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The dielectric constant and molar polarization of cis- and trans-decahydronaphthalene Barrow, Gordon Milne 1947

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THE DIELECTRIC CONSTANT AND MOLAR POLARIZATION OF CIS- AND TRANS-DECAHYDRONAPHTHALENE by Gordon M. Barrow, B.A.Sc. A Thesis submitted i n P a r t i a l F u l f i l m e n t of The Requirements f o r the Degree of MASTER OF APPLIED SCIENCE i n the Department of CHEMICAL ENGINEERING The U n i v e r s i t y of B r i t i s h Columbia A p r i l 19^7 Acknowledgements I t i s a pleasure to acknowledge the many h e l p f u l suggestions of Dr. W. F. Seyer, under whose d i r e c t i o n the work was c a r r i e d out. I am a l s o very g r a t e f u l to Mr. B.A. D u n e l l f o r a l l the p r e l i m i n a r y work done on the subject and f o r the suggestions and i n f o r m a t i o n which he gave me when the work was undertaken. ( i i ) CONTENTS OBJECT OF RESEARCH THEORY Ordinary d i e l e c t r i c theory Theory f o r behavior at the f r e e z i n g p o i n t METHOD AND APPARATUS Out l i n e of method The e l e c t r i c a l c i r c u i t The t e s t c e l l Heating and Cooling apparatus MATERIALS PROCEDURE AND RESULTS C a l i b r a t i o n R e s u l t s f o r c i s - and t r a n s - d e c a l i n at normal temperatures R e s u l t s f o r c i s - and t r a n s - d e c a l i n at t h e i r f r e e z i n g p o i n t s TREATMENT OF RESULTS ACCURACY OF RESULTS CONCLUSIONS ( i l l ) ILLUSTRATIONS Fo l l o w i n g page F i g . 1. C i r c u i t diagram 7 2. Test C e l l 9 3 . Test C e l l assembly 10 h. The d i e l e c t r i c of g l y c e r o l near i t s f r e e z i n g p o i n t 5 5. D i a l reading v a r i a t i o n w i t h temperature f o r c i s - and t r a n s - d e c a l i n and benzene Ih 6. D i a l reading v a r i a t i o n at l°intervals f o r c i s - d e c a l i n 15 7. D i e l e c t r i c of t r a n s - d e c a l i n at low tempera-tur e s (no supercooling) 19 8. D i e l e c t r i c of t r a n s - d e c a l i n at low tempera-tures ( w i t h supercooling) 19 9. D i e l e c t r i c of c i s - d e c a l i n at low temperatures 19 10. D i e l e c t r i c of cyclohexane at low temperatures 20 11. Molar p o l a r i z a t i o n s as a f u n c t i o n of f o r c i s and trans d e c a l i n and benzene 20 12. I d e a l i z e d curves f o r c i s - and t r a n s - d e c a l i n near t h e i r f r e e z i n g p o i n t s 2h 13. D i e l e c t r i c of c i s - and t r a n s - d e c a l i n over complete temperature range 26 ( i v ) 1 THE DIELECTRIC CONSTANT AND MOLAR POLARIZATION OF CIS- AND TRANS-DECAHYDRONOPHTHALENE I . OBJECT OF RESEARCH The purpose of t h i s work i s the determination of the d i e l e c t r i c constant of c i s - and trans-decahydronaph-thalene ( d e c a l i n ) at va r i o u s temperatures; and, i n p a r t i c u l a r , the v a r i f i c a t i o n of the apparently anomalous behavior of the cis-isomer at about 50°C. Such a be-hav i o r has been i n d i c a t e d i n the measurement, i n t h i s 1 2 3 l a b o r a t o r y , of the s p e c i f i c heat, ' , J the surface If 5 • t e n s i o n , the vapour pressure, and the d i e l e c t r i c con-6 7 s t a n t . P r e l i m i n a r y measurements were made by D u n e l l i n 19^5-^6, but i n order to provide more c o n c l u s i v e r e s u l t s t h i s f u r t h e r work i s undertaken. (1) McLellan - Master's Th e s i s , 19^3 (2) Graham' - Master's T h e s i s , 19M+ (3) Miss Robinson - Master's T h e s i s , 19I+5 (*0 Davenport - Master's Th e s i s , 1938 (5) Mann - Master's T h e s i s , 19M+ (6) D u n e l l - Master's Th e s i s , 19^ -6 (7) I b i d 2. j I n a d d i t i o n , i t i s d e s i r e d to determine the d i e -l e c t r i c constant f o r the l i q u i d - s o l i d t r a n s i t i o n and f o r the s o l i d r e g i o n f o r the two isomers. I I . THEORY A. Ordinary D i e l e c t r i c Theory I n the treatment of r e s u l t s , use w i l l be made of the Debye and C l a u s i u s - M o s o t t i equation from simple d i e l e c t r i c theory. F u l l d e r i v a t i o n s of t h i s equation," as w e l l as treatment of the general theory i n v o l v e d i n the study of d i e l e c t r i c s , can be found I n two e x c e l l e n t 1,2 works. The Debye equation, which i s a general equa-t i o n applying to both p o l a r and non-polar compounds i n .the gaseous s t a t e and applying, approximately t o l i q u i d s i s : -where P = ~jo = " f c n e m°3- a r p o l a r i z a t i o n £ - the d i e l e c t r i c constant M = the molecular weight 1° ~ the d e n s i t y N - Avogadro's number (1) Smyth, C P . , D i e l e c t r i c Constant and Molecu- l a r S t r u c t u r e . Chemical Catalog Co., (193D (2) Debye, P., P o l a r Molecules. Chemical Catalog Co., (1929) c< = the d i s t o r t i o n p o l a r i z a t i o n or p o l a r i z a b i l i t y " the permanent d i p o l e moment k = Boltzmann's constant T = the absolute temperature As i s seen from the equation, the p o l a r i z a b i l i t y " oL " and the d i p o l e moment ™yu " can be determined by p l o t t i n g the molar p o l a r i z a t i o n , ^ ^ , against the r e c i -p r o c a l of the absolute temperature. The i n t e r c e p t w i t h the ^ = 0 a x i s i s t h e n ' r f f i ^ f r o m which «X may be found. The slope of the curve, which t h e o r e t i c a l l y w i l l always be e i t h e r zero or p o s i t i v e , w i l l be from which yM can be found. For non-polar compounds, i.e,^/t-0 , t h i s simple theory p r e d i c t s a l i n e w i t h zero slope. S i m p l i f y i n g as-sumptions made i n the d e r i v a t i o n of t h i s equation, however, r e s u l t i n a v a r i a t i o n from t h i s behavior f o r l i q u i d s , l i k e benzene, which are known t o be non-polar. The best r e s u l t s f o r the d e n s i t y and the d i e l e c t r i c on-st a n t of l i q u i d benzene give a l i n e of s l i g h t l y negative slope (see fi g . 