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LSU Historical Dissertations and Theses Graduate School

1942

Dipole Moments of Some Chlorocarbonates in Solution. Dipole Moments of Some Chlorocarbonates in Solution.

Robert Emerson Wood Louisiana State University and Agricultural & Mechanical College

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Recommended Citation Recommended Citation Wood, Robert Emerson, "Dipole Moments of Some Chlorocarbonates in Solution." (1942). LSU Historical Dissertations and Theses. 7851. https://digitalcommons.lsu.edu/gradschool_disstheses/7851

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LOUISIANA STATE UNIVERSITY LIBRARY

119-a

DIPOLE MOMENTS OF SOME GHLOROCARBONATE8 IM SOLUTIOH

A D is s e r t a t io n

S ubm itted to th e G raduate F acu lty o f the L o u is ia n a S ta te U n iv e r s i ty and

A g r ic u l tu r a l and Mechanical C ollege in p a r t i a l f u l f i l lm e n t o f th e re q u ire m e n ts f o r the deg ree o f

D octor o f P h ilo so p h y

in

The D epartm ent o f C hem istry

byR obert Emerson Wood

B. S . , Rhode I s la n d S ta te C o lleg e , 1937 M* S*, L o u is ia n a S t a t e U n i v e r s i t y , 1939

Ju n e , 1942

UMI Number: DP69229

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th e author w ish es to e g r e s s h is s in c e r e a p p rec ia tio n

to B r. a* B* Gboppin* d ir e c to r o f t h i s work* fo r con­

s id e r a b le h e lp fu l a d v ice a ad a s s i s ta n c e * He i s Indebted

to Br* and Mrs* frank h . P ad g ltt* Dr. E. 3* Amis*

Dr* 0 . f . E irb y , Mr* Edgar I*. Oompere, Mr* James W* Bogers

and Mr* B. 8* S a r r e tt f o r t h e ir a s s is ta n c e and su g g estio n s

throughout th e course o f t h i s study*

11

y > i , %V H 0 1 " 3 4 U f r iw xt , . X

TABLE Of OOHWKfS

I* I n tr o d u c t io n ....................... . .............................. . , . • X

IX . Review o f th e L i t e r a t u r e ............................................. 3

I I I * E x p erim en ta l Work ........................... . 8

1* P u r i f i c a t i o n o f M a t e r i a l s .............................. 8

2 . M easurement o f d i e l e c t r i c

C o n s ta n ts . . . . . . . . . ........................ IE

3 . M easurement o f D e n s i t ie s and

R e f r a c t iv e I n d i c e s . • • 1?

IV , E x p erim en ta l R e s u l ts ............................ 19

V. D isc u ss io n o f R e s u l ts ............................... 26

V I. Summary ....................................... 33

V II . B ib l io g r a p h y ........................................................................ 34

V II I . V i t a ................................................... ....................................... 46

i l l

L I B f or f A M M B

X. P u r if ic a t io n o f M ater ia ls • • • • • • • • • • 11

XI. P o la r iz a t io n s o f Benzene-GHLoroe&rbonate

B in a r ies a t 2 5 °0 . . . ................................................... 24

I I I . D ipole Moments o f the Chlorooarbonates

a t 25°C..................................................................................... 25

i r

LIST OF PI0URSS

1 . D ie le c t r ic Constant Measuring C a ll IS

2 . Weighing B o t t l e ......................................... .... 16

3* P o la r is a t io n t i . C oncentration fo r the

C hlorocarbonates in Benzene S o lu tio n a t

2 S ° C . ........................................................................................... 22

4 . D ipole Moments vs* Humber o f Carbon Atoms

in the Hormal Ghlorooarbonate Chain ..................... 2?

v

A M tm O f

The r e la t io n o f the d ie l e c t r ic p r o p e r t ie s o f chem ical

compounds to th e ir m olecu lar s tru ctu re i s one o f the more

r e c e n t f i e l d s o f th e o r e t ic a l ch em istry . The in v e s t ig a t io n

reported h ere d e a ls w ith a study o f the d ip o le moments o f

se v era l ohlorooarbonatee in benzene s o lu t io n , th e gen era l

method used mas th e b inary m ixture method o f W illiam s.

A heterodyne beat apparatus and a d i e l e c t r i c con­

s ta n t m easuring c e l l have been co n stru cted and used fo r

t h i s work. The d ip o le moments o f m ethy l, e th y l , n -p rop y l,

n -b u ty l and n-amyl ch lorocarb on ates have been measured

a t 25°C. in benzene so lu t io n and found to b e , r e s p e c t iv e ly ,

2 .4 2 , 2 .6 6 , 2 .6 8 , 2 .6 9 and 2 .7 2 Debye u n i t s . For i-p r o p y l

and phenyl ohlorooarbonatee th e v a lu es are 2 .7 7 and 2 .3 1

Debye u n i t s , r e s p e c t iv e ly , c le a r ly in d ic a t in g the change in

p o la r ity occasion ed by the secondary and arom atic carbon

l in k a g e s .

The s tr a ig h t chain a l ip h a t ic ohlorooarbonatee have

been shown to f i t the accepted th e o r ie s o f d ip o le moments

in homologous s e r i e s . A con stan t d ip o le moment fo r the

h igher members o f the s tr a ig h t chain s e r ie s i s in d ic a te d .

Phenyl ch lorocarbonate has been shown to p o sse s s a

mesomeric moment* T his moment i s o f the same order o f

v l

m agnltude ae o th e r v a lu e s r e p o r te d In th e l i t e r a t u r e f o r

m ost a ro m a tic compounds.

Com parison o f th e e x p e r im e n ta lly d e te rm in ed value

o f th e d ip o le moment o f m ethyl oh lo rooarbonat© w ith

c a lc u la te d v a lu e s f o r two p o s s ib le m o le cu la r s t r u c tu r e s

i n d i c a t e s two p la u s ib le h y p o th e ses f o r th e m o le cu la r

form o f lo w er a lk y l e h lo ro c a rb o n a te * I t I s su g g es ted

t h a t m ethyl e h lo ro c a rb o n a te e x i s t s e i t h e r in two

r e s o n a t in g form s o r t h a t i t e x i s t s e s s e n t i a l l y In th e

form f o r w hich a h ig h e r d ip o le moment i s c a lc u la te d .

The a p p a re n t ly anom alous r e s u l t s o f M izushims and

Kubo a r e r e a d i ly acco u n ted f o r in th e l i g h t o f p re v io u s

r e s e a r c h by C hoppin, F re& ian l and K irby who have shown

t h a t th e th e rm a l d eco m p o sitio n tem p e ra tu re o f e th y l

e h lo ro c a rb o n a te i s w e ll below th e te m p era tu re a t which

th e s e I n v e s t ig a to r s were o p e ra t in g .

vii

w m o m c n o ®

The s p e c ia l iz e d f i e l d o f t h e o r e t i c a l c h e m is try d e a l in g

w ith th e perm anent e l e c t r i c p o la r i z a t i o n o f m o lecu les

d a te s from th e in t r o d u c t io n o f th e d ip o le moment co n cep t

by Debye in 1912 ( 9 ) . Through th e l a s t th r e e decades#

t h i s f i e l d h a s p ro v id e d v a lu a b le In fo rm a tio n re g a rd in g

m o le c u la r s t r u c t u r e .

The g e n e ra l e x p e rim e n ta l method o f ap p ro ach f o r

e v a lu a t in g d ip o le moments h as been to m easure th e

d i e l e c t r i c c o n s ta n t . T h is may be done e i t h e r in th e

g a s ph ase o r i n a d i l u t e s o lu t io n o f th e p o la r con­

s t i t u e n t in a n o n -p o la r s o lv e n t . The m ost d i f f i c u l t

ex p e rim e n ta l p roblem to be overcome in work o f t h i s ty p e

i s to s a t i s f a c t o r i l y and p r e c i s e ly d e te rm in e th e d i e l e c t r i c

c o n s ta n t o f th e su b s tan ce whose d ip o le moment i s d e s i r e d .

The aim s o f t h i s in v e s t ig a t io n have been to f u r th e r

in c r e a s e th e a v a i la b le d a ta on d ip o le moments and* in

p a r t i c u la r # to throw some l i g h t on th e m o le cu la r s t r u c tu r e

o f th e c h lo ro e a rb o n a te s . These compound® have been o f

r e c e n t i n t e r e s t in th e f i e l d o f r e a c t io n k i n e t i c s (4# 6# 29)*

S p e c tro sc o p ic and d i e l e c t r i c s tu d ie s o f th e e h lo ro c a rb o n a te s

seemed to be a l o g i c a l s te p in b u ild in g up more e x p e rim en ta l

f a c t s to s u b s t a n t i a t e th e k in e t i c p o s tu la te s w hich may be

advanced f o r th e mechanism o f e h lo ro c a rb o n a te d ec o m p o sitio n s .

1

2

f h l s I n v e s t ig a t io n la a p re l im in a ry s tu d y o f th e d le le c t r lo

p r o p e r t ie s o f the more common o h lo ro o a rb o n a te e . A s im i la r

study I n the sp ec tro sco p ic f i e l d h a s been made by Sm ith (4 ? ) •

RFFXEW OF THE LITERATURE

A q u a l i t a t i v e d i s t i n c t i o n betw een e l e c t r i c a l con­

d u c to r s and e l e c t r i c a l i n s u l a t o r s 3ms been re c o g n ise d

s in c e th e tim e o f F a rad ay . The f i r s t a t te m p t to d e s c r ib e

th e d i e l e c t r i c c o n s ta n t a® an atom ic o r m o le c u la r p ro p e r ty

i s found in th e c l a s s i c a l th e o ry o f C la u s iu s and M oso tti

( 5 # 38)* Molecule® w ere t r e a te d a s co n d u c tin g sp h e re s

tqr th e s e a u th o r s . S ubsequent developm ent o f th e atom ic

th e o ry l e d Debye (9 ) in 1912 to in tro d u c e th e perm anent

d ip o le moment co n cep t and s a t i s f a c t o r i l y e x p la in th e

te m p e ra tu re e f f e c t on d i e l e c t r i c s * The e s s e n t i a l

a ssum ption o f Debye40 th e o ry i® th a t th e r e s u l t a n t

c e n te r o f th e p o s i t iv e c h a rg e s in a m o lecu le 1® n o t a

p r i o r i s p e c ia l ly c o in c id e n t w ith th e r e s u l t a n t c e n te r

o f th e n e g a tiv e c h a rg e s . T h is f i r s t c l e a r p ic tu r e o f

p e rm an en tly p o la r i s e d m o lecu les i s now re g a rd e d a s th e

b e g in n in g o f modern d ip o le th e o ry . An im m ediate con­

sequence o f th e new th e o ry was th e e x p la n a tio n o f th e

anom alous d is p e n s io n o r d e c re a se o f th e d i e l e c t r i c

c o n s ta n t w ith in c re a s e i n freq u en cy f i r s t o b serv ed by

Drude (1 1 ) . Debye (10) gave a q u a n t i t a t iv e d e s c r ip t io n

o f t h i s e f f e c t f o r some o rg a n ic l i q u i d s .

