Electric and bond moments of some carbon, silicon and titanium organic compounds
by Walter Katz
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 Walter Katz (1949)
Abstract:
A further study of the dielectric end cheated properties of titanium-tetraethylate has been ede. This
compound forms aggregates in solution up to approximately a trimer, a type of association which is
apparently not based upon hydrogen bonding but rather upon the coordination valence of titanium.
X-ray diffractions of titaniumtetraethylete crystals could be used to determine whether this is actually
true. The dipole moments of Ti(OC2H5)4, Ti(OC3H7)4, Ti(OC4H9)4, TiCl(OC2H5)3, SiCl(OC2H5)3
end HC(OC2H5)3. were determined in hexane solution at 25°C and. found to be 1.58, 1.32, 1.04, 2.50,
1.75 and 0.7 Debye units respectively. The method used for the determination of the electric moments
consisted of measuring the dielectric constants and specific volumes of dilute solutions of the
compounds in hexane and extrapolating the resulting straight lines to infinite dilution. The slopes and
Intercepts were then used to calculate the molar polarisation from en equation derived by Halverstadt
and Kumler (8). The electronic and atomic polarisations were obtained either from refractive index and
density measurements of the pure compound or by measuring the refractive Indices of dilute solutions
of the compound in hexane solution and using the slope end intercept of the plot of the square of the
refractive index against mole fraction in the Halverstadt and Kumler equation. The molar polarisations
of titanium tetraethylete at low tea-peretures were a#*cored cad the polarization plotted sgeinet 1/T. SLSCTRIC /.ED BOSB MOMEMfS QI SOMX CARBOS,
SILICON m TITAXIUM OWiItC C0MP0US1-S
By
WALTgR XAfZ
A THESIS
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TABLE Og COBTmi TB
X.
ABSTRACT....................................................................................................
4
TI.
INTRODUCTION.................................................................................................
5
[II.
LITERATURE STUDY..................................................................................
6
IV.
PREPARATION 0? COMPOUNDS USED........................................................
11
1.
T ltr n lu m te tr F e th y le te . , ................................... . . . . .
11
2.
T lte n lu m te tr e p r o p y ls te ........................................................
«
H
3.
T l t - n l u a t e t r e b u t y l e t e .....................
•
11
h.
Mono c h l o r o t r Ie th o x y tlte n lu m . .................................................
12
5.
D leh ltro d Ieth o x y t l t r n l u a . . . . . . . . . . . . . . .
12
6.
M o n o e h lo ro trle th o x y e lllc o n ...........................................
12
7.
E t h y lo r th o f o r a r te
13
V.
V I.
........................................ . . . . . . .
ELECTRIC MOMENT DETERMINATIONS ....................................................
. . .
14
1.
Ie th o d u sed f o r d e te rm in a tio n end c r l c u l r t l o n
14
2.
E l e c t r i c moment o f t l t e n l u a i t e t r s e t h y l e t e .......................
16
3.
E l e c t r i c moment o f t t t m l u m t e t r r p r o p y l s t e .......................
I?
4.
E l e c t r i c moment o f t l t r n l u m t e t r r b u t y l p t e .......................
19
5.
E l e c t r i c moment o f m o n o c h lo ro trle th o x y tlte n tu a . . .
20
6.
E l e c t r i c moment o f a o n o c h lo r o tr le th o x y e lllc o n . . . .
21
7.
E l e c t r i c moment o f e t h y l o r t h o f o r w t e ...............................
21
MOLAR POLARIZATIONS Oi TITANILTiTETRA.ETHYL/TE AT LOW TEH?,
37
V II.
CRYSTALS' Oi TITAaIUMTETRAHTHILAfB................................................
42
V III.
MOLECULAR WEIOKT DETERMINATIONS OfTITANIUMTETRAETHYLATE
43
IX.
CALCULATION Of BOND HO IENTS.............................................................
46
98? Al
-
X.
3
-
DTRC’iSSlOS o r SXPSHmBSTAL RESULTS..................................................
ti8
X I.
ACOOXLEDlE'-i^STE........................................ ........................................................ 50
.,I I .
CT?: / i : COJfEJLTSD............................... .................................. 51
-U !•
ABSTRACT
A f u r t h e r stu d y o f th e d i e l e c t r i c end C h e a tc e l p r o p e r tie s o f t l t e a l u a t e t r e e t h y l s t e h ee been a e d e . ^ i l e compound forme a g g re g a te # l a s o lu tio n up
to ppproxla«= t e l y p t r l n e r , » ty p e o f s e s o c le ti o n which I s e p p s r e n tly a c t
b ased upon hydro^e a bonding b u t r a t h e r upon th e c o o rd in a tio n v a le n c e o f
tita n iu m . X -ray d i f f r a c t i o n s o f t l t a n l u a t e t r e e t h y l e t e c r y s t a l s could be
n eed to d e te rm in e w h eth er title i s a c tu a lly t r u e . She d ip o le moments o f
T K o c 2B ,)!., Tl(OC-H7 ) a , Tl(OCa H9 )b , TiCl(OC 2H5) 3 , SlCl(OC 2H5 ) 3 and
HC(OCJi5) - were d eterm in ed in hexane s o lu tio n a t 25*0 and fo u M to be 1 .5 8 ,
I . 3 2 , 1 .0 » , 2 .5 0 , 1 .7 5 and 0 .7 Debye u n ite r e s p e c tiv e ly . The method u sed
f o r th e d e te rm in a tio n o f th e e l e c t r i c moment* c o n s is te d o f m easuring th e
d i e l e c t r i c c o n s ta n ts and s p e c i f i c volum es o f d i l u t e s o lu tio n s o f th e com­
pounds In hexane and e x tr a p o la tin g th e r e s u l t i n g s t r a i g h t l i n e s to i n f i n ­
i t e d i l u t i o n . The s lo p e s and I n te r c e p ts were th e n u sed to c a lc u la te th e
m o lar p o l a r i s a t i o n from ©n e q u a tio n d e riv e d by H a lv e re ta d t and ;:umler ( 8 ) .
The e l e c t r o n i c and atom ic p o l a r i s a t i o n s w ere o b ta in e d e i t h e r from r e f r a c ­
t i v e Index end d e n s ity m easurem ents o f th e p u re compound o r by m easuring
th e r e f r a c t i v e In d ic e s o f d i l u t e s o lu tio n s o f th e compound in hexane
s o lu tio n and u s in g th e slo p e and in t e r c e p t o f th e p l o t o f th e sq u are o f
th e r e f r a c t i v e Index a g a in s t mole f r a c t i o n In th e H e lv e r s ta d t and S u s le r
e q u a tio n . The m o lar p o l a r i s a t i o n s o f tita n iu m t e t r a e t h y l e t e a t low tomp e r p tu r e e were m eeeured ead th e p o l^ r lz F tlo n p l o t t e d ageI a e t l/T *
-
II.
5
-
IKTRODUCTIOM
The ln o r f e a io tl t p n p t e e h e re been known end. u sed »e d i e l e c t r i c s f o r
aeny y e a r s .
% e o r» p n tc d e r i v a t i v e s o f TiCl% have been p re p a re d ( I ) , b a t
p r a c t i c a l l y no work h as been done to d e te rm in e p h y s ic a l p r o p e r t i e s o r
s tru c tu re s .
S in ce th e in o rg a n ic t i t a n s t e e have very 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 t I s re a so n a b le to in q u ir e In to th e p r o p e r tie s o f o rg a n ic
d e r iv a tiv e s o f TlC1%.
fu rth e rm o re , d e te r m in a tio n o f s t r u c t u r e s and
p h y s ic a l p r o p e r t i e s o f th e s e compounds h a s so f a r been n e g le c te d .
Thus
i t i s th e p u rp o se o f t h i s work to stu d y t h e i r d i e l e c t r i c and o th e r p ro p e r^
tie s .
tro v e Cl)) d eterm in ed th e d ip o le momenta o f t i t a n i u a t e t r a e t h y l a t e ,
monoc h lo r o tr le th o a y tita n iu m end tric h lo ro a a n o p h e n o z y tl t a n i u a , u s in g benzene
a s p s o lv e n t.
s o lv e n t e f f e c t .
T h e o re tic a l c a lc u la tio n in d ic a te s th e p o s s i b i l i t y o f some
The a u th o r h a s re d e term in ed th e d ip o le moments o f t i t e n t o a -
t e t r s e t h y l a t e end m o n o c h lo ro tr ie th o a y tita n iu a in hexane to s tu d y th e e f f e c t
o f u s in g a d i f f e r e n t s o lv e n t.