1 1 ) . S i m i l a r o r g a n i c , non-polar l i q u i d s would be expected to show approximately the same d e v i a -t i o n from the simple theory. I n view of t h i s v a r i a t i o n from theory it,seems ad v i s a b l e to c a l c u l a t e °( not from the i n t e r c e p t w i t h the - — • = . 0 a x i s but r a t h e r from one of the molar p o l a r i z a -t i o n s c a l c u l a t e d d i r e c t l y from the measured d i e l e c t r i c s . The d i f f e r e n c e between the molar p o l a r i z a t i o n s c a l c u l a t e d from the d i e l e c t r i c s measured at d i f f e r e n t temperatures i s q u i t e s m a l l , only when the r e s u l t s are e x t r a p o l a t e d to i s there any appreciable d i f f e r e n c e . Only very s l i g h t p o l a r i t y i s to be expected i n hydros carbons and t h i s p o l a r i t y i s p o s s i b l e only when the mole-c u l e s e x h i b i t some l a c k of symmetry. We w i l l then expect the symmetrical t r a n s isomer to have no d i p o l e whereas the unsymmetrical c i s isomer may have a small permanent d i p o l e moment• The problem of d i e l e c t r i c s of s o l i d s has only r e c e n t l y been considered and the theory i s t h e r e f o r e l i m i t e d . Some theory has been developed f o r long-chain 1 ketones which, being p o l a r , show a pronounced change of p o l a r i z a t i o n when they become f i x e d i n a c r y s t a l l a t t i c e . Changes i n the d i e l e c t r i c of non-polar compounds are r e -2 l a t i v e l y s m a l l . M u l l e r n o t i c e d t h a t the d i e l e c t r i c of a long-chain hydrocarbon increased at the f r e e z i n g p o i n t by 2 to 6% f o r d i f f e r e n t experiments. H i s work, however, was d i r e c t e d toward the measurement of polar compounds and he considered the changes f o r the hydrocarbon to be n e g l i g i b l e . There i s , t h e r e f o r e , to the best of the author's knowledge, no accurate work on the d i e l e c t r i c constant of non-polar compounds at and below the f r e e z i n g p o i n t . The d i f f i c u l t i e s of measuring the d i e l e c t r i c con-(1) F r f i h l i c h , H., Proc. Roy. S o c . A, 185, 399 (19W (2) M u l l e r , A., Proc. Roy. S o c . A, 15$, *+03 (1937) s t a n t of s o l i d s w i t h the type of c e l l used here are at once apparent* The d i e l e c t r i c change when the m a t e r i a l i n the c e l l c r y s t a l l i z e s w i l l depend somewhat on the r a t e of c r y s t a l l i z a t i o n , the type of c r y s t a l s formed, the v i s c o s -i t y of the m a t e r i a l at the f r e e z i n g p o i n t , and the piace where the c r y s t a l l i z a t i o n s t a r t s . A l l these f a c t o r s w i l l probably e f f e c t the presence of vo i d s between the p l a t e s of the condenser. These v o i d s , having a d i e l e c t r i c of about u n i t y , w i l l lower the measured d i e l e c t r i c an inde-terminate amount. S e v e r a l c e l l s of the type necessary f o r the accurate measurement of d i e l e c t r i c s of s o l i d s are des-- 1 e r i b e d by Morgan and Lowry • As a r e s u l t of these d i f f i c u l t i e s we w i l l not expect to get accurate r e s u l t s f o r the t r a n s i t i o n r e g i o n and f o r the s o l i d phase. We should be a b l e , however, t o get an i n d i c a t i o n of the behavior of the d i e l e c t r i c i n these regions and we should a l s o get a comparison of the behavior of the two isomers. U n f o r t u n a t e l y no data i s a v a i l a b l e on the type of c r y s t a l s formed, the l a t e n t heat of f u s i o n , or the v i s c o s i t y at the f r e e z i n g p o i n t f o r c i s -and t r a n s - d e c a l i n . A l l previous work on these isomers at higher temperatures, however, has i n d i c a t e d a g e n e r a l l y p a r a l l e l behavior and i f t h i s holds t r u e f o r the s o l i d phase the v a r i o u s p h y s i c a l p r o p e r t i e s of the two isomers should be s i m i l a r . (1) Morgan, S.O., and Lowry, H.H., J . Phys. Chem.. 3*+, 2385 (1930) 6 - so a'o /co F i g . h. The d i e l e c t r i c constant of g l y c e r o l near i t s f r e e z i n g p o i n t {IQ.T^O1. The presence of a small d i p o l e i n e i t h e r isomer (presumably the c i s isomer) however, w i l l produce a s l i g h t decrease i n the d i e l e c t r i c as the compound f r e e z e s and the molecules become f i x e d i n the c r y s t a l l a t t i c e . A t y p i c a l curve f o r the d i e l e c t r i c constant near the f r e e z i n g p o i n t f o r a p o l a r compound i s shown i n f i g . T h i s type of be-h a v i o r , but to a much smaller e x t e n t , may be expected f o r the c i s isomer. I I I . METHOD AMD APPARATUS A. Out l i n e of Method D i e l e c t r i c s are measured using~an e l e c t r i c a l c i r -(1) R. Bock Z.S.. f u r Phys . . 3 7 , 3 3 ^ 3 9 1925 7. . 