The m ost r a p id grow th o f th e d ip o le th e o ry h as

ta k e n p la c e w ith in th e l a s t two d ecad es . Some d ip o le

3

4moments have b ee s d e te rm in ed by p a s s in g a beam o f

m o lecu le s th ro u g h an In te n s e non-homogeneoua a l e e t r i e

f i e l d and m easuring th e d e v ia t io n o f th e beam from i t s

s t r a i g h t c o u rs e . Kalim an and R eiche (2 8 ) , S te m (5 6 ) ,

Wrede ( ? 2 ) , and Ssterm ann (14) have s u c c e s s f u l ly u sed

th e m o le cu la r beam te c h n iq u e . Most i n v e s t i g a t o r s ,

how ever, have u sed d i e l e c t r i c c o n s ta n t m easurem ents f o r

d e te rm in in g d ip o le moments.

D ie l e c t r i c c o n s ta n ts have been d e te rm in ed by

m easu rin g th e e l e c t r i c fo rc e a c t in g th ro u g h a d i e l e c t r i c

o r by d e te rm in in g th e v e lo c i ty o f e le c tro m a g n e tic waves

th ro u g h a d i e l e c t r i c . However, th e m ost w id e ly u sed

method to d ay i s b ased on th e m easurem ent o f e l e c t r i c a l

c a p a c i ty . Smyth and h i s cc*w orkers (64) have p e r fe c te d

an e l e c t r o n tu b e W heatstone b r id g e s u i t a b le f o r d i e l e c t r i c

c o n s ta n t m easurem ents. Walden, U lio h , and Werner (6 6 , 66)

and S tra n a th a n ( 68) h a v e , p e rh a p s , been m ost s u c c e s s fu l

w ith a re so n an ce method o f c a p a c i ty m easurem ent. The

h e te ro d y n e b e a t method h a s come in to g e n e ra l u se a s th e

m ost r e l i a b l e means o f m easuring e l e c t r i c a l c a p a c i ty o f

in s u l a t o r s o f low d i e l e c t r i c c o n s ta n t . Zahn (73) in

1924 developed a h e te ro d y n e b e a t c i r c u i t f o r m easuring

th e d i e l e c t r i c c o n s ta n ts o f g a s e s . R efinem en ts and

v a r i a t i o n s o f t h i s method a re in g e n e ra l u se to d a y .

Berweg (2 2 ) , W illiam s (6 9 ) , S tu a r t (6 9 ) , S anger and

S te ig e r (4 6 ) , and numerous o th e r s have f u r t h e r im proved

in s t ru m e n ta t io n in th e h e te ro d y n e b e a t c i r c u i t s .

5

The d ip o le moment i s g e n e ra l ly c a lc u la te d from

ca p a c ity measurements o f a vapor o r a b in a ry l i q u i d

m ixture* L&nge ( S I ) , W illiam s (70)* and E r r e r a (15)

d ev e lo p ed th e b in a ry m ix tu re te ch n iq u e and i t h as s in c e

become th e m ost w id e ly u sed ex p e rim e n ta l method f o r

d ip o le moment d e te rm in a tio n s* The vap o r p h ase method

i s more a c c u r a te , b u t ex p e rim en ta l d i f f i c u l t i e s have

l im i te d i t s use* Kuho <36) and h i s c o l l a b o r a to r s ,

Smyth and McAlpine <51, 52) , Bryan ( 3 ) , m d Coop and

S u tto n (? ) a re a few o f th e p ro m in en t modern w orkers

who have u sed t h i s method e f f e c t i v e l y . T h e o r e t ic a l ly ,

d ip o le moments d e te rm in ed in th e l i q u i d p h ase by th e

b in a ry m ix tu re method sh o u ld a g re e w ith th o se d e te rm in ed

in th e v ap o r phase* I t h a s been found t h a t s o lv e n t

e f f e c t s e x i s t which u s u a l ly te n d to g iv e lo w er d ip o le

moments in th e l i q u i d phase th a n in th e v apo r p h a se .

M u lle r (3 9 ) , J e n k in s (2 7 ) , and Sug&en (60) have p roposed

e m p ir ic a l r u l e s f o r th e q u a n t i t a t iv e i n t e r p r e t a t i o n o f

s o lv e n t e f f e c t . O neager (40) h a s t r e a te d th e problem

t h e o r e t i c a l l y and d ev e lo p ed an eq u a tio n f o r c a lc u l a t i n g

th e d ip o le moments o f l iq u id s * H is c o n t r ib u t io n i s

p e rh a p s th e m ost im p o r ta n t one In r e c e n t y e a r s , f o r I t

in v o lv e s t h e o r e t i c a l re f in e m e n ts o f th e o r ig in a l

C la u s lu s -M o e o tti ap p ro ach to th e p roblem . A ttem pts to

in c lu d e p r o p e r t i e s o f th e s o lu te in e x p la in in g so lv e n t

e f f e c t have been made by W elgle (6 7 ) , M lgashi (2 3 ) , and

F rank (1 6 ) .

6Many problem s o f m o le c u la r s t r u c t u r e have been so lv ed

by a p p l ic a t io n o f th e th e o ry o f d ip o le moments# The sim ple

c a s e , where one m o le c u la r form i s p o la r and th e o th e r

n o n -p o la r , i s i l l u s t r a t e d in th e work o f U rre ra ( I S ) , who

d i f f e r e n t i a t e d betw een “e ls * and ® trans* iso m ers by

d ip o le moment m easurem ents. More com plex s t r u c t u r a l

p rob lem s have n o t been so p r e c i s e ly so lv e d by th e d ip o le

moment ap p ro ach . Such c o m p lic a tin g f a c t o r s a s re so n a n c e ,

m utual d ip o le in d u c t io n , d e fo rm a tio n o f bond a n g le s , and

in a d e q u a te d a ta on th e geom etry o f m olecule® have made

i t e x c e e d in g ly d i f f i c u l t to c a lc u l a te d ip o le moments

from a knowledge o f th e m o le cu la r s t r u c t u r e ; to r e v e r s e

th e problem i s a ls o d i f f i c u l t , n e v e r th e le s s , much can

be g a in ed by a p p ly in g th e co n c e p ts p ro p o sed by

S i r J . 1 . Thomsen (6 2 ) , who was th e f i r s t to ap p ly a

v e c to r a n a ly s i s to th e c a lc u l a t i o n o f d ip o le moments

from m o le cu la r s t r u c t u r e . W illiam s ( 68}, In g o ld (26)

and numerous o th e r s have made im p o rta n t c o n t r lb u t io n s

to th e v e c to r method o f c a lc u la t in g d ip o le moments. In

t h i s m ethod, each bond o f a m olecu le i s a s s ig n e d a

d e f i n i t e “bond moment® which i s r e p re s e n te d by a v e c to r .

G eo m etrica l c o n s id e r a t io n o f th e m o lecu la r s t r u c tu r e

a llo w s th e c a lc u l a t i o n o f a r e s u l t a n t d ip o le moment.

A ttem pts to c a lc u l a te th e In d u c tiv e e f f e c t o f one

d ip o le upon a n o th e r have been made by s e v e ra l a u th o r s .

Among th e se a re Smallwood and H erz fe ld (46) who

s u c c e s s f u l ly t r e a t e d in d u c t iv e e f f e c t s in benzene

¥

d e r iv a t iv e s * &?0VeS and

Bmyth and Hs&lpine (51 ) •

Hecent in t e r e s t in

has been oon eeotrated on a so re

approach to th e problem o f

pore p o la r l iq u id a .

Oasage? theory in t h i s

b ein g t e s te d by se v era l

s u c c e s s .l i t t l e d ata i s rep orted in

d t s l e s t r l e p r o p e r t ie s o f the

compounde* f e e vapor

(1 9 ) , Thomsen (6 1 ) , and

o f d ip o le th e o ry

t h e o r e t i c a l

o f

M s equation, i s now

w ith

l i t e r a t u r e on

d ip o le moments o f e th y l and

and Kuho (36) • fhomsen (01) h as

and e th y l c a rb o n a te s . H ssensaoe in

h a s been s tu& led by B e ll ( 1 ) .

f e e p r e s e n t s t a t e o f r e s e a rc h in th e

f i e l d i s m ain ly concerned w ith

th e d i e l e c t r i c p r o p e r t i e s o f

s tu d ie s o f

EXPERIMENTAL WDHK

The b in a ry m ix tu re method f o r d e te rm in in g d ip o le

moments was f i r s t p ro p o sed by Lange (3 1 ) . W illiam s,

E rr e ra , and Smyth ( 48) and o th e r s ha ire m o d ified th e

method to some e x t e n t . The neoese& ry ex p e rim e n ta l

m easurem ents a r e d i e l e c t r i c c o n s ta n t , d e n s i ty , and

r e f r a c t i v e in d e x .

