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UBC Theses and Dissertations

The variation of the refractive index and disperson with temperature of the cis and trans isomers of… Mizuhara, Shaw Joseph 1941

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frni  THE VARIATION OF THE REFRACTIVE INDEX AND DISPERSION WITH TEMPERATURE OF THE CIS AND TRANS ISOMERS OF DE CAHYDR0NAPHTHALENE  "by SHAW J . ' MIZUHARA A THESIS SUBMITTED I N PARTIAL FULFILMENT OF THE REQUIREMENTS FOR THE DEGREE OF MASTER OF ARTS I N THE DEPARTMENT OF CHEMISTRY  '  THE UNIVERSITY OF B R I T I S H COLUMBIA A P R I L , 1941  fit, V"~u  ACKNOWLEDGEMENT 00O00 I t i s , Indeed, a p l e a s u r e t o acknowledge  the a s s i s -  t a n c e o f D r . W. F. S e y e r , u n d e r whose g e n e r a l g u i d a n c e work was p e r f o r m e d .  this  CONTENTS I  Introduction  I I Propa.ra.txon • •  ..  „ . <>. 1  © • • r * » « o « » * » » * » « > « * « *  3  IXT. ( a ) S e p a r a t i o n (b) P u r i f i c a t i o n  (a)  Refractometer  (b) T e m p e r a t u r e  corrections  (c) Source o f l i g h t IV  General observations of r e f r a c t i o n . .  (a) T r a n s (b) C i s VI  Treatment o f r e s u l t s  15  (a) T r a n s (b) C i s VII  Conelixsxoxis  13  &  I  INTRODUCTION.. For  s e v e r a l y e a r s c o n s i d e r 3 . M e work has "been c a r r i e d o u t  i n t h e s e l a b o r a t o r i e s on t h e p h y s i c a l p r o p e r t i e s o f d e c a h y dronap,thalene (C]_oHi8) Dr.- W. F. S e y e r .  1  o  r  d e c a l i n under the d i r e c t i o n of  This napthene'is believed to e x i s t i n f i v e :  s t e r e b - i s o m e r i c f o r m s , t h e c i s ahd t r a n s f o r m s b e i n g t h e l i m i t ing  p o s i t i o n s and , t h e r e f o r e , o f g r e a t e r s t a b i l i t y .  In the  p r e v i o u s i n v e s t i g a t i o n s o f the temperature e f f e c t on  p h y s i c a l p r o p e r t i e s such as s p e c i f i c h e a t s  2  and s u r f a c e  t e n s i o n ^ , t h e t r a n s f o r m .has shown no'' a b n o r m a l i t i e s , b u t t h e cis  f o r m has r e v e a l e d d e f i n i t e d i s c o n t i n u i t i e s .  These  dis-  c o n t i n u i t i e s a r e p r o b a b l y due t o t r a n s f o r m a t i o n s -of i s o m e r i c forms. twofold:  The p u r p o s e first,  of the f o l l o w i n g research i s ,  to find  therefore,  the temperature c o e f f i c i e n t of the  r e f r a c t i v e i n d i c e s and d i s p e r s i o n , s e c o n d l y , t o n o t e i f t h e s e o b s e r v a t i o n s a l s o show t h e d i s c o n t i n u i t i e s i n t h e c i s f o r m . 1.  S e v e r , W. F.  A s s o c . P r o f , o f Chem. E n g . U n i v e r s i t y o f B.C  2.  D a v i e s , G. F.  3.  D a v e n p o r t , C. H.  M.A.  S c . T h e s i s 1939  B.A. S c . T h e s i s 1938  II  PREPARATION the  first  s u c c e s s f u l s e p a r a t i o n o f t h e two i s o m e r s was  a c c o m p l i s h e d i n 1936-37 by D r . W. F. S e y e r and R. D.  Walker.  The f o l l o w i n g p r e p a r a t i o n and p u r i f i c a t i o n i s e s s e n t i a l l y of  t h e o r i g i n a l w o r k e r s w i t h some m i n o r  4  that  changes.  C o m m e r c i a l d e c a l i n o b t a i n e d f r o m E a s t m a n Kodak Co. was used.  