1 c u l t designed by Alexander and constructed by D u n e l l . The method c o n s i s t s of measuring changes i n the d i e l e c t r i c constant of the m a t e r i a l i n the t e s t c e l l by determining the r e s u l t i n g changes i n the c a p a c i t y of the c e l l . The amount of these c a p a c i t y changes i s determined by changing a c a l i b r a t e d v a r i a b l e condenser, i n p a r a l l e l w i t h the t e s t c e l l , so th a t the c i r c u i t i s returned to resonance. The c i r c u i t c o n s i s t s o f'a vacuum tube o s c i l l a t o r w i t h a para-l l e l bank of three v a r i a b l e condensers, the t e s t c e l l , and an inductance on the p l a t e c i r c u i t ; and a c r y s t a l o s c i l -l a t o r i n p a r a l l e l w i t h a r e s i s t a n c e on the g r i d c i r c u i t . A type 6E5 " e l e c t r o n r a y " vacuum tube i s used, p r o v i d i n g both o s c i l l a t i o n s and a means of d e t e c t i n g resonance i n the c i r c u i t . When the p l a t e c i r c u i t i s tuned to o s c i l l a t e to the c h a r a c t e r i s t i c frequency of the c r y s t a l the shadow of the tube "snaps i n " g i v i n g a v i s u a l I n d i c a t i o n of r e s -onance. B. The E l e c t r i c a l C i r c u i t The c i r c u i t i s shown d i a g r a m a t i c a l l y i n f i g . l and 2 i s e s s e n t i a l l y the same as t h a t described by D u n e l l . I t was necessary, however, t o r a i s e the p l a t e v o l t a g e from 90 v o l t s to 160 v o l t s to e l i m i n a t e the troublesome d r i f t pre-v i o u s l y encountered. (1) Alexander, F.C., D i e l e c t r i c Constant Meter, E l e c t r o n i c s . 18, #^ f, p 116 ( A p r i l 1 9 W ( 2 ) D u n e l l , o p . c i t . , pp 7-9. 8.-The p l a t e c i r c u i t , drawing a cu r r e n t of two m i l l i a m -peres, was f e d by four M-5 v o l t , no.386 Everready dry c e l l s . The f i l a m e n t was supplied w i t h 6.3 v o l t s and 0.28 amperes from a lead storage c e l l . The c r y s t a l o s c i l l a t o r was a 3502 k i l o c y c l e , P e t e r -son Co. Type Z-2 quartz c r y s t a l . The condensers C^ and C2 had a c a p a c i t y of 250 and 1 5 f r e s p e c t i v e l y and were used to produce resonance at the d e s i r e d p o s i t i o n on the d i a l of condenser C 3 . When d i e l e c t r i c s beyond the range of the d i a l were to be measured these condensers could be adjusted to re-tune the c i r c u i t so that resonance occurred w i t h i n the range of the d i a l . The inductance c o n s i s t e d of 9 turns of c o t t o n -i n s u l a t e d copper wire wound on a l£ i n c h p l a s t i c form. The condenser C3 had a f u l l c a p a c i t y of 23 . T h i s condenser was a 2 5 0 / condenser from which s e v e r a l p l a t e s had been removed. A d i a l , c a l i b r a t e d from 0 to 100 through 180°, was mounted on the condenser so t h a t the zero of the d i a l corresponded to minimum c a p a c i t y and the 100 of the d i a l corresponded to maximum c a p a c i t y . T h i s condenser 1 had been c a l i b r a t e d by Du n e l l w i t h a Boonton Radio Corpora-t i o n , type 160-A, Q-Meter and the ca p a c i t y had been found t o vary l i n e a r l y w i t h the d i a l reading f o r d i a l readings between 15 and 85. The e n t i r e e l e c t r i c a l c i r c u i t was s h i e l d e d by a (1) D u n e l l , o p . c i t . , p 10. grounded metal box and th e r m a l l y i n s u l a t e d . Temperature c o n t r o l on the c i r c u i t was found to be unnecessary. C. The Test C e l l The t e s t c e l l ( f i g . 2 ) was s i m i l a r to t h a t designed by Smyth"'" but had two important m o d i f i c a t i o n s . I n the f i r s t p l a c e , the arms of the c e l l c ontainer were shortened so t h a t the c e l l could be placed i n a sm a l l c o n t a i n e r beside the c i r c u i t c o n t a i n e r . By t h i s arrangement, o n l y s m a l l a d d i t i o n a l c a p a c i t y was produced i n the l e a d s . I n the second p l a c e , o n l y two c o n c e n t r i c brass c y l i n d e r s were used i n s t e a d of three as i n the o r i g i o n a l . Smyth's c e l l was constructed so t h a t the grounded outer and inner c y l i n d e r s provided s h i e l d i n g f o r the otherwise exposed middle c y l i n d e r . I n the present arrangement, however, the e n t i r e c e l l i s placed i n a grounded metal c o n t a i n e r . The brass c y l i n d e r s , w i t h an annular space of 0.09 cms. were separated and h e l d i n p o s i t i o n by mica b l o c k s . Copper wire l e a d s , soldered t o the c y l i n d e r s , were taken o f f through the arms of the g l a s s c o n t a i n e r , one through a s h i e l d e d g l a s s tube to the e l e c t r i c a l c i r c u i t , the other to ground. The g l a s s container h e l d about kO cc's of the t e s t l i q u i d . T h i s type of c e l l was used, i n s t e a d of the a l l - m e t a l (1) Smyth and Morgan, J.Am.Chem.Soc., 5 0 , l ^ , (1928) 10. one proposed by A l e x a n d e r 1 , to overcome the d i f f i c u l t i e s of evaporation encountered by D u n e l l . The a l l - m e t a l type of c e l l cannot be used w i t h any success when the vapour pressure of the l i q u i d to be t e s t e d i s at a l l a p p r e c i a b l e . The e l e c t r i c a l c a p a c i t y of the t e s t c e l l was l i m i t e d on one hand by the degree of accuracy d e s i r e d and on the other hand by the c h a r a c t e r i s t i c s of the c i r c u i t . To ob-t a i n a h i g h degree of accuracy i t was necessary t o have a h i g h c a p a c i t y t e s t c e l l . T h i s would give l a r g e c a p a c i t y changes f o r small d i e l e c t r i c changes. I f a l a r g e c e l l i s used, however, only a s m a l l inductance I s r e q u i r e d and the r a t i o ^- i . e . , the "q" of the c i r c u i t , becomes s m a l l . This leads to f l u t t e r i n g and unstable o p e r a t i o n . In view of these c o n d i t i o n s the most s a t i s f a c t o r y c a p a c i t y was taken to be 150y^//and the c y l i n d e r s were machined to give approximately t h i s v a l u e . D. Temperature C o n t r o l - Heating and Cooling Apparatus 'The complete t e s t c e l l assembly i s shown i n f i g . 