P u r i f i c a t i o n o f M a te r ia l s ,

Because o f th e n e c e s s i ty o f c a r e f u l ly p u r i f i e d

l i q u i d s f o r d i e l e c t r i c c o n s ta n t and d e n s i ty m easurem ents,

i t was c o n s id e re d e s s e n t i a l to c o n s t ru c t a s e rv ic e a b le

f r a c t i o n a t in g colum n. T his column c o n s is te d o f an

e l e c t r i c a l l y h e a te d , a ir - J a c k © te d V lgreaux tu b e , 105 cm.

lo n g and ab o u t 1 .8 cm* in d ia m e te r . A Whltmore-Lux

s t i l l head (3 ?) w ith t o t a l c o n d e n sa tio n , v a r ia b le ta k e o f f ,

was c o n s tru c te d and f i t t e d to th e column w ith s ta n d a rd

ta p e r ground g la s s J o i n t . Ground g la s s J o in t s and

u n lu b r ic a te d s to p co ck s were used f o r th e v a r io u s n e c e ssa ry

co n n e c tio n s i n th e f r a c t i o n a t in g system . The compound

b e in g p u r i f i e d came in c o n ta c t w ith n o th in g bu t p y rex

g l a s s . An o i l b a th was u sed to b o l l th e l i q u i d being

f r a c t io n a te d . R e flu x r a t i o s o f th e o rd e r o f 20 to 1 o r

g r e a t e r were u se d . The te ch n iq u e employed was e s s e n t i a l l y

t h a t recommended by M orton (3 7 ) .

8

Baker*e 99-100# benzene was p u r i f i e d by ©baking

w ith s u c c e s s iv e p o r t io n s o f c o n c e n tra te d s u l f u r i c a c id

u n t i l no v i s i b l e d i s c o lo r a t i o n o f th e a c id l a y e r appeared*

A f te r w ashing r e p e a te d ly w ith d i l u t e sodium c a rb o n a te

s o lu t io n fo llo w ed by w a te r , th e benzene l a y e r was d i s ­

t i l l e d o v e r sodium w ire , and f r a c t i o n a l l y c r y s t a l l i z e d

fo u r t im e s . When r e e r y s t a l l i z a t l o n showed no change in

d e n s i ty i n th e f o u r th p la c e , a f i n a l d i s t i l l a t i o n o v e r

sodium was c a r r i e d o u t i n th e f r a c t i o n a t in g column* She

d e n s i ty o f th e d i s t i l l e d p ro d u c t ag reed in th e f o u r th

p la c e w ith th e d e n s i ty a f t e r th e f o u r th c r y s t a l l i z a t i o n .

The f i n a l d i s t i l l a t i o n was alw ays used to in s u re com plete

d ry n e ss o f th e p u re benzene . The p h y s ic a l c o n s ta n ts o f

th e benzene o b ta in e d by t h i s method o f p u r i f i c a t i o n w ere:

D e n s ity a t 25°C .—Q.8754B o ilin g P o in t a t 762 mm* Hg— 80 ± 0 .0 6 °C . (u n o o rre c te d )

These c o n s ta n ts a re in s a t i s f a c t o r y agreem ent w ith th©

b e e t v a lu e s in th e l i t e r a t u r e ( 21) .

The e h lo ro c a rb o n a te s were p u r i f i e d by a double

f r a c t io n a t io n u s in g th e same d i s t i l l a t i o n column and

te c h n iq u e a s t h a t em ployed in th e p u r i f i c a t i o n o f benzene .

Calcium c h lo r id e was used a s th e d ry in g ag en t in a l l c h lo ro

ca rb o n a te p u r i f i c a t i o n s . The f i r s t d i s t i l l a t i o n s were made

o v e r ra n g e s o f £ l ° C . The a p p ro p r ia te f r a c t io n s from t h i s

d i s t i l l a t i o n w ere th e n r e f r a o t lo n a te d o v e r calcium c h lo r id e

The b a l l i n g ra n g e s o f th e p u r i f i e d su b s ta n c e s a re l i s t e d

in T able I . Vacuum d i s t i l l a t i o n was employed on those

10

ch lo ro o & rb o n a tes w hich decompose a p p re c ia b ly cm d i s ­

t i l l a t i o n a t a tm o sp h e ric p re s su re *

In s p e c tio n o f t a b le 1 shows t h a t th e m ost im pure

e h lo ro c a rb o n a te , th e n -p ro p y l compound, was f r a c t io n a te d

o v e r a b o i l in g ran g e o f ± 0 .3 5 ° C . There i s c o n s id e ra b le

d is c re p a n c y i n th e l i t e r a t u r e r e g a rd in g th e p h y s ic a l

c o n s ta n ts o f c e r t a i n c h lo ro c a rb o n a te s* However, p re c e d e n t

i n d i c a t e s t h a t th e p ro d u c ts o b ta in e d from t h i s method o f

p u r l f i c a t i o n were ad eq u a te f o r p u ro o se s o f d i e l e c t r i c

c o n s ta n t m easurem ents. W illiam s (?G ), Smyth (55) and

numerous o th e r s have s u c c e s s f u l ly u se d d ip o le moment d a ta

o b ta in e d from compounds w hich showed b o i l in g ra n g e s o f a s

much a s i .X .0°C .

Phenyl e h lo ro c a rb o n a te was s y n th e s is e d from pheno l

and phosgene u s in g a m o d if ic a tio n o f th e method employed

by H a lfo rd and Inman (4 3 ) . k s o lu t io n c o n ta in in g tw enty

p e r c e n t by w eig h t o f phosgene in bengene was p re p a re d by

slow ly b u b b lin g phosgene gas in to benzene a t 10° - 20°C.

k s to ic h io m e tr ic q u a n t i ty o f p heno l was d is s o lv e d In a

q u a n t i ty o f d im e th y la n i l in e c a lc u la te d to be 10 p e r c e n t

in e x c e ss o f t h a t r e q u ir e d to r e a c t w ith th e hydrogen

c h lo r id e form ed In th e phosgene p h e n o l r e a c t io n . The

p h e n o l-d im e th y la n il in e s o lu t io n was th en co o led and

s lo w ly added to th e phosgene s o lu t io n . The tem p era tu re o f

th e r e a c t in g m ix tu re was m a in ta in ed betw een 10° and S0°C.

Phosgene g as e scap in g from th e r e a c t io n f l a s k was tra p p e d

11

TABUS I

P u r i f i c a t i o n o f C h io ro c a rb o n a te s

C hlo ro -ea rb o n a teP u r i f i e d

B i s t i l l a t i o n P re s s u re mm. Hg.

B o ilin g Range U ncorreo ted °C .

D en s ity a t 25°0 .

R e f r a c t iv e Index a t 25°Q.

M ethyl 761 7 1 .1 - 7 1 .7 1 .2190 1 .3846E th y l 762 9 1 .5 - 9 1 .6 1 .1311 1 .3 9 2 ?a -P ro p y l 769 1 1 6 .0 - 1 1 6 .7 1 .0821 1 .4012i-P ro p y l 165 5 2 .8 - 5 3 .4 1 .0356 1 .3950n -B u ty l 762 138 .1 - 1 3 8 .5 1 .0448 1 .4090Amyl 45-65 # 1 .0268 1 .4165Phenyl 18 8 9 .9 - 9 0 .2 1 .2386 1 .5089

* The b o i l in g p o in t s were n o t re c o rd e d f o r amyl o h lo ro - o a rb o n a te due to th e n e c e s s i ty o f f r a c t io n a t in g a w r y sm all amount a t s e v e r a l d i f f e r e n t d i s t i l l a t i o n p r e s s u r e s . The b o i l in g ran g e was 0 *6°C .

12

o v e r aqueous ammonia. The r e a c t io n m ix tu re m s s t i r r e d

f o r one hou r a f t e r th e e v o lu t io n o f phosgene from th e

m ix tu re had c e a s e d . A f te r s ta n d in g f o r an a d d i t io n a l

h o u r , th e m ix tu re was cau sed to s e p a ra te i n to two l a y e r s

by ad d in g & sm all amount o f w a te r . The benzene l a y e r ,

w hich c o n ta in e d th e e h lo ro c a rb o n a te , was drawn o f f , and

washed f i r s t w ith d i l u t e h y d ro c h lo r ic a c id and th e n w ith

w a te r . An i n i t i a l d i s t i l l a t i o n o v e r ca lc iu m c h lo r id e

removed m ost o f th e b en zen e . The r e s id u a l e h lo ro c a rb o n a te

was th e n f r a c t io n a te d tw ice o v e r ca lc iu m c h lo r id e , a t a

p r e s s u r e o f 18 mm. o f m ercu ry . A 26 p e r c e n t y ie ld o f

p h en y l e h lo ro c a rb o n a te , h av in g a b o i l in g ran g e o f i 0 . 3° C .,

was o b ta in e d .

M easurement o f D ie l e c t r i c C o n s ta n ts :V M M MrtMMMMMMMMMaMMMMMMPMtoMMfNBMMMt M M M M M M B N H llM M M M iM e i

The h e te ro d y n e b e a t a p p a ra tu s p r e v io u s ly c o n s tru c te d

by th e a u th o r (71) was u sed f o r c a p a c i ty m easurem ents.

In o rd e r to f u r th e r m inim ize u n d e s ira b le in d u c tiv e e f f e c t s ,

th e two e le c t r o n tub© o s c i l l a t o r s were s e p a ra te d by a

d is ta n c e o f ab o u t th r e e f e e t . In a d d i t io n to th e s h ie ld in g

p re c a u tio n p r e v io u s ly u se d , s e p a ra te grounded s h ie ld s were

p la c e d o v e r a l l w ire c o n n e c tio n s betw een th e ungrounded

p l a t e s o f th e c o n d e n se rs in th e r e s o n a t in g c i r c u i t . Con­

s id e r a b le d i f f i c u l t y was ex p e rien ce d in m a in ta in in g

fre q u en cy s t a b i l i t y . The e n t i r e a p p a ra tu s was re w ire d ,

r i g i d l y su p p o rte d , and th o ro u g h ly I n s u la te d a g a in s t

m echan ica l and e l e c t r i c a l d is tu rb a n c e s . I t was a ls o found

13

t h a t r i g i d m echanical sw itc h e s had to be s u b s t i t u t e d i n

a l l l e a d s where i t was e s s e n t i a l t h a t le a d c a p a c i ty be

e o n s ta u t .