T h i s was t r e a t e d f i r s t w i t h a n a c i d wash, t h e n a n a l k a l i  wash, f o l l o w e d w i t h a w a t e r wash u n t i l n e u t r a l .  The s e p a r a -  t i o n o f t h e two i s o m e r s was o b t a i n e d by r e p e a t e d l o w p r e s s u r e rectification  ( a p p r o x i m a t e l y 10 num.  o f Hg.)  The f i n a l p u r i f i c a t i o n o f t h e i s o m e r s o b t a i n e d by f i c a t i o n is a c c o m p l i s h e d by r e p e a t e d f r a c t i o n a l tion.  the  crystalliza-  The p r o c e d u r e i s t o save t h a t f r a c t i o n w h i c h  i z e s o u t b e f o r e an e u t e c t i c i s f o r m e d .  recti-  crystall-  By r e p e a t e d o p e r a t i o n s ,  f r a c t i o n retained e v e n t u a l l y reaches a constant f r e e z i n g  p o i n t w h i c h shows i t t o be o f g r e a t p u r i t y * The f o l l o w i n g t a b l e shows a c o m p a r i s o n o f t h e v a l u e s o b t a i n e d f o r f r e e z i n g p o i n t s and r e f r a c t i v e i n d i c e s o f t h e various workers.  4.  W a l k e r , R. D.  M.A.  S c . T h e s i s 1937  3 Trans.  Cis  Int. C r i t tables 5  III  n20  f , p.  1.4828  — — .  1.4701  D  Huckel  Q.  - 51. ° C  1.47950  • -56°C  1.46958  'Walker  ?  - 42.60° C  1.48084 -50.30° C  1.46948  Sample u s e d f o r „ T h i s r e s e a r c h 8 -43.22°C . 1.48098 -30.84°C  1.46934  APPARATUS (a) R e f r a c t o m e t e r ' The  optical  - >•  a p p a r a t u s .used I s a P u l f r i c h principle  of which 1st :  Equations f o r the l i g h t r e f r a c t i o n n/Sin S=n sin 0  A  1  angle)  £W1  .-. n,=n„sin for  from  -r)  l e t E—>o ( t h e l i m i t i n g sin  r e f r a c t o m e t e r , the  (^~r)  —  (l)  t h e emergence o f t h e l i g h t r a y . f r o m - t h e p r i s m ,  International C r i t i c a l H u c k e l , W,  Tables  A m i a l e n d e r Chemie 441-1-1925  7,  Loc, c i t .  •8,  Morel,- Watson, & Y i p .  B.A. S c . T h e s i s 1940  n s i n r -.-'-n^sin I = s i n i  •  0  n =l  (g)  (for air)  a  s q u a r e & combine ( l ) & ( 2 ) n, = y n i - s i n * i Since n  (5)  i s g i v e n f o r t h e p r i s m and a n g l e  D  11, c a n be c a l c u l a t e d ,  i i s observed,  The i n s t r u m e n t i s s e t i n . s u c h a man-  ner that o n l y the g r a z i n g r a y i s r e f r a c t e d , t h a t i s , the light  source  a circle  i s a t A.  The a n g l e o f emergence, i , I s r e a d on  b y a v e r n i e r c o r r e c t t o SO" o f a r c w h i c h  t o ^t.00005 f o r n, o r l e s s t h a n  (b)  corresponds  ,003?? e r r o r ,  Temperature C o r r e c t i o n The  v a l u e o f t h e r e f r a c t i v e i n d e x was o b t a i n e d by t h e u s e  of t a b l e s c a l c u l a t e d from sumed n  0  t o be c o n s t a n t  t h e above f o r m u l a .  (the value of n  0  The t a ^ e s a s -  u s e d i s ^y) > t h e r e -  f o r e , t h e r e must be a c o r r e c t i o n a p p l i e d f o r d e v i a t i o n s f r o m 15° C. let n  c =  r e f r a c t i v e i n d e x o f t h e p r i s m a t 15°C  -£>n =  "  0  "  c o r r e c t i o n p e r degree  uncorrected refractive  index,  t h e n n^ n + K =  c  where K = c o r r e c t i o n v a l u e n * =n* - s i n " ! 2  n*-[n. i- ( t - 1 5 ) ^ n ^ - s i n 1 2  B  K=i2?