3 « The c e l l was enclosed i n a grounded metal box and was h e l d by two clamps on a f i x e d u p r i g h t support.. The container was covered by a l a y e r of asbestos paper around which was wrapped the heating element. Outside t h i s heater, and separated from i t by another l a y e r of asbestos was a metal j a c k e t covering three s i d e s of the c e l l c o n t a i n e r . A s m a l l variable-speed f a n provided c i r c u l a t i o n of (1) Alexander, l o c , c i t . / V G . 2 TEST CELL F/6. 3 T/T5T CZTIZ. A S5£MBL V 11. the a i r i n the c o n t a i n e r . The heating c o i l c o n s i s t e d of 30 f e e t of Chromel A, no.22 gauge r e s i s t a n c e w i r e . Power was provided by a v a r i a c connected t o the 110 v o l t l i n e . Temperatures were c o n t r o l l e d to w i t h i n about a t e n t h of a degree by manual-l y changing the v a r i a c s e t t i n g . . o Temperatures between room temperature and -4-0 C were obtained by r e c i r c u l a t i n g acetone through the ja c k e t and a copper c o i l immersed i n a dry ice-acetone bath. Temperatures below t h i s and down to -60°C were obtained by adding dry i c e d i r e c t l y t o the c e l l c o n t a i n e r . Above room temperature, the temperature was measured by a mercury thermometer placed i n the a i r bath. The mercury thermometer could not be placed i n the centre of the c e l l because the mercury column would c a r r y induced cu r r e n t s to the unshielded centre p l a t e . For measuring low temperatures a pentane thermome-t e r was used. This was immersed i n a l i q u i d i n the centre c a v i t y of the c e l l (see f i g . 3 ) . G a s o l i n e , being non-polar and having a low f r e e z i n g p o i n t , was used as the l i q u i d . This arrangement gave temperatures which at a l l times were very c l o s e to t h a t of the l i q u i d i n the c e l l i t s e l f . With the mercury thermometer arrangement, however, considerable time was r e q u i r e d f o r the l i q u i d i n the c e l l to come to the temperature i n d i c a t e d by the thermometer. The e n t i r e assembly was ther m a l l y i n s u l a t e d w i t h two 12. inches of rock wool. IV. MATERIALS The benzene used f o r c a l i b r a t i n g the condenser was recry s t a ] I i z e d "Merck thiophene .free benzene". Four c r y s t a l l i z a t i o n s d i d not r a i s e the f r e e z i n g temperature, which remained constant over the e n t i r e f r e e z i n g p e r i o d . The f r e e z i n g temperature as measured by a Leeds and Northrup platinum r e s i s t a n c e thermometer was 5.33°C. The sample was then taken as being pure. The two isomers of d e c a l i n were separated from the mixture i n Eastman Kodak d e c a l i n by d i s t i l l a t i o n a t 9 mm. 1 absolute pressure i n a Stedman Column • The ci s - i s o m e r from the column was about 99*5% pure and was repeatedly c r y s t a l l i z e d i n a dry i c e bath u n t i l the f r e e z i n g temperature remained constant. A f t e r s i x r e -c r y s t a l l i z a t i o n s the f r e e z i n g temperature was constant at -h3,h70C. I n a d d i t i o n t o t h i s samplej other samples of c i s - d e c a l i n which had been d i s t i l l e d and r e c r y s t a l l i z e d over s i x months p r e v i o u s l y were t e s t e d . T h i s ensured t h a t the measured d i e l e c t r i c was r e p r e s e n t a t i v e and was not due to the e f f e c t of the h i g h temperature (about 80°C) t o which the f i r s t sample had r e c e n t l y been subjected t o dur i n g d i s t i l l a t i o n . The t r a n s - d e c a l i n ( f r e e z i n g p o i n t -30.6h°C) used was (1) Angley, P o t k i n s , Rush - Bachelor's T h e s i s , 19^2. 13. 1 t h a t prepared by Dunell . The cyclohexane used i n the l a t t e r work was the very pure commercial product and was not f u r t h e r p u r i f i e d ex-cept f o r d r y i n g . A l l samples were kept over sodium. V. PROCEDURE AND RESULTS, A. C a l i b r a t i o n The d i e l e c t r i c constant corresponding t o the d i a l reading of the v a r i a b l e condenser was determined by ob-se r v i n g the d i a l reading f o r resonance f o r benzene at a f i x e d temperature. The c e l l was f i l l e d w i t h benzene and the condensers C^ and C2 were set so t h a t the d i a l s e t t i n g f o r c i r c u i t resonance was at the lower end of the d i a l f o r benzene at about 50°C. With t h i s s e t t i n g , the d i e l e c t r i c constants of both c i s - and t r a n s - d e c a l i n between 0 and 100°C were i n the d i a l range.' The d i a l readings f o r ben-zene at other temperatures were a l s