Vapor-Liquid Equilibria in Binary Systems

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PU R D U E UNIVERSITY

T H IS IS TO C ER TIFY TH A T T H E T H E S IS P R E P A R E D U N D E R MY S U P E R V IS IO N

Norman A l p e r t

BY

EN T IT L E D

VAPOR» LI QUID EQUILIBRIA IN BINARY SYSTEMS

C O M PL IE S W ITH T H E U N IV E R S IT Y R E G U L A T IO N S O N G R A D U A T IO N T H E S E S

A N D IS A P P R O V E D B Y M E A S F U L F IL L IN G T H IS P A R T O F T H E R E Q U IR E M E N T S

FOR THE D EG R E E OF

D o cto r o f P h ilo so p h y

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TO T H E L IB R A R IA N :---T H IS T H E S IS IS N O T TO B E R E G A R D E D A S C O N F ID E N T IA L .

P B O F B S S O R XSf O H A B O B

G S A D . S C H O O I i P O i m S —3 . 4 0 —I M

VAPOR-LI(^ÜID EQUILIBRIA IN BINARY SYSTEHS A T h e sis Su bm itted , t o t h e F a c u l t y of Purdue U n i v e r s i t y by Norman A l p e r t In P a r t i a l F u lf illm e n t o f th e R e q u ir e m e n ts f o r t h e D e g ree of D o c to r o f P h ilo so p h y A u g u s t , 1949

ProQuest Number: 27712179

All rights reserved INFORMATION TO ALL USERS The quality of this reproduction is d e p e n d e n t upon the quality of the copy subm itted. In the unlikely e v e n t that the a u thor did not send a c o m p le te m anuscript and there are missing pages, these will be noted. Also, if m aterial had to be rem oved, a n o te will ind ica te the deletion.

uest ProQuest 27712179 Published by ProQuest LLO (2019). C opyright of the Dissertation is held by the Author. All rights reserved. This work is protected against unauthorized copying under Title 17, United States C o d e M icroform Edition © ProQuest LLO. ProQuest LLO. 789 East Eisenhower Parkway P.Q. Box 1346 Ann Arbor, Ml 4 8 1 0 6 - 1346

ACKNOWLSDŒÆEtîT

The a u t h o r w is h e s t o e x p r e s s h i s s i n c e r e a p ­ p r e c i a t i o n to P r o f e s s o r P h i l i p J* E lv in g f o r h i s i n v a l u a b l e a i d a n d g u id a n c e i n t h e p u r ­ suance o f th e s e i n v e s t i g a t i o n s .

The a u t h o r

a l s o w is h e s t o t h a n k t h e P u rd u e R e s e a r c h F o u n d a t i o n and t h e A tom ic E n e rg y Com m ission f o r p r e d o c t o r a l f e l l o w s h i p s upon w h ic h t h e work d e s c r i b e d was p e r f o r m e d .

TABLE OF CONTENTS Page ABSTRACT ................................................................................................ PART I

ETHYLENE DICHLORIDE-TOLUENE AND FORMIC ACID-ACETIC ACID

..................................

In tro d u c tio n

. . . . . .

1

E x p e r i m e n t a l Work

.............................

3

......................

5

S u m m a r y ........................................................................

8

L i t e r a t u r e C i t e d ....................................................

14

V a p o r - L l q u l d E q u i l i b r i u m D a ta

PART I I

i

CIS- AND TRANS- 1 , 2-CYCLOPENTANEDIOL In tro d u c tio n

•

. .

. . . . .

E x p e r i m e n t a l ............................

l6 20

C y c l o p e n t a n o n e ..........................................

20

C y clo p en ta n o l

20

.................................

C y c lo p e n te n e ..........................................................

21

C y c l o p e n te n e O xide . . . . . . . . . .

21

t r a n s - l , 2 - C y c l o p e n t a n e d l o l . .......................

22

T r e a tm e n t o f t r a n s - l , 2 - C y c l o p e n t a n s d i o l w i t h Sodium and M e th y l I o d i d e

PART I I I

. . . .

22

S u m m a r y .....................................

22

L i t e r a t u r e C i t e d ....................... ..... .......................

24

SYSTEMS INVOLVING CIS- OR TRANSDICHLOROETHYLENE

................................................

In tro d u c tio n

............................

E x p e r i m e n t a l ......................................................... ....

25 29

TABLE OP CONTENTS, c o n tM Page P re p a ra tio n of M a te ria ls A p p aratu s

....................

...............................................

29

.

31

T e c h n ic and P r o c e d u r e ..............................

31

D a t a ........................................................................

32

V a p o r - L i q u i d E q u i l l h r i u m D a ta . . . D iscu ssio n o f R e su lts

..................................

32 36

A c tiv ity C o e ffic ie n ts

.............................

36

C a lc u la tio n s

.

.

39

. . . . .

42

S u m m a r y ..................................................................

46

L i t e r a t u r e C i t e d ...........................................

89

.

.

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.

.

.

E f f e c t o f S t r u c t u r e and P h y s i c a l P ro p e rtie s

VITA

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LIST OP TABLES PART I T a b le 1.

Page V a p o r - L i q u i d E q u i l i b r i u m D a ta f o r System E t h y l e n e D i c h l o r i d e - T o l u e n e a t 760 Mm.........................

9

2.

V a p o r - L i q u i d E q u i l i b r i u m D a ta f o r System F o rm ic A c i d - A c e t i c A c id a t 760 Mm............................................................................................ 10

3.

Smoothed D a ta f o r System Form ic A c i d A c e t i c A c id a t 760 Mm........................................ ..... .

11

PART I I I 1.

A z e o t r o p e s and V a p o r - L i q u i d E q u i l i b r i u m D a ta I n v o l v i n g c i s - t r a n s I s o m e r s from H o rsely * s T a b l e s .................................................................... 48

2.

R e f r a c tiv e In d ic e s f o r B in a ry S o lu tio n s o f c i s - o r tr a n s -D lc h lo ro e th y le n e and M eth y l A lc o h o l a t 2 0 . 0 ^ 0 .......................................... 5 l

3.

R e f r a c tiv e I n d ic e s f o r B in a ry S o lu tio n s o f c i s - o r t r a n s -D ie h lo re e th y le n e w ith M e t h y l a l , T e t r a h y d r o f u r a n , and I s o ­ p r o p y l E t h e r a t 2 0 °C . . . . . . . . . . .

52

R e f r a c tiv e I n d ic e s f o r B in ary S o lu t io n s of c i s - o r tr a n s - P ic h io ro e th y le n e w i t h E t h y l F o r m a te , M e th y l A c e t a t e , A c e to n e a n d 2 -B u ta n o n e a t 2 0 °C . . . . . .

53

D a ta on B i n a r y A z e o t r o p e s o f c i s D i c h l o r o e t h y 1 e ne an d j t r a n s - D i e h l o r o ­ e t h y l e n e w i t h M e th y l A l c o h o l . . . . . . .

54

4.

5.

6.

V a p o r - L i q u id E q u i l i b r i u m D a ta f o r System c i s - D l c h l o r o e t h y l e n e M e th y l A lc o h o l a t 7 6 0 .0 Mm. . ................................. 54

7.

V a p o r - L i q u i d E q u i l i b r i u m D a ta f o r System t r a n s - D l c h i o r o e t h y l e n e M e th y l A lc o h o l a t 7 6 0 .0 Mm., ................................. 55

8.

Smoothed E q u i l i b r i u m D a ta an d A c t i v i t y C o e f f i c i e n t s f o r System c i s - D i c h l o r o e t h y l ene-Me t h y l A lc o h o l a t 7 6 0 .0 Mm.

. . .

55

LIST OP TABLES, c o n t* d T ab le 9.

10.

Page Smoothed E q u i l i b r i u m D a ta and A c t i v i t y C o e f f i c i e n t s f o r S y stem t r a n s - D l c h l o r o e t h y l e n e - M e t h y l A lc o h o l a t 7 6 0 .0 Mm....................................................................................

56

A c t i v i t y C o e f f i c i e n t s C a l c u l a t e d from A z e o t r o p i c D a ta f o r System c i s D i e h l o r o e t h y l e n e - E t h y l A lc o h o l U s in g Van L a a r E q u a t i o n s ........................................................

57

11. A c t i v i t y C o e f f i c i e n t s C a l c u l a t e d from A z e o t r o p i c D a ta f o r System t r a n s D i c h l o r o e t h y l e n e - E t h y l A lc o h o l U sin g Van L a a r E q u a t i o n s . ............................................

57

12.

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14.

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V a p o r - L i q u id E q u i l i b r i u m D a ta f o r System c l s -D ic h lo ro e th y le n e-M e th y la l a t ■76Ô.O Mm................................................................................

58

V a p o r - L i q u i d E q u i l i b r i u m D a ta f o r System tra n s -D ie h io ro e th y le n e -M e th y la l a t 7 6 0 .0 Mm...............................................................................

58

V a p o r - L l q u l d E q u i l i b r i u m D a ta f o r System c l s -D lc h lo ro e th y le n e -T e tra h y d ro fu ra n a t 7 6 0 .0 Mm......................................................................

59

V a p o r - L l q u l d E q u i l i b r i u m D a ta f o r System tr a n s -D lc h lo ro e th y le n e -T e tra h y d ro fu ra n a t 76"0.0 Mm......................................................................

60

V a p o r - L i q u i d E q u i l i b r i u m D a ta f o r System c i s -D lc h lo ro e th y le n a -Is o p ro p y l E th er a t 7 6 0 .0 Mm......................................................................

60

V a p o r - L i q u id E q u i l i b r i u m D a ta f o r System tr a n s -D ie h lo ro e th y le n e -Is o p ro p y l E th er a t 7 6 0 .0 Mm. .............................................

6l

Smoothed E q u i l i b r i u m D a ta and A c t i v i t y C o e f f i c i e n t s f o r System c i s - D i c h l o r o e t h y l e n e - M e t h y l a l a t 7 6 0 .0 Mm. . . . . .

6l

Smoothed E q u i l i b r i u m D a ta a n d A c t i v i t y C o e f f i c i e n t s f o r Sy stem t r a n s - D i c h l o r o e t h y l e n e - M e t h y l a l a t 7 6 0 ,0 Mm. . . .

62

LIST OP TABLES, c o n t* d T a b le 20.

21.

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23.

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26.

27.

28.

29.

30.

31.

a n o o th e d E q u i l i b r i u m D a ta and A c t i v i t y C o e f f i c i e n t s f o r System c ^ - D i c h l o r o ­ e t h y l e n e - T e t r a h y d r o f u r a n a t 7 6 0 .0 Mm. .

•

Smoothed E q u i l i b r i u m D a ta an d A c t i v i t y C o e f f i c i e n t s f o r System t r a n s - D i c h lo ro e th y le n e -T e tra h y d ro fu ra n a t 7 6 0 .0 Mm•

63

Smoothed E q u i l i b r i u m D a ta and A c t i v i t y C o e f f i c i e n t s f o r S y stem c i s - D i c h l o r o e t h y l e n e - I s o p r o p y l E t h e r a t 7 6 0 . 0 Mm. .

.

a n o o th e d E q u i l i b r i u m D a ta a n d A c t i v i t y C o e f f i c i e n t s f o r S ystem t r a n s D ic h lo ro e th y le n e -Iso p ro p y l E th er a t 7 6 0 .0 Mm....................................................................

64

V a p o r - L i q u i d E q u i l i b r i u m D a ta f o r System c i s - D i c h l p r o e t h y l e n e - E t h y l F o rm a te a t 760.0 Mm..........................................

64

V a p o r - L i q u i d E q u i l i b r i u m D a ta f o r System t r a n s - D i c h l o r o e t h y l e n e E t h y l F o rm a te a t 7 6 0 .0 Mm. . . . . . . . . V a p o r - L i q u i d E q u i l i b r i u m D a ta f o r System c i s - D i c h l o r o e t h y l e n e - M e t h y l A c e t a t e a t 7 6 0 .0 Mm..........................................

62

63

65

65

V a p o r - L l q u l d E q u i l i b r i u m D a ta f o r System t r a n s - D l c h l o r o e t h y l e n e M e th y l A c e t a t e a t 7 6 0 .0 Mm....................................

66

V a p o r - L i q u id E q u i l i b r i u m D a ta f o r System c i s - D i c h i o r o e t h y l e n e - A c e to n e a t 7 6 0 .0 Mm.............................................................

67

V a p o r - L i q u id E q u i l i b r i u m D a ta f o r System t r a n s - D i e h l o r o e t h y l e n e A c e to n e a t 7 6 0 .0 Mm. .......................................

67

V a p o r - L i q u id E q u i l i b r i u m D a ta f o r System c i s - D i c h l o r o e t h y l e n e 2 -B u ta n o n e a t 7 6 0 .0 Mm........................................

68

V a p o r - L i q u i d E q u i l i b r i u m D a ta f o r System t r a n s - D i c h l o r o e t h y l e n e 2 -B u ta n o n e a t 7 6 0 .0 Mm..............................................

69

LIST OP TABLES, c o n t ’ d T ab le 32.

33.

34.

35.

36.

37 .

38.

39.

40. 41. 42.

Pag© Smoothed E q u i l i b r i u m D a t a a n d A c t i v i t y C o e f f i c i e n t s f o r System c l s - D i c h l o r o e t h y l e n e - E t h y l F o rm a te a t 7 6 0 .0 Mm. . .

69

Smoothed E q u i l i b r i u m D a ta a n d A c t i v i t y C o e f f i c i e n t s f o r System t r a n s D i e h l o r o e t h y l e n e - E t h y l F o rm a te a t 7 6 0 .0 Mm...................................................................................

70

Smoothed E q u i l i b r i u m D a ta and A c t i v i t y C o e f f i c i e n t s f o r System c l s - D i c h l o r o e th y l© n e -M e th y l A c e t a t e a t 7 6 0 ,0 Mm. . . .

70

Smoothed E q u i l i b r i u m D a ta a n d A c t i v i t y C o e f f i c i e n t s f o r S y stem t r a n s - D i e h l o r o e t h y l e n e - M e t h y l A c e t a t e a t 7 6 0 .0 Mm. . . .

71

Smoothed E q u i l i b r i u m D a ta an d A c t i v i t y C o e f f i c i e n t s f o r System c i s - D i c h l o r o e t h y l e n e -Ac e t on© a t 7 6 0 .0 Mm................................

71

Smoothed E q u i l i b r i u m D a ta and A c t i v i t y C o e f f i c i e n t s f o r System t r a n s D i e h l o ro e t h y l e n e - A c e t one a t 76 0 . 0 ....................

72

S n o o th e d E q u i l i b r i u m D a ta an d A c t i v i t y C o e f f i c i e n t s f o r System c i s - D i c h l o r o e t h y l e n e - 2 - B u t a n o n e a t 7 6 0 .0 Mm. . . . .

72

Smoothed E q u i l i b r i u m D a ta and A c t i v i t y C o e f f i c i e n t s f o r System t r a n s - D i c h l o r o e t h y l e n e - 2 - B u t a n o n e a t 7 6 0 .0 Mm. . .

73

V apor P r e s s u r e - T e m p e r a t u r e R e l a t i o n s f o r M e t h y l a l .........................................

73

V apor P r e s s u r e - T e m p e r a t u r e R e l a t i o n s f o r T e t r a h y d r o f u r a n .....................................................

73

P i t o f E x p e r im e n ta l D a ta f o r B i n a r y S y ste m s to T h e o r e t i c a l E q u a t i o n s ......................

74

LIST OP FIGURES PART I F ig u re 1.

2.

Page B o l l i n g P o i n t - C o m p o s i t i o n D iagram f o r System F o rm ic A c i d - A c e t i c A c id a t 760 Mm, o f M e r c u ry P r e s s u r e ........................................................................................ V a p o r - L i q u id E q u i l i b r i u m D iagram f o r System F o rm ic A c i d - A c e t i c A c id a t 760 Mm. o f M e rc u ry P r e s s u r e .......................................................................

• .

12

13

PART I I I 1.

2.

V apor P r e s s u r e - C o m p o s i t i o n P l o t s f o r c i s o r t r a n s Is o m e r s with. a Second Component o f C l a s s I I ............................

75

D iag ram o f M o d i f i e d C o lb u r n V a p o rL i q u i d E q u i l i b r i u m S t i l l ...........................................

76

3.

D iagram o f P r e s s u r i n g A p p a r a t u s .

........................

77

4.

B o i l i n g P o i n t - C o m p o s i t i o n D ia g ra m s . c i s - o r tr a n s -D ie h lo ro e th y le n e w ith M e t h a n o l ......................................................................

78

E q u i l i b r i u m Mole F r a c t i o n o f L ow erB o i l i n g Component i n t h e V a p o r, , v s . Mole F r a c t i o n i n th e q u i d , X ,, a t 760 Mm. o f M ercu ry P r e s s u r e ....................................................

79

A c t i v i t y C o e f f i c i e n t v s . Mole F r a c t i o n L o w er-B o ilin g Component i n th e L i q u i d , , a t 760 Mm. o f M e rc u ry P r e s s u r e .............................

80

B o i l i n g P o i n t - C o m p o s i t i o n D ia g r a m s . T e m p e r a tu r e , ° C . , v ^ . Mole F r a c t i o n o f L o w e r - B o i l i n g Component a t 76O Mm. o f M e rc u ry P r e s s u r e , c l 3- o r t r a n s -D ic h lo ro e th y le n e w ith M e th y la l, T e t r a h y d r o f u r a n an d I s o p r o p y l E t h e r .

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LIST OF FIGURES, co n t^ d F ig u r e s 8.

9.

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E q u i l i b r i u m Mole F r a c t i o n o f L o w e r - B o i l i n g Component i n th e V a p o r, Yl * v s . Mole F r a c t i o n i n t h e H i q u i d , Xl» a t 760 Mm. o f M e r c u ry P r e s s u r e . Same S y ste m s a s i n F i g . 7 . . . * ............................ *

82

A c tiv ity C o e ffic ie n t 2Ë " F r a c t i o n L o w e r - B o i l i n g Component i n t h e L i q u i d , X^, a t 760 Mm. o f M ercu ry P r e s s u r e . Same S y stem s as in F ig . 7.

83

B o i l i n g P o i n t - C o m p o s i t i o n D ia g ra m s . T e m p e r a tu r e , ° C . , v s . M ole F r a c t i o n L o w e r - B o ili n g Component a t 760 Mm. o f M e rc u ry P r e s s u r e , c is - or tra n s D i c h i o r o e t h y l © n e w i t h E t h y l F o rm a te and M e th y l A c e t a t e . .....................................................

84

B o i l i n g P o i n t - C o m p o s i t i o n D ia g r a m s . T e m p e r a t u r e , ° C . , v s . Mole F r a c t i o n L o w e r - B o i l i n g Component a t 7 6 0 .0 Mm. o f M ercu ry P r e s s u r e , c i s - o r t r a n s - D l c h l o r o e t h y l en e w i t h A c e to n e a n d 2 - B u ta n o n e .

85

E q u i l i b r i u m Mole F r a c t i o n o f L ow erB o i l i n g Component i n t h e V a p o r, Y i, v s . Mole F r a c t i o n i n t h e L i q u i d , Xl^ a t 7 6 0 .0 Mm. o f M e rc u ry P r e s s u r e T Same S y ste m s a s i n P i g . 1 0 .....................

86

E q u i l i b r i u m Mole F r a c t i o n B o i l i n g Component i n t h e v s . Mole F r a c t i o n i n t h e a t 7 6 0 .0 Mm. o f M e rc u ry Same System s a s i n F i g .

87

o f L ow erV a p o r, Yt , L i q u i d , X^, P re ssu re ." ” 1 1 ...........................................

A c t i v i t y C o e f f i c i e n t v s . Mole F r a c t i o n L o w e r - B o i l i n g Component i n t h e L i q u i d , X^, a t 7 6 0 ,0 Mm. o f M e rc u ry P r e s s u r e . Same S ystem s a s i n F i g . 10 a n d F i g . 1 1 .