Crowe a ls o n o tic e d th a t t i t e n i u a t e t r e e t h y l s t e
a s s o c ia te s in benzene s o lu tio n ; th u s m o le c u la r w e ig h ts have been d eterm in ed
to c o n s id e r th e e x te n t o f th e a s s o c ia ti o n .
A lti nigh th e work i s p r im a r ily concerned w ith tita n iu m compounds, th e
d ip o le moments o f th e two s i m i l a r compound.e o f carbon and s i l i c o n were
m easured to e s t a b l i s h some c o r r e l a t i o n betw een d ip o le moment end a o le c u ls r
s t r u c t u r e among enalpgoue o rg a n ic compounds o f carb o n , s i l i c o n and t i t a n ­
ium.
The moments o f e th y lo rth o fo rm s te and m o n o c h lo ro fc rie th o x y silic o n have
n o t been m easured b e f o r e , a lth o u g h some d i e l e c t r i c s tu d ie s have been made
n c e r t a i n e s t e r s o f carbon ( 6 ) and s i l i c o n ( 23 ) t e t r a c h l o r i d e s .
—6 —
III.
LI?%RATUR3 STUDY
^ g r e e t saeny p u b lic a tio n s here sppeered la the I a e t twenty y ea rs in
the f i e l d o f d i e l e c t r i c c o n sta n ts, d ip o le eoaente end r e la te d pheaoaea*.
One cannot adequately cover In e llt e r e t u r e study e l l the a r t i c l e s .
Ex­
c e ll e n t r e v ie s ere found In Debye’ s wP o ls r -Solecules (5 ) sod Sayth1e
" D ie le c tr ic Constant and M o l e c u l Structure" (2 2 ).
Onesger ( l 6 ) has
m odified the Debye theory o f d ie le c t r ic * by d e r iv in g en a lte r n a tiv e ex­
p r e ssio n fo r th e in te r n a l f i e l d induced by e d ip o le p laced in m e l e c t r i c
fie ld .
d ip o le .
Onerger co n sid ers a s p h e r ic a l, p o la r liq u id a s le c u le as the
The environment o f the d ip o le i s trea ted se bein g s homogeneous
continuum.
T his i s , o f c o u rse, a s im p lific a tio n o f the a c tu a l s it u a t io n .
Sirkwood (I l1) has p oin ted out th a t flu c tu a tio n s in the induced moment o f * mole­
c u le I et'd to c o r r e c tio n terms in the lo r e n ts equation ( $ ) , which i s used
fo r the d e r iv a tio n o f th e Debye eq u ation .
/in e x te n s iv e search through the lit e r a t u r e revealed th a t very
l i t t l e Is known concerning th e d i e l e c t r i c p r o p e r tie s o f titanium organ ic
compounds, p a r tic u la r ly the e s t e r s o f TlClji.
B isc h o ff and tdicmg ( 2 )
and Jennin gs, Wardlrw and Wpy (1 3 ) have prepared v a rio u s e s t e r s o f TiClfc
and chloro d e r iv a tiv e s o f the e s t e r s .
The p h y sic a l p r o p e r tie s o f th ese
titanium o rgan ic compounds were not s tu d ie d , however.
Schtnsann (21)
r eected TlClfc w ith phenol and obtained Ti(OC^H^)fc*HCl but no e x te n siv e
study o f th e p h y sic a l p r o p e r tie s o f th e compound was made.
Kauser and
L ev ite ClO prepared compounds from the r e a c tio n o f TiClfc w ith aainophenole
and Soeenhelm and Sorge (2 0 ) analysed the product from th e r ea c tio n o f
- ? -
TlCXi1 w ith o x y -c* rb o x y llc $>cld tlt e n p t e s pad p olyp henolIc tltm n etea .
Theee »uthere e le o f e lle d to rep ort oa the p h y e lc e l p r o p e r tie s o f the com­
pounds prepared.
The th e o r e tic a l c s lc u ls t lo n e o f m olecul*r rad head moments hpve been
considered by mrny la v e s t lf a t o r e fo r sim ple «md eomple* m o lecu les.
The
sim p leFt and most cornea method Ie v e c to r a d d itio n o f th e ;rotip o r bond
momente c o n s tI tn tI n f th e m olecu le.
The w ater molecule* fo r example* hes
c le r f e permanent d ip o le moment rad, th e r e fo r e , i t cannot be a symmetrical
lin e a r m olecu le,
jrroa an exam ination o f the spectrum o f water vepor (9 )
th e ettfle between the O-H lin k a g e s has been found to be 106° pad, there­
f o r e , knowledge o f the t o t a l d ip o le moment enables one to c a lc u la te ,
w ith a f a i r degree o f secu rec y , the O-H bond moment,
f o r diatom ic
m o lecu les, such as HC1, the observed d ip o le moment i s I d e n tic a l w ith the
H-Cl bond moment.
The problem. In th e l e t t e r ca se, however. Is complicated,
by the deform ation o f th e e le c tr o n system o f the halogen atom by the
hydrogen atom.
Thus the d ip o le value fo r HCl o f 6 .1 Debye u n its c a lc u la te d
from Infrared measurements o f the d ista n c e between the e l e c t r i c a l cen te rs
d i f f e r s markedly from th e observed v a lu e o f 1.0 3 Debye u n it e .
The th e o r e tic a l c a lc u la tio n o f d ip o le moments i s fu rth e r com plicated
by the r e s t r ic t e d r o ta tio n o f p o la r groups.
The e th y len e d lc h lo r ld e mole­
c u le ( 22) i l l u s t r a t e s the e f f e c t o f r e s t r ic t e d r o ta tio n , th e r e s t r ic t io n
b ein g due to th e nrntuel in te r a c tio n o f th e two CKgGl groups r o ta tin g about
th e C-C a x le .
U sing the C-Cl valency angle as ?0° and th e C-Cl bond
moment as 1 ,5 , le a d s to a d ip o le moment o f 2 .1 as r l i m i t .
Observed v a lu es
In variou s s o lv e n ts , la d if f e r e n t s t a t e s end a t d if f e r e n t tem peratures show
«• 8 «•
none h i 'her than 1 .8 D.
Meyer ( 7 ) he# mode f fu rth er study o f the e f f e c t
o f r e s tr ic te d r o ta tio n on th e d ip o le moment by t eking Into co n sid era tio n
the mutual p o t e n t ia l energy o f the two r o ta tin g d ip o le s .
He conclude#
th a t I f th i# energy l e ap p reciab ly le e s than th e energy o f thermal a g ita ­
t io n , k f, then r o ta tio n can occur f r e e ly .
However, the mutual p o te n tia l
energy o f th e two r o ta tin g d ip o le s in e th y le n e d ic h lo r id e 1# about two to
th ree tim es kT and, th e r e fo r e , r o ta tio n w i l l be hindered.
Hydroquinone
d ie th y l e th e r ( 9 ) shows a mutual p o t e n tia l energy o f r o ta tin g group# very
much em aller than kT, s in c e th e O-CpH^ SroyPe are eep sreted by a t le a s t
6 x ID"2-® cm and th e group moment# are o n ly 1 ,1 x 10""2^ .
fr e e r o ta tio n
in p o s s ib le and the r e s u lta n t moment, 1 .7 3 comperes favorably w ith the
c a lc u la te d v a lu e o f l . h 6 .
y r ln g , ( 8 ) assuming fr e e r o ta tio n , ha# developed an exp ression fo r
th e r e e u lt m t moment o f complex r o ta tin g m olecules by means o f m atrix
a lg e b r a .
H is formula i s a c tu a lly an e x te n sio n o f the law o f c o sin es which
i s employed in th e v e c to r a d d itio n o f moments in sim ple m o lecu les.
The
Eyrlng formula s t a t e s In words, "for fr e e r o ta tio n about connecting l i n e s
the mean square sum o f n v e c to r s i s equal to the sum o f th e squares o f the
le n g th s o f the sep arate v e c to r s p lu s tw ice a l l the p o s s ib le products o f the
le n g th s o f the two v e c to r s m u ltip lie d by th e cosin e o f the a n g le, 0^ , made
by th e d ir e c te d lin e s con n ectin g the p a ir " .
The a eth em a ticel exp ression i s
This equation o f f e r s a means o f c a lc u la tin g th e th e o r e tic a l d ip o le moments
9
o f rmaerous coapounds i f one hs« m knowledge o f the in d iv id u a l bond momenta.
Pmuling ( I ? ) hee shown th e t n r e la tio n e x ie t e between the e le c tr o n e g a tiv it y
s c e le . bmeed upon s in g le bond e n e r g ie s , sad the bond moments.
According to
t h i s , the d iffe r e n c e in e le c tr o n e g a tiv it y should equal the bond moment in Debye
u n it e .