o observed. From these r e s u l t s and from the known values of the d i e l e c t r i c con-st a n t of benzene a c a l i b r a t i o n curve could be drawn g i v i n g the d i a l readings i n terms of the d i e l e c t r i c con-s t a n t . Since the condenser had been found to vary l i n e a r l y , the curve could be e x t r a p o l a t e d t o d i a l readings between 15 and 8 5 . The d i e l e c t r i c constants of benzene used i n the (1) D u n e l l , op. c i t . , p 2 IK-c a l i b r a t i o n are taken from the r e s u l t s of C l a y , Dekker, and Hemelrijh and are e x t r a p o l a t e d to higher temperatures on the b a s i s of the l i n e a r r e l a t i o n found by previous i n -v e s t i g a t o r s . Whenever i t became necessary to change the s e t t i n g of the condenser C2 i n order to measure d i e l e c t r i c s i n a d i f f e r e n t range, a known d i e l e c t r i c i n the new range had to be measured and the c a l i b r a t i o n curve had to be s h i f t e d a c c o r d i n g l y . I n order to f i n d an unknown d i e l e c t r i c i t was now only necessary to determine the d i a l reading f o r any f i x e d temperature. The d i e l e c t r i c constant could then be read o f f the c a l i b r a t i o n curve. B. R e s u l t s f o r C i s - and T r a n s - d e c a l i n at Normal Temper- at u r e s . The d i e l e c t r i c constants and corresponding d i a l readings f o r a t y p i c a l run f o r c i s - and t r a n s - d e c a l i n and benzene at a number of temperatures above room temperature are shown i n t a b l e s 1 and 2 . The l i n e a r r e l a t i o n of these r e s u l t s i s shown i n fig.Jp* To make c e r t a i n t h a t an anomalous behavior had not been missed between the p o i n t s determined, a d d i t i o n a l readings f o r c i s - d e c a l i n were taken. With the temper-ature slowly r i s i n g , d i a l readings were taken at one degree I n t e r v a l s . Since the thermometer was i n the a i r bath, however, temperatures about two degrees higher than t h a t In the c e l l i t s e l f were i n d i c a t e d . Another set of readings was t h e r e f o r e taken, i n the same way, but w i t h the temperature f a l l i n g i n s t e a d of r i s i n g . The average of two readings at a given thermometer reading would then give the c o r r e c t value a t that temperature. The data for" t h i s set of r e s u l t s i s given i n t a b l e 3 and the r e s u l t s are p l o t t e d i n f i g . 6 . Table 1. R e s u l t s f o r Benzene - C a l i b r a t i o n Data. Time ! D i a l Reading Temperature D i e l e c t r i c at 3:10 ! 14.0 3:15 . 14.9 3:25 15.4 3:40 15.5 4:20 \ 22.1 4:25 23.0 4:30 23. 4 4:35 23. 4 5:10 28.9 5:20 j 29.3 5:30 29.J* 5:40 j 29. 4 6:05 ! 35.3 6:15 i 35.7 6:20 j 35.8 6:30 j 35.8 e q u i l i b r i u m temp_. 52.3 52.4 52.3 52.3 58.3 58.1* 58.5 58. 4 63.9 64.1 64.0 64.0 70.0 70.2 70.1 70.0 2.236 2.226 2.217 2.207 C. R e s u l t s f o r C i s - and Trans-Decalin at and Below Their  F r e e z i n g P o i n t s . I n measuring the d i e l e c t r i c at the l i q u i d - s o l i d t r a n s i t i o n p o i n t s e v e r a l d i f f i c u l t i e s were encountered. These d i f f i c u l t i e s were due t o the f a c t that the c e l l and the c i r c u i t were designed s p e c i f i c a l l y f o r the measurement of l i q u i d d i e l e c t r i c s at and above room temperature. Table 2. R e s u l t s f o r C i s and Trans-Decalln Above Room Temperature Time CIS-DECALIN 1:50 1:55 2:00 2:05 2:30 2:45 2:55 3:00 3:30 3:35 3:45 3:50 4:20 4:30 4:35 4:40 TRANS-DECALIN 2:00 2:30 2:45 2:50 3:20 3:25 3O0 3:35 >:05 4:10 4:15 4:20 5:15 5:20 5:25 5:30 D i a l 29.2 28.9 28.9 28.9 43.2 44.0 44.3 44.3 *?•? 56.4 56.4 56.5 67.7 68.4 69.9 70.0 50.2 49.6 |f9.5 49.5 57.7 58.0 58.1 58.1 69.6 70.1 69.8 70.0 86.2 87.6 88.0 88.1 Temperature 21.3 21.2 21.2 21.2 44 .2 44 . 1 44.0 44.0 62.1 62.2 62.1 62.1 80.0 9.9 1.0 81.0 19.0 18.9 18.8 18.8 31.5 31.6 31.5 31.5 48.8 49.1 49.2 4^.1 76.2 76.2 76.0 76.1 D i e l e c t r i c (from c a l i b r a t i o n curve) 2.217 2.194 2.167 2.155 2.186 2.173 2.155 2.128 17 Table 2 (Continued) Further R e s u l t s f o r C i s - D e c a l i n . Temperature BENZENE 37.3 k6.7 56.0 64-. 7 CIS-DECALIN 25.8 30.9 36.1 4-5.2 51.4-55.0 62.1 68.5 D i a l 19.0 30.0 39.6 hQ.3 50.4-54-.0 57.5 64-.9 68.0 71.5 75.5 79.0 D i a l - 18.0 _ 1.0 12.0 21.6 30.3 32.4-36.0 39.5 »+6.9 50.0 53.5 57.5 61.0 I n the f i r s t p l a c e , the temperature c o n t r o l was r a t h e r rough. The temperature could be c o n t r o l l e d to w i t h i n a few degrees by r e g u l a t i n g the f l o w of the c o o l i n g acetone, but t h i s was not very s a t i s f a c t o r y since the temperature could not e a s i l y be kept constant over a long p e r i o d of time. Most readings i n t h i s temperature range, t h e r e f o r e , were taken w i t h the temperature sl o w l y f a l l i n g or r i s i n g and no attempt was made to reach an exact (1) D i a l s e t t i n g 18.0 d i v i s i o n s higher than f o r r e s u l t s in Tables 1 and 2. ( 18. temperature e q u i l i b r i u m . Table 3. R e s u l t s f o r C i s - d e c a l i n Between 30° and 90 C. Temp. °C D i a l (up) D i a l (down1) D i a l (ave.) Temp. °C D i a l -(up) D i a l (down) D i a l (ave.) 30 39.4- 44.6 4-2.0 61 61.4 67.4 64.4 31 4-0.2 J+5.1 4-2.6 62 62.1 68.1 65.1 32 4-0.9 4-5.9 4-3.4- 63 62.9 68.8 65.8 33 1+1.5 4-6.5 44.0 64- 63.3 69.I 66.2 3* 4-2.1 4-7.1 44.6 . 