. . .

88

VAPOR-LIQUID EQUILIBRIA IN BINARY SYSTMS SYSTMS INVOLVING C IS - OR TRANS-DICHLOROETHYLENE^

^ A b s t r a c t e d from t h e d o c t o r a l t h e s i s o f Norman A l p e r t , P u rd u e U n i v e r s i t y , A u g u s t , 1 9 4 9 .

Norman A l p e r t and P h i l i p J , E l v i n g P urdue U n i v e r s i t y a n d P u rd u e R e s e a r c h F o u n d a t i o n L a fa y e tte , In d ia n a

AN ABSTRACT B ec a u se o f i n c r e a s e d a p p l i c a t i o n o f f r a c t i o n a l d i s ­ t i l l a t i o n to i n d u s t r i a l p r o c e s s e s , v a p o r - liq u i d e q u ilib riu m d a t a h a v e assum ed c o n s i d e r a b l e i m p o r t a n c e .

E q u ilib ria

s tu d ie s a r e u s u a ll y u n d e rta k e n f o r t h i s re a s o n , b u t in t h i s i n v e s t i g a t i o n , i t was d e s i r e d t o u s e v a p o r - l i q u i d e q u i l i b r i a a s a means o f s t u d y i n g t h e e f f e c t o f h y d r o g e n - b o n d i n g , d i p o l e m om ents, a n d s t e r l c f a c t o r s i n n o n - i d e a l s y s t e m s . A s y ste m a tic stu d y o f th e v a p o r - liq u id e q u ilib riu m r e l a t i o n s i n v o l v i n g c i s - t r a n s i s o m e r s was u n d e r t a k e n .

T h e re

i s a p p a r e n t l y o n l y a s m a l l amount o f p u b l i s h e d d a t a a v a i l ­ a b l e on v a p o r - l i q u i d e q u i l i b r i u m r e l a t i o n s h i p s and a z e o t r o p e f o r m a t i o n i n s y s te m s i n v o l v i n g c i s - t r a n s i s o m e r s . r e c e n t c o m p i l a t i o n o f a z e o t r o p e s (^ ) l i s t s

The m o s t

23 c a s e s w h e re

d a ta f o r v a p o r- liq u id e q u i l i b r i a o r a ze o tro p e fo rm atio n have b e e n p u b l i s h e d f o r e a c h o f a p a i r o f c i s - t r a n s is o m e r s w i t h a t h i r d compound. The g e n e r a l i z a t i o n s o f E w e l l , H a r r i s o n a n d B erg (5 )

11

c o n c e rn in g h y d ro g e n -b o n d in g and a z e o tro p e f o r m a tio n a r e u s e f u l in c o r r e l a t i n g th e e x i s t i n g v a p o r - liq u id e q u ilib riu m d a ta In v o lv in g c i s- tr a n s iso m e rs.

I n m o st o f th e s y s te m s

s t u d i e d , th e c i s - t r a n s iso m e rs have b e e n l i q u i d s o f c l a s s e s IV and V an d t h e o t h e r com ponent h a s u s u a l l y b e e n a l i q u i d of c la ss I I (5 ,

.

L i q u i d s o f c l a s s I I a r e t h o s e composed

o f m o l e c u l e s c o n t a i n i n g b o t h a c t i v e h y d r o g e n atom s a n d d o n o r a to m s ; c l a s s IV l i q u i d s a r e t h o s e com p o sed o f m o l e c u l e s c o n ­ t a i n i n g a c t i v e h y d r o g e n a to m s b u t no d o n o r a to m s ; an d c l a s s V l i q u i d s a r e t h o s e h a v i n g no h y d r o g e n - b o n d - f o r m i n g c a p a b i l ­ itie s .

I n su m m a riz in g d e v i a t i o n s from R a o u l t ’s l a w , i t was

p o i n t e d o u t ( 5 ) t h a t when l i q u i d s o f c l a s s I I and c l a s s V a r e m ix e d , h y d r o g e n b o n d s a r e b r o k e n , an d p o s i t i v e d e v i a ­ t i o n s fro m R a o u lt* s la w r e s u l t .

Mien l i q u i d s o f c l a s s I I

and c l a s s IV a r e m ix e d , h y d r o g e n b o n d s a r e b o t h b r o k e n a n d fo r m e d , b u t t h e d i s s o c i a t i o n o f th e c l a s s I I l i q u i d i s t h e more i m p o r t a n t e f f e c t , an d h e n c e p o s i t i v e d e v i a t i o n s from R a o u l t ^ 8 la w r e s u l t . I n t h e s y s te m s r e p o r t e d i n v o l v i n g c i s - t r a n s i s o m e r s , in a l l b u t 5 c a se s

, th e

l i q u id of c la s s I I h as been

m e th y l, e t h y l , o r p ro p y l a lc o h o l. v o lv in g c i s - t r a n s is o m e rs, th e

In th e o th e r c ase s in ­

l i q u i d o t h e r t h a n th e c i s

o r t r a n s is o m e r h a s b e e n w a t e r , s u l f u r d i o x i d e , e t h y l e n e o x i d e , 1 - b u t y n e an d m e th y l f o r m a t e . The a c t u a l f o r m a t i o n o f a n a z e o t r o p e w i l l d e p e n d upon t h e m a g n itu d e o f t h e d e v i a t i o n s fro m R a o u lt* s la w

Ill

a n d t h e b o i l i n g p o i n t d i f f e r e n c e b e tw e e n t h e two c o m p o n e n ts . The s m a l l e r t h e d e v i a t i o n fro m R a o u l t * s la w f o r a p a i r o f liq u id s,

th e s m a lle r th e d i f f e r e n c e i n b o i l i n g p o i n t m ust b e

fo r a z e o tro p e fo rm a tio n .

I f an a z e o t r o p e i s fo rm e d i n t h e

s y s te m , p o s i t i v e d e v i a t i o n s fro m R a o u l t * s la w c a n r e s u l t o n l y i n a m in im u m - b o ilin g a z e o t r o p e , w h e re a s n e g a t i v e d e v i ­ a t i o n s may c a u s e o n l y m a x im u m -b o ilin g a z e o t r o p e s .

The c o n ­

s t r u c t i o n o f v ap o r p r e s s u r e v s . co m p o sitio n p l o t s f o r th e s y s te m s i n v o l v i n g c i s - t r a n s i s o m e r s ( c l a s s IV and V) a n d liq u id s of c la ss I I ,

i n w h ic h d e v i a t i o n s fro m I d e a l i t y w i l l

be p o s i t i v e , p e rm its c o r r e l a t i o n o f m ost of th e e x i s t i n g d a ta in th e l i t e r a t u r e . I n s e l e c t i n g a p a i r o f c i s - t r a n s iso m e rs f o r s tu d y , i t was d e c i d e d t o s t a r t w i t h c i s - and t r a n s - d l c h l p r o e t h y l e n e , T h ese i s o m e r s a r e r e a d i l y a v a i l a b l e and c an b e r e a d i l y p u r i ­ f i e d by f r a c t i o n a l d i s t i l l a t i o n .

As c l a s s IV l i q u i d s , i t

w ould b e e x p e c t e d t h a t b o t h is o m e r s s h o u l d form weak h y d r o ­ gen b o n d s .

M in im u m - b o ilin g a z e o t r o p e s h a v e b e e n r e p o r t e d

f o r e a c h i s o m e r w i t h w a t e r and e t h y l a l c o h o l .

A s im ila r

a z e o t r o p e h a s b e e n r e p o r t e d f o r t h e c i s fo im w i t h m e th y l a lc o h o l.

I n a d d i t i o n , minimum b o i l i n g a z e o t r o p e s f o r t h e

t e r n a r y s y ste m o f e a c h is o m e r w i t h w a t e r a n d e t h y l a l c o h o l w ere r e p o r t e d ( ^ ) .

I t was d e c i d e d t o d e t e r m i n e t h e v a p o r -

l i q u i d e q u i l i b r i u m r e l a t i o n s h i p s o f t h e c i s a n d t r a n s fo rm s w i t h m e th y l a l c o h o l and t o c a l c u l a t e th e r e l a t i o n s h i p s from t h e a z e o t r o p i c d a t a a v a i l a b l e f o r t h e b i n a r y s y s te m s

iv

o f e a c h is o m e r w i t h e t h y l a l c o h o l . In c o n tin u in g th e stu d y o f th e v a p o r - liq u i d e q u i­ l i b r i u m r e l a t i o n s i n b i n a r y s y s te m s w i t h c i s - o r t r a n s - d i c h l o r o e t h y l e n e a s one c o m p o n e n t, i t was d e c i d e d t o i n v e s t i ­ g a te th e b e h a v io r o f th e s e iso m ers w ith c l a s s I I I l i q u i d s ( 5 ) , l i q u i d s c o n t a i n i n g d o n o r ato m s b u t no a c t i v e h y d ro g e n a to m s .

The c l a s s I I I l i q u i d s f i r s t s e l e c t e d f o r s t u d y i n

t h i s i n v e s t i g a t i o n w ere m e t h y l a l ( d im e th y o x y m e th a n e ) , t e t r a ­ h y d ro fu ra n , and is o p ro p y l e t h e r . I n c o n t i n u a t i o n o f t h e s t u d y o f th e v a p o r - l i q u i d e q u i l i b r i u m r e l a t i o n s i n b i n a r y s y s te m s w i t h c i s - o r t r a n s d i c h i o r o e t h y l e n e a s one c o m p o n e n t, t h e o t h e r com ponent b e i n g a l i q u i d o f c l a s s I I I , e s t e r s an d k e t o n e s w ere t h e n s e l e c t e d . The e s t e r s s t u d i e d w ere e t h y l f o r m a t e sued m e th y l a c e t a t e ; t h e k e t o n e s w ere a c e t o n e a n d 2 - b u t a n o n e . EXPERIMENTAL P rep a ra tio n o f M a te ria ls .

Some o f t h e c i s - and

t r a n s - d i o h l o r o e t h y l ene u s e d was f u r n i s h e d by t h e Dow C h em ica l Company to whom t h e a u t h o r s w a n t t o e x p r e s s a p p r e c i a t i o n ; t h e compounds h a d a p u r i t y o f 9 9 .5 m ole p e r c e n t .

The r e ­

m a in d e r o f t h e c i s - and t r a n s - d i c h i o r o e t h y l e n e was p r e p a r e d b y c a r e f u l f r a c t i o n a l d i s t i l l a t i o n th r o u g h a 1 2 0 - c m . , 12-mm. I . D. g l a s s h e l i c e - p a c k e d colum n a t a r e f l u x r a t i o o f a b o u t 3 0 :1 o f m a t e r i a l p u r c h a s e d from C olum bia O r g a n ic C h e m ic a ls Company.

The i s o m e r s p r e p a r e d i n t h i s m an n er h a d t h e same

b o i l i n g p o i n t s an d r e f r a c t i v e i n d i c e s a s t h a t f u r n i s h e d b y

Dow; t h e v a l u e s f o r t h e c i s i s o m e r w ere b . p . 6 0 . 3 G. , a n d 20 hjj 1 . 4 4 8 3 * a n d f o r t h e t r a n s i s o m e r , b . p . 4 8 . 3 ^ 0 . and n^® 1 . 4 4 5 5 .

The m e th y l a l c o h o l was p u r i f i e d b y c a r e f u l

f r a c t i o n a l d i s t i l l a t i o n o f c o m m e rc ia l a b s o l u t e m e th y l a l c o ­ h o l ; t h e m a t e r i a l u s e d b o i l e d 6 4 .6 ° C . an d h a d a r e f r a c t i v e in d e x ,

o f 1 .3 2 8 7 *

M e t h y l a l was p u r c h a s e d fro m t h e

P aragon T e s tin g L a b o r a t o r i e s .

The f r a c t i o n b o i l i n g a t

4 2 . 6 ^ 0 , was c o l l e c t e d and h a d a r e f r a c t i v e i n d e x , n ^ ^ . o f 1 . 3535.

T e t r a h y d r o f u r a n was E astm an -K o d ak # i l t e l a b e l a n d

was c o l l e c t e d a t 6 6 . 1 ^ 0 . (n ^ O I . 4 0 6 9 ) , a f t e r a c o n s i d e r a b l e forerun .

I s o p r o p y l e t h e r was E a stm an -K od ak w h i t e l a b e l an d I . 368O ),

d i s t i l l e d a t 6 8 .0 ^ 0 .

E t h y l f o r m a t e was p u r ­

c h a s e d fro m P a r a g o n T e s t i n g L a b o r a t o r i e s ; t h e f r a c t i o n b o i l i n g a t 5 4 . 0 ^ 0 . was c o l l e c t e d a n d h a d a r e f r a c t i v e i n ­ d e x , n^^ = 1 . 3 5 9 8 .

Eastm an Kodak y e l l o w l a b l e m e th y l a c e t a t e

was p u r i f i e d b y t h e m etho d o f German a n d J a m s e t t ( 8 ) ; f i n a l p u r i f i c a t i o n was a c h i e v e d by d i s t i l l a t i o n . b o i l i n g a t 5 7 *2 °C . was c o l l e c t e d

The f r a c t i o n

■ 1 .3 6 1 4 ) C. P . a c e to n e

was d i s t i l l e d a t a r e f l u x r a t i o o f 2 0 : 1 .

The f r a c t i o n c o l ­

l e c t e d h a d a b o i l i n g p o i n t o f 5 6 . 4 ° C. (n^Q = 1 . 3 5 8 6 ) . 2 -B u ta n o n e (E astm an -K o dak y e llo w l a b e l ) was c o l l e c t e d a t 7 9 .6 ° C . ( s 2 0 = 1 . 3 7 8 5 ) . A p p a ratu s.

The e q u i l i b r i u m s t i l l

em ployed was c o n ­

s t r u c t e d a s i n d i c a t e d b y J o n e s , S c h o e n b o rn , and C o lb u rn ( l O ) . The s t i l l was m o d i f i e d fro m t h e o r i g i n a l d e s i g n b y s e a l i n g a s m a ll d r o p p i n g f u n n e l t o t h e t u b e l e a d i n g fro m t h e c o n ­

Vi

d e n s e r to t h e U - t u b e .

T h is g r e a t l y f a c i l i t a t e d th e c h a rg in g

o f t h e sam ple t o t h e s t i l l . a t i o n o f th e s t i l l (l^, 1 0 ) .

O b se rv a tio n s c o n ce rn in g th e o p e r­

a r e t h e same a s t h o s e n o t e d p r e v i o u s l y

A s i d e fro m f u r n i s h i n g r e l i a b l e v a p o r - l i q u i d e q u i ­

l i b r i u m d a t a , t h e J o n e s - S c h o e n b o r n - C o l b u r n s t i l l was s e l e c t e d f o r th e s m a ll volume o f l i q u i d t h a t c o u l d b e h a n d l e d , w i t h th e r e s u l t a n t s a v i n g o f tim e i n p u r i f y i n g l i q u i d s f o r s t u d y . The t o t a l volume o f l i q u i d c o n t a i n e d i n t h e s t i l l d u r i n g o p e r a t i o n was a p p r o x i m a t e l y 15 t o l 8 m l. The s t i l l was c o n n e c t e d t o a p r e s s u r e - r e g u l a t i n g s y s ­ tem s i m i l a r to t h a t d e s c r i b e d b y B a k e r ( 2 ) .

The t e m p e r a t u r e -

m e a s u r in g s y s te m was t h e same a s t h e one d e s c r i b e d p r e v i o u s l y (l)

and was c a l i b r a t e d by b o i l i n g t h e p u r e s a m p le s o f w a t e r ,

t o l u e n e , an d a l l l i q u i d s s t u d i e d i n t h i s i n v e s t i g a t i o n i n t h e still.

The b o i l i n g p o i n t s o f t h e s e l i q u i d s w ere c h e c k e d on

a th e rm o m e te r t h a t h a d b e e n c a l i b r a t e d b y t h e N a t i o n a l B u re a u o f S ta n d a rd s.

A ll te m p e ra tu re s in t h i s p a p e r have been c o r ­

re c te d . T e c h n ic a n d P r o c e d u r e .

The g e n e r a l t e c h n i c f o r e x ­

p e rim e n ta lly d e te rm in in g v a p o r - liq u id e q u i l i b r i a has b e en d e sc rib e d in th e l i t e r a t u r e of s till

and i n p a r t i c u l a r f o r t h e t y p e

em ployed i n t h e s e i n v e s t i g a t i o n s ( 1 0 ) .

A p p ro x im a te ­

l y 15 t o l 8 m l. o f one com ponent was c h a r g e d to t h e s t i l l , and m i x t u r e s w i t h s u c c e s s i v e a d d i t i o n s o f t h e o t h e r compon­ e n t were a l l o w e d t o come t o c o n s t a n t t e m p e r a t u r e .

A fte r

smooth o p e r a t i o n o f t h e s t i l l was o b t a i n e d , 40 m i n u t e s was

v il

a llo w ed f o r th e e s ta b lis h m e n t o f e q u i l i b r i u m .

S a m p le s o f

l i q u i d and v a p o r w ere t h e n w ith d ra w n s i m u l t a n e o u s l y an d a n aly z e d .

E q u i l i b r i u m s a m p le s w ere a n a l y z e d b y r e f r a c t i v e

i n d e x m e a s u re m e n ts a t 20°C .

DATA V ap o r-L iq u id E q u ilib riu m D a ta .

A l l s y s te m s w ere

s t u d i e d a t a p r e s s u r e o f 7 6 0 ,0 + 0 . 5 mm. o f m e r c u r y .

The

d a t a on t h e a z e o t r o p e s f o m e d a r e p r e s e n t e d i n T a b le I . The c o m p o s i t i o n s a n d b o i l i n g p o i n t s o f t h e a z e o t r o p e s f o m e d w i t h m e th y l a l c o h o l w ere c a r e f u l l y c h e c k e d b y p r e ­ p a rin g m ix tu re s a p p ro x im a tin g th e a z e o tr o p ic c o m p o sitio n s and f r a c t i o n a l l y d i s t i l l i n g t h e m i x t u r e s t h r o u g h a n e f ­ f i c i e n t column (50 t h e o r e t i c a l p l a t e s ) .

The a z e o t r o p e was

t h e n w ith d ra w n a t a h i g h r e f l u x r a t i o an d a n a l y z e d b y r e ­ f r a c t i v e i n d e x m e a s u re m e n t a n d a n a l y s i s f o r c h l o r i n e .

The

th e rm o m e te r u s e d f o r o b s e r v i n g t h e b o i l i n g p o i n t s o f t h e a z e o t r o p e s was c a l i b r a t e d a g a i n s t a th e r m o m e te r c a l i b r a t e d b y t h e N a t i o n a l B u re a u o f S t a n d a r d s .

The c o m p o s i t i o n and

b o i l i n g p o i n t s o f t h e a z e o t r o p e s fo rm e d w i t h t e t r a h y d r o ­ f u r a n , m e t h y l a l , m e th y l a c e t a t e , and a c e t o n e , c o u l d n o t b e checked by f r a c t i o n a l l y d i s t i l l i n g m ix tu r e s a p p ro x im a tin g t h e a z e o t r o p i c c o m p o s i t i o n s i n c e t h e colum n a v a i l a b l e d i d n o t have s u f f i c i e n t r e s o l v i n g pow er.

The v a p o r - l i q u i d e q u i ­

l i b r i u m r e l a t i o n s a r e s u c h t h a t s t a r t i n g on e i t h e r s i d e o f th e a z e o t r o p i c c o m p o s i t i o n g ave a r e s i d u e t h a t was r i c h e r

v lii

t h a n t h e a z e o t r o p i c c o m p o s i t i o n w i t h r e s p e c t t o t h e compon­ ent o rig in s d ly p re se n t in ex cess.