*n (t-15) 0  rise  Values  g i v e n f o r the p r i s m usedsC ^n  ,000024  f e  n^ The  D  5  F  .000028  1.61839  1,62533  r e f r a c t o m e t e r and  liquid  ±0,01  C, b u t  The  1.63573  i s kept  p e r a t u r e by c i r c u l a t i n g w a t e r t h r o u g h temperature bath.  .OD0039  at a constant  i t from a l a r g e  method Used g i v e s a c o n s t a n c y  temconstant  of  the t h e r m o m e t e r r e a d i n g c a n be r e a d o n l y t o  dr0,02°C a c c t i r a c y . (c) Source of L i g h t The  source  of  and  drogen discharge tube.  l i n e s i s a G u i l d type  I t was  l y w i t h h y d r o g e n gas w h i c h was and  then p u r i f i e d  pressure  filled  and  generated  of  evacuated  hy-  repeated-  electrolytically, .  by a b s o r p t i o n o f I m p u r i t i e s .  The"final  o f t h e h y d r o g e n i n the t u b e i s o f t h e o r d e r o f  ra.m. o f m e r c u r y ,  The  0.01  e x c i t a t i o n o f t h e h y d r o g e n atoms i s  e f f e c t e d by a 6 v o l t h i g h t e n s i o n v i b r a t o r y c o i l 5 t o 10 t h o u s a n d v o l t s I n t h e s e c o n d a r y  generating  circuit.  H -C=6562A V  H^-F 4861 A =  The  sodium D l i n e was  o b t a i n e d by b u r n i n g  c h l o r i d e w i t h a bunse.n b u r n e r .  fused  T h i s gave a s h a r p ,  sodium  intense  line. NOTE.  T h e r e were a few d i f f i c u l t i e s  making of the tube,  t h e m a j o r one  t h e optimum p r e s s u r e .  encountered i n the  b e i n g the d e t e r m i n a t i o n  Since the i n t e n s i t y of the  t i o n i s a f u n c t i o n of the p r e s s u r e  of  illumina-  and v o l t a g e , d u r i n g  <5 e v a c u a t i o n t h e secondar-'" c i r c u i t '"as c o m p l e t e d ,  anc5 a t th<=>  p o i n t o f maximum i n t e n s i t y e v a c u a t i o n was s t o p p e d ,  But a t  t h e maximum i n t e n s i t y , t h e p r e s s u r e b e i n g v e r y l o w , tb° mean f r e e p a t h o f t h e e x c i t e d atoms i s so l a r g e t h a t It  caused  " b u r n i n g " o f t h e g l a s s a t t h e end o f t h e c a p i l l a r y  which  causes  a diminution of the available l i g h t .  The b u r n i n g  e v e n t u a l l y cause a l e a k a t t h e " b u r n t " p o i n t . many t r i a l s ,  However, a f t e r  a n optimum c o n d i t i o n was a t t a i n e d .  f i c u l t y was e n c o u n t e r e d  Another  i n the making o f e l e c t r o d e s .  were made o f t h e p u r e s t a l u m i n i u m  will  dif-  They  a v a i l a b l e and were h e l d bv  tungsten wire fused t o the " l a c s w a l l of the tube.  IV  T  GENERAL OBSERVATIONS ON , B E g M £ ™ l ' The  law of Gladstone  and D a l e  states that the s p e c i f i c  and m o l e c u l a r r e f r a c t i v i t i e s a r e n e a r l y c o n s t a n t w i t h ternT) e v a t u r e vs. r 1 a t i on s r-specific n  r - ( ~~0 s. f ;  R=molecular  refractivity refractivity  d  s u b s c r i p t s r e f e r t o whose R  =  G (l^l).M  equation d=d.ensity M=molecular  A g r e a t e r constancy L o r e n t z and L o r e n t z . a  t* - ( n - l ) 1  " ~bm) l  i  ct  (n +2) d  weight  i s o b t a i n e d by u s i n g t h e f o r m u l a o f  The p u r e l y e m p i r i c a l f o r m u l a f o u n d by  Eykman t o f i t  o r g a n i e l i r u i d s has shown