65 64.2 70.0 67.1 35 4-2.9 4-7.9 4-5.4- 66 65.0 70.2 67.6 36 ft-7 1+8.7 4-6.2 65.8 70.4 68.1 37 44.4- 4-9.4- >+6.9 68 66.2 71.4 68.8 38 4-5.1 50.1 4-7.6 69 67.0 72.0 69.5 39 4-5.9 50.9 4-8.4- 70 67.7 72.7 70.2 4-0 1+6.6 51.6 4-9.1 71 68.1 73.3. 70.7 4-1 4-7.3 ! 52.3 1+9.8 72 68.7 74-.2 71.4 4-2 J+8.1 52.9 50.5 73 69.O 75.6 72.3 ft 4-8.8 53.6 51.2 74- 69.4- 76.2 72.8 M+ 4-9.7 54.3 52.0 75 69.9 77.2 73.5 *5 51.3 5^ .9 53.1 76 70.2 78.2 74-. 2 4-6 52.0 55.6 53.8 70.7 78.9 74.8 4-7 52.3 56.3 5<.3 78 71.1 79.8 75.4 4-8 52.9 56.9 54-.9 ?9 71.4 8O.3 75.8 4-9 53.3 58.1 55.7 80 72.0 81.0 76.5 50 54-.0 59.1 ' 56.5 81 72.4 81.7 77.0 51 54-.7 60.0 57.3 82 73.0 82.3 77.7 52 55-3 60.9 58.0 83 73.8 83.O 78.4 53 56.0 61.5 58.7 84- 75.0 • 83.5 79.2 5h 56.6 62.1 59.3 85 75.9 W.O 80.0 55 57.1 63.O 60.0 86 77.0 84-. 2 80.6 56 57.8 63.8 60.8 8Z 77.9 84-. 9 81.4 57 58.4- 64.4- 61.4- 88 7816 85.6 82.1 58 59.2 65.1 62.2 89 79.4 86.2 82.8 59 59.9 65.9 62.9 90 79.9 86.9 83.4 60 60.8 66.4- 63.6 Since the design of the c e l l made i t r a t h e r d i f f i -c u l t to add a seed c r y s t a l , supercooling was another d i f f i c u l t y . With t r a n s - d e c a l i n the l i q u i d f r o z e immediate—. 19. l y on reaching the f r e e z i n g p o i n t on s e v e r a l runs. When supercooling took p l a c e , however, i t amounted to only three or four degrees w i t h the temperature r a p i d l y r i s i n g to the f r e e z i n g p o i n t once f r e e z i n g s t a r t e d . With c i s -d e c a l i n , on the other hand, much greater s u p e r c o o l i n g , about 11°, was encountered, and i t was always necessary to add a seed c r y s t a l . k t h i r d d i f f i c u l t y was f l u t t e r i n g and u n c e r t a i n t y due to the l a r g e changes i n the d i e l e c t r i c constant at the f r e e z i n g p o i n t . The c i r c u i t was constructed p a r t i c u l a r l y f o r the accurate measurement of small continuous d i e l e c t r i c changes. This r e q u i r e d a l a r g e c a p a c i t y and small -jjf r a t i o j r e s u l t i n g i n considerable i n s t a b i l i t y when abrupt . d i e l e c t r i c changes were encountered. E i g h t runs were made w i t h t r a n s - d e c a l i n , the d i e l e c -t r i c being determined f o r both f a l l i n g and r i s i n g temper-a t u r e . Two t y p i c a l curves showing the r e s u l t s w i t h and without supercooling are given i n f i g s . 7 and 8 . For the e i g h t runs, the maximum p o i n t was between 2.29 and 2 .30, and the s o l i d phase was between 2.25 and 2.27. Both the c o o l i n g and heating curves were e n t i r e l y reproducable to the extent shown i n the f i g u r e s . Considerably more d i f f i c u l t y was encountered w i t h the c i s isomer. Only the general behavior and not the exact curves were reproducable. Two t y p i c a l curves, show-i n g the type of v a r i a t i o n which was encountered, are shown i n f i g . 9 . 20. The v a r i a t i o n of the d i e l e c t r i c f o r the heating and c o o l i n g curves f o r the l i q u i d i s due t o the temperature Hag. I n view of the r e s u l t s f o r d e c a l i n i t was thought ad v i s a b l e to determine the d i e l e c t r i c of cyclohexane f o r a comparison. One run was made w i t h cyclohexane ( f r e e z i n g p o i n t 6°C) over the temperature range 20°C to -15°C. The r e s u l t s are p l o t t e d i n f i g . 1 0 . These r e s u l t s w i l l be discussed l a t e r . V I . TREATMENT OF RESULTS The molar p o l a r i z a t i o n s - 7 ^ 4r f o r c i s - and t r a n s -fix < ' d e c a l i n are c a l c u l a t e d f o r a few temperatures up t o 100°C and are p l o t t e d , along w i t h the r e s u l t s f o r benzene, agai n s t -f? i n f i g . 1 1 . The s m a l l negative slope i s seen t o be about the same as tha t f o r benzene i n d i c a t i n g no appreci-able p o l a r moment i n e i t h e r the c i s or t r a n s isomer. Table 4.  P o l a r i z a t i o n Data f o r Benzene Temperature D e n s i t y 1 D i e l e c t r i c T 15 0.8840 2.2976 26.68 0.00347 20 0.8793 2.2895 26.71 0.00341 30 0.8685" 2.2728 26.79 0.00330 40 0.8579 3 2.2563 26.87 0.00319 60 0.8370 (2.223) 27.03 0.00300 80 0.8163 (2.191) 27.20 0.00283 £1) I n t . C r i t . T a b l e s , V o l I I , 29, McGraw H i l l , (1928) (2) C l a y , Dekker, and He m e l r i j h , CA.., 5120, (1944) (3) E x t r a p o l a t e d values. 21, The p o l a r i z a b i l i t y ^ e ^ , i s c a l c u l a t e d from the molar p o l a r i z a t i o n s at 20°C by assuming t h a t both isomers are non-polar and using the equation These r e s u l t s are shown i n t a b l e (6)., Table 5. P o l a r i z a t i o n Data f o r C i s - and Trans-Decalin. •,^rnn-1"1"n^ Temperature Density j D i e l e c t r i c / CIS-DECALIN 20 50 80 100 0.897 0.874 0.852 0.836 2.219 2.188 2.156 2.136 44.4 44.8 45.1 45.4 0.00353 0.00310 0.00283 0.00268 TRANS-DECALIN 20 50 80 100 0.870 0.848 0.825 0.810 2.184 2.150 2.123 2.103 44.9 45.2 45.6 45.8 0.00353 0.00310 0.00283 0.00268 The s l i g h t l y l a r g e r value of »i and P f o r the trans isomer than f o r the c i s isomer i s to be expected i n view of the l e s s compact s t r u c t u r e of the tr a n s isomer. This d i f f e r e n c e i s so s m a l l , however, t h a t the question a r i s e s as to whether the d i f f e r e n c e i s r e a l or merely due t o a small e r r o r i n the measured d i e l e c t r i c s . The d i f f e r e n c e i n the molar p o l