The bond moment fo r As-Hw obtained la t h is meaner, i s id e n t ic a l w ith
the observed bond moment.
Likew ise the v a lu es fo r P -C lw Ae-Pw S b -Iw H-Cl
end o th e r s , agree very c lo s e ly w ith the -c tu a l v a lu e s .
On th e o th er hand,
w h ile C-O Is 0 .7 , th e bond moment from e le c tr o n e g a tiv ity i s 1 .0 .
C-Cl
y ie ld s r bond moment o f o n ly 0 .5 when computed according to the Peuling
ta b le when i t I s a c tu a lly 1 . 5.
Shiaerous aefc*l~he.logen moments e x h ib it the
erme marked d iffe r e n c e , in clu d in g th e t o f T l-C l.
Tl-O appear* in the eecme
category as C-O; a corrected v a lu e fo r t h is bond moment was used fo r the
t h e o r e tic a l c a lc u la tio n o f the T i-C l bond moment.
Tbicken and Meyer ( 7) have analysed the d ip o le c o n s titu e n ts o f a mole­
c u le "nd have taken in to c o n sid e ra tio n the d ir e c tio n s o f o p era tio n o f the
c o n s titu e n ts .
V e c to r ia l a d d itio n o f the v a rio u s lin k a g es gave the stan­
dard bond moments fo r C-Cw H-Cw C-Ow C-Clw (th e more p o s it iv e elem ent being
p laced f i r s t ) which are need In d ip o le c a lc u la tio n s .
M attem pt was made
on th e ir p e r t to c o n sid er the probable e lta r in g e f f e c t s on the bond mom­
e n ts by the environment in which the bond fin d s i t s e l f in the m olecule.
Such an in d u ctiv e e f f e c t i s evidenced in the s u b s titu tio n o f « methyl
r a d ic a l fo r a hydrogen atom in the fo llo w in g compounds5 CHCl^w CH2C lg.
CH^CI .
The r e s u ltin g compounds, CH^Cl-,, CH^CHCl2 end CH^CH^Cl show
v a r ia tio n o f d ip o le moment o f 0 ,8 , 9 ,5 end 0 .2 , from the v a lu e s o f CHCli. ,
— 10 —
CH^Cl^ pnd CE^Cl, which one would n o t p r e d ic t on the b eele o f th e sub­
s t i t u t i o n o f a hydrogen » too by a m ethyl red lca l*
p ttea p t to u se the same moment fo r e p a r tic u la r bond In d if fe r e n t
compounds by c a lc u la tin g q u a n tita tiv e ly the charges Induced by the other
bonds In the m olecule wee made by Eemtck ( 19) ,
This author a p p lie s the
g e n e r a lly accepted E n glish e le c tr o n ic theory to the c a lc u la tio n o f d ip o le
moments and thereby o b ta in s e more n ea rly v a lid r e s u lt fo r th e o r e tic a lly
c a lc u la te d e le c t r ic moments.
So f a r , t h is procedure has not been used fo r
many compounds but I t has p o s s i b i l i t i e s .
In sener*! we can say th at bond moaents are a t b e e t on ly approxim ations
o f the a c tu a l p h y sic a l s itu a t io n ; the computations which appear here are
J u s t if ie d under th a t r e s t r ic t io n .
— 11 —
1.
T i t e a l ^ t e t r p e t h y l f t f . Ti^QC^S^);, r
Thle eo#roaad w*e p fe y fr e d
mccordln; to the method o f $ le c h o ff end M klne ( 2 ) by the repot le n t
TlCl^ + GKeOCgHg --------- » Tl(OCgRg)A + M*C1
Th* d e t e l l e o f the m repprftlon *re described by Crowe
Upon etendln g
tltfta itu a te tr e e th y le te Ohsnfee to «• p a le y e llo w lte u ld which soon deepens
In c o lo r e v e n tu a lly becoming m orm-r*, red or brown liq u id ,
P u r lf lc e t lo a
wps neeompllehed by vpcuim d i s t i l l a t i o n , * l i t t l e a c tiv a te d ch arcoal bein g
added to remove the c o lo r .
This procedure wee found to be e f f e c t iv e In
ob ta in in g * c o lo r le e s , pure oomwmnd*
^n e n e ly e le fo r t lt r n lu e by *****
o f hydroly p le to t i t a n Ivm- d io x id e end ig n itio n gave e tlte n tu a co n ten t o f
2 1 .1 0 , 2 1.06 end 21.00''.
2.
The th e o r e tic a l v a lu e Ie 21,05-S.
T ltr nlu at* trap ropy I , t a.
Thle compound was prepared
In r manner Rftrlrgous to the uethod employed In the pret: rr e t ton o f fcItentunK
t e t r e e t b y l* t e .
f c o lo r l e s s , v lsco u * llr u ld we# ob tain ed which did not
hyd rolyse r* rep Id ly in p lr os did the ttten im a te trp e th y ls to j a ft e r * few
week* the compound turned p p a le y ello w c o lo r but did not become d eeper in
c o lo r .
I t Ie apparently s much more s ta b le compound.
The r ea c tio n 1# »#
follow**
TlClf, f I'
-------- ^ Tl(OCyEy)A + GleCl
Am a n e ly s ig fo r the titanium con ten t gave value* o f 1 6 ,8 5 ^nd 16. 53S.
th e o r e tic a l valu e ip 1 6 .8 4 .
2«
T ltp n lu s te tr e b u ty lr te . l l ( 0C*,Ey)h:
I t was p o s s ib le to prepare
t h is compound In a meaner *aelpgoae to th a t used In preparing tita n iu m -
The
12
t e t r r ^ t h y l » t e : In tk l* CF.se b u ty l f le o h o I w»e u eed .
T h e o r e tle s l T l c o n te n t:
h.
JFound T l:
lh*06, I ? . 96%.
llt.OBS.
i^onochlorotrlethonrtltenluB i. !plCl(OCgH<)^:
This compound was
prepFred f-ceordlng to the method o f Jennln ps, Werdlew end Way (13) by the
r e a c tio n :
Tl(OC2H5 )2, f CH3COCl----- > TlCl(OC2H5 ) 3 4 CH3COOC2H5
I t maintained » p o le y ellow c o lo r even a f t e r repeated d i s t i l l a t i o n and was
kept In a sea le d f la s k to prevent h y d r o ly s is .
titan iu m p ercen tage o f 2 1 .7 7 .
A titanium a n a ly s is gave e
The th e o r e tic a l valu e la 2 1 .9 7 -«
Cl found:
1 6 .3 7 , th e o r e tic a l 16.223.
£•
I lc h lo rod Ie tho zy t I t an turn. TlCl2 (PC2H5 ) 2 :
199 grams o f TlCl2t and
100 grams o f a b so lu te e th y l a lc o h o l were r eflu x e d recording to th e reac­
tio n ( 2 ):
TtClii 4 ZC2H5CH ------ ^ TlCl2 (OC2H5) 2 4 2 n d
/ t the end o f tw enty-four hours a w hite v is c o u s liq u id was obtained which
was d i s t i l l e d under reduced p r e ssu r e .
A w h ite sublim ate d i s t i l l e d over and
began to s e t t l e In the sid e arm o f the d i s t i l l i n g f la s k .
The residu e then
gave o f f HClt apparently decomposing In th e p ro cess and no fu rth er d i s t i l l a t e
was ob tain ed .
An a n a ly sts o f the y e llo w ish -w h ite liq u id # which soon s e t to
a s o lid , gave a titan iu m com position o f 29.39% where®e 2 2 .9 1 I s req uired .
Apparently a very low p ressu re In the d i s t i l l a t i o n p rocess Is necessary
fo r p u r if ic a t io n .
The e l e c t r i c moment o f t h i s m a teria l was n o t determined
s in c e I t wee considered Impure.
H onochlorotrlethoxya11ic o n . SlCl(OC2H5 ) 3 :
30 Ce. o f a c e ty l
-
13-
ch lo rtd e v«e ?d<5ed d ropy te e to HO oo o f e th y l orth os l l t c e t e over * period
o f two h e u r t , ececrdlR g to the method o f
-Il(QC2E5 )^ i CE CCGl
----- ^
'oet ?od Horton (1 5 ) .