As a r e s u l t , a z e o t r o p i c

c o m p o s i t i o n s and b o i l i n g p o i n t s were d e t e r m i n e d fro m t h e sm oothed v a p o r - l i q u i d e q u i l i b r i u m d a t a .

C are was t a k e n t o

d e term in e s u f f i c i e n t e x p e r im e n ta l p o i n t s i n th e v i c i n i t y o f t h e a z e o t r o p e s t o p e r m i t d r a w in g o f a good a v e r a g e c u r v e . The e x p e r i m e n t a l r e s u l t s o b t a i n e d w e re c o l l e c t e d i n t a b u l a r and g ra p h ic f o m f o r th e b o i l i n g p o i n t c o m p o sitio n and t h e c o r r e s p o n d i n g v a p o r - l i q u i d e q u i l i b r i u m r e l a t i o n s . The a n o o th e d d a t a f o r t h e s y s te m s and t h e a p p a r e n t i s o p i e s t i c a c t i v i t y c o e f f i c i e n t s f o r e a c h com ponent w ere c a l c u l a t e d an d recorded.

The p l o t s o f t h e s e c o e f f i c i e n t s

(lo g a rith m ic

s c a l e ) a g a i n s t t h e m o le f r a c t i o n o f th e m ore v o l a t i l e com­ p o n e n t i n t h e l i q u i d ( l i n e a r s c a l e ) w ere p r e p a r e d .

S n o o th ­

in g o f t h e d a t a was j u s t i f i e d by t h e c l o s e n e s s o f t h e e x 2 p e r im e n ta l p o i n t s to th e c u r v e .

M e ta lle d ta b le s of th e d a ta o b ta in e d , th e c a lc u la te d r e ­ l a t i o n s a n d t h e c o r r e s p o n d i n g d ia g r a m s a r e a v a i l a b l e i n N, A l p e r t ' s d o c t o r a l t h e s i s on f i l e w i t h t h e D e p a rtm e n t o f C h e m is tr y and t h e G e n e r a l L i b r a r y , P u rd u e U n i v e r s i t y . The d a t a i n t h e l i t e r a t u r e on t h e a z e o t r o p e s fo rm e d i n t h e s y s te m s c i s - o r t r a n s - d i c h l o r o e t h y l e n e - e t h y l a l c o h o l ( ^ ) h a v e b e e n e x t e n d e d b y u s e o f t h e v a n L a a r e q u a t i o n s to c a lc u la te th e a c t i v i t y c o e f f ic ie n t cu rv es.

The v a p o r - l i q u i d

e q u ilib r iu m r e l a t i o n s th u s c a l c u l a t e d f o r c i s - o r t r a n s -

ix

d i c h i o r o e t h y l e n e - e t h y l a l c o h o l w ere co m p ared w i t h e x p e r i m e n t ­ a l l y d e term in e d r e l a t i o n s f o r c i s- o r t r a n s - d ic h lo r o e th y le n e m e th y l a l c o h o l .

DISCUSSION OP RESULTS A c tiv ity C o e ffic ie n ts .

C a r l s o n a n d C o lb u r n (4 ) s u g ­

g e s t e d t h a t t h e th e rm o d y n a m ic c o n s i s t e n c y o f v a p o r - l i q u i d e q u i l i b r i u m d a t a may b e t e s t e d b o t h q u a l i t a t i v e l y and q u a n t ­ i t a t i v e l y by p l o t t i n g th e lo g a rith m of th e a c t i v i t y c o e f f i c i e n t s f o r e a c h b i n a r y s y s te m a g a i n s t t h e m o le f r a c t i o n o f t h e m ore v o l a t i l e com ponent i n t h e l i q u i d .

F u r t h e r c o m p a r i s o n may be

made by c o m p a rin g t h e s e p l o t s w i t h t h o s e o b t a i n e d fro m t h e v a r i o u s i n t e g r a t e d fo rm s o f th e Gibbs-Duhem e q u a t i o n , t h a t i s , t h e van L a a r , M a r g u l e s , and S c a tc h a r d - H a m e r e q u a t i o n s (4 )•

I t was p o i n t e d o u t (4 ) t h a t t h e c l u e a s t o w hich e q u a ­

t i o n s t o u s e i s i n d i c a t e d by t h e m o la r v o lu m e s .

When t h e

m o la r v o lu m es a r e d i f f e r e n t , t h e van L a a r e q u a t i o n s a r e i n ­ d i c a t e d ; t h e M a r g u le s e q u a t i o n s may b e a p p l i c a b l e on s y s te m s where th e m o la r vo lu m e s a r e n e a r l y e q u a l b u t where t h e v a l u e s o f A and B d i f f e r g r e a t l y .

The v a n L a a r e q u a t i o n s h a v e f o u n d

w i d e s t a p p l i c a t i o n and f i t many s y ste m s w e l l .

The f i t o f t h e

van L a a r and M a r g u le s e q u a t i o n s a lo n g w i t h o t h e r p e r t i n e n t d a t a i s p r e s e n t e d i n T a b le I I .

C a r l s o n a n d C o lb u rn (4 )

h a v e d i s c u s s e d t h e e v a l u a t i o n and e x t e n s i o n o f v a p o r - l i q u i d e q u i l i b r i u m d a t a when t h e y a r e c a l c u l a t e d a s a c t i v i t y c o e f ­ fic ie n ts.

In f i t t i n g

t h e e x p e r i m e n t a l d a t a t o t h e van L a a r

o r M a r g u le s e q u a t i o n s , A o r B v a l u e s w ere d e t e r m i n e d b y t a k i n g t h e l o g a r i t h m o f t h e end v a l u e s o f t h e a c t i v i t y c o e f f i c i e n t c u r v e s o r w ere c a l c u l a t e d fro m a z e o t r o p i c d a t a . E f f e c t o f S t r u c t u r e and P h y s i c a l P r o p e r t i e s .

Ex­

a m i n a t i o n o f t h e d a t a f o r s y s te m s i n v o l v i n g l i q u i d s o f c l a s s I I I r e v e a l s s e v e r a l p o i n t s t h a t a re w o rth n o t i n g .

S w e ll

and Welch (£ ) an d E w e l l , H a r r i s o n and B erg ( 5 ) p o i n t e d o u t I t h a t compounds w i t h t h e s t r u c t u r e -C C l-C H C l- w i l l form weak h y d ro g e n b o n d s w i t h s u i t a b l e d o n o r ato m s su ch a s o xy ­ gen i n e s t e r s , k e t o n e s , e t h e r s , e t c .

I t w ould b e e x p e c t e d

t h a t b o t h c i s - an d t r a n s - d i c h l o r o e t h y l e n e w i l l fo rm h y d r o ­ gen b o n d s i n t h e p r e s e n c e o f s u c h o x y g e n a te d m o l e c u l e s . T h i s w ould b e on e f a c t o r i n e x p l a i n i n g t h e v a p o r - l i q u i d e q u ilib riu m r e l a t i o n s .

A n o th e r f a c t o r wDuld b e t h e d i p o l e

moments o f t h e c i s and t r a n s i s o m e r s , an d th e d i p o l e mo­ m e n ts o f t h e h y d r o g e n - b o n d e d com plex fo r m e d .

I t has been

shown t h a t th e v a l u e o f t h e d i p o l e moment f o r c i s - d i c h i o r o e t h y l e n e i s 1 . 8 d e b y e s ( i d ) , w h i l e t h e t r a n s is o m e r h a s a z e r o d i p o l e moment.

A c c o r d i n g l y , t h e c i s is o m e r w ould b e

e x p e c t e d t o show g r e a t e r d e p a r t u r e fr o m i d e a l i t y t h a n t h e t r a n s i s o m e r , b e c a u s e t h e com plex fo rm ed t h r o u ^ h y d r o g e n b o n d in g i n t h e c a s e o f t h e c i s is o m e r w ould s t i l l

have an

a p p r e c i a b l e d i p o l e moment and t e n d t o a s s o c i a t e th r o u g h e le c tro sta tic a ttra c tio n .

A t h i r d f a c t o r t h a t m u st b e c o n ­

s i d e r e d i s t h e c l o s e n e s s o f th e b o i l i n g p o i n t o f t h e s e c o n d com ponent t o t h e c i s o r t r a n s i s o m e r .

T h is i s e s p e c i a l l y

xl

im p o rta n t in p r e d i c t i n g a z e o tro p e fo rm a tio n (5 ,

7 ).

The

c l o s e r t h e b o i l i n g p o i n t o f t h e s e c o n d c o m p o n e n t, t h e m ore l i k e l y t h a t a maximum o r minimum w i l l o c c u r i n t h e t o t a l vapor p re s su re cu rv e.

Thus, i n th e sy ste m s, c i ^ - d i c h l o r o ­

e t h y l en e - m e t h y l a l and t r a n s - d i c h i o r o e t h y l en e-me t h y l a l , t h e t r a n s is o m e r f o m s a m a x im u m -b o ilin g a z e o t r o p e , t h e o n l y m a x im u m -b o ilin g a z e o t r o p e w i t h t h e t r a n s is o m e r o b s e r v e d in th ese s tu d ie s .

A s i d e fro m t h e f a c t t h a t m e t h y l a l b o i l s

much c l o s e r t o t h e t r a n s is o m e r t h a n t h e c i s , a s t e r l c f a c t o r may b e i n v o l v e d .

T h i s a b i l i t y o f e i t h e r is o m e r t o form l o n g

c h a in s w ith m e th y la l th ro u g h h y d ro g e n -b o n d in g , p lu s th e p ro x ­ i m i t y o f t h e b o i l i n g p o i n t o f t h e t r a n s is o m e r t o m e t h y l a l f a v o r s t h e f o r m a t i o n o f an a z e o t r o p e w i t h t h i s i s o m e r .

C h ain

f o r m a t i o n t h r o u g h h y d ro g e n -b o n d i n g i s a p p a r e n t l y n o t t h e p r e ­ d o m in a n t f a c t o r , b e c a u s e t h e c i s s y ste m s t i l l shows g r e a t e r n e g a t i v e d e v i a t i o n s fro m i d e a l i t y . The v a p o r - l i q u i d e q u i l i b r i u m r e l a t i o n s w i t h i s o p r o ­ p y l e th e r and te tr a h y d r o f u r a n a re i n t e r e s t i n g .

S w e ll an d

Welch (£ ) showed t h a t h a l o g e n a t e d h y d r o c a r b o n s fo rm m a x i­ m u m - b o ilin g a z e o t r o p e s v e r y r e a d i l y w i t h c y c l i c e t h e r s , a s com pared to o t h e r e t h e r s .

Brown ( ^ ) h a s shown t h a t t h e b a s e

s tre n g th s of a s e r ie s o f e th e rs are in th e o rd e r:

te tra ­

h y d r o f u r a n > m e th y l e t h e r > e t h y l e t h e r > i s o p r o p y l e t h e r , when b o r o n t r i f l u o r i d e was t h e a c i d .

The r e s u l t s w ere

e x p l a i n e d on t h e b a s i s o f s t e r i c s t r a i n o f t h e r e s u l t i n g a d d i t i o n c o m p le x , t h e s t r a i n b e i n g l e a s t i n t h e c a s e o f t e t -

xil

r a h y d r o f u r a n an d g r e a t e s t i n t h e c a s e o f i s o p r o p y l e t h e r . T h u s , a s t e r i c f a c t o r may b e i m p o r t a n t i n e x p l a i n i n g t h e l a r g e n e g a t i v e d e v i a t i o n s from i d e a l i t y w i t h t e t r a h y d r o ­ f u r a n and t h e s m a l l e r n e g a t i v e d e v i a t i o n s fro m i d e a l i t y w ith is o p ro p y l e t h e r .

E w e ll a n d W elch ( £ ) fo u n d a m a x i­

m u m - b o ilin g a z e o t r o p e i n t h e s y s te m c h i o r o f o r m - i s o p r o p y l e t h e r , b u t h e re th e h y d ro g en -b o n d in g te n d en c y o f c h lo r o foimi i s much g r e a t e r t h a n w i t h c i s - o r t r a n s - d i c h l o r o e th y le n e . The r e s u l t s o f t h e s e i n v e s t i g a t i o n s o f c i s - and t r a n s -d ic h lo r o e th y le n e w ith l i q u i d s of c la s s I I I

(5) i n ­

d i c a t e s e v e r a l p r i n c i p l e s t h a t may b e o f u s e i n t h e s e p ­ a r a t i o n o f c i s - t r a n s is o m e r s s i m i l a r t o c i s - and t r a n s d ic h lo ro e th y le n e .

The c i s - i s o m e r u s u a l l y shows t h e g r e a t ­

e r n e g a t i v e d e v i a t i o n fro m i d e a l i t y and th e g r e a t e r te n d e n c y t o fo rm a maximum b o i l i n g a z e o t r o p e . e r c o u ld be a l i q u i d o f c la s s

The e n t r a î n ­

I I I such a s an e s t e r , k eto n e

o r e t h e r , w h ic h fo rm s a m a x im u m -b o ilin g a z e o t r o p e w i t h th e c i s iso m er, th u s p e r m i t t i n g g r e a t e r e a se in th e sep­ a r a t i o n o f th e c i s - t r a n s iso m ers

b y i n c r e a s i n g th e b o i l i n g

p o i n t d i f f e r e n c e b e tw e e n s e p a r a b l e f r a c t i o n s c o n s i s t i n g o f t h e p u r e t r a n s is o m e r an d t h e m a x im u m -b o ilin g a z e o t r o p e form ed b y t h e e n t r a î n e r a n d th e c i s i s o m e r .

A fte r d is ­

t i l l a t i o n o f t h e t r a n s i s o m e r , i f t h e e n t r a î n e r w ere w a t e r - s o l u b l e a n d c i s is o m e r w a t e r - i n s o l u b l e , t h e s t i l l r e s i d u e c o u l d b e w ashed w i t h w a t e r t o r e c o v e r t h e e n -

x iii

t r a i n e r , and t h e r e l a t i v e l y p u r e c i s i s o m e r o b t a i n e d . T h ese p r i n c i p l e s h a v e n o t b e e n t r i e d w i t h c i s - and tr a n s -d ic h io re e th y le n e b ecau se o f th e a p p re c ia b le b o ilin g p o in t d if f e r e n c e (1 2 ^ C ,).

The a p p l i c a t i o n to o t h e r s y s te m s

s h o u ld b e i n t e r e s t i n g .

STMMARY The v a p o r - l i q u i d e q u i l i b r i u m d a t a on o l s - t r a n s is o m e r s a v a i l a b l e i n t h e l i t e r a t u r e and d e t e r m i n e d i n t h i s in v e s tig a tio n have been c o r r e l a t e d by a c o n s id e r a tio n of h y d ro g en -b o n d in g , vap o r p r e s s u r e - c o m p o s itio n r e l a t i o n s h i p s , b o i l i n g p o i n t s , d i p o l e moments an d s t e r i c f a c t o r s . V a p o r-liq u id e q u ilib riu m r e l a t i o n s in b in a ry sy s­ tem s w i t h c i s - o r t r a n s - d i c h l o r o e t h y l e n e a s one com ponent h a v e b e e n d e t e r m i n e d a t 7 6 0 .0 ^ 0 . 5 mm. o f m e r c u r y p r e s s u r e . The s e c o n d c o m p o n en ts w ere m e th y l a l c o h o l , m e t h y l a l , t e t r a h y d r o f u r a n . I s o p r o p y l e t h e r , e t h y l f o r m a t e , m e th y l a c e t a t e , a c e t o n e , and 2 - b u t a n o n e .

The a c t i v i t y c o e f f i c i e n t s o f t h e

com po nents w ere c a l c u l a t e d .

I n some c a s e s , t h e d a t a f i t t e d

t h e v a n L a a r a n d M a r g u le s e q u a t i o n s . M in im u m -b o ilin g a z e o t r o p e s w ere o b s e r v e d i n t h e b i n a r y s y s te m s c i s - d i c h i c r o e t h y l e n e - m e t h y l a l c o h o l and t r a n s d i c h i o r o e t h y l en e -me t h y l a l c o h o l .

Maximum b o i l i n g a z e o t r o p e s

w ere o b s e r v e d i n t h e b i n a r y s y s te m s t r a n s - d i c h l o r o e t h y l e n e m e th y la l, c i s - d i c h l o r o e t h y l e n e - t e t r a h y d r o f u r a n , c l s -d ic h lo ro * e th y le n e -m e th y l a c e t a t e , and c i s - d ie h lo r o e th y le n e - a c e to n e .

x lv

A m e th o d f o r s e p a r a t i n g o l s - t r a n s is o m e r s by a z e o t r o p i c d i s ­ t i l l a t i o n i s su g g e ste d .

ACmOWLEDGMmT The a u t h o r s w is h t o t h a n k th e P u rd u e R e s e a r c h Found­ a t i o n an d t h e A to m ic E n e rg y Com m ission f o r th e g r a n t o f p r e do c t o r a l f e l l o w s h i p s t o Norman A l p e r t ; t h e work r e p o r t e d was done on t h e s e f e l l o w s h i p s .

XV

LITERATURE CITED (1)

A l p e r t , N , , and E l v l n g , P . J . , I n d . E n g . Chem. , a c c e p t e d fo r p u b lic a tio n .

(2 )

B a k e r , E . M ., H u b b a rd , R. 0 . H ., H u g u e t, J . H. and M i s c h a l o w s k i , S . S . , I b i d . , 3 1 , 1260 ( 1 9 3 9 ) .

(3 )

Brown, H. C. , and Adams, R. M ., J . Am. Chem. S o c . , 6 4 , 2557 ( 1 9 4 2 ) .

(4 )

C a r ls o n , H. C ., and C olburn, A. P . , I n d . Eng. Chem. , 3 4 , 584 ( 1 9 4 2 ) .

(5)

E w e l l , R. H ., H a r r is o n , J . M ., and B e r g , L . , I b i d . , 3 6 , 871 ( 1 9 4 4 ) .

(6 )

E w e l l , R. H . , an d Welch, L. M ., J . Am. Chem. S o c . , 6 3 , 2475 ( 1 9 4 1 ) .

(7)

F l e e r , K. B . , J . Chem. E d u c a t i o n ,

588 ( 1 9 4 5 ) .

(8 )

German, W. L. and J a m s e t t , R. A . , J . Chem. S o c . , 1 9 4 0 ,

1360 . (9 )

H o r s l e y , L . H . , A n a l . Chem., 1 9 , 508 ( 1 9 4 7 ) ; 2 1, 831 (1949).

(1 0 )

J o n e s , C. A , , Schoenborn, E. M. , and C olburn, A. P . , I n d . Eng. Chem. ,

(1 1 )

3 5 , 666 ( 1 9 4 3 ) .

T ran s. F araday Soc. ,

3 0 , A p p e n d ix ( 1 9 3 4 ) .

xvl

T a b le I A z e o tr o p e s I n v o lv i n g c i s - o r t r a n s - D tc h l o r o e t h y l e n e

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S y stem s I n v o lv i n g c l s - D l c h l o r o e t h y l e n e , B .P , 6 0 .3 ° C .

F o r e ig n Component and B . P , , ®C. A c e to n e , 5 6 ,4 °G . ^ M eth y l A c e t a t e , 5 7 ,2 C. M eth y l A lc o h o l, 6 4 .6 ° C . T e tr a h y d r o f u r a n , 66*1 C. E th y l A lc o h o l, 7 8 .3 C.

B.

A z e o tro p e B .P ., ^ 0 .

A z e o tro p e C o m p o sitio n M ole % CgSgClg

6 l# 9 6 1 .7 5 1 .5 6 9 .9 5 7 .7

6 7 .4 6 7 .4 6 5 .2 3 8 .6 g o .2

S y stem s I n v o lv i n g t r a n s - D l c h i o r o e t h y l e n e , B .P . 4 8 .3 ^ 0 .