a g r e a t e r c o n s t a n c y t h a n t h e G l a d s t o n e — D a l e and L o r e n t z - L o r e n t z f o r m u l a e i n t h e measurements of  t e m p e r a t u r e — p r e s s u r e e f f e c t on t h e r e f r a c t i v i t y  of  benzene >9 2  •  r  =  E  fn ~l) (nto.4)  1 d  &  ~{n+o-4) d  P r e v i o u s i n v e s t i g a t o r s have shown, t h a t , i n g e n e r a l , t h e molecular r e f r a c t i v i t y  i s t h e sum. o f t h e a t o m i c  refractivities;  b u t i n • t h e c a s e o f i s o m e r s t h e l a w s o f a d d i t i o n a r e v e r y comp l e x and c a n n o t be a p p l i e d a c c o r d i n g t o t h e t a b l e g i v e n by EI s e n l o h r , T  C  v "D  r "F  carbon  2.413  2.418  2,438  hydrogen  1,092  1.1Q0  1.115  These v a l u e s were c a l c u l a t e d f r o m t h e L o r e n t z - L o r e n t z formula, and t h e v a l u e s o f R £ , R £ , & R ^ isomers or v a r i a t i o n s w i t h temperature.  D O  N O T  A L L O W  T h i s would e i v e f o r  decalin R £ = ( 2 . 4 1 3 ) (l0)-h(l.092) ( 1 8 ) 4 2 » 7 9 =  RE=(2.418)(10)+(1.100)(18)=43.98 B f r ( 2 , 4 5 8 ) ( 1 0 ) ^ ( 1 , 1 1 5 ) (18) = 4 4 . 4 5  "9. 10.  Gibson & K l n c a i d Eise-olohr,  J.A.C.S.  60-511-1938  Z. P h y s i k a l Chemle.  F O R  1911-75-585  Moreover, l a t e r workers-  11  have shown t h a t t h e r e f r a c t i v e  index i s a f u n c t i o n of d e n s i t y which i s a f u n c t i o n o f temperat u r e and p r e s s u r e .  A p p a r e n t l y , t h e i r r e s e a r c h e s have l e d them  t o t h e c o n c l u s i o n t h a t a l l s a t u r a t e d compounds h a v e a s p e c i f i c d i s p e r s i o n o f a p p r o x i m a t e l y 0,0099 i r r e s p e c t i v e o f t h e i r ing point.  boil-  T h e r e f o r e , by t h e use o f C a u c h y e q u a t i o n s n£=nJ-0.292(n -n ) F  nt nt-0.7 =  and  0 8  (  n F  c  _n ) c  when t h e d e n s i t y i s known, t h e r e f r a c t i v e  calculated.  In effect,  i n d i c e s c a n be  i f the r e f r a c t i v e i n d i c e s are p l o t t e d  a g a i n s t d e n s i t y , t h e r e s u l t w i l l be a s t r a i g h t l i n e . was d e t e r m i n e d  by these  The  line  I n v e s t i g a t o r s and was g i v e n i n t h e  form. ^n 0.60Ad =  or  z\n-f ( r , d) ^ d  w h i c h on i n t e g r a t i o n g i v e s f ( n , d ) = c o n s t a n t . of G l a d s t o n e — D a l e , form,  L o r e n t z - L o r e n t z , and Eykman a r e o f t h i s  i t s h o u l d be p o s s i b l e t o d i f f e r e n t i a t e them t o f i n d t h e  slope of the r e f r a c t i v e - i n d e x d e n s i t y c u r v e . remains t o f i n d  R  G  ^ i  T h e r e f o r e , i t now  the value of the f u n c t i o n f ( n , d ) .  For Gladstone-Dale  equation .  M  ^n=2-i^d  11.  S i n c e the formulae  Ward and K u r t z .  (1)  I n d . & Eng.' Chem, ( A n a l . Ed.) 10-55919-38  For  Lorentz-Lorentz  equation:  *n= (lt^llilL±2) A d Bnd, F o r Eykman p  n  2  (2)  equation: - l  M  n  E-n*-f.o.4'"'a: 4  ^iU^?- ^*As  (s)  a f i r s t approximation, which i s s u b s t a n t i a t e d  published  d a t a on h i g h b o i l i n g p o i n t  compounds, t h e s p e c i f i c 2  dispersion varies l i n e a r l y with temperature^ . expected since d e n s i t y v a r i e s l i n e a r l y w i t h first  a p p r o x i m a t i o n ) and t h e r e f r a c t i v e  connected w i t h d e n s i t y .  