SlCl(OC2K5) 3 + CK3COOC2H5
The a t x t u r e wee d i s t i l l e d pad c t 157°G e t otm oephertc p r e s s u r e s c o lo r le s s
liq u id Ct-Jie o v e r sad th e te m p e ratu re rem ained v i r t u a l l y c o n s ta n t d u rin g
th e d l s t i H i tlo ii p r o c e s s .
a t r ts o s p ite r Ic p r e s s u r e .
onoehlo r e t r I e th o xy>I H eon d i s t i l l s r,t 15?-S°G
The y i e l d was v e ry ;ood; th e cosrpound h r* m
pungent odor s t a l l s r to e th y l o r t i o s l l l c s t e end 1$ s o lu b le In hexane.
r e f r a c t i v e Index I s 1.3057? th e d e n s ity 0.9271 a t 25°C,
Tb*
The l i t e r s t u r e
g iv e* l.O&B) r e the d e n s ity o f a o a o c h lo r o tr le th o x y e I H con r t O0 C.
r e f r a c t i v e index c o n s ta n t wss fcoad i n a v a ila b le l i t e r a t u r e .
Mo
T h erefo re
th e p u r i t y o f t h i s compound hr-s n o t b een e e te b lis h e d ,
2»
^ th vl Orthoform ate. FC'nc^R.)^:
This compound was obtained from
Bestmpn Codeic Goiapeny end eaployed w ith ou t fu rth er p u r if ic a t io n .
fr a c tiv e index o f the compound '%# found to be 1.3923»
The re­
The lit e r a t u r e
g iv e s 1.3922 a s the r e f r a c tiv e index o f e th y l o r tiio fo r a e te .
-
7.
11:
-
TBIC HOMES?
%.
Method Used fo r D eterm lnetloa r»nd C e lcu letlo n s £ S l e e t r le ^ s a s a l:
The epperetue need fo r the e l e c t r i c moment determ inet lone wee the eeae e s
p r e v io u s ly d escrib ed (U )•
The c e l l co n sta n t wee c a lc u la te d u ein ? d i e t t i l e d
bengene, the d i e l e c t r i c co n sta n t o f which wse taken ee 2 .2 7 3 e t 25°•
>»-
hydrous beaten® wee prepared from Beker C. P . Thlophene-fr e e bentene by
drying over sodium fo r s e v e r a l hours end d i s t i l l i n g d ir e c t ly froa the
f l e s k , keeping o n ly the middle th ird o f the d i s t i l l a t e .
benzene wee used alm ost iramedletefcr a f t e r p rep a ra tio n .
The anhydrous
Petroleum hexene
wee need *>s th e so lv e n t fo r the e l e c t r i c moment determ inations end dried
in the s s ie manner.
From e eomperisnn o f the c e l l c e p e c ltr n c e with, e i r e.e
the d i e l e c t r i c and then w ith benzene, the c e l l con stan t could be c a lcu la ­
ted by the form.il a
The c e l l con stan t wee checked u sin g carbon te tr e c h lo r ld e , the d ie le c t r i c
con stan t o f which I s ;lven as 2.2273 a t 25°C in the C r it ic a l T ables.
The
r e s u lt s are shown in Tables I and I I .
T able i .
5
$
t
:
i
i
J__
T ria l
S&*
cX
C a lc u la tio n a £ C e l l C o n stan t
C
S
C
I
7 0 .1 6
.75
27.82
2
7 0.00
3M 7
27.69
Ave .
%
:
i
I
I
27.75
S
S
- 15 Tpble I I .
D eterm laptlon o f D ie le c t r ic Constpnt o f CCl^
:
:
:
T r ia l
No.
I
C
C
6 8 .8 4
34.83
27.75
2.2256
:
2
6 8 .8 4
3 4 .7 5
27.75
2.2281
3
6 8 .7 4
3 4 .7 2
2 7 .7 5
2.2260
Z
8
X
X
•
:
:
The t o t e l s o I p r p o lp r l ^ a t io n wee d eterm in ed from d i e l e c t r i c c o n stp n t
end d e n s ity mepeurementR on d i l u t e s o lu tio n s o f th e compounds In hexane
s t 2$°C.
The d i e l e c t r i c c o n s ta n t pad s p e c if ic volume were found to be e
l i n e a r f u n c tio n o f th e mole f r a c t i o n o f s o lu te ; th u s th e s lo p e s and in ­
t e r c e p t s o f th e s t r a i g h t li n e s were o b ta in e d by u s in g th e method o f l e a s t
sq u ares a p p lie d to th e e x p e rim e n ta l p o i n t s .
These v a lu e s were in s e r te d
in to th e e q u a tio n o f H s lv e r s ts d t and Eumler (Mj) which g iv e s th e t o t a l
m o lar p o l a r i z a t i o n o f th e compound:
x
(e ,
in w hich 6:^ and v^ a re th e i n t e r c e p t 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 s t r a i g h t l i n e s , r e s p e c tiv e ly , and A pad B a re th e resp ec­
t i v e s lo p e s .
i s th e m o le c u la r w eig h t o f th e s o lv e n t and Mg i s th e
m o le c u la r w eight o f th e s o lu te .
The i d e n t i c a l p ro c e d u re was u se d on a l l
th e compounds m easured.
In o rd e r to c a l c u l a t e th e e l e c t r i c moment i t i s n e c e s s a ry to c a lc u ­
l a t e th e e l e c t r o n i c ^nd atom ic p o l a r i z a t i o n s and s u b tr a c t t h e i r sum from
th e t o t a l p o l a r i z a t i o n to o b ta in Pffi.
Thus th e d ip o le moment can be c a lc u ­
l a te d from th e Debye e q u a tio n in th e form :
ji = 0.0127"jKp—P4
where p. i s
th e d ip o le moment in Debye u n i t s , P i s th e t o t a l p o l a r i z a t i o n and P e +/7
Is
— 16 —
th e eura o f the e le c t r o n ic »nd r to a ic p o ls r ia e t lo n e .
s e t lo n wee meesured In two d if f e r e n t
The e le c tr o n ic poI e r i-
( I ) the d e n s ity snd r e fr a c tiv e
index o f th e pure coapmmd were meesured u s Inp rn Oswald type pycnometer »ad
m d ip pin g r e fr s c to meter; th e v e lu e s obtained were used fo r th e c a lc u la tio n
o f the e le c tr o n ic p o V r ir e t io n from the fo llo w in g fo r a u le o f Lorents (5 h
Pe =
X
. iL.
d
n
- 2
in which n i s th e r e f r a c tiv e index, H the a c le c u le r w eig h t, rad d the den­
s i t y o f the pure compound.
%e atomic p o la r is a tio n wee assumed to be jjJ o f
the e le c t r o n ic p o la r is a tio n and then added to the l a t t e r .
(2 )
Several
d il u t e s o lu tio n s o f th e compound In hexane were made xtp and the r e fr a c tiv e
in d ic e s taken.
A p lo t o f the square o f the r e f r a c tiv e index age In st mole
fr a c tio n o f s o lu te was a stra i # t l i n e .
The v a lu es fo r the slo p e and in te r -
c e r t and t h is s tr a ig h t lin e were used in p ie c e o f the ones fo r d ie le c t r i c
co n stan t »nd in serted in to the H alv ersta d t and Kualer formula.
The con­
sta n t* V1 rnd B p r e v io u sly determined fo r the compounds were used again
fo r t h is c a lc u la tio n .
Pe fo r U ts n iu a te t r e e th y la t e , m onochlorotriethoxy-
s t l i c o a =nd e th y l o r th o fo r a ste were determined by method Cl ).
The e le c tr o n ic
p o la r is a tio n s o f tita n lu m te tr a p r o p y la te , tlt a n lu a t e t r s b u ty le te and monoohlorotr ie th o x y tita n iu m
were determined by method ( 2 ) .
The fo llo w in g ta b le s and graphs show the experim ental r e s u lt s used
to c a lc u la te the v a lu e s given in Table I ? .
£.
T ltan lU D tetreeth ylf t e . SjJLSSLpii^lhS
- 17T cble 3 (See H g . I )
D ie le c t r ic Conetrnte o f S o lu tio n s o f
I
I
I
*
!
*
5
2
!
i
In Hexrne
S o lu tio n Ho.
;4ole
F re p tlp n
I
0.004265
1.928
2
0.005091
1.929
3
0.008050
1.941
4
0.010560
1 .946
D ie le c tric
C o n sten t
:
!
1
2
2
S
2
2
2
T able & (s e e F ig . 2)
s p e c if ic g a la a a a a l a
1
!
:
S
s
£
TI(QCoH^)l, l a Iisaaag
Mole
D ie le c tric
0.004769
1.4579
2
0.007158
1.4492
3
0.016280
I . 436O
4
0.007518
1.4491
5
0.002709
1.4575
6
0.017508
1.4334
1
:
2
I
1
?
1
2
2
2
a
2
1—
Z.
f Itm lu u ite trp D ro p y lg te . Tl(QC 3H7 )f.!