M e th y l a l, 4 2 .6 ^ C . M eth y l A lc o h o l, 6 4 .6 C. E th y l A lc o h o l, 7 8 .3 C.

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VAPOR-LK^ÜID EQUILIBRIA IN BINARY SYSTEMS PART I . ETHYLENE DICHLORIDE-TOLUSNE AND FORMIC ACID-ACETIC ACID

INTRODUCTION The a s s o c i a t i o n o f f o r m ic a c i d an d a c e t i c a c i d I n t h e l i q u i d and v a p o r p h a s e s h a s b e e n t h e s u b j e c t o f many i n v e s t i g a t i o n s .

R e c e n t w ork ( 2 ,

6 , 8 , 2*

h a s shown t h a t t h e v a p o r s o f f o r m ic an d a c e t i c a c i d s c o n s i s t p a r t l y o f d im e r s , t h e a s s o c i a t i o n o c c u r r i n g th r o u g h h y d ro g e n b o n d in g b e tw e e n c a r b o x y l g r o u p s .

The d im e r p r o b a b ly c o n t a i n s

a n o n p la n a r r i n g s t r u c t u r e , a lt h o u g h t h e r e i s e v id e n c e f o r d im e rs w ith a c h a in s t r u c t u r e .

I n t h e v a p o r p h a s e e v id e n c e

f o r th e monomer an d p o ly m e rs h i g h e r th a n t h e d im e r h a s b e e n advanced.

I n t h e l i q u i d a c i d s , h y d ro g e n b o n d s a r e p r o b a b ly

e f f e c t i v e I n fo rm in g lo n g c h a in s o f a s s o c i a t e d m o l e c u l e s . I n v ie w o f th e f o r e g o i n g . I t was d e c id e d to d e ­ te rm in e th e v a p o r - l i q u l d r e l a t i o n s I n t h e sy ste m f o r m ic a c l d a c e tic a c id .

A lth o u g h b o t h a r e m em bers o f a hom ologous

s e r i e s , th e d l m e r l z a t l o n a n d h i g h e r p o l y m e r i z a t i o n o f th e v a p o rs th r o u g h h y d ro g e n b o n d in g I n b o t h a c i d s an d t h e p o s s i b i l i t i e s o f c r o s s d l m e r l z a t l o n b e tw e e n f o r m ic an d a c e t i c a c i d s u g g e s te d t h a t th e v a p o r - 1 I q u l d e q u i l i b r i u m r e ­ l a t i o n s h i p s m ig h t b e u n u s u a l . S in c e I t was d e s i r e d t o u s e an e q u i l i b r i u m

s till

c a p a b le o f h a n d lin g s m a ll q u a n t i t i e s o f m a t e r l s i l , a s t i l l o f

th e C o lb u rn ty p e ( j ) was s e l e c t e d . The p r i n c i p l e s I n v o lv e d I n t h e o p e r a t i o n o f th e C o lb u rn s t i l l h a v e b e e n d i s c u s s e d ( 7 ) .

The s t i l l c o n s i s t s

o f ( a ) a h e a te d r e s i d u e and v a p o r i z a t i o n ch am b er I n id ilc h I s Im m ersed a th e rm o c o u p le o r th e rm o m e te r w e l l , (b ) an o v e r ­ h e ad c o n d e n s e r l e a d i n g to ( c ) a U -sh a p e d c o n d e n se d v a p o r c h am b er, and (d )

a h e a t e d tu b e l e a d i n g fro m

th e condensed

v a p o r cham ber to

t h e r e s i d u e c h am b e r. The l a t t e r f u n c t i o n s

a s a f l a s h b o i l e r an d d e l i v e r s th e v a p o r s b e n e a th t h e s u r f a c e o f th e l i q u i d I n t h e r e s i d u e c h a m b e r.

T h u s, s u p e r h e a te d

v a p o rs a r e a v o id e d s in c e s u c h v a p o r s a r e b ro u g h t t o th e b o i l ­ in g p o i n t on c o n t a c t i n g t h e bod y o f l i q u i d I n t h e r e s i d u e cham ber w h ic h I s I t s e l f a t th e b o i l i n g p o i n t . Two a d v a n ta g e s c la im e d f o r s t i l l s o p e r a t i n g I n t h i s m an n er a r e :

( a ) The

v a p o rs l e a v i n g t h e l i q u i d s u r f a c e a r e I n e q u i l i b r i u m w i th th e m ain body o f

l i q u i d In th e s t i l l ,

form ed fro m a s m a ll p o r t i o n o f l i q u i d

s in c e th e y a r e n o t whose c o m p o s itio n h a s

b een c h an g ed b y s im p le d i s t i l l a t i o n a n d , (b ) h e t e r o g e n e i t y In v o lv e d I n r e t u r n i n g th e c o n d e n s e d v a p o r to a b o i l i n g l i q u i d I s a v o id e d . S in c e o n ly one p a p e r (7 ) h a s a p p e a re d on t h e co n ­ s t r u c t i o n an d o p e r a t i o n o f t h i s s t i l l , i t was d e c id e d to r e ­ p e a t th e w ork on one o f th e two sy ste m s s t u d i e d by J o n e s , S c h o en b o rn and C o lb u rn , u s in g t h i s s t i l l .

The d a t a o b t a i n e d

f o r th e sy ste m e t h y l e n e d l c h l o r i d e - t o l u e n e w ere fo u n d to b e I n good a g re e m e n t w ith t h a t o f t h e s e i n v e s t i g a t o r s .

B e c a u se

o f th e good a g re e m e n t o f t h e e t h y l e n e d l c h l o r l d e - t o l u e n e

d a t a , th e d a t a o b t a i n e d f o r t h e sy ste m f o r m ic a c i d - a c e t i c a c i d w ere Ju d g e d t o b e r e l i a b l e .

The th e rm o d y n a m ic co n ­

s i s t e n c y o f t h e v a p o r - l i q u i d e q u i l i b r i u m d a t a f o r th e sy ste m fo r m ic a c l d - a c e t l c a c i d c o u ld n o t b e e v a l u a t e d fro m th e p l o t o f t h e lo g a r i t h m o f t h e a c t i v i t y c o e f f i c i e n t s o f t h e c o m p o n en ts a g a i n s t th e m ole f r a c t i o n o f t h e m ore v o l a t i l e com ponent i n th e l i q u i d b e ca u se o f th e c o n s id e ra b le d e p a r tu r e o f th e v a p o rs from I d e a l i t y th r o u g h a s s o c i a t i o n . EXPERIMENTAL mRK V a r io u s e q u i l i b r i u m

s t i l l s have b een p ro p o se d

f o r th e d e t e r m i n a t i o n o f t h e v a p o r - 1 I q u ld e q u i l i b r i u m r e ­ l a t i o n s o f m is c ib le l i q u i d s .

Some o f t h e s t i l l s u s e d In

r e c e n t I n v e s t i g a t i o n s w ere d e s ig n e d by G i l l e s p i e ( £ ) , Langdon and K eyes ( l O ) , O thm er ( l ^ ) , R o g e r s , R h lg h t, and C hoppln ( 1 6 ) , Y ork a n d Holmes ( l 9 ) . an d J o n e s , S c h o e n b o rn , and C o lb u rn ( 7 ) ; th e s t i l l em ployed i n t h e s e s t u d i e s was c o n s t r u c t e d a p p r o x im a te ly t o th e d im e n s io n s I n d i c a t e d by J o n e s , S c h o e n b o rn , and C o lb u rn (%)# The t o t a l volum e o f l i q u i d c o n ta i n e d I n t h e s t i l l d u r in g o p e r a t i o n was a p p r o x im a te ly 50 t o 55 m l.

The h e a t i n g

c o l l s w ere s i m i l a r t o th o s e d e s c r i b e d ( 7 ) , t h e te m p e r a tu r e on a l l t h r e e h e a t e r s b e in g c o n t r o l l e d by a d j u s t a b l e t r a n s ­ fo rm e rs.

I t was fo u n d c o n v e n ie n t t o s t a r t o p e r a t i o n o f th e

s t i l l by f i r s t t u r n i n g on t h e e l e c t r i c a l h e a t e r s an d th e n f u r t h e r w arm ing th e r e s i d u e cham ber w ith a s m a ll g a s f l a m e . By t h i s p r o c e d u r e , sm ooth o p e r a t i o n c o u ld b e a c h ie v e d a b o u t

l 5 m in u te s a f t e r c h a r g in g t h e sam p le to t h e s t i l l .

Ob-

4

s e r v a t l o n s on o p e r a t i o n o f th e s t i l l a g r e e w i th th o s e o f J o n e s , S c h o e n b o rn , and C o lb u rn ( j ) .

I t m ig h t b e p o i n t e d o u t t h a t

some p r a c t i c e I s r e q u i r e d b e f o r e sm o o th o p e r a t i o n I s o b t a i n e d , b u t o nce t h e n e c e s s a r y s k i l l I s a c q u i r e d , t h e s t i l l may b e u s e d a lm o s t a s c o n v e n i e n t l y a s t h e O thm er ty p e o f s t i l l

(^ ).

The m an n er o f c h a r g in g t h e sam p le t o t h e s t i l l was fo u n d to b e somewhat I n c o n v e n i e n t .

The sam p le was c h a r g e d b y a p p ly ­

in g s u c t i o n a t t h e v a p o r v e n t t o t h e a tm o s p h e re a n d I n t r o d u c i n g th e sam ple th r o u g h t h e s to p c o c k u s e d f o r w ith d ra w in g t h e v a p o r s a m p le .

I t I s s u g g e s te d t h a t a s m a ll d r o p p in g f u n n e l b e

s e a l e d t o t h e tu b e l e a d i n g fro m t h e c o n d e n s e r t o t h e T J-tu b e . D u rin g a l l d e t e r m i n a t i o n s , t h e s t i l l was c o n n e c te d to a p r e s s u r e r e g u l a t i n g s y ste m s i m i l a r t o t h a t u s e d b y B a k e r (l).

A ll d e t e r m i n a t i o n s w ere made a t a p r e s s u r e o f 7 6 0 ,0 4^ 0 , 5

mm. o f m e r c u r y .

A c o p p e r - C o n s ta n ta n th e rm o c o u p le c o n n e c te d

t o a R u b ico n Type B p o t e n t i o m e t e r was u s e d t o m e a s u re te m p e r­ a t u r e , th e c o ld j u n c t i o n b e in g m a in ta in e d a t 0 °C . b y m eans o f an I c e b a t h .

The te m p e r a tu r e v a l u e s w ere d e te r m in e d

w ith in +2 0 ,1 ° C .

The te m p e r a t u r e - m e a s u r in g sy ste m was c a l i ­

b r a t e d b y d i s t i l l i n g w a te r an d t o l u e n e I n t h e s t i l l .

A ll

te m p e r a tu r e s g iv e n i n t h i s p a p e r h a v e b e e n c o r r e c t e d . The g e n e r a l te c h n i q u e f o r e x p e r i m e n t a l l y d e te r m i n ­ in g v a p o r - 1 I q u l d e q u i l i b r i a h a s b e e n d e s c r i b e d I n th e l i t e r ­ a t u r e ( l l , 1 2 , 3 3 , 1 4 ) an d I n p a r t i c u l a r f o r th e ty p e o f s t i l l em ployed I n th e s e I n v e s t i g a t i o n s by J o n e s , S c h o e n b o rn , an d C o lb u rn (7 ) • A p p ro x im a te ly 50 t o 55 m l . o f one com ponent was c h a rg e d t o th e s t i l l ,

and m i x t u r e s w i t h s u c c e s s i v e a d d i t i o n s

o f th e o t h e r com ponent w ere a llo w e d t o

ccrnie to c o n s t a n t

te m p e ra tu re .

A f t e r sm ooth o p e r a t i o n o f t h e s t i l l was o b t a i n e d

40 m in u te s was a llo w e d f o r th e e s t a b l i s h m e n t o f

e q u ilib riu m .

S am ples o f l i q u i d and v a p o r w ere t h e n w ith d ra w n s i m u lta n e o u s ­ l y and a n a ly z e d . VAPOR-LIQUID EQUILIBRIUM DATA S am ples o f p u r e t o l u e n e a n d e th y le n e d l c h l o r i d e w ere p r e p a r e d by c a r e f u l r e c t i f i c a t i o n th r o u g h a 36- l n c h , 0 . 8 8 - In c h I . D . g l a s s h e l l c e - p a c k e d c o lu m n .

The r e f r a c t i v e

I n d i c e s o f t h e p u r i f i e d m a t e r i a l s a g r e e d w ith t h o s e r e p o r t e d

(2 ) . The sy ste m e t h y l e n e d l c h l o r l d e - t o l u e n e was s t u d i e d a t a p r e s s u r e o f 7 6 0 .0 j; 0 . 5 mm. o f m e r c u r y .

E q u i li b r i u m

sam p les w ere a n a ly z e d b y r e f r a c t i v e in d e x m e a s u re m e n ts a t 25®C., u s i n g th e r e f r a c t i v e In d e x v e r s u s c o m p o s itio n d a t a o f C o lb u rn an d c o w o rk e rs ( 7 ) . The l a t t e r * s d a t a ( 7 ) , f o r th e v a p o r - 1 I q u ld e q u i l i b r i u m r e l a t i o n s , t h e e x p e r im e n ta l d a t a o b ta in e d In t h i s I n v e s t i g a t i o n , t h e sm oothed d a t a , an d t h e d e v i a t i o n o f t h e sm oothed d a t a from C o lb u rn * s d a t a f o r c o r r e s p o n d in g l i q u i d p h a s e c o m p o s itio n s a r e shown I n T a b le 1 . J o n e s , S c h o e n b o rn an d C o lb u rn (%) h ave shown t h a t , b a s e d on th e a c t i v i t y c o e f f i c i e n t s c a l c u l a t e d fro m t h e e x p e r I m a i t a l d a t a and on th e c o m p a riso n o f th e sm o o th ed d a t a w ith th o s e com puted on th e b a s i s o f R a o u lt* s la w , t h e sy ste m e th y le n e d l c h l o r l d e - t o l u e n e b e h a v e s In an I d e a l m a n n e r. The g e n e r a l a g re e m e n t o f t h e e x p e r im e n ta l r e s u l t s w ith t h e v a lu e s c a l c u l a t e d f o r an I d e a l sy ste m was c o n s id e r e d by t h e s e a u th o r s a s e v id e n c e f o r t h e r e l i a b i l i t y o f t h e r e s u l t s

y i e l d e d toy th e new ty p e o f e q u i l i b r i u m

s till.

A n h y d ro u s a c e t i c a c i d was p r e p a r e d by r e f l u x l n g g l a c i a l a c e t i c a c i d w ith a s m a ll am ount o f a c e t i c a n h y d r id e and d i s t i l l i n g o f f t h e d r y a c e t i c a c i d th r o u g h t h e 36- I n c h r e c t i f y i n g colum n p r e v i o u s l y m e n tio n e d .

A n h y d ro u s f o r m ic

a c i d was p r e p a r e d by d r y i n g 90^ m a t e r i a l o v e r c o p p e r s u l f a t e and d i s t i l l a t i o n i n v a c u o ; t h i s was f o llo w e d b y f i n a l p u r i ­ f i c a t i o n b y f r e e z i n g , u s in g th e m eth o d o f Sm ith ( 1 7 ) , The sy ste m f o r m ic a c l d - a c e t l c a c i d was s t u d i e d a t a p r e s s u r e o f 7 6 0 ,0 + 0 ,5 mm. o f m e r c u r y .

E q u i lib r iu m

sam p les w e ig h in g a p p r o x im a te ly o n e gram w ere a n a l y z e d by t i t r a t i o n w ith 0 ,5 N sodium h y d r o x id e s o l u t i o n .

The c a l c u ­

l a t i o n s w ere s i m p l i f i e d b y p l o t t i n g w e ig h t p e r c e n t o f fo r m ic a c i d a g a i n s t m i l l i m o l e s o f a c i d p e r gram o f sam p le fo u n d b y t i t r a t i o n , 1 . e . , 1 ,0 0 0 0 gram o f p u r e f o r m ic a c i d w o u ld r e ­ q u i r e 3 3 .3 3 m l. and w ould c o n t a i n l 6 . 6 6 m i l l i m o l e s .

Any

m ix tu r e o f th e two a c i d s w ould r e q u i r e a n I n t e r m e d i a t e volum e o f t i t r a n t a n d w ould c o n t a i n an I n t e r m e d i a t e num ber o f m i l l i ­ m o les o f a c i d .

The te r m i n a l v a l u e s o f th e c u r v e w ere

c a l c u l a t e d f o r p u r e a c e t i c a c i d a n d p u r e fo r m ic a c i d an d a s t r a i g h t l i n e draw n th r o u g h t h e s e p o i n t s .

D e te r m in a tio n o f

th e m i l l i m o l e s o f b a s e r e q u i r e d to t i t r a t e a o n e -g ra m sam ple p e r m i t t e d d i r e c t I n t e r p o l a t i o n f o r w e ig h t p e r c e n t o f f o r m ic a c id I n t h e s a m p le .

The w e ig h t p e r c e n t a g e s w ere th e n co n ­

v e r t e d to m o l e - f r a c t l o n s , The e x p e r im e n ta l r e s u l t s o b t a i n e d a r e p r e s e n t e d I n T a b le 2 . an d shown g r a p h i c a l l y I n F ig u r e 1 ; th e c o rre sp o n d *

irig v a p o r - l i q u i d e q u i l i b r i u m i s shown i n F ig u r e 2 .

The sm oothed

d a t a f o r t h e sy ste m a r e r e c o r d e d I n T a b le 3 ; sm o o th in g o f th e d a t a was j u s t i f i e d b y th e c l o s e n e s s o f th e e x p e r im e n t a l p o i n t s to t h e c u r v e . The e x p e r im e n ta l d a t a was u s e d to c a l c u l a t e th e a c t i v i t y c o e f f i c i e n t s , ^ ^ and ^ 2 *

th e ra n g e o f

(m o le -

f r a c t i o n o f f o m l c a c i d ) i n c r e a s i n g fro m 0 .1 to 0 . 9 , th e a c t i v ­ i t y c o e f f i c i e n t f o r f o r m ic a c i d ,

i n c r e a s e d fro m 0 ,8 5 t o

0 .9 8 w h ile th e a c t i v i t y c o e f f i c i e n t f o r a c e t i c a c i d , ^ g . I n c r e a s e d from 1 . 0 7 to 1 . 4 6 .

A lth o u g h b o t h c u r v e s I n d i c a t e d a c t i v i t y

c o e f f i c i e n t s o f 1 .0 0 f o r th e p u r e com pounds, a s e x p e c te d , th e c u rv e s d i d n o t I n t e r s e c t .

The r e a s o n s f o r t h i s b e h a v io r I s

e x p l i c a b l e from t h e f a c t t h a t t h e c a l c u l a t i o n made f o r th e a c t i v i t y c o e f f i c i e n t s I s b a s e d on th e v a p o r s o v e r t h e l i q u i d b e h a v in g a s I d e a l g a s e s ; w here t h e l a t t e r I s n o t t r u e a s In th e s y ste m s a c e t a l d e h y d e - w a t e r an d w a t e r - a c e t i c a c i d , th e c u sto m a ry c u r v e s o f v a l u e s o f l o g (4 ).

v s . x do show u n u s u a l s h a p e s

An a t t e m p t was made t o sm ooth th e x - y d a t a b y c a l c u ­

l a t i n g t h e l a t t e r fro m th e sm oothed v a lu e s o f t h e a c t i v i t y c o e f f i c i e n t s ; t h e r e s u l t s w ere no b e t t e r th a n t h o s e sm oothed d i r e c t l y fro m th e e x p e r im e n ta l x - y d a t a ( T a b le 3 )# The p o s s i b i l i t y o f a z e o t r o p e f o r m a tio n a t low and h ig h c o n c e n t r a t i o n s o f f o r m ic a c i d In th e l i q u i d was c a r e ­ f u lly In v e s tig a te d .