a r i z a t i o n s i s about 0.45 and we w i l l determine whether the accuracy of our d i e l e c t r i c measurements permits any s i g n i f i c a n c e being placed i n t h i s amount. (1) Seyer and. Davenport, J.A.C.S.. 63, 2426, (1941) 22, The equation can be d i f f e r e n t i a t e d w i t h r e spect to £ to give or /° (€+zY and the d i f f e r e n c e i n d i e l e c t r i c s corresponding to a p o l a r i z a t i o n d i f f e r e n c e of 0.45 i s , t a k i n g average values of /p and £• , {/39./J/3J T h i s amount, as we w i l l see l a t e r , i s c o n s i d e r a b l y l a r g e r than the experimental e r r o r i n v o l v e d and we can t h e r e f o r e conclude t h a t the d i f f e r e n c e i n molar p o l a r i z a t i o n s and p o l a r i z a b i l i t y of the two isomers i s r e a l . T h i s d i f f e r e n c e i n p o l a r i z a t i o n s i s due to the atom p o l a r i z a t i o n , i . e . the d i s t o r t i o n of the atoms i n the molecule r a t h e r than the e l e c t r o n i c p o l a r i z a t i o n , due t o d i s t o r t i o n of the e l e c t r o n i c s h e l l s i n the molecule. Since the atom p o l a r i z a t i o n i n most molecules amounts to only 2 or 3 c c ' s , the d i f f e r e n c e of 0.45" cc's f o r the two isomers i s as l a r g e as could be expected. Table 6. . Comparison of the Molar P o l a r i z a t i o n s and P20 Benzene C i s - d e c a l i n T r a n s - d e c a l i n 26.71 44.4 44 .9 1.05 * 10 -25 . 1.75 x 10 -25 1.77 * 10 A comparison of the d i e l e c t r i c constants and the squares of the r e f r a c t i v e i n d i c e s i s made i n t a b l e 7 f o r c i s - and t r a n s - d e c a l i n and benzene. I n view of the f a c t t h a t we have ap p l i e d the simple theory to the case of l i q u i d s , f o r which i t does not r e a l l y apply, the agreement i s q u ite s a t i s f a c t o r y . The behavior of the two isomers at t h e i r f r e e z i n g p o i n t s though not e n t i r e l y e x p l a i n e d , i s of considerable i n t e r e s t . The changes observed are small and, indeed, are much smaller than the p o s s i b l e e r r o r introduced from the number of sources p r e v i o u s l y mentioned. The behavior i s s i g n i f i c a n t , however, because of the general r e p r o d u c a b i l -i t y and the d i f f e r e n c e f o r the two isomers. Table 7. Comparison of the D i e l e c t r i c Constant w i t h the Square of the R e f r a c t i v e Index. n 20 (n2o)^ *20 £ 2 0 " ( n 2 0 Benzene 1.5014-2 2.254- 2.289 0.035 C i s - d e c a l i n 11.4-8113 2.194 2.219 0.025 T r a n s - d e c a l i n 1l.»f6968 2.160 2.184- 0.024-I t .is not p o s s i b l e , without f u r t h e r measurements w i t h d i f f e r e n t kinds of c e l l s , to a s s i g n t h i s d i f f e r e n c e i n behavior s p e c i f i c a l l y to d i f f e r e n c e s i n the behavior of the d i e l e c t r i c s of the two isomers. I n s p i t e of the l a c k of t h i s v a r i f i c a t i o n , however, the r e s u l t s w i l l be (1) Seyer and Walker, J.&n.C.S.. 60, 2125 (1938) 2k. b r i e f l y discussed and an ex p l a n a t i o n sought. I d e a l i z e d curves have been drawn (fig. 1 2 ) f o r c i s - ' and t r a n s - d e c a l i n at t h e i r f r e e z i n g p o i n t s , i n which the temperature lags and d i s c r e p a n c i e s between m e l t i n g and f r e e z i n g p o i n t s have been e l i m i n a t e d . I f , f o r the moment, only the heating curves, i . e . , where melting takes p l a c e , are considered, the r e s u l t s can be i n t e r p r e t e d as f o l l o w s . The curve f o r c i s - d e c a l i n has the same shape at the f r e e z i n g p o i n t as the curve f o r g l y c e r o l (fig.5 ) . This then p o i n t s to the presence of a small permanent d i p o l e i n the c i s molecule. A comparison of the curves shows t h a t the change of d i e l e c t r i c on f r e e z i n g i s about 32 d i e l e c t r i c u n i t s f o r g l y c e r o l and only about 0.02 d i e l e c t r i c u n i t s f o r c i s - d e c a l i n . I f t h i s d i p o l e r e a l l y e x i s t s , i t i s so sm a l l t h a t i t i s not s u r p r i s i n g t h a t i t was not observed i n the previous measurements on the l i q u i d . The curve f o r t r a n s - d e c a l i n i s very s i m i l a r to t h a t f o r cyclohexane and the d i e l e c t r i c i s higher f o r the s o l i d phase than f o r £he l i q u i d phase. I n c o n t r a s t to the c i s isomer, the tra n s isomer, as was a n t i c i p a t e d , contains no permanent d i p o l e . The increase i n the d i e l e c t r i c f o r the s o l i d phase i s probably due to increased d e n s i t y . The c o o l i n g curves are not as r e a d i l y e x p l a i n e d . They might represent unstable c r y s t a l s t r u c t u r e s which, w i t h longer time or decreasing temperature, go over to a more r i g i d c r y s t a l l a t t i c e . This gives q u i t e a reasonable 25. e x p l a n a t i o n f o r the r e s u l t s f o r c i s - d e c a l i n but does not throw much l i g h t on the reason f o r the maximum i n the trans-decalin.and the cyclohexane r e s u l t s . I n t h i s con-n e c t i o n i t i s i n t e r e s t i n g to note, however, th a t both t r a n s - d e c a l i n and cyclohexane have f l a t , p l a t e - l i k e molecules. V l l . ACCURACY OF RESULTS The maximum v a r i a t i o n of the d i a l reading f o r successive runs was 2 d i a l d i v i s i o n s , corresponding to ^ ( 2 3 ) ^ . ^ / or ^ 0 . 