1
*
$
$
I
I
2
2
2
2
2
I
2
2
j
-IQ T able £ (See F ig . 3)
D ie le c t r ic Constants of S o lu tio n s o f Tl(OC,Hy)^ in Hexane
I
I
I
I
I
I
I
I
I
S
I
I
I
I
S o lu tio n No.
Ifole F r a c tio n
D i e l e c t r i c C o n stan t
I
O.OO66 I1O
1.9k3
2
0.01050
1.952
3
0.01250
1.957
h
0.0056U
1.9k0
5
0.01020
1.95k
6
0.00251
1 .933
:
f
:
:
:
s
8
f
I
z
8
I
1
*
T ab le 6 (See F ig . It)
S p e c if ic Volumes o f S o lu tio n s o f Ti(OC-JH7 ) t. i n Hexane
I
I
I
I
I
I
t
I
:
S o lu tio n No.
1£o1 g F r a c tio n
S p e c if ic Volume
I
0.002621
1 . 1*616
2
0.007565
1.1*537
3
0 . OllttiO
l.k 3 7 1
U
0.009111*
l.k 5 0 2
t
1
1
t
1
1
1
1
1
*
T able 7 (See F ig . 5)
R e f ra c tiv e In d ic e s o f S o lu tio n s o f Ti(OC^H^)^ i n Hexane
t
I
S
t
I
t
I
«
I
I
t
S o lu tio n No.
Mole
F r a c tio n
R e f ra c tiv e
In d ex
Square
o f R .I.
I
0.003730
1.3Q517
1.92036
2
0.00lt652
1.36599
1.92066
3
0.0150k
1.3095k
1.93002
U
0.011*39
1.3607k
1.92660
*
1
*
:
1
t
1
1
t
1
1
-
3#
19
Tltpnlti.-ntetrpbu*,ylft e .
:
T eble S. CRee Fig* 6 )
M e le o t r lC C o a a te n ta a £ S o lu tio n s &£ lllSSlfSgul^ l a HamaG
S
I
I
:
i
*
S olu tion So.
Mole fr a c tio n
I
0.004923
1.937
1
:
i
2
0.102479
1.929
I
I
3
0.002285
1.928
t
I
:
i -------
U
0.0003458
1.924
t
D ie le c t r ic Conatent
t
$
____ L
Table 2 (See f i g . 7)
S r e c lf lc Voiuaea o f Solu tion ? o f T l( 0 0 ^ 9^t 12. HfiSSSS.
M nle -hrection
S o l u t i o n Ho.
S p e c i f I c Volii
I
0.004923
1.4490
2
0.002489
1.4556
3
0.002289
1.4557
4
0.001497
1.4578
Table 10 (S ee i l g . 8 )
R efra ctiv e In d ic e s s £ Sol u t l o Ufl & S M S S l ^ h i. l a SfiZLaft
:
1
t
*
*
1
:
t
:
I
x_
S o lu tio n S o .
Hole
f r a c tio n
B efrp cttv e
... ______ Indeat----------
Square
o f B. I*_____
I
0.002360
1.38090
1.90688
2
0.905314
1.38195
1.90840
3
0.007660
1.38271
1.91189
4
0.009174
1.38309
1.91294
i
5
t
i
j
!
5
t
»
5
- 20 k'
IgaQgfcklajQ.tirirB.to?art
^ i c i ( oc^
)^ i
StPble 11 (See F1&. 9)
.fiUJLsg.trU Gsastsata siL .SalaUaaa a t .TIHUPS.^!^ ia He&g^e
t
I
I
^rtn
Mole S1VeetlnM
I
*
I
0.00781
1.978
:
2
0.00285
1 .9 4 7
*
•
t
i
t
S
s
$
i
i
5
S
3
0.00373
1.952
$
I
1
$
$
J
e
5
I
4
0.00904
1 .982
5
0.0(^ 20
1.979
6
0.00806
1 .962
7
0.90623
1.964
8
0.01310
2.001
I
9
9.00646
1 .9 6 4
i
$
i
10
0.00565
1 .968
;
2
2
1
t
:
:
2
2
2
$
S
I
Ip b le 12 ( See F ig . 10)
S m e t f lc Volumes o f S o lu tio n s o f IlClfOQgBW- in Hexpne
:
:
:
S p e c ific Voluae
Snli^ttnn So.
I
0.00781
1.4436
I
I
2
0.00285
1.4589
t
8
3
O.OO565
1.4543
4
0.01210
1.4400
:
i
t
I
i
:
2
2
2
2
£
i
I
- 21
5.
M o n o c h lo r o trie th o x y s lllcon, S i Cl(OC9Hg)^t
T able 13 (See F ig . 11)
D i e l e c t r i c C o n sta n ts o f S o lu tio n s o f SiCl(OCpHg ) i n Hexane
!
:
S o lu tio n No.
t
Mole F r a c tio n
D i e l e c t r i c C o n stan t
I
T
I
:
I
0.009580
1.9k5
X
2
0.08677k
2.10k
i
3
0.062035
2.052
U
0.026k90
1.977
5
0.053030
2 . Okl
I
:
X
X
X
X
X
I
i
X
X
t
_____ L
T able Ik (See F ig . 12)
S p e c if ic Volumes o f S o lu tio n s o f SiCl(OC0Hg)^ i n Hexane
I
:
:
S o lu tio n No.
t
t
t
I
t
I
I
Mole F r a c tio n
S p e c if ic Volume
I
t
:
I
0.009580
I.k5k6
2
0.030321
l.k 3 8 2
3
0.058030
l .k l 9 3
k
O.O0677k
1.3950
6.
i
t
S
t
I
i
S
E th y l o rth o fo rm a te , HC(OCgHg)y
T able 1$ (See F ig . 13)
D i e l e c t r i c C o n sta n ts o f S o lu tio n s o f HC(OCgHg )^ i n Hexane
I
I
:
:
S o lu tio n No.
Mole F raction
D ie le c tr ic Constant
I
0.18676
1.971
2
0.17689
1.969
3
0.20385
1 .9 7 k
t
t
t
:
____I
22
I
I
U
0.07068
1 .9 8 1
t
I
5
0.33067
2.007
*
i
i
i
T able 16 (S ee F ig . 18)
S p e c if ic Volumes o f S o lu tio n s o f HG(OCyHt;)^ i n Hexane
I
t
I
I
I
I
I
I
I
0.18676
1.8523
i
t
t
*
2
0.17689
1.8535
I
I
3
0.20385
1.8885
h
0.07068
1.8623
I
I
I
5
0.0 ltlb 9
1.8689
t
$
6
0.35692
1.8820
I
I
7
0.82759
1.8383
S p e c if ic Volume
Mole F ra ctio n
S o lu tio n No.
t
t
I
I
I
I
I
I
I
I
i
t
i
Table 17
Summary o f E l e c t r i c Moment D e term in atio n s
CD
A
t-i
Compound
<u
I
t
vi
P
Pe
a
;
Ti(OC2H5 ) ji
3.0681*
1.9186
-1 .6 9 9 2
1.8612
119.3
6 8 .8
1 .5 8 i
Tl(OC3H7 ) lt
2
I Tl(OCitH9 ) lt
2.1*582
1.9266
-2 .0 3 7 1
1.8681
1 1 8 .8
02.3
1 .3 2 I
2.6U ili
1.9227
-2 .5 7 8 9
1.8617
1 2 9 .7
102.0
1 .0 8 :
2 .5 1 t
S
1 .7 5 t
I
0 .7 t
t
I
I
I
I
I
TiCl(OC2H5 ) 3
7.1230
1.9210
-2 .0 8 1 5
1.8652
1 8 5 .1
5 8 .9
2
t
SiCl(OC2H5 ) 3
2.5957
1.9237
-0 .7 6 2 9
1.8620
116.7
5 0 .3
HC(OC2H5 ) 3
0.02515
1.9237
-0 .0 6 3 7 8
1.8655
*
*
5 1 .7 8
3 9 .8
1 .930
D ie le c t r ic co n sta n ts o f s o lu tio n
p lo tte d a g a in st mole fr a c tio n
tita n iu m te tr a e th y la te in hexane
a t 25 C.
1.920
1.910
1.900
Mole F raction o f S o lu te
0.014
I dJnSTj:
D ie le c t r ic Constant
1.940
1 .460
S p e c if ic volume o f s o lu tio n p lo tte d
a g a in st mole fr a c tio n tita n iu m te tr a e th y la te
in hexane a t 25 C
1 .4 5 0
1.445
1.440
1.435
1.430
0,014.
Z aJn S u
S p e c if ic Volume
1.455
Mole F raction o f S o lu te
C aan S T j
D ie le c t r ic Constant
D ie le c t r ic co n sta n ts o f
s o lu tio n p lo tte d a g a in st
mole fr a c tio n tita n iu m te tg a p ropylate in hexane a t 25 C.