I n T a b le 2 a n d F i g u r e 2 , a lth o u g h two

o f th e e x p e r im e n ta l p o i n t s a t lo w c o n c e n t r a t i o n s o f fo r m ic a c i d f a l l b e lo w th e b a s e l i n e , th e m a g n itu d e o f th e e x p e r im e n t­ a l e r r o r I s s u c h t h a t t h e s e p o i n t s c o u ld f a l l a b o v e th e b a s e

lin e .

The p o s s i b i l i t y o f a m a x lm u m -b o llln g a z e o t r o p e i n

t h i s r e g io n was n o t I n d i c a t e d b y te m p e r a t u r e m e a s u re m e n ts , a l l v a l u e s b e in g w e ll b e lo w t h a t o f p u re a c e t i c a c i d .

The

te m p e r a tu r e m e a s u rin g sy ste m u s e d was c a p a b le o f d e t e c t i n g v a r i a t i o n s o f + 0.01® G. SUMMARY V a p o r - 1 I q u ld e q u i l i b r i u m d a t a a t a tm o s p h e r ic p r e s s u r e a r e p r e s e n t e d f o r t h e s y s te m s e th y le n e d l c h l o r l d e to lu e n e and f o m l c a c l d - a c e t l c a c i d .

The a g re e m e n t o f th e

d a t a f o r e t h y l e n e d l c h l o r l d e - t o l u e n e sy ste m iid t h p r e v i o u s work I s show n.

B o l l i n g p o l n t - e o m p o s i t l o n an d v a p o r - l i q u i d

e q u ilib r iu m d ia g ra m s a r e p r e s e n t e d f o r t h e sy ste m f o r m ic a c ld -a c e tlc a c id .

The lo g a r i t h m o f t h e a c t i v i t y c o e f f i c i e n t s

o f th e com ponents a g a i n s t t h e m ole f r a c t i o n o f th e m ore v o l ­ a t i l e com ponent I n th e l i q u i d was p l o t t e d b u t d i d n o t p e r m it an e v a l u a t i o n o f t h e e x p e r im e n ta l d a t a b e c a u s e o f th e c o n ­ s i d e r a b l e d e p a r t u r e o f t h e v a p o rs from I d e a l i t y th r o u g h a s s o c ia tio n .

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10

T a b le 2 .

V a p o r-L iq u id E q u i lib r iu m D a ta f o r S ystem F orm ic A c id - A c e tic A c id a t ?60 Mm.

Temp. °0.

M o l e - F r a c t io n L i q u id

F o rm ic Ac V apor y^

1 0 0 .8

1 .0 0 0

1 .0 0 0

1 0 1 .0

0 .9 5 5

0 .9 7 3

1 0 1 .1

0 .9 4 3

0 .9 6 8

1 0 1 .5

0 .8 9 2

0 .9 0 9

1 0 2 .7

0 .7 9 8

0 .8 3 4

1 0 3 .8

0 .7 2 7

0 .7 7 0

1 0 5 .1

0 .6 4 2

0 .6 9 9

1 0 6 .1

0 .5 7 2

0 .6 3 4

1 0 6 .7

0 .5 1 1

0 .5 9 6

1 0 8 .3

0 .4 4 5

0 .5 2 5

1 0 9 .7

0 .3 6 1

0 .4 3 5

1 1 1 .1 ,

0 .2 7 7

0 .3 6 2

1 1 2 .3

0 .2 2 9

0 .2 9 5

1 1 4 .1

0 .1 5 1

0 .2 0 1

1 1 4 .7

0 .1 2 7

0 .1 6 7

1 1 6 .0

0 .0 5 3

0 .1 0 1

1 1 7 .0

0 .0 1 4

0 .0 1 4

1 1 7 .5

0 .0 0 7

0 .0 0 2

1 1 8 .1

0 .0 0 0

0 .0 0 0

11

T a b le 3*

Sm oothed D a ta f o r S ystem F o rm ic A c id - A c e tic A c id a t 760 Mm.

Temp. ®C.

M o l e - F r a c tio n L iq u id

F o rm ic A c id V apor y^

1 1 8 .1

0 .0 0 0

0 .0 0 0

1 1 6 .0

0 .0 5 0

0 .0 8 0

1 1 5 .4

0 .1 0 0

0 .1 4 6

1 1 2 .8

0 .2 0 0

0 .2 6 0

1 1 0 .7

0 .3 0 0

0 .3 8 0

1 0 8 .8

0 .4 0 0

0 .4 8 5

1 0 7 .0

0 .5 0 0

0 .5 7 6

1 0 5 .4

0 .6 0 0

0 ,6 6 0

1 0 3 .9

0 .7 0 0

0 .7 4 6

1 0 2 .5

0 .8 0 0

0 .8 3 6

1 0 1 .4

0 .9 0 0

0 .9 2 2

1 0 1 .0

0 .9 5 0

0 .9 6 4

1 0 0 .8

1 .0 0 0

1 .0 0 0

12

F ig , 1 ,

B o i l i n g P o i n t - C o m p o sitio n D iagram f o r System F o rm ic A c id - A c e tic A c id .

T e m p e ra tu re , °C . , v s .

M ole F r a c t i o n o f F o rm ic A c id a t % 0 Mm. o f M ercu ry P ressu re.

.2

.4

.6

MOLE FRACTION-FORMIC ACID

.8

13

F ig . 2 .

V a p o r-L iq u id E q u i lib r i u m D iag ram f o r S y stem F o rm ic A c id - A c e tic A c id a t 76O % i. o f M ercu ry P r e s s u r e .

.2

.4

.6

.8

MOLE FRACTION-FORMIC ACID IN LIQUID

14

LITERATURE CITED

(1 )

B a k e r, E . M ,, H u b b a rd , R . 0 . H ., H u g u e t, J . H ., an d M ic h a lo w s k i, S . S . , I n d . E n g . Chem. , 3 1 , 1260 (1 9 3 9 ) *

(2 )

B a s t i a n s e n , 0 , , P in b a k , G h r ., and H a s s e l , 0 . , T i d e . K.jemi, B erR v e sen M e t. 4» 8 l ( 1 9 4 4 ) .

(3 )

B a tu e v , M, I . ,

Cornut. r e n d , a c a d . s o l . U . R. S . S . 5 2 ,

401 ( 1 9 4 6 ) . (4 )

C a r l s o n , H. C . , and C o lb u rn , A. P . , I n d . E ng. Chem. ,

34.

584 (1 9 4 2 ). (5 )

G i l l e s p i e , D. T . C . , I n d . Bu r . C hem ., A n a l. E d . , l 8 , 575 (1 9 4 6 ).

(6 )

H a lf o r d , J . 0 . , J . Chem. P h y s . 1 4 , 395 ( 1 9 4 6 ) .

(7)

J o n e s , C. A ., S c h o e n b o rn , E . M ,, an d C o lb u rn , A . P . , I n d . E ng. Chem. , 3 5 . 666 ( 1 9 4 3 ) .

(8 )

E a r l e , J . and B rockw ay , L . 0 . , J . Am. Chem. S o c . 6 6 , 574 (1944) .

(9 )

L a n d e e , P . A ., a n d J o h n s , I . B. I b i d . , £ 3 , 2091 ( l 9 4 l ) .

( 1 0 ) L an g d o n , W, M ., and K e y e s, D. B . , I n d . E ng. C h an . , 3 4 . 938 ( 1 9 4 2 ) . (1 1 )

O th m er, D. P . , I b i d . .

2 0 , 743 ( 1 9 2 8 ) .

(1 2 )

O th m e r, D. P . , I n d . Eng. C hem ., A n a l. E d . , 4 , 232 ( 1 9 3 2 ) .

(13)

O th m e r, D . P . , I n d . E ng. C hem ., 3 5 . 6 l 4 ( 1 9 4 3 ) .

(1 4 )

O th m e r, D. P . , and B e n e n a tl, R. P . , I b i d . ,

(1 5 )

R i t t e r , H. L . and S im o n s, J . H ., J . Am. Chem. S o c . 6 7 ,

3 7 , 299

(1 9 4 5 ).

757 ( 1 9 4 5 ) . ( 1 6 ) R o g e r s , J . W ., K n i ^ t , J . W., an d C h o p p in , A . R . , J . Chem.

15

LITERATURE CITED, c o n t 'd

E d u c a t i o n . 2 4 . 491 ( 1 9 4 7 ) . (1 7 )

S m ith , G. P . , J . Chem. S o c . . 1 9 3 1 . 3 2 é 0 ,

(1 8 )

W r ig h t, R. H ., J . Chem. E d u c a tio n 2 0 , 179 ( l 9 4 3 ) .

(19)

Y o rk , R ., and H o lm es, R. G ., I n d . E n g . Chem. , 3 4 . 345 (1942) .

16

PART I I . CIS- AND TRANS- 1 , 2-CYCLOPMTANEDIOL INTRODUCTION

The s t r u c t u r e s and p r o p e r t i e s o f t h e s e iso m e r s are in d ic a t e d b e lo w : H

H CSg—

\

H

CH2 'CH.

\

c

\

CH2— C^

\ OH

OH HO

\ CH.

\ OH

c is

\H

tr a n s

b o i l i n g p o in t a t

b o i l i n g p o in t a t

10 mm.

1 . 5 mm.

1 0 5 .5 -1 0 6 ° C .

9 9 -1 0 1 °C .

m e ltin g p o in t 5 0 -5 2 ° C ,

m e lt in g p o in t 29°C .

I t was f e l t t h a t t h e s e iso m e rs or t h e i r d im e th y l e th e r d e r i v a t i v e s o f f e r i n t e r e s t i n g p o s s i b i l i t i e s f o r v a p o r l l q u i d e q u ilib r iu m s t u d i e s .

T hus, compounds su ch a s e th y le n e

d i c h lo r id e m i ^ t be e x p e c te d t o h yd rogen -b on d w ith th e c i s isom er t o form a c y c l i c com plex I n v o lv in g one m o le c u le o f th e d i o l and one m o le c u le o f th e d i c h l o r i d e .

W ith th e tr a n s d i o l ,

the d i c h lo r id e w ould n o t be e x p e c te d t o span or b r id g e th e tr a n s oxygen atom s and a

c h a in com plex would be e x p e cted *

T h is a n t ic i p a t e d d i f f e r e n c e i n t h e ty p e o f h y d ro g en -b o n d in g sh ou ld b e e v id e n t from th e v a p o r - li q u id e q u ilib r iu m r e l a t i o n s . B ecause o f t h e h ig h b o i l i n g p o i n t s o f th e d i o l s , i t was

17

th o u g h t d e s ir a b le t o i n v e s t i g a t e th e p o s s i b i l i t y o f c o n v e r t­ in g e a ch d i o l to th e c o r r e sp o n d in g d im e th y l e t h e r .

A ccord­

i n g l y , a l i t e r a t u r e su r v e y was made t o d e te r m in e th e f e a s i b i l ­ i t y o f p r e p a r in g th e s e d i o l s and e t h e r s . A c o n s id e r a b le amount o f l i t e r a t u r e i s a v a i l a b l e on c i s - and t r a n s - 1 . 2 - o y c lo p e n t a n e d io l.

In g e n e r a l, th e

p r e p a r a tio n s o f th e s e d i o l s h a v e in v o lv e d th e o x id a t io n o f c y c lo p e n te n e a s in d ic a t e d b e lo w ( l .,

/

,GH,

CH

p e r b e n z o ic a c id or

CH,

■■■■

CH.

CH

.

d i l u t e H2 SO4 "

■

C&

p e r a c e t i c a c id CHCl, 0 ° C .^

C yclop en ten e

CH

CH2'

/ CH

CH.

H ,0 lOO^C.

c y c lo p e n te n e o x id e

H, 'OH CH2

(

\H

tr a n s - 1 , 2 c y c lo p e n ta n e d io l CH2

CH

yC H 2

c

KMnÛ4,H20 CH2

'OH CH2

o r 0 g0 4 CH2

CH

CH2 — - c OH c i s - l , 2 - c y c lo p e n t a n e d io l

B oesek en ( l )

con fîm ed th e c i s - c o n f ig u r a t io n by

o b s e r v in g th e in c r e a s e in co n d u cta n ce o f a b o r ic a c id s o l u t i o n

18

g iv e n b y t h e d i o l r e s u l t i n g from t h e p e rm a n g a n a te o x i d a t i o n . W ith t h i s d i o l h e a l s o o b s e r v e d th e f o r m a t i o n o f a compound w ith a c e to n e a n d th e n o n - r e s o l v a b i l i t y o f th e m o le c u le , a l l i n d i c a t i n g th e e l s c o n f i g u r a t i o n .

H e l f e r i c h a n d H iltm a n

( 5 ) s u c c e e d e d i n r e s o l v i n g t h e d i o l fro m th e p e r b e n z o ic a c i d o x i d a t i o n an d th u s e s t a b l i s h e d t h e t r a n s c o n f i g u r a t i o n . S in c e c y c lo p e n te n e was r e q u i r e d f o r t h e s e s y n t h e s e s , i t s a v a i l a b i l i t y was i n v e s t i g a t e d .

The P h i l l i p s P e tro le u m

Company s e l l c y c lo p e n te n e a t 20 c e n t s p e r g ra m .

A c c o r d in g ly ,

i t was d e c id e d to p r e p a r e th e m a t e r i a l , a s i n d i c a t e d b y t h e f o ll o w i n g s e q u e n c e : re d u c tio n N a, m b is t e t h e r CH,

COOH ((^

4

COOH CH.

B a(0H )2 290°C ,

C& C=0

CH.

Hp , R aney H i LÎAIH4

CH. CH.

CH H^PO^

^ C H

CHOH CH.

CH'

CH:

CH

M o u ssero n an d G ra n g e r (J7) r e p o r t e d th e p r e p a r a t i o n o f mono- and d i e t h e r s o f c y c l o p e n t a n e d i o l , a n d fro m t h e m eth o d o f p r e p a r a t i o n , t h e s e p r o b a b ly h a d th e t r a n s c o n f i g u r a t i o n . M o n o e th e rs w ere p r e p a r e d by h e a t i n g th e c h i o r o h y d r i n s w ith sodium a lc o h o l a t e 8 .

The d i e t h e r s w ere p r e p a r e d b y p r o lo n g e d

h e a t i n g o f th e d i-b ro m o d e r i v a t i v e s w i t h c o n c e n t r a t e d a l c o h o l i c p o ta s s iu m h y d r o x id e o r w it h p o ta s s iu m a l c o h o l a t e s .

The e t h e r s

19

p r e p a r e d i n t h i s m an n er and th e o b s e r v e d b o i l i n g p o i n t s w e re : B o llin g p o in t 2 -m e th o x y c y c lo p e n ta n o l

175

2 - 8 th o x y c y lo p e n ta n o l

182

1 . 2 - d im e th o x y c y c lo p e n ta n e

108

1 .2 - d ie th o x y c y c l o p e n ta n e

124

740 Mm.

I t was th o u g h t t h a t e l s - o r t r a n s - 1 . 2 - d im e th o x y c y c lo p e n ta n e c o u ld b e p r e p a r e d from th e c o r r e s p o n d i n g g l y c o l s b y c o n v e r s io n to th e s o d i o - d e r i v a t i v e s f o llo w e d b y tr e a tm e n t w ith m e th y l i o d i d e .

The t r a n s d i o l a p p e a re d

e a s i e r to p r e p a r e th a n th e c i s , and th e p r e p a r a t i o n an d a tte m p te d c o n v e r s io n to th e d im e th y l e t h e r was u n d e r ta k e n .

The t r a n s

g ly c o l i s e x p e c te d when t h e o x id e i s an i n t e r m e d i a t e , a s shown by th e f o l l o w i n g m ech an ism : CH

.CH,

p e r b e n z o ic a c i d

CH CH,

.CH.

CH

CH,

CH

CH

•CH

>

H CH-

\

CH

\ OH

CH.

CHp

Hs

C

HgO

OH CHp

‘CH.

HO,\

-H'

/

HgO

‘CH2

'

\

H

ra c e m ic The p r e p a r a t i o n o f t r a n s - 1 , 2 - c y c l o p e n t a n e d i o l was a c c o m p lis h e d , b u t a t t e m p t s a t c o n v e r s io n to th e d im e th y l

20

e t h e r w ere u n s u c c e s s f u l .

The p r o j e c t was d ro p p e d b e c a u s e o f

th e a n tic ip a te d d i f f i c u l t i e s in p r e p a r in g s u f f i c i e n t p u re m a te r ia ls f o r s tu d y . EXPERIMENTAL C y c lo p e n ta n o n e .

T h is k e to n e was p r e p a r e d by th e

e x c e l l e n t m eth o d o f T h o rp e and Kon (11 ) •

The r e a c t i o n was

ru n w ith l i tim e s t h e q u a n t i t i e s s p e c i f i e d w ith no i n c r e a s e in th e s i z e o f t h e a p p a r a tu s * was u s e d a s th e s o u r c e o f h e a t .

A G l a s s - c o l h e a t i n g m a n tle The r e p o r t e d y i e l d s w ere

d u p lic a te d . C y c l o p e n ta n o l.

C y c lo p e n ta n o l h a s b e e n p r e p a r e d

from c y c lo p e n ta n o n e by r e d u c t i o n w ith l i t h i u m alum inum h y d r i d e ( lO ) , c a t a l y t i c a l l y w ith R aney n i c k e l o r p la tin u m ( 4 , by m eans o f sodium an d m o is t e t h e r ( 8 ) »

an d

The l a t t e r m eth o d

was s e l e c t e d f o r th e r e d u c t i o n b e c a u s e o f th e te m p o ra ry u n a v a i l ­ a b i l i t y o f a c a t a l y t i c h y d ro g e n a to r. The r e d u c t i o n was p e rfo rm e d i n th e f o ll o w i n g m a n n e r; 57 g« o f c y c lo p e n ta n o n e , 225 m l. o f e t h e r , 75 m l. o f m e th y l a lc o h o l and 300 m l. o f w a te r w ere p l a c e d I n a 1 1 . f l a s k a t t a c h e d t o an e f f i c i e n t r e f l u x c o n d e n s e r .

Sodium c u t i n s m a ll

p i e c e s (86 g . ) was a d d ed s lo w ly t h r u th e c o n d e n s e r

o p e n in g ,

r e a c t i o n o c c u r r i n g i n t h e u p p e r m o is t e t h e r l a y e r .

Vi/hen h a l f

th e sodium h a d b e e n a d d e d , t h e a q u e o u s l a y e r was r e p l a c e d w ith f r e s h w a t e r .

A t th e e n d , t h e e t h e r l a y e r was w ashed w ith

two 75- m l. p o r t i o n s o f w a t e r .

The e t h e r l a y e r was th e n

d i s t i l l e d th r o u g h a colum n r a t e d a t 50 t h e o r e t i c a l p l a t e s . A f t e r t h e e t h e r f l a t , a v e r y s m a ll m e th y l a l c o h o l f l a t was

21

o b ta in e d .

T h is was f o llo w e d b y a tw o -p h a s e f l a t b o i l i n g a t

9 6 -9 8 ® C ., A llo w ed b y a s m a ll w a te r f l a t . r o s e s h a r p ly to 139®C. ra n g e 1 3 9 -1 4 0 ^ 0 .

The te m p e r a tu r e th e n

The c y c lo p e n ta n o l d i s t i l l e d o v e r th e

No c y c lo p e n ta n o n e f l a t was o b s e r v e d .

The

y i e l d o b t a in e d was 46 g . R e a c tio n s r u n on tw ic e t h e ab o v e s c a l e g av e no d e c re a se in y ie ld . C y c lo p e n te n e . was u s e d i 3 ) •

The m eth o d o f C o rso n and I p a t i e f f

The c y c lo p e n ta n o l (1 3 8 g . ) was d e h y d r a te d w i th

24 m l. o f 85^ p h o s p h o r ic a c i d .