Because o f th e c o r ro s iv e n a tu re o f th e o h lo ro o a rb o n a te e ,

a t te m p ts to u se a g o ld - p la te d b ra s s c e l l were u n s u c c e s s fu l *

and a c e l l w ith p la tin u m co n d en se r p l a t e s had to be con­

s t r u c t e d . IV© p ie c e s o f p la tin u m f o i l * 0 ,0 0 2 5 in c h e s

th ic k , and 6 in c h e s long* were form ed in to two c o n c e n tr ic

c y l in d e r s , fh e l a r g e r c y l in d e r was ab o u t 1 in c h in

d ia m e te r and th e s m a lle r ab o u t 0 ,? 5 in c h e s in d ia m e te r .

P la tin u m le a d w ire s were w elded on each c y l in d e r and th e

two c y l in d e r s were mounted c o n c e n t r i c a l ly by p la c in g th e

l a r g e r one in s id e a t i g h t l y f i t t i n g p y re x tu b e (F ig u re 1)

and th e s m a lle r one a round th e o u ts id e o f a t i g h t l y

f i t t i n g p y rex tu b e . S u i ta b le i n l e t and o u t l e t c o n n e c tio n s

and le a d w ire c o n ta c ts were p ro v id e d , fh e c e l l was

e n c lo se d in a g la s s J a c k e t th ro u g h w hich m in e ra l o i l from

a th e rm o s ta t was c i r c u l a t e d by means o f & sm all tu rb in e

pump. J a c k e t te m p e ra tu re s w ere c o n t r o l l e d to t 0 .0 1 ° 0 ,

Tem perature o b s e rv a t io n s were made on a c a l i b r a t e d

therm om eter a c c u ra te to f 0 , 01°C , I t was found im p ra c t ic a l

to immerse th e c e l l in a th e rm o s ta t . P ro x im ity to th e

n e c e ss a ry e l e c t r i c a l a p p l ia n c e s f o r th e o p e ra t io n o f a

c o n s ta n t te m p e ra tu re b a th i n t e r f e r e d w ith th e c a p a c i ty

m easurem ents on th e d i e l e c t r i c c o n s ta n t c e l l .

F ig u re 1 shows th e e s s e n t i a l f e a tu r e s o f th e

14

d i e l e c t r i c c e l l and i t s th e rm o s ta t J a c k e t . T h is g e n e ra l

ty p e o f c e l l has been u sed by Smyth (5 3 ) , Zahn (73) and

s e v e ra l o th e r s .

A ccording to th e l i t e r a t u r e (2 1 ) , th e te m p e ra tu re

c o e f f i c i e n t o f th e d i e l e c t r i c c o n s ta n t o f benzene o v e r

th e te m p era tu re ran g e u sed th ro u g h o u t t h i s work i s

*0 .0020 . As a l l b in a ry m ix tu re s u sed had te m p e ra tu re

c o e f f i c i e n t s o f th e same o rd e r o f m agnitude a s t h a t o f

benzene , te m p e ra tu re c o n t r o l to t 0 *01°C . was c o n s id e re d

e n t i r e l y s a t i s f a c t o r y , fhe in h e re n t e r r o r in d i e l e c t r i c

c o n s ta n t from te m p e ra tu re v a r i a t io n in th e s e ex p e rim en ts

would n o t exceed 1 0 . 00002.

In m aking d i e l e c t r i c c o n s ta n t m easurem ents o f th e

b in a ry m ix tu re s , th e s o lu t io n s to be m easured were made

up by w eigh t u s in g th e s p e c ia l ly b u i l t w eigh ing b o t t l e

shown in F ig u re 2 . fh e f i l l i n g c o n n e c tio n was a t ta c h e d

to th e c e l l a t c o n n e c tio n WB*. fhe c e l l was f i l l e d in

t h i s manner to a d e f i n i t e l e v e l , ab o u t a h a l f in c h above

th e to p o f th e p la tin u m c y l in d e r s . A f te r te m p e ra tu re

e q u il ib r iu m was re a c h e d , f iv e re a d in g s were ta k en o f

c e l l c a p a c i ty , and f iv e re a d in g s o f le a d c a p a c i ty .

The c e l l was th en em ptied by a p p ly in g a i r p re s s u re

to c o n n e c tio n •’A*’, a t th e to p o f th e c e l l , and fo rc in g th e

l i q u i d back in to th e w eigh ing b o t t l e . The w eighing b o t t l e

was rem oved, and a ca lc iu m c h lo r id e tube in s e r t e d in to

c o n n e c tio n HBn# E v acu a tio n th ro u g h c o n n e c tio n MAH drew

d ry a i r th ro u g h th e c e l l u n t i l i t was c o m p le te ly d r ie d .

IB

Figure 1 . D ie le c tr ic Constant Measuring C e ll .

Mecury Cup Leads

\

in le t

m

R u b b e r S to p p er

Platinum L e a d W /res

O u te r Jacket "~Z_

Platinum cyf/naters

R u b b e r S t o p p e r

Tt? ermom e t e r

O it Oott&f

16

F igure 2 . W eighing B o t t le

F ittin g C onnection a

W eig h in g B o t t le

1 7

The c e l l im s th e n re a d y f o r th© n ex t d e te rm in a t io n .

F re q u en t c e l l c a l i b r a t i o n s w ith p u r i f i e d bensene

were made. C a lc u la t io n o f th e c e l l c a p a c i ty was based on

th e v a lu e s f o r th e d i e l e c t r i c c o n s ta n t o f bensene a s

r e p o r te d by H a rtsh o rn and O liv e r (2 1 ) , The e ^ e r im e n ta l

e r r o r i n d e te rm in in g tii© c e l l c o n s ta n t was £ 0 * 0 3 p e r cen t*

M easurement o f D e n s i t ie s and H e tra c t iv e I n d i c e s ;

D e n s i t ie s were d e te rm in ed a c c o rd in g to th e te ch n iq u e

employed by H a r tle y and B a r r e t t (2 0 ) , In t h i s m ethod, an

O s tw s ld -S p re n g le r ty p e pycnom eter o f 28 c c , c a p a c i ty ,

f i t t e d w ith ground g la s s c a p s , i s c o u n te rp o ise d a g a in s t

a s im i la r pycnom eter h av in g th e same e x te r n a l volume a s th e

m easu rin g pycn o m ete r.

T em perature e f f e c t s on th e d e n s i ty were e l im in a te d by

im m ersing th e pycnom eter i n a th e rm o s ta t# A f te r tem p era tu re

e q u i l ib r iu m was reached* e x c e ss l i q u i d was removed from th e

pycnom eter, and th e l i q u i d l e v e l a d ju s te d to th e c a l i b r a t i n g

m ark. A f te r ad ju s tm e n t o f th e l i q u i d l e v e l In th e

pycnom eter, th e pycnom eter was removed from th e b a th , and

wiped d ry , The pycnom eter and c o u n te rp o ise were p la c e d in

an a n a ly t i c a l b a la n c e , a llo w ed to com© to a c o n d itio n o f

c o n e te n t h u m il i ty , and w eighed, .

W ater was em ployed a s th e b a th l i q u i d in th e th e rm o sta t#

The th e rm o s ta t was m a in ta in ed a t 28.QQ°Q - 0*O1°O* Such a

te m p e ra tu re v a r i a t i o n would cau se a v a r ia t io n in d e n s i ty o f

two u n i t s in th e f i f t h decim al p la c e , w e ll w ith in th e l im i t s

o f p r e c i s io n o f t h i s w ork.

18U sing a © ottsterpois© o f th e same e x te r n a l volume a s

th© pycnom eter and a p p ly in g a i r buoyancy c o r r e c t io n s , th e

fo llo w in g formula i s g iv en by H a r tle y and B a r r e t t (20) , f o r

th e c a lc u l a t i o n o f d e n s i t i e s !

dx = *3 - W1 - P<vo - vng> ^#2 - % - P (^o “ ^pg)

where;

= d e n s i ty o f th e l i q u i d r e f e r r e d to w a te r a t 3.98°U .

= d e n s ity o f w a te r a t ex p e rim e n ta l te m p e ra tu re .

Wg = a p p a re n t w eigh t o f pycnom eter f u l l o f l i q u i d , ( c o r r e c te d f o r b ra s s w eigh t buoyancy)

Wg = a p p a re n t w e ig h t o f pycnom eter f u l l o f w a te r , ( c o r r e c te d f o r b r a s s w eigh t buoyancy)

s a p p a re n t w eig h t o f empty pycnom eter.{c o r r e c te d fo r b r a s s w eight buoyancy)

ve = e x te r n a l volume o f th e c o u n te rp o is e , ©o.

▼pg = volume o f g la s s in pyonom eter, o e .

p = av e rag e a i r d e n s i ty , = 0.0012 gm ./ esc.

R e f r a c t iv e in d ic e s were d e te rm in ed in an Abbe

r e f r a c to m e te r , u s in g a sodium vapor lamp a s th e l i g h t

s o u rc e . F re s h ly d i s t i l l e d w a te r was u sed f o r c a l ib r a t i o n

o f th e r e f r a c to m e te r . The p r ism s o f th© r e f ra c to m e te r

were m aintained a t 26 .0°C . * 0 .1 °C . toy c ir c u la t in g

th e r& o s ta te d w a te r th ro u g h th© p rism J a c k e ts .