Mole F raction o f S o lu te
t7 aanSTj
S p e c if ic Voli
1.4700
cn
N
O
O
*
§
4r
8
♦
O
Mole F ra ctio n Ti(OCjHy)^
2
o
N
ae
o
IfTneO
o
o
O
o
1.930
1.925
1 .920 -
1.915
1.910
0.014
F ig u re 5
Square o f r e f r a c t i v e in d ic e s
v s . mole f r a c t i o n o f T i ( X - H )
--- 0 (4
4~
Mole F r a c tio n T i(X -H 7 )
1.945
9 aJnSTji
D ie le c t r ic Const
§ 1 .9 4 0
D ie le c t r ic co n sta n ts o f
s o lu tio n p lo tte d a g a in st
mole fr a c tio n o f titanium te tr a b u ty la te in hexane
a t 25°C.
1.935
1.930
1 .9 2 #
8
O
S
O
(N
C
O.
O
CO
O
O
O
O •
O
O
«
O
O
O
Hole F raction o f S o lu te
VO
•
8
O
8
O
1.465
I OJnSx1J
S p e c if ic Volume
1.460
S p e c if ic volumes o f s o lu tio n p l o tte d
a g a in s t mole f r a c t i o n o f tita n iu m £ e tr a -
1.455
1.450
1.445
900*0
Mole F r a c tio n o f S o lu te
1 .9 0 9 Square o f th e r e f r a c t i v e in d ex
s o lu tio n p lo tte d a g a in s t mole
f r a c t i o n o f tita n iu m te tr a b u ty la te
i n hexane a t 25 C.
1.907
I
w
0
1
1.905
1.903
1 .9 0 1 o
§
O
S
O
U3
8
I
O
O
Mole F r a c tio n o f S o lu te
O
3
0.014
8 3Jn2Tji
Square o f th e R e f r a c tiv e In d ex
1.911
D ie le c t r ic Constant o f S o lu tio n
2 .0 0 0
1.980
D ie le c tr i c c o n s ta n ts o f s o lu tio n s
p lo tte d a g a in s t mole f r a c t i o n
TiCl(OC2H^)^ i n hexane s o lu tio n a t
1.960
1.940
1 .920
O
O
O
O
C
Mole F ra ctio n o f S o lu te
O
O
OT aanSTd
S p e c ific Volume o f S o lu tio n
1 .4 7 0
S p e c ific volumes o f s o lu tio n s p lo tte d
a g a in st mole fr a c tio n T iC l(OCJ I - ) - in
hexane a t 25 C.
1.460
1.450
I
CzJ
W
1 .440
1.430
I
O
O
O
S
O
O
I
I
O
O
O
a
§
2.100-
2.080
TI 3J n S t j
D i e l e c t r i c C o n sta n t
2.060
2.040
2.020
D i e l e c t r i c c o n s ta n ts o f
s o lu tio n p l o tte d a g a in s t
mole f r a c t i o n o f S i C l ( X 9Hc ) -
2 .0 0 0
1.980
1 .960
1.940
1.920
O
O
O
O
O
Mole F ra ctio n o f S o lu te
O
O
080*0
O
1.4600
S p e c if ic volumes o f s o lu tio n p lo tte d
a g a in s t mole f r a c t i o n SICl(OC 2H5)^
1.4500
1.4300
1.4200
1.4100
1.4000,
0.070
Z l a-mST-i
S p e c if ic Volume
1.4400
Hole F ra ctio n o f S o lu te
2.020 r
2.000
g
I
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 e ^ h y lo rth o fo rm a te
i n hexane a t 25 C.
CO
^
° 1 .980
■p
il
" I
'Z l.9 6 0
0
1
1.940
I
O
8
rH
O
§
O
OOC‘0
1.920
o
h o le F r a c tio n o f S o lu te
o
o
M aJnSrlJ
S p e c if ic Volume o f S o lu tio n
1*462 —
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
e th y lq rth o fo rm a te i n hexane
a t 25 C.
1.454
1 .446
1.438
1 .430
Mole F ra ctio n o f S o lu te
- 37H*
NOW* POLARIZATIONS Of TITARIUN TBTBASTRILATS J £
T^lrgRAfUBBS
The molar p o ls r ls a t lo a * o f U tsnlasa ta tr e e thy la t e were date rained In
th e ease manner ee d escrib ed a t Z5°C.
The low te-speretures were obtained
by c ir c u la tin g e d r y -ic e a lc o h o l m ixture through th e c e l l .
A m odified
Oswald pycnometer wee used end t h i s lmaersed In a beaker c o n ta in in g the
d r y -le e a lco h o l m ixtu re.
The c e l l co n sta n t end the pycnometer volume la
th e temperature range were determined u sin g petroleum hexane; th e d ie le c ­
t r i c con stan t ^nd d e n s ity la th e temperature range were obtained from
data given by H e ll ( 1 2 ) .
The v a lu e s given were r ev ise d to c o in c id e w ith
th e d i e l e c t r i c co n sta n t and d e n s ity o f th e hexane obtained a t 2$°C.
S a le
w»s done sin c e d if f e r e n t l o t s o f petroleum hexane appear to have d if f e r ­
e n t d ie le c t r i c co n sta n ts and d e n s i t i e s .
T ables 18 and 19 g iv e th e e x ­
perim en tal data obtained fo r the d i e l e c t r i c con stan t* and s p e c if ic
volumes o f tit a n lu a t e t r a e th y le t e s o lu tio n s In hexane,
fa b le 20 summarises
the e lo p e s and I n te r c e p ts , end s o la r p o la r is a tio n s ? t the v a r io u s tempera­
tu r e s .
Table 18 (S ee F ig . 15)
D ie le c t r ic C onstants o f S oln t Ions o£
Vprloua Tenneratures
I
? Wnle VreCtion
t
- 2a
2 .182
! 0.05071
I
2.057
t 0.00809
t
S 0.003&08 2 .0 4 7
:
2.087
t 0.01788
t
JLS SfiXfiftb SJt
2 .1 8
E l e le c t r le Constant
Teimerature C
-2 2
-2 2
2.128 2.110 2.092
2 . 1I
2.042
2.027
2 .0 1 3
1 .998
2.032
2 .016
2.001
2 .069
2 .053
2.037
-1 2 ,
2 .0 7 4
2 ,
2.056
1 .983
1 .9 6 8
1.953
1 .9 8 6
1.971
1 .956
1.941
2.019
2.002
1 .9 6 5
1.969
t
:
t
:
.
t
I
I
•
1
___L
—
J&
—
Table 19 (S ee F ig . 16)
Srieelfie Yolwaee qX Solutions s i TKOCgH^i, ifi SflSCM M lfiit 1633.t
I
J_
I
I
I
:0.02171
t
: 0 .01509
1
*0.009843
t
10.005615
1
-SO
“60
S n e e ifie Vdlumefi
Teauereturee
-OO , - 2 2 - .
-4 0
1
;
. r-JLft..
1.3860
1.4 0 2 4
1.3054
1.3215
1.3375
I .3506
1.3700
1.3161
1.3325
1.3490
1.3658
1.3825
1.3990
1.4161
1.3235
1.3400
1.3566
1.3734
1.3900
1.4068
1.4238
1.3317
1.3490
1.3660
1.3832
1.4000
1.4172
1.4346
O
1
1.4189 *
T
1.4330 I
S
1.4410 I
I
1.4518 t
I
Table 22 (See f i g . I ? )
Suamary s i Holar m l e r i s s t l o a I e l l
fpmam, C
1/T
:
____2---------------L
I_________£
*
-7 0
0.004922
2.0355
2.8855
1.3379
- I .8396
-6 0
0.004691
2.0202
2.8228
1.3553
—1.9098
9 7 .8 9
-5 0
0.004481
2.9951
2.7691
1.3726
-1 .9 7 1 2
9 7 .2 0
-4 0
0.004289
1.9994
2.6944
1.3901
-2 .0 3 7 3
9 5 -9 1
-3 0
0.004113
1.9756
2.6288
1.4070
-2 .0 5 7 2
9 5 .7 6
- 20
0.003950
1.9607
2.5645
1.4245
-2 .1 3 7 6
9 4 .3 5
- 10
0.003800
1.9457
2.5002
1.4422
-2 .1 9 6 7
9 3 .3 6
O
O.OO366I
1.9310
2.4343
1.4486
-1 .3 9 6 7
111.82
9 8 .9 3
:
t
:
t
s
$
:
*
*
;
:
*
*
$
*
:
2,170
D i e l e c t r i c C o n stan t of
S o lu tio n s of Ti(OCgKg)^
i n Benzene v s c o n c e n tra ­
t i o n a t v a rio u s te m p e ra tu re s
2.13C
2 .0 5 C -
1 .970
0.052U
SI aJnSTj
D i e l e c t r i c C onst
§ 2.09C
Mole F r a c tio n S o lu te
91 3«m3Tj
S p e c if ic Voliime
S p e c if ic Volume o f S o lu tio n s of
T i ( OC7Iir.) i n Benzene v s . Concent r a t i o n 'V t V a rio u s T e m p e ra tu re s.