E ig h ty g . o f c y c l o p e n te n e ,

b o i l i n g a t 44.0® C . was o b t a i n e d . C y c lo p e n te n e O x id e .

B e c a u se th e d i r e c t i o n s o f

V erkade and c o w o rk e rs ( l ^ ) w ere n o t c o m p le te , an d th e o t h e r l i t e r a t u r e r e f e r e n c e s w ere n o t r e a d i l y o b t a i n a b l e , th e p r e p a r a t i o n o f t h i s o x id e was p a t t e r n e d a f t e r th e p r e p a r a t i o n o f s t y r e n e o x id e ( £ ) . m ethod o f B raun ( 2 ) •

P e r b e n z o ic a c i d was p r e p a r e d by th e The c o l d , d r y c h lo r o f o r m s o l u t i o n o f

p e r b e n z o ic a c i d p r e p a r e d fro m 50 g . o f b e n z o y l p e r o x id e was ad d ed s lo w ly to 13 g . o f c y c lo p e n te n e i n 200 m l. o f c h lo ro fo r m a t 2- 5^ 0 ,

The r e a c t i o n m ix tu r e was a llo w e d t o s ta n d i n a r e ­

f r i g e r a t o r f o r 48 h o u r s .

The c h lo r o f o im s o l u t i o n was t h e n

w ashed w ith 10% sodium h y d r o x id e , f o ll o w e d by w a t e r .

The

c h lo ro fo r m s o l u t i o n was t h e n d r i e d o v e r sodium s u l f a t e . t r a t i o n o f 5 m l, o f t h e r e a c t i o n m ix tu r e w ith O .09I W

T i­

sodium

t h l o s u l f a t e ( a f t e r a d d i t i o n o f sodium io d i d e an d a c e t i c a c i d ) r e q u i r e d a b o u t one d ro p o f s o l u t i o n f o r th e i o d i n e l i b e r a t e d . The r e a c t i o n m ix tu r e was th e n d i s t i l l e d

th r o u g h a colum n

22

r a te d a t 50 t h e o r e t i c a l p l a t e s . "chased" w ith d ih u t y l e t h e r .

The c y c lo p e n te n e o x id e was

E i ^ t g . o f m a t e r ia l b o i l i n g

a t 100®C. was o b t a in e d . t r a n s - 1 , 2 - C y c lo p e n t a n e d io l. C y c lo p e n te n e o x id e was c o n v e r te d to th e d i o l by b o i l i n g under r e f l u x c o n d e n se r w ith 10 tim e s i t s volum e o f O.OIH s u l f u r i c a c id f o r one hour ( 1 2 ) . The r e a c t io n m ix tu r e was th en n e u t r a l i z e d , th e w ater d i s t i l l e d o f f and th e d i o l r em a in in g p u r i f i e d by vacuum d i s t i l l a t i o n . The m a te r ia l was c o l l e c t e d a s a l i q u i d a t 1 0 5 -1 1 0 ° C . a t 10 mm. and soon s e t to a w h ite s o l i d . T reatm ent o f t r a n s - 1 ,2 - C y c lo p e n t a n e d io l w ith Sodium and M ethyl I o d id e .

Pour g . o f th e d i d

100 m l. o f warm b e n z e n e .

was d i s s o l v e d in

The f l a s k was a tt a c h e d to a r e f l u x

condenser and a p p r o x im a te ly 1 g . o f sodium in sm a ll p i e c e s was add ed .

A sm a ll amount o f b u b b lin g o c c u r r e d .

was warmed and r e f lu x e d g e n t ly o v e r n ig h t .

The m ix tu r e

M ost o f t h e sodium

appeared to rem ain a s a d e p o s it w ith a b la c k , g e la t in o u s c o a t in g .

The u n r e a c te d p i e c e s o f sodium were se p a r a te d

m e c h a n ic a lly and th e c o n te n t s o f th e f l a s k t r a n s f e r r e d t o a 500 m l . , 3 -n ec k e d f l a s k .

The c o n t e n t s o f th e f l a s k were

s t i r r e d w h ile 30 m l. o f m eth y l io d id e was added drop by d r o p . The r e a c t io n m ix tu r e was th e n warmed f o r two h o u r s .

F r a c t io n a l

d i s t i l l a t i o n o f th e r e a c t io n m ix tu re d id n o t y i e l d any m a te r ia l t h a t co rr e sp o n d e d t o t r a n s - 1 , 2 -d im e th o x y c y c lo p e n ta n e . SUMMARY A l i t e r a t u r e su r v ey on the p r e p a r a tio n o f c i s - and t r a n s - 1 , 2 -c y c lo p e n t a n e d io l was c o m p le te d .

The tr a n s d i o l

23

was p r e p a r e d i n s a t i s f a c t o r y y i e l d , b u t an a tte m p t t o c o n v e r t t h i s d i o l th r o u g h t h e s o d i o - d e r i v a t i v e to t h e c o r r e s p o n d i n g d im e th y l e t h e r was n o t s u c c e s s f u l .

24

LITERATURE CITED (1 )

B o e s e k e n , J . , R e c . t r a v . c h l m ., 4 7 , 6 8 3 -9 3 ( 1 9 2 8 ) .

(2 )

B ra u n , G ., O rg . S y n . C o l l . V o l.

(3 )

C o rs o n , B.

B .,

I , 1941, 431.

and I p a t i e f f , V. N ., I b i d . C o l l . V o l . I I ,

1943, l 5 l . (4 )

G oheen, G.

E . ,J . Am. Ghem. S o o . , 6 3 , 744 ( l 9 4 l ) .

(5 )

H e lfe ric h ,

B .,

a n d H iltm a n , R . , B e r . , 70B, 308 ( l 9 3 7 ) .

(6 )

H i b b e r t , H ., and B u r t , P . , O rg . S y n . C o l l . V o l. I , 1 9 4 1 » 494,

(7 )

M o u ss e ro n , M ., a n d G ra n g e r , R . , Com pt. r e n d . , 2 0 5 , 327 (1 9 3 7 ) .

(8)

N e n itz e s o u , G. D ., a n d l o n e s c u , C. H . , B u i, s o c . c h lm . R om ania, 1 4 , 6 5 -8 ( 1 9 3 2 ) .

(9 )

H o l l e r , C. R ., and Adams, R ., J . Am. Chem. S o c . , 4 8 , 1 0 8 4 (1926) .

(1 0 )

N y stro m , R . P . , a n d Brow n, W. G ., I b i d .

1197 ( 1 9 4 7 ) .

(11)

T h o rp e , J . F . and Kon, G. A . R . , O g. S y n . C o l l . V o l. I , 1941, 19 2 .

(1 2 )

V e rk a d e , P . E ., C o o p s, J r . , J . , M aan, C . J . , an d V e rk a d e -S a n b e rg e n , A . , A n n ., 4 6 7 , 221 ( 1 9 2 8 ) .

25

PART I I I SYSTEMS INVOLVING C ^ - OR TRANS-DICHLOROETHYLME INTRODUCTION

B e c a u se o f in c r e a s e d , a p p l i c a t i o n o f f r a c t i o n a l d i s t i l l a t i o n to i n d u s t r i a l p r o c e s s e s , v a p o r - l i q u i d e q u i l i b r i u m d a t a h a v e assum ed c o n s i d e r a b l e im p o rta n c e *

E q u ilib ria s tu d ie s

a r e u s u a l l y u n d e r ta k e n f o r t h i s r e a s o n , b u t i n t h i s i n v e s t i ­ g a t i o n , i t was d e s i r e d to u s e v a p o r - l i q u i d e q u i l i b r i a a s a m eans o f s tu d y in g th e e f f e c t o f h y d r o g e n - b o n d in g , d i p o l e m om ents, an d s t e r i c f a c t o r s i n n o n - i d e a l s y s te m s . A s y s t e m a t i c s tu d y o f th e v a p o r - 1 1 q u id e q u i l i b r i u m r e l a t i o n s in v o lv in g c i s - t r a n s is o m e rs was u n d e r t a k e n .

T h e re

i s a p p a r e n t l y o n ly a s m a ll am ount o f p u b l i s h e d d a t a a v a i l a b l e on v a p o r - l i q u i d e q u i l i b r i u m r e l a t i o n s h i p s and a z e o tr o p e fo r m a tio n in s y s te m s i n v o l v i n g c i s - t r a n s i s o m e r s . r e c e n t c o m p ila tio n o f a z e o t r o p e s (1 2 ) l i s t s

The m o st

23 c a s e s vihere

d a t a f o r v a p o r - l i q u i d e q u i l i b r i a o r a z e o tr o p e f o r m a ti o n h a v e b e e n p u b l i s h e d f o r e a c h o f a p a i r o f c i s - t r a n s is o m e rs w ith a t h i r d com pound.

T hese c a s e s a r e shown i n T a b le 1 .

I t was f e l t t h a t one o f th e im m e d ia te r e s u l t s o f th e p ro p o s e d p r o j e c t w ould b e th e f u r n i s h i n g o f d a t a on t h e v a p o r l i q u i d e q u i l i b r i a i n s y s te m s i n t e r e s t i n g b o th fro m th e th e o ­ r e t i c a l and p r a c t i c a l v ie w p o in ts w h ic h s y s te m s h a v e h e r e t o f o r e e i t h e r n o t b e e n s t u d i e d o r o n ly m e a g e rly i n v e s t i g a t e d .

The

s tu d y o f th e f o r m a ti o n o r l a c k o f f o r m a ti o n o f a z e o t r o p i c

26

m ix tu r e s b y c i s - t r a n s is o m e r s , a s w e ll a s t h e d e v i a t i o n s fro m I d e a l i t y , may y i e l d in f o r m a t i o n o f v a lu e on t h e fu n d a m e n ta l c a u s e s o f a z e o t r o p ism w h ich w ould b e o f v a lu e n o t o n ly to o r g a n ic a n d p h y s i c a l c h e m is ts b u t a l s o t o c h e m ic a l e n g i n e e r s . The g e n e r a l i z a t i o n s o f E w e ll, H a r r i s o n , an d B erg ( j ) c o n c e rn in g h y d ro g e n -b o n d in g and a z e o tr o p e f o m a t i o n a r e u s e f u l i n c o r r e l a t i n g th e e x i s t i n g v a p o r - l i q u i d e q u i l i b r i u m d a ta i n v o lv in g c i s - t r a n s is o m e r s . I n m o st o f t h e s y ste m s s t u d i e d , th e c i s - t r a n s is o m e rs h a v e b e e n l i q u i d s o f c l a s s e s IV and V and th e o t h e r co m p o n en t h a s u s u a l l y b e e n a l i q u i d o f c la s s I I

1 2 ) . L i q u i d s o f c l a s s I I a r e th o s e com posed

o f m o le c u le s c o n t a i n i n g b o t h a c t i v e h y d ro g e n ato m s an d d o n o r a to m s; c l a s s IV l i q u i d s a r e th o s e com posed o f m o le c u le s c o n ta i n in g a c t i v e h y d ro g e n ato m s b u t no d o n o r a to m s ; and c l a s s V l i q u i d s a r e th o s e h a v in g no h y d ro g e n -b o n d -fo rm in g c a p a b ilitie s .

I n su m m arizin g d e v i a t i o n s fro m R aoult?s la w ,

i t was p o i n t e d o u t ( ? ) t h a t when l i q u i d s o f c l a s s I I and c l a s s V a r e m ix e d , h y d ro g e n b o n d s a r e b r o k e n , and p o s i t i v e d e v i a t i o n s from R a o u l t*s la w r e s u l t .

When l i q u i d s o f c l a s s I I a n d c l a s s

IV a r e m ix e d , h y d ro g e n b o n d s a r e b o th b ro k e n a n d fo rm e d , b u t th e d i s s o c i a t i o n o f t h e c l a s s I I l i q u i d i s th e m ore im p o r ta n t e f f e c t , an d h e n c e p o s i t i v e d e v i a t i o n s fro m R a o u lt* s la w re s u lt. I n th e s y s te m s r e p o r t e d in v o l v i n g c i s - t r a n s is o m e r s , in a l l b u t 5 c a s e s ( 1 2 ), th e l i q u i d o f c la s s I I h as b een m e th y l, e t h y l , o r p r o p y l a l c o h o l .

In th e o th e r c a se s in v o lv in g

27

c i s - t r a n s i s o m e r s , th e l i q u i d o t h e r t h a n th e c i s o r t r a n s is o m e r h a s b e e n w a t e r , s u l f u r d i o x i d e , e t h y l e n e o x i d e , 1 b u ty n e an d m e th y l f o r n a t e . The a c t u a l f o r m a ti o n o f an a z e o tr o p e w i l l d e p en d upon th e m a g n itu d e o f t h e d e v i a t i o n s fro m R a o u lt* s la w a n d th e b o i l i n g p o i n t d i f f e r e n c e b e tw e e n th e two c o m p o n e n ts. The s m a l l e r t h e d e v i a t i o n fro m R a o u lt^ s la w f o r a p a i r o f l i q u i d s , th e s m a lle r t h e d i f f e r e n c e i n b o i l i n g p o i n t m u st be f o r a z e o tr o p e f o r m a t i o n .

I f an a z e o tr o p e i s fo rm ed i n

th e s y s te m , p o s i t i v e d e v i a t i o n s fro m R a o u lt* s la w can r e s u l t o n ly i n a m in im u m -b o ilin g a z e o t r o p e , w h e re a s n e g a t i v e d e v i ­ a t i o n s may c a u s e o n ly m a x im u m -b o ilin g a z e o tr o p e s . The c o n s t r u c t i o n o f v a p o r p r e s s u r e v s . c o m p o s itio n p l o t s , a s s h o rn i n F ig u r e 1 , f o r th e s y s te m s in v o l v i n g c i s t r a n s is o m e rs ( c l a s s IV an d V) and l i q u i d s o f c l a s s I I ,

in

w hich d e v i a t i o n s from i d e a l i t y w i l l b e p o s i t i v e , p e r m it s c o r r e l a t i o n o f m o st o f t h e e x i s t i n g d a t a i n th e l i t e r a t u r e . T h e re h a s b e e n some c o n f u s io n a s to w h ic h is o m e r o f a g iv e n p a i r i s th e c i s o r t r a n s m o d i f i c a t i o n .

F o r p u r p o s e s o f th e

fo llo w in g d i s c u s s i o n , th e te rm s h i g h e r - b o i l i n g is o m e r and l o w e r - b o i l i n g is o m e r r e p l a c e c i s o r t r a n s ; i n many c a s e s , th e te rm s a r e synonom ous.

D e n o tin g th e l i q u i d o t h e r th a n

th e c i s o r t r a n s is o m e r a s th e se c o n d co m p o n en t, t h r e e c a s e s may b e c o n s i d e r e d ; th e sec o n d com ponent b o l l s lo w e r th a n e i t h e r is o m e r ; th e se c o n d com ponent b o i l s b e tw ee n e i t h e r is o m e r , and th e se c o n d com ponent b o i l s h i g h e r th a n

28

e it h e r is o m e r .

In a l l th r e e c a s e s , i f a zeo tro p e s a r e form ed

w ith b o th is o m e r s , t h e system in v o lv in g th e h ig h e r - b o i l i n g isom er w i l l have an a z e o tr o p e w ith the h i ^ e r b o i l i n g p o in t and be r ic h e r in th e second component than th e system i n v o lv ­ in g th e lo w e r - b o ilin g isom er*

In th e f i r s t c a s e , in which th e

second component b o i l s lo w e r than e i t h e r iso m e r , the h ig h e r b o il in g isom er i s l e s s l i k e l y to form an a z e o tr o p e b e c a u se the b o i l i n g p o in t i s f u r t h e r from t h a t o f th e seco n d compon­ e n t than i s th a t o f th e l o w e r - b o i l i n g Iso m e r .

In th e second

c a s e , in w hich the secon d component b o i l s b etw een th e is o m e r s , the iso m er b o i l i n g c l o s e r to th e second component i s th e one more l i k e l y t o form an a z e o t r o p e .

In t i e t h ir d c a s e , in w hich

the second component b o i l s h ig h e r th an e i t h e r iso m e r , th e h ig h e r - b o ilin g isom er is more l i k e l y to form an a z e o tr o p e b e­ cau se the b o i l i n g p o in t i s c l o s e r to th e second com ponent. In s e l e c t i n g a p a ir o f c i s - tr a n s iso m ers f o r s tu d y , i t was d e c id e d to s t a r t w ith c i s - and t r a n s - d ic h lo r o e t h y le n e > These iso m e rs a re r e a d i l y a v a il a b le and can be r e a d ily p u r i­ f i e d by f r a c t i o n a l d i s t i l l a t i o n . would

As c l a s s IV l i q u i d s , i t

be e x p e c te d th a t b o th iso m ers sh o u ld form weak hydro­

gen b o n d s.

M in im u m -b oilin g a z s o tr o p e s have b een r e p o r te d

fo r ea ch isom er w ith w ater and e t h y l a l c o h o l . a zeo tro p e h a s been r e p o r te d f o r th e a lc o h o l.

A s im ila r

c i s form w ith m ethyl

In a d d it io n , minimum b o i l i n g a z e o tr o p e s f o r th e

te r n a r y system o f e a ch iso m e r w ith w a ter and e t h y l a lc o h o l were r e p o r te d ( l ^ ) .

I t was d e c id e d to d eterm in e th e v a p o r-

liq u id e q u ilib r iu m r e l a t i o n s h i p s o f th e c i s and tr a n s form s

29

w ith m e th y l a l c o h o l an d to c a l c u l a t e t h e r e l a t i o n s h i p s fro m th e a z e o t r o p i c d a t a a v a i l a b l e f o r th e b i n a r y s y s te m s o f e a c h is o m e r w ith e t h y l a lc o h o l# I n c o n t i n u i n g th e s tu d y o f th e v a p o r - l i q u i d e q u i l i b ­ riu m r e l a t i o n s i n b i n a r y s y s te m s w ith c i s - o r t r a n s - d i c h l o r o e th y le n e a s one c o m p o n en t, i t was d e c id e d t o i n v e s t i g a t e th e b e h a v io r o f t h e s e is o m e rs w ith c l a s s I I I l i q u i d s ( 7 ) , l i q u i d s c o n t a i n i n g d o n o r a to m s b u t no a c t i v e h y d ro g e n a to m s .

The

c l a s s I I I l i q u i d s f i r s t s e l e c t e d f o r s tu d y i n t h i s i n v e s t i ­ g a t i o n w ere m e th y la l ( d im e th y o x y m e th a n e ) , t e t r a h y d r o f u r a n , and is o p r o p y l e th e r * I n e v a l u a t i n g an d i n t e r p r e t i n g th e e q u i l i b r i u m d a t a o b ta in e d , i t was n e c e s s a r y t o c a l c u l a t e t h e i s o p i e s t i c a c t ­ i v i t y c o e f f i c i e n t s , f o r w h ich v a p o r p r e s s u r e d a t a i s n e e d e d . The v a p o r p r e s s u r e d a t a f o r t e t r a h y d r o f u r a n and m e th y la l w ere k i n d l y f u r n i s h e d b y t h e du P o n t Company, t h e d a t a f o r t e t r a h y d r o f u r a n s u b s e q u e n tly b e in g p u b l i s h e d (£ )♦ I n c o n t i n u a t i o n o f th e s tu d y o f th e v a p o r - l i q u i d e q u ilib r iu m r e l a t i o n s i n b i n a r y sy ste m s w ith c i s - o r t r a n s - d i c h lo r o e th y le n e a s one c o m p o n en t, t h e o t h e r com ponent b e in g a l i q u i d o f c l a s s I I I , e s t e r s and k e to n e s w ere th e n s e l e c t e d . The e s t e r s s e l e c t e d f o r s tu d y w ere e t h y l f o r m a te an d m e th y l a c e t a t e ; th e k e to n e s w ere a c e to n e an d 2 - b u ta n o n e . EXPERIMENTAL P re p a ra tio n o f M a te r ia ls .

