c o n ta in e r .
I t was powdered and. k e p t u n d er cover
when not. needed, . I n ab o u t an h o u r's , tim e h a lf, o f th e frag m e n ts had hy­
d r o ly z e d .to .th e ..e x te n t .th a t v a l i d o p t i c a l d ata, could n o t be o b ta in e d .
However, some g r a in s showed v e ry l i t t l e a l t e r a t i o n a f t e r an h o u r, t h i s
in c lu d e d many o f th e v e ry m inute p a r t i c l e s .
" 50 •“
■IX .
DISCUSSION OF EXPERIMENTAL RESULTS
The d e c re a se i n th e curve o b ta in e d by p l o t t i n g th e v a lu e s o f 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 b f T i( OC2H ^)^ a g a in s t th e r e c i p r o c a l
o f th e a b s o lu te te m p e ra tu re can no t be s a t i s f a c t o r i l y e x p la in e d by Debye’ s
e q u a tio n ( 3 ) .
S in c e .th e p o l a r i z a t i o n o f p o la r su b sta n c e s sh o u ld in c re a s e
w ith d e c re a s in g te m p e ra tu re a c c o rd in g to th e Debye e q u a tio n (3 ) th e r e i s
e v id en c e Of a n e g a tiv e tr e n d i n some f a c t o r o r f a c t o r s .
When th e p o la r ­
i z a t i o n o f p o la r compounds d e c re a s e s w ith d e c re a s in g te m p e ra tu re , th e
c o n tr ib u tio n ..a r is in g , fro m . th e perm anent moment may c a n c e l o u t and th e
v a lu e f o r th e t o t a l p o l a r i z a t i o n drop to t h a t o f th e e le c tr o n i c and atom­
i c . p o l a r i z a t i o n s .. The. sum o f th e e le c tro n lc .. and
atom ic p o l a r i z a t i o n s ,
a r r iv e d a t b y .r e f r a c t i v e in d e x m easurem ents, i s a p p ro x im a te ly 6k Debye
u n its ' ( I ) .
S ince th e curve d e c re a s e s s l i g h t l y i n t h i s re g io n and does
n o t f a l l o f f to th is , v a lu e , t h i s s t i l l in d ic a te s a c o n tr ib u tio n from th e
perm anent moment.
However, by an ex am in atio n o f th e Debye e q u a tio n i t
i s se e n t h a t th e moment would have to be a n e g a tiv e o n e.
I f th e p o la r ­
i z a t i o n d e crea se d and in c r e a s e s when p l o t t e d a g a in s t th e r e c i p r o c a l o f
th e a b s o lu te te m p e ra tu re , th e n a p o s s ib le e x p la n a tio n may be sought i n
r e s t r i c t e d .r o t a t i o n o f th e groups i f th e .molecules, have a t e t r a h e d r a l
c o n f ig u r a tio n which i s g e n e r a lly a c c e p te d f o r q u a d riv a le n t tita n iu m .
S in c e th e curve i s a p p ro x im a te ly l i n e a r w ith in t h i s , .reg io n , t h i s does
not. a p p e a r t o be. th e re a s o n .
The a s s o c ia ti o n o f th e
o r t h o - ti t a n a t e s may be due to th e f a c t t h a t
tita n iu m has a c o o rd in a tio n number o f s i x .
I n th e. o r t h o - t i t a n a t e s th e r e
.a re f o u r oxygen atoms, su rro u n d in g each tita n iu m a to m ,..th e re fo re , i n
" 51
o r d e r f o r a s s o c ia ti o n to o c cu r t h e r e may p o s s ib ly be a d i s t o r t i o n o f
th e s e bonds to p e rm it c o o rd in a tio n w ith p a i r s o f a v a ila b le e le c tr o n s on
oxygens from o th e r m o le c u le s .
I n r u t i l e , a form o f TiO2, each tita n iu m
atom i s su rro u n d ed by s ix oxygen atoms w ith bond a n g le s o f 9 0 ° .
T here­
f o r e , th e r e may be a p o s s i b i l i t y t h a t th e t e t r a h e d r a l bonds i n th e o rth o t i t a n a t e s change from 109° to 90° t o a llo w th e a d d itio n a l c o o rd in a tio n .
I f th e bonds do d i s t o r t i n t h i s m anner, th e n a s t a b l e t h e o r e t i c a l s t r u c ­
t u r e can be pro p o sed i n w hich,tw o m olecules o f T i (OC2H^)^ a re bound to
a n o th e r th ro u g h th r e e c o o rd in a te v a le n c e s .