0 0 3 d i e l e c t r i c u n i t s . The maximum v a r i a t i o n , t h e r e f o r e , i n the d i e l e c t r i c constant of c i s - and t r a n s - d e c a l i n at any temperature i s 0.003. Successive readings on the same sample never v a r i e d from the average curve by more than 1 d i a l d i v i s i o n or 0.0015 d i e l e c t r i c u n i t s . A l l the r e s u l t s , however, depend on the benzene c a l i b r a t i o n , a n d any e r r o r i n t h i s w i l l produce a propor-t i o n a t e e r r o r i n a l l the r e s u l t s . The r e s u l t s obtained by D u n e l l are of the same magnitude as those obtained here but the v a r i a t i o n w i t h temperature which he r e p o r t s i s co n s i d e r a b l y d i f f e r e n t . The d i e l e c t r i c constants reported by Lautsch"*" and 2 Estermann of 2.13 and 2.11 r e s p e c t i v e l y f o r t r a n s - d e c a l i n are low. (1) Lautsch, W., Z.Phvsik. Chem.. ( B ) l . 115 (1928) (2) Eastermahn, J . , Z.Phvsik. Chem.. ( B ) l . l 6 l (1928) 26. The e r r o r s involved i n the d i e l e c t r i c s of the s o l i d phase have already been considered. I n view of the • general r e p r o d u c a b i l i t y of the r e s u l t s the e r r o r s i n t r o -duced by the r a t e of c r y s t a l l i z a t i o n and the place of i n i t i a l c r y s t a l l i z a t i o n must be small since these e f f e c t s would produce d i f f e r e n t e r r o r s f o r d i f f e r e n t experiments. The p r o p o r t i o n of voids between the condenser p l a t e s , however, may s t i l l be q u i t e l a r g e and the d i e l e c t r i c of the s o l i d compound would then be c o n s i d e r a b l y low. V I I I . CONCLUSIONS (1) The d i e l e c t r i c constant of c i s - d e c a l i n has been measured at 3*5 negacycles and 20°C and has been found to be 2.219 ± 0.003. Tne temperature c o e f f i c i e n t between the f r e e z i n g p o i n t and 100°C i s 0.0010 per C°. No anomalous behavior i n any of the samples t e s t e d was observed be-tween -40 and 100°C. (2) The d i e l e c t r i c constant of t r a n s - d e c a l i n has been measured and has been found to be 2.184£.0.003 at 20°C. The temperature c o e f f i c i e n t between the f r e e z i n g p o i n t and 100°C i s a l s o 0.0010 per C°. As i n the c i s isomer no anomalous behavior was observed. The d i e l e c t r i c constants of c i s r and t r a n s - d e c a l i n over the e n t i r e temperature range considered are shown i n f i g . 1 3 . (3) The molar p o l a r i z a t i o n s of c i s - and t r a n s - d e c a l i n have been c a l c u l a t e d at a number of temperatures and- the D/e/ecfr/c Consf<7nr v a r i a t i o n w i t h temperature (fig.11) has been found t o be the same as the v a r i a t i o n of the p o l a r i z a t i o n of l i q u i d benzene w i t h temperature. Furthermore, the squares o f the r e f r a c t i v e indeces (Table 6) are i n c l o s e agreement w i t h the d i e l e c t r i c c onstants. Both these r e s u l t s i n d i c a t e a zero or very s m a l l ( d i p o l e moment f o r both isomers. (4) The molar p o l a r i z a t i o n of the trans-isomer i s s l i g h t l y l a r g e r than t h a t of the c i s isomer (Table 7 ) . This i n d i c a t e s a l o o s e r or l e s s compact molecular s t r u c -t u r e f o r the tra n s isomer. (5) The d i e l e c t r i c constant has been measured through the f r e e z i n g p o i n t and s o l i d phase. A marked d i f f e r e n c e i n the behavior of the two isomers was observed (see F i g . 12). Furthermore, the curves f o r heating and c o o l i n g f o r both the d e c a l i n isomers and cyclohexane are q u i t e d i f f e r e n t , A small decrease i n the d i e l e c t r i c constant of c i s -d e c a l i n at the f r e e z i n g p o i n t i n d i c a t e s the p o s s i b l e presence of a small d i p o l e moment. Both t r a n s - d e c a l i n and cyclohexane show a pronounc-ed and unexplained maximum at the f r e e z i n g p o i n t . BIBLIOGRAPHY A l b e r t , A.L., Fundamentals of E l e c t r o n i c s and Vacuum Tubes. New York, MacMillan Co., 193b. Alexander, F . C ; E l e c t r o n i c s . 18, #4, p 116, A p r i l 1945 Angley, P o t k i n s , and Rush, Bachelor's T h e s i s , 1942 Bock, R., Z.S. f u r Phys., 37, 334-43, 1925 C l a y , Dekker, and He m e l r i j h , The absolute value of the  d i e l e c t r i c constant of l i q u i d s : Chem A b s t r a c t s , 3b*, 5120, 1944. Debye, P., P o l a r Molecules. Chemical Catalog Co., 1929. Dornte, Smyth, D i e l e c t r i c Constants of Hydrocarbons e t c : J.A.C.S., 52, 3546, 1930. Eastermann, J . . Z. physik chem., (B) 1, 161, 1928; 2, 287, 1928. F r o h l i c h , H., D i e l e c t r i c p r o p e r t i e s of d i p o l a r s o l i d s : Proc.Roy.Soc. A 185, 399, 1946. Lautsch, W. Z. physik chem., (B) 1, 115, 1928. Morgan and Lowry, D i e l e c t r i c p o l a r i z a t i o n of some pure  organic compounds: J . Phys.Chem., 34, 2385,1930. M u l l e r , A., The d i e l e c t r i c p o l a r i z a t i o n of a long chain  ketone": Proc.Roy.Soc., A 166, 316, 1938. Seyer and Davenport, J.A.C.S., 63, 2^26, 1941. Seyer and Walker* J.A.C.S., 50, 2125, 1938. Smyth, C P . , D i e l e c t r i c Constant and Molecular Structure, Chemical Catalog Co., 1931. I n t . C r i t . Tables, Vol . 1 1 , p 29, 1928. (v) 

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