Soma o f th e c i s - and

t r a n s - d i c h l o r o e t h v l e n e u s e d was f u r n i s h e d by th e Dow C h em ical

30

Company to whom th e a u t h o r w a n ts to e x p r e s s h i s a p p r e c i a t i o n ; th e com pounds h a d a p u r i t y o f 99*5 m o le p e r c e n t .

The r e ­

m a in d e r o f t h e c i s - a rd t r a n s - d i c h l o r o e t h y l e n e was p r e p a r e d by c a r e f u l f r a c t i o n a l d i s t i l l a t i o n th r o u g h a 1 2 0 -c m ., 12-mm. I . D. g l a s s h e l i c e - p a c k e d colum n a t a r e f l u x r a t i o n o f a b o u t 3 0 :1 o f m a t e r i a l p u r c h a s e d fro m C o lu m b ia O rg a n ic C h e m ic a ls Company.

The Is o m e rs p r e p a r e d i n t h i s m an n er h a d t h e same

b o i l i n g p o i n t s an d r e f r a c t i v e i n d i c e s a s t h a t f u r n i s h e d b y Dow; t h e v a lu e s f o r t h e c i s is o m e r w ere b . p . 6 0 .3 ° C ., an d 20 £D 1 .4 4 8 3 , and f o r th e t r a n s is o m e r , b . p . 4 8 .3 G. and 20 n^ 1 .4 4 5 5 . The m e th y l a l c o h o l was p u r i f i e d by c a r e f u l f r a c t i o n a l d i s t i l l a t i o n o f c o m m e rc ia l a b s o l u t e m e th y l a l c o h o l ; t h e m a t e r i a l u s e d b o i l e d a t 6 4 * 6 ^ 0 , a n d la d a r e f r a c t i v e i n d e x , n^®, o f 1 . 3 2 8 7 .

M e th y la l was p u r c h a s e d fro m th e P a ra g o n

T e s tin g L a b o r a t o r i e s .

The f r a c t i o n b o i l i n g a t 42.6® C . was c o l ­

l e c t e d a n d h a d a r e f r a c t i v e i n d e x , n ^ ^ , o f 1 .3 5 3 5 .

T e tra ­

h y d r o f u r a n was E astm an -K o d ak w h ite l a b e l an d was c o l l e c t e d a t 6 6 .1 ° C . (n ^ ^ I . 4 0 6 9 ) , a f t e r a c o n s i d e r a b l e f o r e r u n .

Iso ­

p r o p y l e t h e r was S astm an -K o d ak w h ite l a b e l an d d i s t i l l e d a t 68.0® C .

1 . 3680) .

E th y l f o r m a te was p u r c h a s e d fro m P a r a ­

gon T e s t i n g L a b o r a t o r i e s ; th e f r a c t i o n b o i l i n g a t 5 4 .0 ° C . was 20 c o l l e c t e d and h a d a r e f r a c t i v e I n d e x , ■ 1 .3 5 9 8 . E a stm a n Kodak y e llo w l a b e l m e th y l a c e t a t e was p u r i f i e d by th e m eth o d o f German and J a m s e t t ( l l ) ; f i n a l p u r i f i c a t i o n was a c h ie v e d by d i s t i l l a t i o n .

The f r a c t i o n b o i l i n g a t 57.2® C . was c o l l e c t e d

■ 1 . 3 6 1 4 ). C .P . a c e to n e was d i s t i l l e d a t a r e f l u x r a t i o

31

o f 2 0 :1 . 5 6 .4 ^ 0 ,

The f r a c t i o n c o l l e c t e d had a b o i l i n g p o in t o f = 1 .3 5 8 6 ).

2-B utanone ( Sastm an-K odak y e llo w

l a b e l ) was c o l l e c t e d a t 79*6°C A p p a ra tu s .

- 1 * 3 7 8 5 ).

The e q u i l i b r i u m

s till

em p lo y ed was co n ­

s t r u c t e d a s i n d i c a t e d b y J o n e s , S c h o e n b o rn , a n d C o lb u rn ( l ^ ) . The s t i l l was m o d if ie d fro m th e o r i g i n a l d e s ig n b y s e a l i n g a sm all d ro p p in g f u n n e l to th e tu b e l e a d i n g fro m th e c o n d e n s e r t o th e TJ-tube ( F ig u r e 2 ) ,

T h is g r e a t l y f a c i l i t a t e d th e c h a r g ­

in g o f th e sam p le t o th e s t i l l .

O b s e r v a tio n s c o n c e r n in g th e

o p e r a t i o n o f t h e s t i l l a r e th e

same a s th o s e n o t e d p r e v i o u s l y

(l 4 an d P a r t I ,

A s id e fro m f u r n i s h i n g r e l i a b l e

th is th e s is ) .

v a p o r - l i q u i d e q u i l i b r i u m d a t a , th e J o n e s - S c h o e n b o m - C o lb u r n s t i l l was s e l e c t e d f o r t h e s m a ll volum e o f l i q u i d t h a t c o u ld b e h a n d le d , w ith th e r e s u l t a n t s a v in g o f tim e i n p u r i f y i n g liq u id s f o r s tu d y .

The t o t a l volum e o f l i q u i d c o n ta i n e d

i n th e s t i l l d u r i n g o p e r a t i o n was a p p r o x im a te ly 15 to l 8 m l. The s t i l l was c o n n e c te d to a p r e s s u r e - r e g u l a t in g system s im ila r t o t h a t d e s c r ib e d b y Baker (2 ) (F ig u r e 3 ) . The te m p er a tu r e -m e a su r in g sy stem was th e same a s th e one d e s c r ib e d p r e v io u s ly (P a r t I , t h i s t h e s i s ) and was c a li b r a t e d by b o i l i n g in th e s t i l l pure sam ples o f w a te r , t o lu e n e , and a l l l i q u i d s s t u d ie d i n t h i s i n v e s t i g a t i o n .

The b o i l i n g p o i n t s

o f th e s e l i q u i d s were c h eck ed on a th eim om eter th a t had b e e n c a lib r a t e d by th e N a tio n a l Bureau o f S ta n d a r d s.

A ll tem pera­

tu r e s in t h i s pap er have been c o r r e c t e d . T ech n ic and P r o c e d u r e . The g e n e r a l t e c h n ic f o r

32

e x p e r i m e n t a l l y d e te r m in in g v a p o r - l i q u i d e q u i l i b r i a h a s b e e n d e s c r i b e d i n th e l i t e r a t u r e an d i n p a r t i c u l a r f o r t h e ty p e o f s t i l l em ployed i n t h e s e i n v e s t i g a t i o n s ( l 4 ) .

A p p ro x im a te ­

l y l 5 to 18 m l. o f one com ponent was c h a r g e d to t h e s t i l l , and m i x tu r e s w ith s u c c e s s i v e a d d i t i o n s o f th e o t h e r com ponent w ere a llo w e d to come to c o n s t a n t t e m p e r a t u r e .

A f t e r sm ooth

o p e r a t i o n o f th e s t i l l was o b t a i n e d , 40 m in u te s was a llo w e d f o r th e e s t a b l i s h m e n t o f e q u i l i b r i u m .

S am p les o f l i q u i d

and v a p o r w ere th e n w ith d ra w n s i m u lta n e o u s ly a n d a n a l y z e d . E q u ilib r iu m sa m p le s w ere a n a ly z e d b y r e f r a c t i v e in d e x m e a s u re ­ m en ts a t 2 0 ° C ., u s i n g th e d a t a p r e s e n t e d i n T a b le s 2 , 3 , an d 4. DATA V ap or-L lq u ld E q u ilib r iu m D a ta .

A ll sy ste m s were

s tu d ie d a t a p r e s s u r e o f 7 6 0 . 0 ;;h 0 . 5 mm, o f m ercu ry . The e x p e r im e n ta l r e s u l t s o b t a in e d f o r th e s y s te m s c i s - o r t r a n s - d i c h l o r o e t h y 1 e n e -m e th y 1 a lc o h o l a r e p r e s e n t e d i n T a b le s 6 and 7 and a r e shown g r a p h i c a l l y in F ig u r e 4 ; th e c o r r e s p o n d in g v a p o r - l i q u i d e q u i l i b r i u m d ia g ra m s a r e shown i n F ig u r e 5 .

The sm o o th ed d a t a f o r th e s y s te m s a n d th e a p ­

p a r e n t i s o p i e s t i c a c t i v i t y c o e f f i c i e n t s f o r e a c h com ponent w ere c a l c u l a t e d an d a r e r e c o r d e d i n T a b le s 8 a n d 9 .

The p l o t s

o f t h e s e c o e f f i c i e n t s ( l o g a r i t h m i c s c a l e ) a g a i n s t th e m ole f r a c t i o n o f t h e more v o l a t i l e com ponent i n t h e l i q u i d s c a l e ) a r e shown i n F ig u r e 6 .

(lin e a r

S m o o th in g o f th e d a t a was

j u s t i f i e d b y t h e c l o s e n e s s o f t h e e x p e r im e n ta l p o i n t s to th e

33

curve. The d a t a on th e a z e o t r o p e s f o m e d a r e p r e s e n t e d i n T a b le 5 .

The c o m p o s itio n s and b o i l i n g p o i n t s o f t h e a z e o t r o p e s

form ed w ere c a r e f u l l y c h e c k e d b y p r e p a r i n g m ix tu r e s a p p r o x i ­ m a tin g th e a z e o t r o p i c c o m p o s itio n s and f r a c t i o n a l l y d i s t i l l i n g th e m ix tu r e s th r o u g h an e f f i c i e n t c o lu m n .

The colum n em ployed

was t h e s p i r a l - p a c k e d Todd ty p e ( l 8 ) an d was r a t e d a t 50 t h e o ­ re tic a l p la te s .

The p r e s s u r e on th e colum n was m a in t a in e d a t

7 6 0 .0 ^ 0 .5 mm. b y t h e same p r e s s u r i n g a p p a r a t u s u s e d on th e e q u ilib riu m s t i l l .

A f te r e q u ilib riu m c o n d itio n s h ad been

e s t a b l i s h e d , t h e m ix tu r e i n t h e s t i l 1 - p o t was a llo w e d to r e ­ flu x fo r about 3 h o u rs . a 30 to 1 r e f l u x r a t i o

The a z e o tr o p e was th e n w ith d ra w n a t an d a n a ly z e d b y r e f r a c t i v e in d e x m e a s u re ­

m ent a n d a n a l y s i s f o r c h l o r i n e .

The th e rm o m e te r u s e d f o r ob­

s e r v in g th e b o i l i n g p o i n t s o f t h e a z e o t r o p e s was c a l i b r a t e d a g a i n s t a th e rm o m e te r c a l i b r a t e d b y th e N a t i o n a l B u re a u o f S ta n d a rd s . The d a t a i n t h e l i t e r a t u r e on th e a z e o t r o p e s fo rm e d in t h e s y s te m s c i s - o r t r a n s - d i c h l o r o e t h y l e n e - e t h y 1 a l c o h o l ( 1 2 ) h a s b e e n e x te n d e d b y u s e o f t h e v a n L a a r e q u a t i o n s to c a lc u la te th e a c t i v i t y c o e f f i c i e n t c u rv e s ( 5 ) .

T h ese c u r v e s

a r e shown i n F ig u r e 6 an d th e d a t a a r e r e c o r d e d i n T a b le s 10 and 1 1 , a lo n g w ith t h e x - y d a t a c a l c u l a t e d fro m t h e a c t i v ­ ity c o e ffic ie n ts .

The v a p o r - 1 i q u i d e q u i l i b r i u m r e l a t i o n s

th u s c a l c u l a t e d f o r c i s - o r t r a n s - d i c h l o r o e t h y l e n e - e t h y l a lc o h o l a r e shown i n F ig u r e 5 , a lo n g w ith th e e x p e r i m e n t a l l y

34

d e te r m in e d c u r v e s f o r c i s o r t r a n s - d i c h l o r o e t h y l e n e - m e t h y l a lc o h o l. The e x p e rim en ta l r e s u l t s o b ta in e d f o r th e b in a r y system s c i s - or t r ^ o s - d ic h io r o e t h y le n e w ith m e t h y la l, t e t r a ­ hyd rofu ran and is o p r o p y l e t h e r a r e p r e s e n t e d in T a b le s 1 2 to 17 and shown g r a p h ic a lly in F ig u r e 7 ; th e c o r r e sp o n d in g v a p o r - liq u id e q u ilib r iu m d iagram s a r e shown i n F ig u r e 8 . The sm oothed d a ta f o r th e sy ste m s and th e a p p a ren t i s o p i e s t i c a c t i v i t y c o e f f i c i e n t s f o r e a ch component were c a lc u l a t e d and reco rd ed in T a b les l 8 to 2 3 .

The p l o t s o f t h e s e c o e f f i c i e n t s

( lo g a r ith m ic s c a l e ) a g a in s t th e m ole f r a c t i o n s o f th e more v o l a t i l e component i n th e l i q u i d F ig u re 9*

( l i n e a r s c a l e ) a r e shovm in

Sm oothing o f th e d a ta was j u s t i f i e d by th e c l o s e ­

n e s s o f th e e x p e r im e n ta l p o i n t s to th e c u r v e . The e x p e r im e n ta l r e s u l t s o b t a i n e d f o r th e b i n a r y sy ste m s c i s - o r t r a n s - d i c h l o r o e t h y l e n e w ith e t h y l f o r m a te , m e th y l a c e t a t e , a c e t o n e , a n d 2 -b u ta n o n e a r e r e c o r d e d i n T a b le s 24 to 31 a n d a r e shown g r a p h i c a l l y i n F i g u r e s 10 a n d 1 1 ; th e c o r r e s p o n d in g v a p o r - l i q u i d e q u i l i b r i u m d ia g ra m s a r e shown i n F ig u r e s 1 2 an d 1 3 .

The sm o o th ed d a t a f o r th e s y s ­

tem s an d t h e a p p a r e n t I s o p i e s t i c a c t i v i t y c o e f f i c i e n t s f o r e a c h com ponent w ere c a l c u l a t e d an d r e c o r d e d i n T a b le s 32 to ,3 9 .

The p l o t s o f t h e s e c o e f f i c i e n t s

(lo g a rith m ic s c a le )

a g a i n s t t h e m ole f r a c t i o n o f th e m ore v o l a t i l e com ponent i n th e l i q u i d

( l i n e a r s c a l e ) a r e shown i n F i g u r e 1 4 .

S flo o th in g

o f th e d a t a was j u s t i f i e d b y t h e c l o s e n e s s o f th e e x p e r im e n t-

35

a l p o i n t s t o th e c u r v e . The c o m p o s itio n an d b o i l i n g p o i n t s o f th e a z e o t r o p e s form ed i n t h e s y s te m s , c i s - d i c h l o r o e t h y l e n e - t e t r a h y d r o f u r a n tr a n s -d ic h lo r o e th y le n e - m e th y la l, c l s -d ic h lo ro e th y le n e -m e th y l a c e t a t e , an d c i s - d i c h l o r o e t h y l e n e - a c e t o n e , c o u ld n o t b e c h e c k e d by p r e p a r i n g m ix tu r e s a p p r o x im a tin g th e a z e o t r o p i c c o m p o s itio n and f r a c t i o n a l l y d i s t i l l i n g t h e m ix tu r e s s i n c e th e m o st e f ­ f i c i e n t colum n a v a i l a b l e

(6 0 t h e o r e t i c a l p l a t e s ) d i d n o t h a v e

s u f f i c i e n t r e s o l v i n g p o w e r.

The v a p o r - l i q u i d e q u i l i b r i u m r e ­

l a t i o n s a r e s u c h t h a t s t a r t i n g on e i t h e r s i d e o f t h e a z e o t r o p i c c o m p o s itio n g a v e a r e s i d u e t h a t was r i c h e r th a n th e a z e o t r o p i c c o m p o s itio n w i th r e s p e c t to t h e com ponent o r i g i n a l ­ ly p re s e n t in e x c e ss.

As a r e s u l t , a z e o t r o p i c c o m p o s itio n s

and b o i l i n g p o i n t s w ere d e te r m in e d from t h e sm oothed v a p o r liq u id e q u ilib riu m d a ta .

C are was ta k e n t o d e te r m in e s u f f i c i e n t

e x p e r im e n ta l p o i n t s i n t h e v i c i n i t y o f th e a z e o tr o p e s to p e r m it d ra w in g o f a good a v e r a g e c u r v e .

I n t h e s y s te m , c i s - d i c h l o r o -

e t h y l e n e - t e t r a h y d r o f u r a n , a maximum b o i l i n g a z e o t r o p e , b o i l i n g a t 69.9*^0, and c o n t a i n i n g 0 .3 8 6 m o le f r a c t i o n c i s - d l c h l o r o e th y le n e was f o u n d .

I n th e s y ste m t r a n s - d i c h i o r o p e t h y l e n e -

m e th y la l, a m a x im u m -b o ilin g a z e o t r o p e , b o i l i n g a t 4 8 .6 ° C . an d c o n t a i n i n g 0 .2 5 0 m o le f r a c t i o n m e th y la l was f o u n d .

I n th e

sy stem c l s - d i c h i o r o e t h y l e n e - m e t h y l a c e t a t e , a maximum b o i l i n g a z e o tr o p e , b o i l i n g a t 6l.7 e rim e n ta l d a t a t o th e v an L a a r o r M a rg u le s e q u a t i o n s , A o r B v a lu e s w ere d e te r m in e d b y t a k i n g th e lo g a r ith m o f th e end v a lu e s o f th e a c t i v i t y c o e f f i c i e n t c u rv e s o r w ere c a l c u l a t e d from a z e o t r o p i c d a t a .

The s t e p s

in v o lv e d i n su c h c a l c u l a t i o n s sœe a s f o l l o w s ; s in c e th e a z e o ­ t r o p i c l i q u i d and v a p o r c o m p o s itio n s a r e i d e n t i c a l ,

( l ) red u ces

to

T hus, know ing th e v a p o r p r e s s u r e s o f th e p u r e co m p o n en ts a t th e a z e o t r o p i c t e m p e r a t u r e ,

an d Ifp a r e r e a d i l y o b ta in e d *

These v a lu e s a r e th e n s u b s t i t u t e d i n th e e q u a ti o n s o f v a n L a a r ( s o lv e d s i m u lta n e o u s ly f o r A an d B ) .

41

^2

A = lo g

log 4

1

lo g

(3 )

^

logX ^ X2 ~ lo g 3^

(4 )

The v a lu e s o f x^ and x g a re known from th e a z e o ­ tr o p ic c o m p o s itio n .

Once A and B v a lu e s are o b ta in e d th e y

may be s u b s t it u t e d in th e van Laar (5 ) o r M argu les (6 ) e q u a tio n s and th e a c t i v i t y c o e f f i c i e n t

lo g X j

A A x -l " I

cu rves c a lc u la te d .

L og ïp =

^

^

(5)

1+

AXn

lo g K i = (2B-A) x | 4- 2(A -B) Xg3 (6 )

l o g 3^2 = (2A-B)

4- 2(B-A ) x^^

To c a l c u l a t e x - y v a lu e s from a c t i v i t y c o e f f i c i e n t c u r v e s , s e v e r a l m ethods a re a v a i l a b l e .

7i

=

A ls o ,

P_ p^

y^ -p

S o lv in g ( l ) f o r y^ and

w Y *p.2 • "2^2— —

« 1

(7 )

(8)

I f the vapor p r e ss u r e -te m p e r a tu r e r e l a t i o n s are shown f o r b o th com ponents, ap p roxim ate te m p er a tu r e s c o r r e sp o n d in g to s p e c i f i c

42

v a lu e s o f

niay b e s e l e c t e d and th e c o r r e s p o n d in g v a l u e s o f

and ? 2 d e te r m in e d . m it an e v a l u a t i o n o f

S u b s t i t u t i o n o f t h e s e v a lu e s i n ( ? ) p e r ­ an d j p .