A d d itio n a l c o o rd in a tio n o f
th e tr im e r to o th e r monomers could o ccu r b u t w ould.be l e s s s t a b l e due
to t h e .f a c t, t h a t o n ly two c o o rd in a te bonds would be p o s s ib le .
T h e re fo re ,
th e . tr im e r ..appears to be th e. most s ta b l e i n th e p ro p o sed s t r u c t u r e .
F ig u re 17 i s a diagram, o f the. pro p o sed s t r u c t u r e o f th e .tr im e r w ith th e
R g roups, n o t.in c lu d e d .
- 52 -
Proposed S tr u c tu r e f o r [Ti(ORii) J 3 w ith R1s not In c lu d e d
F ig u re 16
*■ 5>3 "
X. • SUMMARY
Io
The 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 o f Ti(C)C2H ^ . ) p l o t t e d a g a in s t
th e r e c i p r o c a l o f th e a b s o lu te te m p e ra tu re was found to be a p p ro x im a te ly
a
s t r a i g h t l i n e i n th e re g io n from 17bC to -60°C 5 d e c re a s in g o n ly
s l i g h t l y .w ith d e c re a se i n te m p e ra tu re 0
2*
The a s s o c i a t i o n f a c t o r o f t i t a n i u m t e t r a b u t y l a t e , tita n iu m te tr a p r o p y l-
a t e , and monoc h lo ro tr ie th o x y tita n iu m has been found to be a p p ro x im a te ly
th re e e
3.
The c r y s t a l l i n e s t r u c t u r e o f t i t a n i u m - t e t r a e t h y l a t e i s p ro b a b ly
m o n o clin ic*
H .
ACKNOWLEDGEMENTS
The a u th o r w ishes to ta k e t h i s o p p o rtu n ity to e x p re ss h i s s in c e re
a p p r e c ia tio n and. th an k s t o D r0 C harles N0 Caughlan f o r h is p e rs o n a l
guidance and i n s p i r a t i o n d u rin g t h i s r e s e a r c h , and t o D r0 Forbes R obert­
son o f Montana School o f M ines, f o r th e c r y s t a l l i n e i d e n t i f i c a t i o n ^ and
t o B r0 Ce L0 G raverson, a ls o o f Montana School .of M ines, f o r h is h elp
and a d v ic e o He a ls o w ishes to th an k th e R esearch C o rp o ra tio n o f New
York f o r making 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 6
“ 55 ~
X II. ' LITERATURE CITED AND CONSULTED(1 )
Crowe, wD i e l e c t r i c P r o p e r tie s o f Some E s te r s o f T it an iu m -t e t r a c h lo r­
id e C o n tain in g O rganic Groups’*, Montana S ta te C o lleg e, Bozeman,
M ontana.
(2 )
K a tz , "The E l e c t r i c and
Bond Moments o f Some Carbon, S i l i c o n , and
T itanium O rganic Compounds", Montana S ta te C o lle g e, Bozeman, M ontana.
(3 )
Debye, " P o la r M o le c u le s" , The Chem ical C atalo g Cd., I n c . , New York
(1 9 2 9 ).
(U)
Smyth, " D ie le c tric ...C o n sta n t and M o lec u la r S tr u c tu r e " , The Chemical
C alalo g Coc, I n c =, New. York (1931) =
(5 )
O nsager,. J i ' Am. Chem. .So6 ., 58
( 6)
B is c h o ff and, A dkins, J . Am. Chem= S o c ., J46 27, (19210..
(7 )
J e n n in g s , Wardlow and Way, J . Am. Chem= S o c ., P a r t . I , 637 (1 9 3 6 ).
(8 )
Hodgson, " D i e l e c t r i c C onstan t of. Te t r a e t h o x y - t i t anium a t Radio F req­
u e n c ie s and Low. T em p eratu res.
llf86, (1936) =
The S p e c if ic C o n d u c tiv ity o f Mono-
■
c h lo r o - tr ie t h o x y - tita n iu m " , Montana. S ta te G b lleg e, Bozeman, M ontana.
(9.)
(10)
H eil,. Phy. R ev.,, 39:. 670, (1 9 3 2 ).
H a lv e r s ta d t and K um ler, J= Am. Chem. S o c ., 61^ 2988, (1 9 l|2 ).
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'
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MONTANA STATE UNIVERSITY LIBRARIES
7 6 2 1001
2 4
98375
cop *2
of