t  The  perature:  (to a  coefficient  dispersion  A  ^  ^M=molecular  dispersion  a d v a n t a g e o f m e a s u r i n g mean d i s p e r s i o n  a refractive  i s t o be  temperature  However, t h e t e m p e r a t u r e  t n  This  index i s d i r e c t l y  of s p e c i f i c d i s p e r s i o n i s s m a l l . 6~k=np-n^ ^specific  /^_Pj?~ Q  by un-  1 3  rather  index i s that the former v a r i e s l e s s with  i t i s also possible  tem-  t h a t m o l e c u l a r d i s p e r s i o n and  s p e c i f i c d i s p e r s i o n have a l a r g e r t e m p e r a t u r e c o e f f i c i e n t the  12.  mean s p e c i f i c  dispersion.  G r o s s e , A. V. & Wackher, R. C.  I n d . & E n g . Chem. Nov.  13.  than  Cheneveau e t V a u r a b o u r g . B u l l .  1939  p g . 614  S o c . Chim. M e m o i r s s 1928  4e s e r i e 43  than  V RESULTS (a) f o r t r a n s  Temp •  decahydronapthalene  Angle  9.2 °C  42°26'SO"  c 1.47096  42°49'30"  Temp *  Angle  Temp «  10.  *C  42*56'30"  1.47345  . 1.46872  15.  *C  43*13'  1.47145  15.  *C  43*38'50"  1.46934  20.  1.46732  30.. °Q  9.2 *G  Angle  ;4  44°15'30"  1.47936  °C  44° 3 9 '  1.47700  °C  45°  1.47501  45*40»30"  1.47106  15.  •C;  20.  *C . 43*10'30"  1.46669  20  30.  «C  43*50'30"  1.46271  25. °c  43*59'  35.  °C  44"11'  1.4606 8  30.  *c  49*19'  1.46536  35.  °C  46*03'  1.46 885  45.  *C  44*51'30"  1.45676  3 5 . *C  44* 4 0 '  1.46328  40.  •c  46*23'50"  1.46685  50.  •c  45°12'  1.45479  45. *c  45*19'30"  1.45938  45.  "G  46*45'50"  1.46489  54.5 °c  45°29'  1.45294  50. °c  45*40'30"  1.45731  50.  *C  47 03'30"  1.46293  *C  45°51'30"  1.45080  60. °c  46*19'  ' 1.45349  60.  °C  47*45'  1.45885  69.7 •c  46*28'30"  1.44702  69.7 °c  46°59'30"  1.44947  69.7 *c  48*24'  1.45479  79.8  47 09'  1.44299  79.2 *c  47°36'30"  1.44579  79.2 °C  49°04'  1,45111  84.8 •c  47°28'30"  1.44103  84.6 *c  47*58'  1.44366  84.7 °C  49*28''  1.44879  60.  !  6  -  s  (b) f o r . . c i s decahydronap„thalea temp.  angle  n  c  "' •  temp-.  angle  nj  temp  6. 2 °C  40"40'30"  1.48671 1,48488  10.  40°26 '  1.48274  10.  °C  40° 59-30"  °c  40° 48'30"  1.48056  15.  °c  41° 1 8  f  1.48510  15.  SO. °c  41*10'30"  1*4.7844  20.  °c  41*'40-»  1.48098  20.  25.  °c  41°30'30"  1.47649  °c  42°02'  50.  °c  41°55'50"  1.47426  30.  35.  a  42*15'50"  1.47211  35.  10. 1°C 15.  c  °c  angle  »  42°14'  1.49121  °C  42°38'  1.48892  °c  42°58'30"  1,48694  1.47884  .25. °c  45°19'30"  1.48479  42°23'30"  1.47675  30.  °c  43°44'  1.48252  42°45'  1,47472  35.  °c  44*04'30"  1.48054  44°17'  1.47935  44°28'30"  1.47819  44 47r  1.47639  38.2 °e 40. ec  42°36'  1.47011  40.  °c  43° 07'30"  1.47246  40.  1.46820  45.  6  C  43° 2 5 '  1.47074  °c •45-. '•  •1.46628  50.  °c  45° 4 8 '  1,46848  50.  °c  '45° 0 7 '  1.47445  1.46799  50.9 °c  45° 1 1 '  1.47405  45"21'  1.47306  45.  °c  42°55'50"  50.  °c  43°15'  50. 9 °c  43°18'30"  1.46593'  51. 2*C  43* 5 3 '  52. 9°C  43"S0'.  1.46479  53. .. °c  44 0' 30"  1.46727  52.9  54. 9 X  45°38'30"  1.46397  55.  °c  44"07'50"  1.46662  55.  60.  43°58'  1.46203  60.  °c  44°27'30"  1.46459  44°25'50"  1.45952  65. 