D e n s i t ie s and r e f r a c t i v e in d ic e s a re g iv en in

f a b le I .

e » e h im s h t a l r e s u l t s

The p o la r iz a t io n s o f each ehlorooarbonate a t

v a r io u s c o n ce n tra tio n s in d i lu te benzene s o lu t io n were

c a lc u la te d from the experim ental measurementa by applying

t h e u su a l extended CX&ualus-Mosotti e q u a t io n s f o r b in a ry

m ixtu res;

P jo - U - 1) O h f t . f Wpfy)( e + - 2 ) d

po = J x 2. z S.1b .f S>

The sym bols are d efin ed a s:

e - ex p er im en ta lly determ ined d ie le c t r ic eo n s tan t

d = ex p er im en ta lly determ ined d e n s i ty , grams p er 0 0 .

* m o le c u la r f re igh t o f th e n o n p o la r c o n s t i t u e n t

K-3 s m o le c u la r f re ig h t o f th e p o l a r c o n s t i t u e n t

* mol f r a c t io n o f the n o n p o la r c o n s t i t u e n t

t 0 = mol f r a c t io n o f the p o la r co n st itu e n t

p12 s Po l a r i z a t io n o f th e m ix tu re , c e . (m olar)

?1 s p o l a r i z a t i o n o f th e p u re n o n p o la r c o n s t i t u e n t , e o . (m olar)

?« = p o l a r i z a t i o n o f th e p o la r c o n s t i tu e n t a t a s o l f r a c t i o n o f f g , 00 . (m olar)

In Table I I a r e p re s e n te d th e n o la r lz a t lo n e o f th e

v a r io u s b in a r i e s a t 26°C. By p l o t t i n g Pg v e rsu s f g f o r

each c h lo ro c a rb o n a te sued e x t r a p o la t in g to f g s th e

19

20

TABLE I I

P o l a r i s a t i o n s o f Benzene-Chlorooarbonate B in a r ies a t 26°C.

Compound t ag m s ./o .c .

e • ! l5 ©*§.

M ethylC h lo ro e a rb o n a te

0 .0 1 8 00 .03090 .0 4 4 70 .0 7 8 1

0 .87810 .88180 .88590 .8950

2 .4112 .5092 .6082 .8 1 6

28 .5629.8131 .0633 .43

1 3 3 .3129 .11 8 5 .61 1 7 .0

S th y l G hloroe& rbonate 0 .0 1 0 3

0 .0 1 5 70 .0 2 7 60 .0650

0.87600 .87730 .88060 .8906

2 .3702 .4212 .5312 .879

2 6 .3 628 .7930 .2934 .63

16 5 .0 1 6 3 .7159 .1 1 4 9 .5

n -P ro p y lC h lo ro ea rb o n a te 0 .0 1 5 0

0 .0 2 2 80 .0 4 0 40 .0 6 4 2

0 .87680 .87860 .88270 .8800

2 .4 1 82 .4 9 62 .6652 .8 8 7

28 .8429 .9632.3135 .53

1 7 6 .51 7 3 .5167 .11 6 5 .1

1 -P ro p y lC h lo ro ea rb o n a te 0 .0 2 7 7

0 .05000 .0 6 9 5

0 .87970 .88460 .8888

2 .5612 .7973 .0 0 2

30 .8634 .0236 .56

179 .11 7 4 .41 6 9 .4

n -B u ty l Chi o ro ca rb o n a te 0 .0 0 9 6

0 .0 3 1 60 .06910 .0715

0 .87660 .88070 .88700 .8900

2 .3 6 42 .5782 .8462 .961

28.0931.3035 .0236 .55

1 7 8 .9174 .1 1 6 8 .41 6 5 .2

n-A sylC h lo ro ea rb o n a te 0 .0 2 0 4

0 .0 2 8 50 .0 3 7 50 .0440

0 .87820 .87980.88210 .8837

2 .4702 .5 4 62 .6 2 32 .683

29.8130.9932 .3633 .06

1 8 1 .91 7 9 .5 174 .11 72 .5

PhenylC h lo ro e a rb o n a te 0 .0 1 8 3

0 .0 4 2 20 .0 6 3 20 .0 6 2 8

0 .88260.89440 .89980 .9044

2 .4092 .5892 .6702 .739

28.8131.6232.7033.70

1 4 5 .6 142 .21 40 .6 139 .0

21

p o l a r i z a t i o n s a t I n f i n i t e d i lu t io n , , w®r© determ ined,

F ig u re 3 shows th e c u rv e s ob ta in ed by p lo t t in g the data o f

T ab le XI In th e manner in d ic a te d above.

The t o t a l p o la r iz a t io n o f a m olecule i s dofined as:

^ PA

w h ere :

P s t o t a l p o la r iz a t io n , oo . (molar)

P0 s o r i e n t a t i o n p o la r iz a t io n , c o . (molar)

= e l e o t r o n ic p o la r iz a t io n , oo . (molar)

^A s a to a io p o la r iz a t io n , c c . (molar)

The e l e o t r o n ic p o la r iz a t io n la id e n t ic a l w ith the

Lorenz and L o re n tz (3 4 , 35) molar r e fr a c t io n :

p = r « I* P . K(n*- +■ 2) 4

w here:

n = r e fr a c t iv e in d ex

K = m olecu lar w eight

d s d e n s ity , grams per c c .

R s molar r e fr a c t io n , c c .

For each ch loroearb on ate , the molar r e fr a c t io n a t 25°G*

h a s been c a lc u la te d from the ex p er im en ta lly determ ined

r e fr a c t iv e in d ex and d e n s ity o f the pure ch loroearb on ate .

k r ig o ro u s treatm ent demands the determ in ation o f

r e f r a c t i v e in d ic e s a t variou s wave le n g th s , and subsequent

e x t r a p o la t io n to i n f i n i t e wave le n g th . However, th e error

I n v o lv e d in u sin g th e r e fr a c t iv e index ob ta ined a t th®

VlCttra 3* M U rtitttM w . Coiwentration for %lm d CkloNMrfMHttM in fMtamna Solation at S3 a.

820

200

O M ethyl C h lo ro ea rb o n a te • E th y l C h lo ro ea rb o n a te o n -P ro p y l C h lo ro ea rb o n a te© 1 -P ro p y l C h lo ro ea rb o n a te ^ n -B u ty l C h lo ro ea rb o n a tea n-Amyl C h lo ro ea rb o n a te ^ P henyl C h lo ro e a rb o n a te

180 F - '

2

160

140 r —

120

0 . 0 60 . 0 40.02 0 . 0 8

w v e le n g th o f th e sodium B l in e I s sm a ll, and as the

e l e c t r o n i c p o l a r i s a t i o n d erived from t h i s I s a sm all p art

o f the t o t a l p o la r iz a t io n , the erx*or hecoates n e g l ig ib le ,

;£he u se o f r e fr a c t iv e in d ic e s ob ta ined a t th e wave le n g th

o f the sodium D l i n e fo r c a lc u la t in g e le c tr o n ic p o la r i­

s a t io n s has become common p r a c t ic e , (48) and hence P*

may be tak en e q u a l v

I f the atom ic p o la r iz a t io n i s n e g le c te d ,

and the d ip o le moment may be c a lc u la te d a s:

As an a lt e r n a t iv e method o f ca lc u la tio n * the atomic

p o la r iz a t io n may be eva lu ated e m p ir ic a lly aa a fr a c t io n o f

the e le c tr o n ic p o la r iz a t io n , D efin in g t h is fr a c t io n as:

the o r i e n t a t i o n p o l a r i z a t i o n t h e n becom es :

? o - P * (1 + o )? s

and th e d ip o le moment c a n t h e n be c a l c u l a t e d from a s

b e f o r e . F o l l o w i n g ' i l izufihima a n d Kudo (>36)* t h e a to m ic

p o l a r i z a t i o n o f e a c h c h l o r o o a r b o n & t e h a s been t a k e n as

10$ o f i t s e l e c t r o n i c p o l a r i z a t i o n . Atomic p o l a r i s a t i o n s

(48)

where

£ - Maxwell-Boltzmann co n sta n t, 1*3? x 10“ *̂®

a = 8.06 x 1023

T s ab aolu t* te a p e r a ta r ,, °K

24

in th e n e ig hborhood o f 3 c c . are ob ta in ed in t h is m y .

Such v a lu es are w ith in the reasonable range o f atom ic

p o l a r i z a t i o n a s summarized by Smyth (4 9 ) . Th®

o r i e n t a t i o n p o la r iz a t io n fo r t h i s r e fin e d method o f

c a l c u l a t i o n i s :

?o = P - 1 .1 i>0

The d ip o le moment may be c a lc u la te d from f 0 a s b e fo re .

b e in g th e above eq u a tio n s , molar re fra c tio n ® ,

o r i e n t a t i o n p o l a r i z a t i o n s , and d ip o le moments have been

c a lc u la te d fo r each ch ioroearb on ate . The molar r e fr a c t io n ,

Bp, f o r th e sodium P - l in e has been c a lc u la te d from the

d e n s i ty and r e fr a c t iv e in dex data g iv en in Table 1

(Page 1 1 ) . T o ta l p o la r iz a t io n h as been taken as id e n t ic a l

w ith th e *©o v a lu e s ob ta in ed from the data in Table I and

F ig u re 3 . One group o f d ip o le moments, d esig n a ted as

i n T ab le I I I , h a s been c a lc u la te d on the assum ption

t h a t th e a to m ic p o l a r i z a t i o n can be n e g le c te d . A second

g ro u p , d e s ig n a te d a s /* ^ ^h) has been

c a lc u la te d on th e assum ption th a t the atom ic p o la r iz a t io n

i s 10/£ o f th e e l e c t r o n i c p o la r iz a t io n .

2 a

’TABLE I I I

D ip o le Moments o f th e C h lo ro ea rb o n a teg a t 26°C.