Mole F r a c tio n S o lu te
109
ti
105
I
S
I
1/T x IO 3
V II.
CBISTAlS 0 2 TITAMIiJMTgTBAETSYLATS
I t wes p o s s ib le by slow evaporation o f * s o lu tio n o f benzene end I IquIA
1 1 trn lu m tetrp eth y lste to prepere c r y s t a ls o f the l e t t e r compound.
wee drewn over the s o lu tio n In e d e s ic c a to r sealed w ith wax.
Dry s i r
A fter sev e r a l
t r i a l rune i t was p o s s ib le to evaporate the benzene w ith ou t h y d ro ly sis o f
the e n tir e t lt a n lu a t e t r s e t h y la t e .
The c r y s t a ls , however, were found
beneath a top la y e r o f titan iu m d io x id e .
They were sm a ll, presumably
o n ly p o r tio n s o f a la r g e r c r y s t a l, but lu c id and showing a d e f in it e c r y s ta l­
lin e s tr u c tu r e .
The h a b it o f the c r y s t a ls was not determined sin c e e
p o la r iz in g a lcroscope was not a v a ila b le .
allow ed to remain a t room tem perature.
They were found to m elt slo w ly i f
X-ray d if f r a c t io n p a tte rn s o f the
c r y s t a ls w i l l be taken In the near fu tu re la an attem pt to determine the
stru ctu re o f the s o lid .
T ill.
MOirgIJLAE WSlQKT DSTBP-MIN*TlOHS 0£ T lfO C g H ^
%@ aoleculipr w eight d e te r a ln e tio n a o f tlt e n lu a t e t r a e t h y le t e s t v erlo u e
con cen tret lone up to e s o le f r e e t ton o f 0 .1 were aede by th e fr e e z in g p o in t
d ep ression aethod In benzene s o lu tio n .
The r e s u lt s sr e shown In T ig . 16
which In d ic a te s e e s o c ls t lo n to tt tr ia e r * t th e higher co n c en tr a tio n s.
Since t it s n iu a hoe *, p o s s ib le coord in a tio n r e le a c e o f s i x ms ex h ib ited in
the r u t il e form o f tit e n lu a d io x id e , e e s o c ls t io n m y occur by t h is manner.
As there ere no a c tiv e hydrogens in the m olecule hydrogen bonding seems
u n lik e ly .
S o lid if ic a t io n o f titanium t e t r e e t h y le t e , which occurs by *
spontaneous p r o c e ss throughout the e n tir e liq u id , fu r th e r su g g ests m ssociet io n .
18.
The fo llo w in g d ate was used fo r the p lo t o f the curve shown in T ig .
The d eterm in a tio n s, numbers fou rteen through n in eteen were ae.de by
Pobert Crowe (I*).
- hh
TRble 1 2 (See n.%. 18)
MoleculRr Weight D eterm inetlona &£ f KOCgH ^pIeazftaa SolNtlQAa
*
6e I u t ion $&»
t
Mole T raction
T reatin g P oint
, Deci re 9 s ion
I
I
J
M olecular
..Weight_______ _____ L
*
I
610
I
0.0428
1 .0 9 7
2
0.0249
0 .7 1 7
635
3
0.0458
1.162
618
U
0.0110
0 .3 3 2
503
I
I
I
I
5
0.0605
1.499
643
I
6
0.0721
1 .6 9 5
663
7
0.1030
2 .5 9 0
665
8
0.0406
1 .145
553
9
0.0157
0 .4 2 0
567
10
0.0 3 5 4
0 .8 5 0
646
11
0.0 1 6 4
0 .4 8 0
502
12
0.00842
0 .2 4 5
517
13
0.00345
0 .8 7 9
607
14
0.0113
0 .3 6 5
468
15
0.0633
0 .2 3
416
16
0.00193
0 .1 1
263
8
17
0.00254
0 .1 5
253
$
I
18
0.00379
0 .1 6
367
I
I
19
0.00290
0 .1 4
323
:
I
I
I
I
I
S
I
I
I
I
I
I
I
i
I
S
I
t
I
I
8
I
I
t
8
I
:
i
t
t
*
i
I
I
t
i
I
I
t
I
I
I
8
I
8
I
I
I
8
I
8
I
8
I
8
I
8
8
I
550-
81 SJnSxjT
o le c u la r W eight
500 _
450M o lecu lar w eig h t o f s o lu te
v e rsu s Mole F r a c tio n .
300250-
Mole F r a c tio n Ti(OCgHg)^
I£.
I.
CAlCUlf TIOW Q l BQNP HQ^MTS
The th e o r e tic a l d ip o le moment o f t Itenium te tr e e th y le t e een be celcx ileted
by u sin g th e Eyring eq u a tio n .
This e q u e tlo n , however, i s based upon f r e e
r o ta tio n end, th e r e fo r e , aey not be a p p lic a b le to th e e s t e r s o f tita n iu m .
R epresenting the m olecular stru ctu re ms d ep icted below, where
i s the
sum o f the bond moments o f C-O and S-C, mg i s the Ti-O bond moment, 6 i s
the an pie made by the bonds Tl-O end O-C, and f
is? the te tra h ed ra l a n g le .
we haves
f- Is 109°28' and 0 i s assumed to be 1 0 5 °i ^
i s the sum o f the C-O
moment, 0 .7 , and the B-C moment, 0 .4 , or 1 .1 .
The sum o f the in te r ­
a c tio n s o f Ug, sin c e th ey are d ir e c t ly te tr s h e d r e lly w i l l be zero end,
th e r e fo r e , wa can equate the sum o f a l l the terms In v o lv in g atg to zero .
The equation reduced to o n ly one unknown end thus can be so lv e d .
A
valu e o f 2 .1 1 i s obtained fo r the average d ip o le moment.
itigcos6 4- f ia s c o s f f 6m^
'llm^agcosOcoaO)
M s
+ l?m ^ co s^co
cos"'"
s”* - ha^2 ( lI + c o sm o s2©)
u = 2 .1 1
2.
The bond moment fo r T l-C l has been c a lc u la te d from the observed d ip o le
moment o f trichlrom onophenoxytitanlum ( 4 ) .
This compound should have
l i t t l e r e s t r ic t e d r o ta tio n , Judging from model r ep re sen ta tio n o f the
m olecule.
The P auling e le c t r o n e g a t iv it y s c a le r a tin g s , breed upon the
- 47 o b serv ed end c»lc u le te d v e lu e e f o r th e C-O bond moment ln d lc e te e en
F-P^reximete h ig h e l e c tro n e g e t l v I t y . r e t la g o f th e Ti-O bond, o f 0 .3 .
Thue
i t Ie p o s s ib le to s u b tr e c t 0 .3 from th e e l e c t r o n s e s t i v i t y velum end o b te tn
1 .6 es r e p r e s e n tin g th e Ti-O bond moment.
T rlch lo ro ao n o p h en o x y titF n iu ai
shows t h a t th e th r e e T t-C l bonds should ;tv e p r e s u ltp n t moment d i r e c t l y
o p p o s ite to th e r e s u i t e a t moment o f th e Ti-O end O-C bonds.
The d ip o le
moment o f th e compound ie , th e r e f o r e , th e d if f e r e n c e o f th e two r e s u l t a n t
moments.
Since Ti-O ie 1 .6 , C-O Ie 0 .7 end th e en ^le betw een them Ie
105° , th e r e e u ltr .n t o f th e two moments, by th e lew o f c o s in e s , le i
*2 z ( 0 .7 ) ' * (1 .6 )" ^ ( 0 .7 ) ( 1 .6 ) (-0 .2 5 8 8 )
u — 1 .7
r Ince th e m easured moment wee 3*0 th e T i-C l bond moment Ie 3 .0 3- 1 .7 o r
h .7 .
— IiQ —
DISCUSSION ( g SXI=KRIM^T' D ^gSULTE
The e x p e rim e n ta l v e lu e e f o r th e d ip o le momenta o f t l t e n t u m t e t r e e th y lp te ^nd m o n o e h lo ro tr le th o x y tlte n lu a l a hexsne s o lu tio n , I . $5 ?nd 2 .50
r e s p e c t i v e l y , e j r e e ap p ro x im a te ly w ith th e v s lu e a o b ta in e d f o r th e se
compounds In benzene eoI u t Io n .