2 °C  44°47'50"  1.46262  'C e  65.. . c  n't  fa  °c  °G  a  J  45° 3g  1.47202  60.5 °Q  45" 5.3 '30"  1,46991  64.5 °C  46°09'30"  1.46834  (b) c o n t i n u t e d te-ip,  angle  ng  . temp.  angle  69.7.°C  44° 5 5 '  1,45839  69.5 "C  45°05'30"  74.  44° 5 1 '  1.45680  74.  °C  SO. 4 °C  45° 18'50"  1.45416  80.4 °C  85.  45* 5 8 '  1«4 5 213  84.8 C  "C  °C  6  ng  temp,  angle  n£  1 .46080  69.3°C  46° 50'30"  1.46639  45 22'  1 .45922  74.  46°49'30"  1.46442  45° 4 7 '  1 .45675  80.4 "C  47°15'  1.46192  46°05'  1 .45498  85. °C  47°35'30"  1.45990  6  °C  VI  TREATMENT OF RESULTS (a) f o r t r a n s decahydronap^thalene Temp.  4  n-p  Density  10 V  1.47094  1.47340  1.47906  .8775  20 °C  1.46670  1.46939  1.47502  . 8700  30 °C  1.46275  1.46540  1.47099  .8627  40 "C  1.45876  1.46139  1.46685  .8^53  50 °C  1.45479  1.45732 '. 1.46289  . 8480  60 °C  1.45085  1.45349  1.45879  .8405  70 °C  1.44690  1.44945  1.45478  .8331  30 °C  1.44295  '1.44549  1.45075  ,8255  90. "C  1,43898  1.44149  1.44675  .8178  above t a b l e was o b t a i n e d f r o m t h e g r ph a on p i , 4  The v a l u e s f o r d e n s i t y were o b t a i n e d f r o m D a v e n p o r t ' s-*equation. d| .8849-.000742t =  By g r a p h i c a n a l y s i s d n = - . 0 0 0 3 9 9 / °C dt c  dn -,000398/"C dt Ds  dnF=-. 0 0 0 4 0 3 / °C dt d| ~.000016/°C dt' M=  £|=>-Q0777+. 000016  4S l.075756-K 002211(t-10) .8849-.000742t Mz  14.  loc.cit,  (t-10)  U s i n g t h e above v a l u e s , t h e e q u a t i o n s o f G l a d s t o n e - D a l e , L o r e n t z - L ' o r e n t z , and Eykman were t e s t s f o r " c o n s t a n c y " .  p., ..n-1  R  m  Temp. n  C  n  4  D  n  G  n -1 M  n  D  j> _xf -1  n  F  n  C  n  M  4  D  10 °c  74.164  74.551  75.443  44. 014  44,212  44.661  97.948  98.436  99.532  20 °C  74.113  74,540  75.451  44. 039  44.256  44.702  97.934  98.464  99.572  30 °C  74.125  74.549  75.444  44. 098  44.315  44,772  98,000  98.527  99.638  40 °C  74.121  74.546  75.428  44. 149  44.367  44.819  98.047  98.575  99,671  50 °C  74.112  74.524  75.431  44. 196  44.408  44.874  98.086  98.625  99.727  60°C  74.126  74.560  75.431  44. 256  44.48  44.928  . 98,155  98.695  99.779  70 *C  74,129  74.552  75.431  44, 311  44.529  44.985  98.211  98.738  99.838  80*0  74.150  74,575  , 75.456  44. 375  44.596  45.052  98.336  98.821  99.918  90°C  74.177  74.602  75.490  44. 546  44.664  45.126  98.379  98.908  100.017  (  The r e s u l t s o f t h e t a b l e , may be condensed t o t h e f o r m d R = E ( t ) ; dRE=K'(t); dR =0 dt .dt dt L  a  n  d  G  T h e r e f o r e , t o f i n d d e n s i t y - r e f r a c t i v e i n d e x e q u a t i o n , we must use t h e G l a d s t o n e form. ^ n = ^ i ^d-r .Ad. G  ?daich g i v e s :for  the C l i n e .  <&n=.529^d.  for  the D l i n e .  <*>nr.539^d.  for  the F l i n e .  <*>n=. 5 4 5 <sd.  (b) f o r c i s d e c a h y d r o n a p t h a l e n e . Davenport's e q u a t i o n f o r d e n s i t y i s g i v e n b y t d|= 9120-.000752t s  which i s l i n e a r t o a f i r s t a p p r o x i m a t i o n over the temperature r a n g e t h a t t h e r e f r a c t i v e i n d i c e s were m e a s u r e d ; and s i n c e 4 the  r e f r a c t i v e i n d i c e s c u r v e s a r e d i s c o n t i n u o u s , t h e r e c a n be  •no g e n e r a l d e n s i t y - r e f r a c t i v e i n d e x e q u a t i o n s e t up f o r t h e whole temperature range.  (5° t o 90°)  I f we assume t h a t a t e a c h d i s c o n t i n u i t y , t h e r e i s a n i s o m e r , t h e n b y g r a p h i c a n a l y s i s , i t i s s e e n t h a t t h e mean d i s p e r s i o n f o r e a c h i s o m e r may be assumed c o n s t a n t ( l e s s t h a n 0.1$ e r r o r ) ; b u t e a c h i s o m e r h a s a d i f f e r e n t mean d i s p e r s i o n . b e l o w 35° 35°-50° above 50°  <5 = .0085 ^=-0082 & =.0080  VII  CONCLUSIONS (a) £ or t r a n s . Although the temperature  c o e f f i c i e n t of mean d i s p e r s i o n  Is very small, a c o r r e c t i o n should be a p p l i e d i n using the Cauchy equations.  •-  (n|-nj) = .00777+. 000016  (t-10)  The l i n e a r v a r i a t i o n of r e f r a c t i v e i n d i c e s with temperature shows that the trans isomer has no v. changes detectable by t h i s method over the. temperature  range of 10°C to 90°C.  (b) f o r c i s The curve f o r c i s shows 2 breaks between 5" and 85". The f o l l o w i n g equation i s derived from the wave theory of l i g h t , which means that r e f r a c t i v e index v a r i e s i n v e r s e l y as the frequency of o s c i l l a t i o n of the atoms and d i r e c t l y p r o p o r t i o n a l t o the number of e l e c t r o n s .  The change of number of e l e c t r o n s per c.cj. i s the d e n s i t y v a r i a t i o n and since t h i s v a r i a t i o n i s l i n e a r over the temperature  range that i s used, i t - f o l l o w s that the  frequency of o s c i l l a t i o n of the atoms must be the cause of the d i s c o n t i n u i t i e s . Now f o r the o s c i l l a t i o n frequency to vary suddenly, i t means that there must be a s h i f t i n atomic s t r u c t u r e . Therefore, a s h i f t i n p o s i t i o n of atoms equivalent to a s t r u c t u r a l change, I conclude that c i s has three isomers, the t r a n s i t i o n temperatures being 38°+, 0.5 and 51°± 0.2 ."  Furthermore,  i n the study of the Raman e f f e c t ,  the c i s isomer has shown a d i f f e r e n c e i n o s c i l l a t i o n  energy  of the atoms above and below 50°6. This has been i n t e r p r e t e d as a s t r u c t u r a l change by the workers. In measurements of the r e f r a c t i v e index near  51°C  there i s a region where the l i g h t rays are i n d i s t i n t , i , e . the rays are sharp, then they become i n d i s t i n c t , then sharp again when e q u i l i b r i u m Is reached. Apparently, t h i s i s due to t r a n s i t i o n of forms taking p l a c e .  15  Zotov, Go  M.A,  Thesis  1940  BIBLIOGRAPHY 1 Cheneveau e t V a u r a b o u r g B u l l Soc Chim 2 D a v e n p o r t , C. H, M.A.Sc. T h e s i s 1959 3 D a v i e s , G. F. M.A.S8. T h e s i s 1939 4 E i s e n l o h r Z P h y s i k a l Chemie 5 Gibson & K i n c a i d  J . A. C. S.  6 G r o s s e & Wackher  I . E. C. ( A n a l . E d . )  7 H u c k e l , W.  A n n a l e n d e r Chemie  8 International C r i t i c a l 9 M o r e l , Watson, & Y i p 10 W a l k e r , R. D. 11 Ward k K u r t z 12 Z o t o v ,  Tables B.A.Sc. THB§IS 1940  M. A. S c . T h e s i s 1937 I . E. C.  ( A n a l Ed.)  G. M.A. T h e s i s 1940  

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