Compound Pe . e . %e . e . O i l / l i a . B )

Debyes

M ethylC h lo ro e a rb o n a te 139*0 1 8 .2 2 .4 4 2 .4 2

E th y lC h lo ro e a rb o n a te 168 .0 22 .9 2 .6 8 2 .6 6

n -P ro p y lC h lo ro e a rb o n a te 1 7 0 .0 2 7 .5 2 .71 2 .6 8

i -P ro p y lC h lo ro e a rb o n a te 187 .1 2 8 .4 2 .8 0 2 .77

n -B u ty lC h lo ro e a rb o n a te 182.1 3 2 .3 2 .7 2 2 .89

n-AmylC h lo ro e a rb o n a te 1 9 0 .5 3 6 .8 2 .7 6 2 .7 2

PhenylC h io ro ea rb o n a te 1 4 9 .5 3 7 .7 2 .3 4 2.31

DISCtfSSXOST OF KSBOLTS

An in s p e c t io n o f the r e s u l t s given In Table I I I

shows th a t the d if fe r e n c e between f J and f* q

in each case i s sm a ll• Th© maximum d i f f e r e n c e , 0 .0 4

Debye u n it s fo r the n-amyl compound, i s a 1 .5 $

d e v ia t io n . Smyth (49) h a s reported th e a tom ic p o l a r i ­

za tio n fo r most compounds to be between 0 and 5 c o . ,

depending on th e m o le c u la r c o m p le x i ty . Smyth* s data

show th e atom ic p o la r is a t io n s o f e s t e r s , a c id s , and

a c y l h a lid e s to ran g e between 2 and 5, go. An atomic

p o la r iz a t io n o f about 3 c o . f o r the c h lo ro e a rb o n a te s

seems more probable than one o f 0 c c . On t h is b a s is

(1 IE) Ta^u es bava been taken a s th© more n ea rly

c o r r e c t d ip o le moments in s o l u t i o n .

P rev iou s s tu d ie s o f the trend o f d ip o le moments in

an a l ip h a t ic homologous s e r ie s (63 , 41 , 48) have shown

th a t the h ig h er s tr a ig h t chain members o f the s e r ie s

e x h ib it a r e la t iv e ly co n sta n t d ip o le moment. Con­

s id e r a tio n o f e t h y l , nnpropyl, a -b u ty l , and n—amyl

ch lorocarb on ates shows th e ir r e sp e c t iv e moment® to

approach a l im it in g v a lu e . In Figure 4 , moments o f the

normal a l ip h a t ic chloroearbonate® are p lo t te d a g a in st the

number o f carbon atoms in the a l ip h a t ic chain* The

n-amyl compound should have a moment o f 2 .69 or 2 .70 I f

the ch loroearb on ates behave according to accep ted th e o r ie s .

26

2?

Figure 4* D ipole Moments vs* Number of Carbon Atoms in the Normal A lip h a tic Chain*

2 .7

2.6

R

m

The h ig h v a lu e s o f 2 .7 2 may c o n c e iv a b ly he due to in a d e q u a te

p u r i f i c a t i o n o f th e n-am yl compound. M easurem ents on

n -h e x y l c h lo ro e a rb o n a te would e s t a b l i s h t h i s p o in t . With­

o u t such d a ta i t can o n ly be s a id t h a t th e d ip o le moment o f

n-am yl c h lo ro e a rb o n a te a s d e te rm in ed in t h i s work seems

h ig h . The l i m i t i n g d ip o le moment v a lu e o f th e s t r a i g h t

c h a in a l i p h a t i c c h io ro c a rb o n a te s i s 2 .6 9 D, i f th e n-am yl

compound i s n o t ta k e n in to c o n s id e r a t io n .

^ o r i - p r o p y l c h lo ro e a rb o n a te th e h ig h v a lu e o f 2 .7 7 0

was fo u n d , a b o u t 4# h ig h e r th a n th e 2 .6 8 0 v a lu e found f o r

n -p ro p y l c h lo ro e a rb o n a te . T h is e f f e c t h as been o b se rv ed

by many o th e r w o rk e rs ; th e moments o f i - p r o p y l c h lo r id e

(4 8 ) , i - p r o p y l c h l o r o s u l f i t e ( 6 3 ) , and i - p ro p y l a lc o h o l

(48) a r e , r e s p e c t iv e ly , 7 0 , 50, and 30 h ig h e r th a n th e

moments o f th e c o rre sp o n d in g n -p ro p y l compounds. Most

a u th o rs (4 8 , 41) a t t r i b u t e th e in c re a s e in moment to th e

in d u c t iv e e f f e c t o f th e b ran ch ed c h a in . A ttem p ts to

q u a n t i t a t i v e l y i n t e r p r e t such e f f e c t s have met w ith l i t t l e

su c c e s s due to th© la c k o f a c c u ra te m o le c u la r m odels and

ad e q u a te th e o r i e s o f in d u c t iv e p o l a r i s a t i o n f o r com plex

m o le c u le s .

Phenyl c h lo ro e a rb o n a te shows a d ip o le moment low er

th a n th e moments o f th e a l i p h a t i c o h lo r© c arb o n a te s .

T h is lo w e rin g o f moment, c h a r a c t e r i s t i c o f th e a ro m a tic

com pounds, i s g e n e r a l ly re g a rd e d a s due to th e phenomenon

o f mesomerism (3 3 ) . The u n s a tu ra te d a r y l group ca u ses an

e le c t r o m e t r ic s h i f t in th e e l e c t r o n s o f th e G0GQC1 p o r t io n

29

o f th© mol soul© * Till© s h i f t g e n e r a lly tends to decrease

th e normal bond moment as found in a l ip h a t ic compounds.

The n e s o n e r io moment fo r th© 0 - OOOCl bond as determ ined

from th e r e s u l t s rep orted in t h i s work i s :

2 .61 • S .69 - -G .S8

The s im p le st compound in t h i s stu d y , methyl ch loro­

earb on ate , i s capable o f a more d e ta ile d treatm en t, Some

c lu e a s to the m olecu lar stru c tu re o f th© ebXorooartoonates

may be gained by an a n a ly s is o f the s tru c tu re o f methyl

ch loroearb on ate . I t must be p o in ted out her© th a t th©

modern trend o f m olecu lar s tru ctu re a n a ly s is has been away

from th e assignm ent o f r ig id geo m etr ica l s tr u c tu r e s to

m o lecu le s . The more complex p h y s ica l p ic tu r e o f reso n a tin g

m olecu les as proposed by P au ling (42) now seems to b est

ex p la in experim ental r e s u l t s . The c a lc u la t io n , th e r e fo r e ,

o f d ip o le moments from r ig id geom etrica l s tr u c tu r e s i s

not e n t ir e ly a cc u r a te . I t i s p o s s ib le , however, to some­

tim e s e lim in a te c e r ta in co n fig u r a tio n s as In c o n s is te n t

w ith the d ip o le moment measurements.

U sing th e co n sta n ts o f Groves and Sugden (19) and

Thomsen (6 1 ) , a v ec to r a n a ly s is o f two n ossib l© extreme

s tr u c tu r e s o f methyl ch loroearbonate has been made. Thes©

authors have developed a method o f c a lc u la t in g the moments

in d u c e d in o th er p a rts o f the m olecule by each primary

bond. However, in t h i s work on ly the primary moments given

by Thomsen have been co n sid ered . Ho induced moments have

been used* The o b je c t o f th e s e c a lc u l a t i o n s f o r m ethyl

ofaloroe&rbon&te was to d e te rm in e w hich o f two p o s s ib le

c o n f ig u r a t io n s : t h a t su g g e s ted by H Izushim s and Ktibo (36)

and t h a t p o s tu la te d p re v io u s ly In th e s e l a b o r a to r i e s (7 1 ),

was m ost l o g i c a l ,

The two o o n f ig u ra t lo n s c o n s id e re d w e re :

cm* 0/ 3 / \

0 0H<* C « 0\ 3 /

0 m 0 01/

Cl

(A) (B)

Bond an g les and bond moments tak en from Thomsen1s

work ( 61) a re g iven below :

Cl - C = 0 a n g le 126°

0 - C * 0 an g le 125°

C - 0 - CHj an g le 111°

0 - bond moment 3.28D

C - Cl bond moment 1.87D

0 - 0 bond moment 1,90©

GHg - 0 bond moment 2 .300

The c o rre sp o n d in g v e c to r d iag ram s a r e :

31

C a lcu la tio n o f the r e s u lta n t moment o f co n fig u ra tio n

g iv e s a value o f 2 .2 8 I). and, o f co n fig u r a tio n WB%

a value o f 2 .4 0 D. The exp erim en ta lly determ ined value

i a benzene s o lu t io n la 2*42 B. Follow ing Thomsen (6 1 ) ,

th e g a s phase moment I s taken ass

/> s £& ig = 2 .6 9 D.0 .9

This gas phase moment I© the true moment o f methyl ch io ro -

oarbonate. Both co n fig u r a tio n "A# and co n fig u ra tio n

have moments In the range o f th© experim ental v a lu e .

K either o f th© two m olecu lar forms can be e lim in a ted as

Improbable on the b a s is o f d ip o le moment measurements.

A p la u s ib le exp lan ation o f the f a c t s i s th a t a s ta te o f

reso n a tin g eq u ilib r iu m e x i s t s between the two forms such

th a t the r e s u lta n t d ip o le moment o f the eq u ilib rium

m ixture i s h ig h er than the moment o f e i th e r component.

A number o f authors have proposed reso n a tin g forms

fo r the low er a lk y l ch loroearb on ates and s im ila r compounds

(36 , 1 ) . The experim ental work o f Choppin, F red ian l and

Kirby (4) on the decom position o f e th y l ©hlorocarbonate

i s b e s t ex p la in ed on the b a s is that a co n fig u ra tio n s im ila r

to i s the l e a s t s ta b le but predominant form. In

q u a li ta t iv e agreement w ith th ese fact® the r e s u l t s o f

t h i s in v e s t ig a t io n show a h igher moment and hene© l e s s

s t a b i l i t y fo r the analogous stru ctu re o f the methyl

compound. The predominance o f the more p o la r co n fig u ra tio n

e e e l4 m% be e x p e c te d l a view n t fhoeeca*® (01) e tw iy

e h le h ehoe#4 th e l # M t t* o la r » fs£ ip it^ t& 0 ® o f imWftflL

w rb o n e t# to lie more e&zi*l»t«&t m tth e x p e rim e n ta l f a c t*

th a n tts® p o l a r m aflgtM M ktioiu ttie Mtfeqrl 4*&rte»ate

ao leeu le i « aymMfrtriaai while the ehXerMerhoeete

molecule t» not* fta » aagr he the haftl* « « « o f the

difference beteeen the tee eewswasa&e*

SUMMART

1* A heterodyne beat apparatus* and l i q u i d m easuring c e l l

fo r th e d eterm in ation o f d ie l e c t r ic c o n s ta n t h as been

co n str u c te d .