The a s s o c ia ti o n o f t l t r n l u m t e t r s e t h y l p t e Is o f n ty p e h i t h e r t o u a r e p o r te d .
Many compounds e x h ib it m o lecu lar a s s o c ia tio n due to hydrogen
bonding b u t i t I s b e lie v e d t h a t t h i s ty p e o f a s s o c ia tio n I s caused by
th e p o s s ib le c o o rd in a tio n v a le n c e o f th e tita n iu m atom o f s i x .
The
t e t r a h e d r a l bond a n g le o f 109° may be s h o rte n e d to 90° to a llo w one
tita n iu m atom to be bonded to s i x oxygen atoms a s in th e c a s e o f th e
r u t i l e form o f TlOri.
The bond between th e tita n iu m atom and th e oxygen
atoms e rn be form ed due to th e ? v * l i a b i l i t y o f two f r e e oxygen e le c tr o n s .
The d ip o le moments o f me th y Io rth o c a rbo w* t e , C(OCH^)jJt, and e th y lo rth o c a rb o n a te (C(OC2^ ) fe, have been r e p o rte d a s 0 .8 and 1 .1 re s p e c tiv e ­
l y ( 6) .
S th y lo r th o s 11t e a t s h a s a re p o rte d d ip o le moment o f 1 .7 In benzene
s o lu tio n (2 3 ) .
However, no c o n c lu s io n can b e reached c o n c e rn in g the v a r i a ­
tio n In e l e c t r i c moment o f th e compounds o f th e element® o f ;roup fo u r u n t i l
a s e t o f m easurem ents e re made in th e same s o lv e n t.
T h e o r e tic a lly e l l th e
te tr a m e te r s o f c arb o n , s i l i c o n and tita n iu m should have th e same d ip o le
moment.
However, th e d is c r e p a n c ie s may be due to r e s t r i c t e d r o ta tio n o f
th e e s t e r lin k a g e s o r to p a r t i a l io n ic c h a r a c te r o f th e bond c o n n ectin g
th e c e n t r a l stem w ith an oxygen ,or c h lo r in e atom .
Uie e x a c t n a tu re o f
th e d if f e r e n c e hae n o t been c o n c lu s iv e ly p ro v en b u t h e a t c a p a c ity o r
e n tro p h y m easurem ents on th e compounds may I n d ic a te w h e th er r e s t r i c t e d
r o t p t l o n Ie n d e c is iv e f a c t o r .
I t wre by e n tro p y a e p e u re a e n te th e t th e
r e s t r i c t e d r o t a t i o n o f e th y le n e d ic h lo r td e wee c o n c lu s iv e ly shown.
The d e c re a s e in a o a e n t s s one 300s from t i t e n l u a t e t r E e t h y l e t e to
titp n iu c n te tr p b u ty ls te a sy be csueed by g r e e t e r r e s t r i c t i o n o f r o t a t i o n
due to th e l a r g e r e s t e r groups r o ta tin g nbout th e t i t e n l u a s t o a .
The In -
c r e s s e in moment ps one goes from methylo r th o c e rb o n # te to e th y lo rth o c e rb o n s te
mey be censed by th e edded in d u c tiv e e f f e c t o f th e s u b s t i t u t i o n o f »n e th y l
r r d i c r l f o r th e m ethyl r e d l c s l .
A ccording to th e d e te g iv e n by U p e sto n e
( 7 ) f o r v a rio u s e lk y l h e l l d e s end e lc o h o le , th e in d u e iv e e f f e c t f e l l s o f f
v e ry r a p id ly a f t e r th e e th y l compound.
In some eases th e b u ty l compound
hp# P low er moment th an th e c o rre sp o n d in g e th y l compound.
Thus i t Ie
p l a u s i b l e t h a t th e h in d e re d r o t a t i o n f a c t o r i s th e s i g n i f i c a n t one in t h i s
case.
The p o l a r i z a t i o n d a te ln d ic e te e d ip o le moment f o r tita n iu m te tr e e th y I e t e o f 1 .1 a s o b ta in e d from th e elope o f th e s t r a i g h t l i n e in th e low er
te m p e ra tu re re g io n .
T h is , how ever, does n o t ap p ear to be co n g ru en t w ith
th e f a c t s e t 25°C which show
p.
h ig h e r p o l a r i z a t i o n end d ip o le moment.
It
aey be t h a t th e p o l a r i z a t i o n o f t l t e n l u m t e t r e e t h y l s t e goes through 0 minimum
end th e n r i s e s a s th e te m p e ra tu re i s in c re a s e d .
The c a l c u l a t i o n o f th e bond moment o f T i-C l i s s i g n i f i c a n t in t h a t I t
s e rv e s to in d ic a te an approxim ate v a lu e f o r th e bond which may be u sed in
th e o r e tic f il c a lc u la tio n s o f compounds c o n ta in in g th e bond.
I t i s s i g n i f i c a n t t h a t th e e s t e r s o f c arb o n , s i l i c o n and tita n iu m
s tu d ie d show no abnorm ally n ig h d ip o le moment and, th e r e f o r e ,
s u i t a b l e f o r d i e l e c t r i c m a te r ia ls in e l e c t r i c a l c o n d e n se rs.
pre n o t
« 50 il.
ACKBOWLSDOtHEBTa
Ihe cuthop w ishes to exp ress h ts thenkg pad s p p r e c ie tio a to Dr.
Charles M. Cm >hlpn fo r h ie ln g p lr e tlo a end u n tir in g d ev o tio n to the
research p r o je c t end to the o th er members o f the Chemistry Department
fo r th e ir many h e lp fu l s u g g e stio n s.
He a ls o w ishes to thank the Beeerrch
Corporation o f Hew York fo r the grant which aade the in v e s tig a tio n p o s s ib le .
H I.
LITERATURE CITED AND CONSULTED
1.
B e i l s t e i n , V ol. I , p . 335.
2.
B is c h o ff and A dkins, J . Am. Chem. Soc. 1*6, 2? (1 9 2 k ).
3.
C r i t i c a l T a b le s, V o l. V I, p . 90.
k.
Crowe, wThe D i e l e c t r i c P r o p e r tie s o f Some E s te rs o f TiCL ," M. S.
T h e s is , Montana S ta te C o lle g e , Bozeman, Montana (1 9 k 8 )• ^
5.
Debye, wP o la r M o le c u le s."
(1 9 2 9 ).
6.
E b e rt, E is e n s c h ifz and H a r te l, z . P h y sik . Chem., (B) I , 9k (1 9 2 8 ).
7.
Eucken and Meyer, P h y s ik . Z e i t s c h r . , 30, 397 (1 9 2 9 ).
8.
E y rin g , Phys. R e v ., 3 9, 7k6 (1 9 3 2 ).
9.
G la ss to n e , "R ecent Advances i n P h y s ic a l C h em istry ," B la k is to n and
Sons, I n c . , P h ila d e lp h ia (1 9 3 6 ).
The Chemical C atalo g C o ., I n c . , New York
10.
H a lv e r s ta d t and Kumler, J . Am. Chem. S o c ., 6k, 2988 (1 9 k 2 ) .
11.
H auser and L e v ite , B e r ., k8, 213 (1 9 1 5 )•
12.
H e il, Phys. R e v ., 3 9 , 666 (1 9 3 2 ).
13.
J e n n in g s , Wardlaw and Way, J . Chem. S o c ., P a r t I , 637 (1 9 3 7 ).
Ik .
Kirkwood, J . Chem. P h y s ., k, 592 (1 9 3 6 ).
15.
Lange, "Handbook o f C hem istry," p . 765.
16.
O nsager, J . Am. Chem. S o c ., 58, lk 8 6 (1 9 3 6 ).
17.
P a u lin g , "The N ature o f th e Chem ical Bond," The C o rn e ll U n iv e rs ity
P r e s s , I th a c a , New York (19kO ).
18.
P o st and N orton, J . O rg. Chem., Jm, 528 (1 9 k 2 ).
19.
Remick, J . Chem. P h y s ., 9 , 655 ( 1 9 k l) .
20.
Rosenheim and S o rg e r, B e r ., 53, (B) 932 (1 9 2 0 ).
21.
Schumann, B e r ., 21, 1079 (1 8 8 8 ).
— f>2 —
22.
Smyth, " D ie l e c tr ic C onstant and M o lecu lar S tr u c t u r e , "
Chem ical C atalo g C o ., I n c . , New York (1 9 3 1 ).
23.
S v ir b e ly and L ander, J . Am. Chem. S o c ., 70, Ll21 (1 9 ^ 8 ).
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