2 . Use d ip o le moments o f m ethy l, e t h y l , n -p ro p y l, 1 -p ro p y l,

n -b u ty l, n-amyl and phenyl chloroearbonate® have been

determ ined in benzene s o lu t io n a t 25°C. and found to

b e , r e s p e c t iv e ly , S .4 2 , 2 .6 6 , 2 .6 8 , 2 .? ? , 2 .6 9 , 2 .7 2 ,

and 2 .31 Debye u n i t s .

3 . A mesomeric moment o f - 0 .3 8 D. has been c a lc u la te d fo r

phenyl ch lo ro ea rb o n a te .

4 . The most p la u s ib le c o n fig u r a tio n o f the low er a lk y l

ch loroearb on ates corresponds to th a t o f the move p o la r

fo r a . However, a p o s s ib le in te r p r e ta t io n o f th e

experim ental d ata may be found In p o s tu la t in g eq u ilib rium

between two re so n a tin g m olecu lar c o n f ig u r a tio n s .

6 . An exp lan ation i s o f fe r e d fo r the anomaly o f th e r e s u l t s

o f Misushima and Kubo on ©thyl ch loroearb on ate .

33

BXBtZO0£UFH3f! • B e l l , H. P*

He ©onanee i n th # o h lo ro a s e t le a s id e .

K ature 146: 1 66 -? (1940)

2* B e t te h e r , C. J .

A m ethod o f e& lou l& tlng th e d ip o le moment from

d a ta o f th e pur® d ip o le l i q u i d .

P h y s i c s . 6 : 53 -81 (1939)

3t Bryan, A. S .

D ie l e c t r i c e o n a ta n t o f a rg o n and neon*

P h y s. H er. 3 4 : 615-7 (1923)

4 , C hoppin, A* F re & ia n i, H« A ., and K irb y , 0 . P*

She homogeneous d e o o e p o e it io n of e th y l o h lo ro -

e a rb o n a te .

J . Am* C h e*. So©. 6 1 : 3176-80 (1939)

5, C la u s iu s , I* .

•D ie Meeh&itiseh® V arfntheorie"

V ol. I I , V ievag, 1879, p . 62 .

6 , Compere, £*. L.

The th e rm a l d eco m p o sitio n o f Iso p ro p y l e h lo ro —

carb on ate .

L o u is ia n a S ta te U n iv e r s i ty , Master*© t h e s i s , 1940

34

35

7* Coop, I . £ . and S u t to n , L . E .

M easurement ©f th© © lectri© p o la r iz a t io n o f

vapor© o f soma substance© hairing anamalous d ip o le

moments and t h e i r bearing on the theory o f atomic

p o l a r i z a t i o n .

J \ Ckem. Soo* 1938*. 1269*86

8 . C on ley , E . 8 . and P a r t in g to n , J . E.

D ie l e c t r i c p o l a r i z a t i o n . XXII. S e r ie s e f f e c t on

th e d ip o le moments o f some a lk y l h a lid e s in

s o lu t io n .

J . Gheifi. 3 o c . 1938; 9??-8 3

t . Debye, P .

Some r e s u l t s o f a k in e t ic theory o f in s u la to r s .

P h y s ik . 2 . 1 3 ; 9?*100 (1912)

0 . A. 6s 1087 (1912)

10* Debye, P .

theory o f s p e c i f i c h e a ts .

Ann. P h y s ik . 3 9 2 789*859

1 1 . D rude, P .

Two m ethods f o r measurement o f the d ie le c t r ic

c o n s ta n ts and e l e c t r i c a l absorption a t h igh

f r e q u e n c ie s .

2 . p h y s ik . Ghem. 23: 26? (189?)

56

12* E r r e r a , J .

In f lu e n c e o f m o le c u la r s t r u c tu r e on th© d ip o la r

c h a r a c te r o f e th y le n io isom ers# C a lc u la tio n o f

th e m o le c u la r moment.

J . Phys# Badium 6 : 590-6 (1925)

13# E rrera , J*

fh e e l e c t r i c a l p o l a r i z a t i o n o f some carbon com­

pounds: g e o m e tr ic a l and p o s i t io n isom erism .

P h y s ik . Z. 27 : 764-9 (1926)

1 4 , Ssterm ann, J .

D e te rm in a tio n o f e l e c t r i c a l d ip o le moments o f

organ ic m o lecu les by th e m o le cu la r beam method.

Z. p h y s ik Chem. B 1 : 161-9 (1928)

1 5 , Eucken, A# and M eyer, L.

The a d d i t iv e n a tu re o f m o lecu la r d ip o le moments.

P h y s ik Z. 30: 397-402 (1929)

16# Prank, F. C.

B ip o le In d u c tio n and th e so lv e n t e f f e c t in d ip o le

moment m easurem ents.

Proc# Hoy# d o e• 152 A: 171-96 (1935)

17# O oss, R. J #

V ecto r a n a ly s i s o f d ip o le moments.

J . Chem. Soc. 1934: 1467

3?

1 8 . Goss* P . H.

m agnitude o f th e s o lv e n t e f f e c t in d ip o le

moment m easu rem en ts. XX. R e so lu tio n o f th e

s o lv e n t e f f e c t in to i t s c o n t r ib u to ry f a c t o r s .

J . Chem. So©. 1940: ?52

1 9 . Groves* L . G. and Sugden, 8 .

The d ip o le moment o f v a p o rs . P a r t VI: Bond

moments and m eso serlo moments.

«T. Chem. Soe. 193?: 1992-2000

3 0 . H a r t le y , H. and B a r r e t t , W. H.

The d e te rm in a t io n o f th e d e n s i ty o f l i q u i d s .

J . Chem. Soo. 99 : l0 ? 2 -4 (1911)

3 1 . H a r tsh o rn , L . and O liv e r* B. A.

On th e m easurem ent o f th e d i e l e c t r i c c o n s ta n ts ©f

l i q u i d s , w ith a d e te rm in a tio n o f th e d i e l e c t r i c

c o n s ta n t o f benzene .

P ro c . Hoy. Soc • A 123: 664-85 (1929)

2 2 . H erveg , J •

E l e c t r i c d o u b le ts i n l i q u i d d i e l e c t r i c s .

Z. P h y s ik . 3 : 36-4? (1920)

3 3 . H ig a s h i, &.

D ipo le moment and s o lv e n t . IX. IS le o tr lc moments

o f some am in es.

S c i . P ap . I n s t . P h y s . Chem. R esearch 31: 311-16

(1936)

38

2 4 . Hobbs* M. S .

Note on th e s o lv e n t e f f e c t in dlpole-m om ent

m easurem ents.

J . Ohem. P h y s . ? : 849-80 (1939)

S 3 . H oeoker, P. K.

D ie l e c t r i c c o n s ta n ts o f ex tre m e ly d ilu te s o lu t io n s .

J . Chem. P h y s. 4 : 431-4 (1938)

2 8 . In g o ld , 0 . K.

A p h y s ic a l t e s t fo r mesomerie a d d it io n .

Ann. R eps. 1926 : 129

2 7 . J e n k in s , H. o .

M o lecu la r p o l a r i s a t i o n s o f n itrobenzene in various

s o lv e n ts a t 2 5 ° .

N atu re 133: 106 (1934)

2 8 . K & llaan , H. and R eich e , F.

P assag e o f e l e c t r o n s and m olecu les through an

unhomogeneous f i e l d o f fo r c e .

Z. P h y s ik . 6 : 352 (1921)

29 . K irb y , 6 . F.

She k i n e t i c s o f th e decom position o f e th y l o liloro-

c a rb o n a te .

L o u is ia n a S ta te U n iv e r s i ty , Ph. D. D is s e r ta t io n , 1940

30 . K irkw ood, J .

The d i e l e c t r i c p o l a r i z a t i o n o f p o la r l iq u id s .

J . Chem. P h y s. 7 : 911-8 (1939)

39

31* L ange, L .

She p s l a t i o n betw een the d ie l e c t r ic p ro p er tie s

and th e m o le c u la r a s s o c ia t io n s o f sev era l l iq u id s .

2. P h y s ik . 33: 189-82 (1925)

3 2 . L eF ev re , C. 3 . and L eF evre , H. J .

R e la tio n , betw een m olecu lar o r ie n ta t io n p o la r is a t io n

o f su b s ta n c e s in l iq u id , d is so lv e d and gaseous

s t a t e s .

J . Chem. Boo. 1955: 1747-51

3 5 . L eF ev re , R. J . W.

D ip o le moments.

London. M enthuen*s M onographs, 1938; p . 66 .

34 . L o re n tz , O.

Ann. P h y s ik . 9 : 841 (1880)

3 5 . L o re n s , P .

Ann. P h y s ik . 11 : 70 (1880)

3 6 . M lzushim a, S. and Kubo, M.

Quantum m ech an ica l resonance and in te r n a l r o ta t io n .

B u ll . Chem. Soc. Japan 13 : 174-81 (1958)

3 7 . M orton, A. A.

"L ab o ra to ry Technique in o rg an ic Chemistry.*1

New Y ork, Modr&w-HIll Book Company, I n c . , 1938; Chap. IV

3 8 . M o so tti, 0 . F.

"Mem. d i Matheme d i f i s i c a in Modena" 24: I I , 49 (1850)

40

3 § . M u lle r , F . H.

In f lu e n c e o f th e s o lv e n t on d ip o le moments.

T ran s . F a r . Soo. 30: 729-34 (1934)

4 0 . Ons&ger? L.

E l e c t r i c moments o f m o lecu les in l i q u i d s .

J . Am. Chem. Soo. 58: 1486-93 (1936)

4 1 . F a r t s , A.

The d ip o le moments o f p r im a ry , se co n d a ry , and

t e r t i a r y a l i p h a t i c h a lo g en d e r i v a t i v e s .

2 . p h y s ik . Chem. B 12 : 312-22 (1931)

4 2 . P a u l in g , L .

^Ehe Mature o f th e Chemical Bond. «

I th a c a , B. Y ., C o rn e ll U n iv e r s i ty P r e s s , 1939;

p p . 1 4 5 -4 9 .

4 3 . R ad fo rd , L . C. and Inm an, £ . 0 .

B en za lo sax o lo n e fo rm a tio n in th© a tte m p t to p re p a re

c e r t a i n mixed d ia o y l d e r iv a t iv e s o f o -am in o p h en o l,

J . A s. Chem. Soo. 56 : 1586-90 (1934)

4 4 . Hemiok, A. E.

fhe e s t im a t io n o f d ip o le moments.

1 . Chem. P h y s . 9 : 653-9 (1941)

4 5 . S anger and S te ig e r

H e lv e tic a P h y s. A cta 1 : 369 (1928)

4 6 . Sm alivood, H. M. and H e r? fe ld , K, F.

Pipol© moments o f th e d ie u b s t l t u t e d bensene®.

J . A®. Chem. Soo. 52: 1919 (1930)

41

4 7 . S m ith , 0 . M.

The near u l t r a v io le t ab sorp tion sp ectra o f some

eh lorocarb on ates *

L o u is ia n a S ta te U n iv ersity * M aster*s T h esis , 1940

4 8 . Smyth, 0 . P .

11 D ie l e c t r i c C onstant and M olecular S tr u c tu r e .11

Hew York, H. Th® Chemical C atalog Company, 1931

4 9 . Smyth, C. P .

The problem o f atom ic p o la r is a t io n .

- J . C hea. P h y s . I : 247-50 (1933)

50 . Steyth, C. P . and MoAlpine, £ . B.

In du ction between bond moments in some h&iogenated

m ethanes.

J . Chen. P h y s. 1 : 190-196 (1933)

51 . Smyth, 0 . P . and MeAlpine, K. B.

D ipole moments o f the m ethyl and e th y l h a lid e s .

J . Chem. P h y s. 2: 499-502 (1934)

5 2 . Smyth, C. P . and MoAlpine, K. B.

D ipole moment o f phosgene, hydrogen cyan ide,

and c e r ta in s u b s t itu te d m ethanes.

J . Am. Che®. Soc. 56s 1697-1700 (1934)

53 . Sayth , C. P . and Morgan, 3 . 0 .

D ie le c t r ic p o la r iz a t io n o f l iq u id s . I I . Temperature

dependence o f the p o la r iz a t io n in c e r ta in l iq u id

m ixtu res.

J . Am. Chem. Soc. 50: 1547-00 (1928)

48

5 4 . Smyth, 0* P . , Morgan, S . 0 . and Boyce, J . 0 .

D ie l e c t r i c p o l a r i z a t i o n o f l i q u i d s , X, D ia lo e tr io

c o n s ta n ts and d e n s i t i e s o f s o lu t io n s o f th e c h io ro ­

be n series i n benzene and hexane*

J . Am* Gbem. Sots. 50: 1 5 3 6 -4 6 (1 9 2 8 )

5 5 . Smyth, C* ? . and W a lls , W. G.

The d ip o le moments and s t r u c t u r e s o f c e r t a in lo n g -

c h a in m o le c u le s .

J . Ghem. P h y s . 1 : 800-204 (1938)

5 5 . S te r n , 0 .

The p o s s i b i l i t y o f an ex p e rim en ta l p ro o f o f s p a c ia l

q u a n t iz a t io n in an e l e c t r i c f i e l d .

P h y s ik . 2 . 23: 476-81 (1922)

5 7 . S te r n , 0 .

The method o f m o le c u la r r a y s .

P h y s lk . 2 . 39 : 751-63 (1926)

5 8 . S tr& n ath an , J . D,

The d i e l e c t r i c c o n s ta n t o f w a te r v ap o r.

P h y s. R ev. 48 : 5 3 8 -4 4 (1935 )

59. S tu a r t , H. A.R e la t io n betw een th e te m p e ra tu re and the d i e l e c t r i c

c o n s ta n ts o f g a s e s and v a p o rs . I . Method and

r e s u l t s in GCg and a i r .

F h y s ik . Z. 47: 457-78 (1928)

6 0 . Sugden , S .

The d e te rm in a tio n o f d ip o le moments in s o lu t io n .

M ature 133: 416-16 (1934)

45

61 • Thomson, 6 .

D ip o le moments and m o le c u la r s t r u c tu r e o f m ethyl

and e th y l c a rb o n a te s .

J . G hea. S oc. 1957: 11X8-1125

6 2 . Thomson, J . 5 .

S tu d ie s In th e e l e c t r o n th e o ry o f c h e m is try . The

changes in ch em ica l p r o p e r t i e s p roduced by th e

s u b s t i t u t i o n o f one e lem en t o r r a d ic a l by a n o th e r ,

w ith a p p l i c a t io n s to ben-sane s u b s t i t u t i o n s .

P h i l . Mag. 46 : 497*514 (1923)

6 3 . T ru n e l, P .

E l e c t r i c moments o f i s o b u ty l , is o p ro p y l and pheny l

c h l o r o s u l f i t e s .

Corsrt. r e n d . 200: 2186-7 (1955)

64 . U h lig , H. H ., K irkwood, J . 0 . , and K eyes, P . 0 .

Dependence c f d i e l e c t r i c co n sta n ts o f g ase s on

te m p e ra tu re and d e n s i ty .

J . flhem. P h y s . 1 : 155-9 (1955)

65 . Walden, P . , I f l ic h , H .t and W erner, 0 .

The d i e l e c t r i c c o n s ta n ts o f e l e c t r o l y t e s o lu t io n s .

I . D e s c r ip t io n o f a p p a ra tu s f o r d e te rm in in g th e

d i e l e c t r i c c o n s ta n t o f co n d u c tin g g a s e s .

Z. p h y s lk . Che®. 115: 177-202 (1925)

44

66* W&lden, F • , U lio h , H ., and W erner, 0*

©a© d i e l e c t r i c c o n s ta n ts o f so lu tio n ® o f

e l e c t r o l y t e s . IX . G enera l su rv ey o f th e in f lu e n c e

o f d is s o lv e d s o lv e n ts on th e d i e l e c t r i c c o n s ta n t

o f v a r io u s s o lv e n ts .

2 . p h y s lk . Che®. 116 : 261-90 (192©)

6 7 . W elg le , j .

f t e o r i e n t a t i o n o f n o n p o la r m o lecu le s by d ip o le s*

H e lv e tic a Phys* A c ta . 6s 68-81 (1933)

68 . W illia m s , 1 . W.

D ip o le moments o f m o le c u la r g ro u p s .

P h y s ik . 2 . 30: 391-7 (1929)

6 9 . W illia m s, J . W.

Th© d l e l e o t r i c c o n s ta n ts o f b in a ry m ix tu re s*

X* The e l e c t r i c moments o f s im p le d e v ia t iv e s o f

eyo lohexane and o f d io x a n .

J . Am. Chem. Soc. 52: 1831-7 (1930)

70* W illia m s , J . W. and Ogg, E. F.

The d i e l e c t r i c c o n s ta n ts o f b in a ry m ix tu re s . V* The

e l e c t r i c moments o f c e r t a i n o rg a n ic m o lecu les in

ca rb o n d i s u l f i d e and hexane s o lu t io n .

J . Am* Chem. Soc* 5 0 1 94—101 (1928)

7 1 . Wood, R . E .

The d i e l e c t r i c p o l a r i z a t i o n o f e th y l c h lo ro -

ca rb o n a te*

L o u is ia n a S ta te U n iv e r s i ty , M aster*s T h es is , 1939

45

72; Wre&e, P.Deflection of molecular rays o f e l e c t r i c d ip o le

molecules i n the inhom ogeneous e l e c t r i c f i e l d .

Z. Physik. 44: 861-8 (1927)73. Zahn, G. 7.

the electric moment o f gaseous m o le cu le s o f

halogen hydrides.Phys. Hey. 84: 400-17 (1924)

V IT A

R o b e rt l&aerson Wood was bo rn in P ro v id e n c e ,

Rhode I s la n d on O c to b e r 2, 1916. H is e lem e n ta ry

e d u c a tio n was re c e iv e d a t th e P ro v id en ce T ech n ica l High

S ch o o l. A f te r fo u r y e a rs o f a t te n d a n c e a t Rhode I s la n d

S ta te C o lle g e , he g ra d u a te d in 196? w ith a B. S . d eg ree

i n ch em ica l e n g in e e r in g .

In S eptem ber, 1937, he e n te r e d th e L o u is ia n a S ta te

U n iv e r s i ty C h em istry D epartm ent a s a te a c h in g f e l lo w . He

re c e iv e d a M aster o f S c ien ce d eg ree in 1939.

D uring th e academ ic year o f 1941-42 , he was th e

r e c i p i e n t o f th e C h a rle s Edward C oates M emorial H esearch

fe llo w s h ip in c h e m is try . The fo re g o in g s tu d y which I s

su b m itte d in p a r t i a l f u l f i l lm e n t f o r th e d eg ree o f D octor

o f P h ilo so p h y c o n s t i t u t e s a summary o f h i s work d u rin g

t h i s p e r io d .

4 6

EXAMINATION AND THESIS REPORT

Candidate: Bsfcert E* WoodMajor Field: Physleal ChemistryTitle of Thesis: The Dipole Moments of Some Chlorooarbonateiin Solution.

Approved:

Major Professor land Chairman

Dean of the Graduate Sfftnrol

EXAMINING COMMITTEE:

Date of Examination:' /

ffr»y 1 f—19dE