I f th e sum o f y^ and yg i s

g r e a t e r th a n o n e , a lo w e r te m p e r a tu r e i s

s e le c te d .

I f th e sum

o f y^ and y 2 i s l e s s th a n o n e , a h i ^ e r te m p e r a tu r e i s s e l e c t e d , By t h i s m eth o d o f s u c c e s s iv e a p p r o x im a tio n s , a te m p e r a tu r e i s e v e n t u a l l y s e l e c t e d t h a t g i v e s v a l u e s o f y^^ and y ^ t h a t t o t a l one . A s im p le r m ethod in v o lv e s s o lv in g ( ? ) f o r y^ b y s u b ­ s titu tin g

(l-y-j^) f o r y g .

T h is g i v e s

The r a t i o o f (P ^ /P ^ ) may b e e v a l u a t e d f o r th e lo w e s t te m p e ra ­ t u r e and h i p e s t te m p e r a tu r e in v o lv e d i n th e sy stem u n d e r s tu d y .

U s u a lly t h i s d o e s n o t i n v o lv e a te m p e r a tu r e d i f f e r e n t i a l

o f m ore th a n 30 d e g r e e s and (P ^ /P g ) d o e s n o t show much v a r i a t i o n , An a v e ra g e v a lu e o f (P ^,/P g) i s th e n u s e d i n (9 ) and v a lu e s o f y^ c a l c u l a t e d . E f f e c t o f S t r u c t u r e and P h y s ic a l P r o p e r t i e s . Ex­ a m in a tio n o f th e d a t a f o r sy ste m s i n v o l v i n g l i q u i d s o f c l a s s I I I r e v e a l s s e v e r a l p o i n t s t h a t a r e w o rth n o t i n g .

E w e ll

and W elch (^ ) and E w e ll, H a r r i s o n and B erg ( ^ ) p o i n t e d o u t

43

t h a t com pounds w ith th e s t r u c t u r e -CC1-CHC1» w i l l fo rm weak h y d ro g e n b o n d s w ith s u i t a b l e d o n o r ato m s su ch a s oxygen i n e s t e r s , k e to n e s , e th e r s , e t c .

I t w ould b e e x p e c te d t h a t

b o th e l s - and t r a n s - d i c h l o r o e t h y l e n e w i l l form h y d ro g e n b o n d s in th e p r e s e n c e o f su c h o x y g e n a te d m o le c u le s .

T h is w ould be

one f a c t o r i n e x p l a i n i n g th e v a p o r - l i q u i d e q u i l i b r i u m r e l a t i o n s . A n o th e r f a c t o r w ould b e t h e d i p o l e m oments o f th e e l s and t r a n s I s o m e r s , a n d t h e d i p o l e moments o f th e h y d ro g e n -b o n d e d com plex fo rm e d .

I t h a s b e e n shown t h a t th e v a lu e o f th e d i p o l e

moment f o r c i s - d i o h l o r o e t h v l e n e i s 1*8 d e b y e s ( l ^ ) , w h ile th e t r a n s is o m e r h a s a z e r o d i p o l e moment*

A c c o r d in g ly , th e

c i s is o m e r w o u ld b e e x p e c te d to show g r e a t e r d e p a r t u r e from i d e a l i t y th a n th e t r a n s is o m e r , b e c a u s e th e com plex fo rm ed th ro u g h h y d ro g e n -b o n d in g i n t h e c a s e o f t h e c i s is o m e r w ould s t i l l h a v e an a p p r e c i a b l e d i p o l e moment and te n d to a s s o c i a t e th ro u g h e l e c t r o s t a t i c a t t r a c t i o n .

A t h i r d f a c t o r t h a t m u st

be c o n s id e r e d i s th e c l o s e n e s s o f th e b o i l i n g p o i n t o f th e second com ponent t o th e c i s o r t r a n s is o m e r .

T h is i s e s ­

p e c i a l l y im p o r ta n t i n p r e d i c t i n g a z e o tr o p e f o r m a tio n ( 7 , The c l o s e r th e b o i l i n g p o i n t o f t h e se c o n d co m p o n en t, th e more l i k e l y t h a t a maximum o r minimum w i l l o c c u r i n th e t o t a l v ap o r p r e s s u r e c u r v e .

T h u s , i n th e s y s te m s , c l s - d i c h l o r o -

e th y le n e - m e th y la l and t r a n s - d l c h l o r o e t h y l e n e - m e t h y l a l , th e t r a n s iso m e r fo rm s a m a x im u m -b o ilin g a ze o t r o p e , th e o n ly m ax im u m -b o ilin g a z e o tr o p e w ith th e t r a n s is o m e r o b s e r v e d i n th e s e s t u d i e s .

A sid e fro m t h e f a c t t h a t m e th y la l b o l l s much

.

44

c l o s e r to th e t r a n s Is o m e r th a n th e c i s , a s t e r i c f a c t o r may he i n v o lv e d .

T h u s , th e c i s o r t r a n s is o m e r w ould b e e x p e c te d

to form c h a in s o f th e ty p e H

\/

H

A

0, 0 C l H CHs H

VII /\

. . . H

Cl

VII A

01

Cl

H . . .

T h is a b i l i t y o f e i t h e r is o m e r to fo rm lo n g c h a in s w ith m e th y la l th ro u g h h y d ro g e n -b o n d in g , p l u s t h e p r o x im it y o f th e b o i l i n g p o in t o f th e t r a n s is o m e r t o m e t h y l a l , f a v o r s th e f o r m a tio n o f an a z e o tr o p e w ith t h i s is o m e r . C h ain f o r m a tio n th ro u g h h y d ro g e n -b o n d in g i s a p p a r e n t ­ l y n o t th e p re d o m in a n t showsg r e a t e r

f a c to r ,because

n e g a tiv e d e v ia tio n s

th e c i s sy stem s t i l l

fro m i d e a l i t y .

The v a p o r - l i q u i d e q u i l i b r i u m r e l a t i o n s w ith i s o p r o ­ p y l e t h e r and t e t r a h y d r o f u r a n a r e i n t e r e s t i n g . (8)

E w ell and W elch

showed t h a t h a lo g e n a te d h y d ro c a rb o n s fo rm m a x im u m -b o ilin g

a z e o tr o p e 8 v e ry r e a d i l y w it h c y c l i c e t h e r s , a s com pared to o th e r e t h e r s *

Brown ( ^ ) h a s shown t h a t th e b a s e s t r e n g t h s

of a s e r ie s o f e th e r s a re in th e o rd e r ;

t e t r a h y d r o f u r a n > m e th y l

e th e r > e t h y l e t h e r > i s o p r o p y l e t h e r , when b o ro n t r l f l u o r i d e was th e a c i d .

The r e s u l t s w ere e x p la i n e d on t h e b a s i s o f s t e r i c

s t r a i n o f t h e r e s u l t i n g a d d i t i o n c o m p le x , th e s t r a i n b e in g l e a s t i n th e c a s e o f t e t r a h y d r o f u r a n an d g r e a t e s t i n th e c a s e

45

o f Iso p ro p y l e th e r .

T h u s , a s t e r i c f a c t o r may b e I m p o r ta n t

In e x p l a i n i n g th e l a r g e n e g a t i v e d e v i a t i o n s fro m i d e a l i t y w ith is o p r o p y l e t h e r .

E w e ll a n d W elch (8 ) fo u n d a maximum-

b o i l i n g a z e o tr o p e i n t h e s y s te m c h lo r o f o r m - is o p r o p y l e t h e r , b u t h e r e th e h y d ro g e n -b o n d in g te n d e n c y o f c h lo ro fo r m i s much g r e a t ­ e r th a n w ith c i s - o r t r a n s - d i c h i o r o e t h y l e n e . The r e s u l t s o f t h e s e i n v e s t i g a t i o n s o f c i s - and t r a n s - d i c h l o r o e t h y l e n e w ith l i q u i d s o f c l a s s I I I ( ? ) i n d i c a t e s e v e r a l p r i n c i p l e s t h a t may b e o f u s e i n t h e s e p a r a t i o n o f c i s - t r a n s is o m e rs s i m i l a r to c i s - an d t r a n s - d i c h i o r o e t h y l e n e . The c i s - is o m e r u s u a l l y shows th e g r e a t e r n e g a t i v e d e v i a t i o n from i d e a l i t y and th e g r e a t e r te n d e n c y to form a maximum b o i l ­ in g a z e o t r o p e .

The e n t r a i n e r c o u ld b e a l i q u i d o f c l a s s I I I

such a s an e s t e r , k e to n e o r e t h e r , w hich f o m s a maximumb o i l i n g a z e o tr o p e w ith th e c i s is o m e r, th u s p e r m i t t i n g g r e a t ­ e r e a s e i n t h e s e p a r a t i o n o f th e c i s - t r a n s is o m e rs b y i n c r e a s ­ in g th e b o i l i n g p o i n t d i f f e r e n c e b e tw e e n s e p a r a b l e f r a c t i o n s c o n s i s t i n g o f th e p u r e t r a n s is o m e r and th e m a x im u m -b o ilin g azeo* tr o p e fo rm ed b y th e e n t r a î n e r an d t h e c i s is o m e r .

A fte r d is ­

t i l l a t i o n o f t h e t r a n s Is o m e r, i f t h e e n t r a î n e r w ere w a te r s o lu b le an d th e c i s is o m e r w a t e r - i n s o l u b l e , th e s t i l l r e s i d u e c o u ld b e w ashed w ith w a te r to r e c o v e r t h e e n t r a î n e r , and th e r e l a t i v e l y p u r e c i s is o m e r o b t a i n e d . T h ese p r i n c i p l e s h av e n o t b e en t r i e d w ith c i s - an d t r a n s - d i c h i o r o e t h v l e n e b e c a u s e o f th e a p p r e c i a b l e b o i l i n g p o i n t d iff e r e n c e ( 1 2 ^ 0 .) .

The a p p l i c a t i o n to o t h e r s y ste m s w ould b e

46

in te re s tin g . SUMMARY The v a p o r - l i q u i d e q u i l i b r i u m d a t a on c i s - t r a n s is o m e rs a v a i l a b l e i n th e l i t e r a t u r e an d d e te r m in e d i n t h i s i n v e s t i g a t i o n h a v e b e e n c o r r e l a t e d by a c o n s i d e r a t i o n o f h y d ro g e n -b o n d in g , v a p o r p r e s s u r e - c o m p o s i t i o n r e l a t i o n s h i p s , b o i l i n g p o i n t s , d i p o l e m om ents and s t e r i c

fa c to rs .

V a p o r-liq u id e q u ilib riu m r e l a t i o n s in b in a ry sy stem s w ith c i s - o r t r a n s - d i c h l o r o e t h y l e n e a s one com ponent have b e e n d e te r m in e d a t 7 6 0 .0 + 0 ,5 mm. o f m e rc u ry p r e s s u r e . The se c o n d com ponents w ere m e th y l a l c o h o l , m e t h y l a l , t e t r a ­ h y d r o f u r a n , i s o p r o p y l e t h e r , e t h y l f o r m a te , m e th y l a c e t a t e , a c e to n e , and 2 - b u ta n o n e .

B o i l i n g p o in t - c o m p o s i t i o n , v a p o r -

l i q u i d e q u i l i b r i u m , and r e f r a c t i v e in d e x - c o m p o s itio n r e l a t i o n s a re p r e s e n t e d f o r a l l s y s te m s .

The a c t i v i t y c o e f f i c i e n t s

( lo g a r it h m ic s c a l e ) o f t h e co m p o n en ts a g a i n s t m o le f r a c t i o n o f t h e m ore v o l a t i l e com ponent i n th e l i q u i d

( li n e a r s c a le )

were p l o t t e d ; th e r e s u l t i n g d ia g ra m s a r e p r e s e n t e d .

I n some

c a s e s , th e d a t a f i t t e d th e v a n L a a r and M a rg u le s e q u a t i o n s . M in im u m -b o ilin g a z e o t r o p e s w ere o b s e r v e d i n th e b in a r y s y ste m s c i s - d i c h i o r o e t h y l e n e - m e t h y l a lc o h o l an d t r a n s d lc h io r o e th y le n e - m e th y l a l c o h o l .

Maximum b o i l i n g a z e o tr o p e s

were o b s e rv e d i n th e b i n a r y s y ste m s t r a n s - d i c h l o r o e t h y l e n e m e th y la l, c i s - d i c h l o r o e t h y l e n e - t e t r a h y d r o f u r a n , c i s - d i c h l o r o e th y le n e -m e t h y l a c e t a t e , a n d c i s - d i c h l o r o e t h y l e n e - a c e t o n e . A m ethod f o r s e p a r a t i n g c i s - t r a n s is o m e rs by a z e o t r o p i c d i s -

47

tllla tio n

i s s u g g e s te d . A z e o tr o p ic d a t a a v a i l a b l e in th e l i t e r a t u r e f o r th e

sy ste m s c i s - d i c h l o r o e t h y l e n e - e t h a n o l an d t r a n s - d i c h l o r o e t h y l e n e e th a n o l h a v e b e e n u s e d t o c a l c u l a t e a c t i v i t y c o e f f i c i e n t s w ith th e a i d o f t h e v a n L a a r e q u a t i o n s .

The a c t i v i t y c o e f f i c i e n t s

were th e n u s e d to c a l c u l a t e th e a p p ro x im a te v a p o r - l i q u i d e q u i­ lib r iu m r e l a t i o n s h i p s , th e c o r r e s p o n d i n g v a p o r - l i q u i d e q u i l i b r i u m d ia g ra m s b e in g p r e s e n t e d .

48

T a b le 1 A z e o tr o p e s and V a p o r-L iq u id E q u i l ib r iu m D a ta I n v o l v i n g c i s t r a n s Is o m e rs from H o r s l e y 's T a b le s ( 1 2 ) .

Name o f 00 mpound

B .P . A

Az eo t r o p e fo rm ed w ith B

B .P . of B

B .P . of Azeo t r o p e

Comp, o f A z e o tro p w t. ^ A

7 8 .3

7 7 .4

3 0 .9

7 4 .9

6 5 .5

7 2 .4

7 3 .3

6 6 ,3

82.

c is -B ro m o -1 , 2 d ic h lo ro e th y lene

1 1 3 .8

E th a n o l

tr a n s - C pHBrCl^

———

E th a n o l

c is - l- B r o m o - 2 cHToroe th y le n e

8 4 .6

E th a n o l

t r a n s-C pHpBrCl

7 5 .3

E th a n o l

c i s - 1 , 26-Dibromo- 1 1 2 .5 0th y le n e tr a n s - C

108

M e th a n o l

6 4 .7

M eth a n o l

c ^ -C g H g B rg

E th a n o l

tran s-C p H p B ro

E th a n o l

c i s - 1 —C h lo ro —2— l l 6 io d o e th y le n e

P ro p a n o l

tra n s-C p H p C lI

P ro p an o l

113

7 8 .3

c i 8 - 1 , 2 - D ic h lo r o e th y le n e

6 0 .2

W ater

tra n s -C g H g C l o

4 8 .3 5 W ater

no a z e o tr o p e 6 4 .1

7 8 .3

97

78

3 2 .5

76

64

94

5 5 .6

' 88 100

96

5 5 .3

9 6 .6 5

4 5 .3

9 8 .1

cls-C gH gC lg

M eth a n o l

6 4 .7

5 1 .5

87

c i s —CgH^Cl2

E th a n o l

7 8 .3

5 7 .7

9 0 .2

t r a n s —CgHgOlg

E th a n o l

4 6 .5

94

49

T ab le 1 , c o n t 'd Hame o f com­ pound

B .P . A

A z e o tro p e fo rm ed w ith B

c l s - 1 , 2-D lbrom ol- p r o p a n e

1 3 5 .2 P ro p a n o l

trans-C ^H /jB po

1 2 5 .9 5 P ro p a n o l

c ts - l- B r o m o - 1 p ro p a n e

5 7 .8 M e th a n o l

tra n s -C iH q B r

6 3 .2 5 M e th a n o l

cls-C ^H ^B r

E th a n o l

tran s-C ^H ^B r

E th a n o l

c ls -l-C h lo ro p ro pene

3 2 .8 E th a n o l

tra n s -C ^ H ^ l

3 7 .4 E th a n o l

c l s - 1 -B rom o-1 but m e

9 4 . 7 E th a n o l

trans-C yjH yBr

8 6 .1 E th a n o l

c i s - 2 - Bromo- 2 b u te n e

9 3 . 5 E th a n o l

tra n s-C ^ H ^ B r

8 5 .5 E th a n o l

c l s - 2 - C h l o r o —2— bub ene

6 7 . 0 E th a n o l

t r a n s-C yjH^Cl

6 2 . 0 E th a n o l

c ls -l-C h lo ro -1 b u te n e

63

E th a n o l

trans-C y|H ^C l

68

E th a n o l

c ls - 2 - B u te n e

3 . 7 SO2

tran8-C y|Sg

1 .0 SO

B .P . of B 9 7 .2

6 4 .7

7 8 .3

7 8 .3

B .P . Comp. 0] A z e o tro î of A z e o tro p e w t . ^ i 9 7 .0 5

3 .4 5

9 5 .7 5

4 1 .9 5

48

88

50

85

5 6 .4

91

5 8 .7

90

3 2 .1

———

3 6 .7 7 8 .3

7 8 .3

7 8 .3

7 8 .3

-1 0

6 9 .7

7 2 .5

7 2 .9

6 4 .3

7 2 .3

6 6 .3

6 9 .1

7 3 .3

6 0 .0

8 1 .6

57

8 4 .6

58

8 5 .2

61

7 9 .8

-1 3

—- —

-1 4

——

50

T a b le 1 , c o n t 'd A z e o tro p e fo rm ed w ith B

B .P . of B

B .P . Corap. o f of A z e o tro p e Az 30 t r o p e w t. % k

1 .0

E th y le n e o x id e

1 0 .7

—- —

—-

3 .7

E th y l ene o x id e

1 0 .7

—- -

-—

1 .0

1 -B u ty n e

8 .7

—-

9 0 .5

tra n s-C ^ H p

3 .5

1 -B u ty n e

---

7 4 .5

C IS-C 4HR

1 .0

M eth y l fo r m a te

-*•-

—-

tr a n s - C 4Hp

3 .5

M eth y l fo rm a te

——-

---

c ls -S th y l 1 0 0 .3 ('2-me t h y lp ro p e n y l) e th e r

E th a n o l

7 6 .3

———

7 7 .5

—-

7 6 .2

——

7 7 .5

—-

——-

53

---

61

—-

30

----

36

Name o f compound

B .P . A

CIS-C4HR t r a n 8-0

trans-C ^H ^^O

1 0 0 .4 5 E th a n o l

e ls - 2 - B u te n y l e th y l e t h e r

1 0 0 .3

trans-C ^H ^oO

1 0 0 .4 5 E th a n o l

E th a n o l

c l s - 1 , 2-D im e th y l- ——c y c lo p e n ta n e

E th a n o l

trans-Cr^Hj^/|

E th a n o l

c i s - 1 , 4-D im e th y l- ——— c y c lo h e x a n e

E th a n o l

trans-CgH-|L^

E th a n o l

—- —

3 1 .9

7 8 .3

7 8 .3

7 8 .3

7 8 .3

51

T a b le 2 R e f r a c t i v e I n d i c e s f o r B in a ry S o l u t i o n s o f c i s - o r t r a n s * D ie h lo r o e th y le n e a n d M e th y l A lc o h o l a t 2 0 .0 ° C ,

Mole F r a c t i o n M ethyl A lc o h o l 0 .0 0 .1 0 0 0 .2 0 0 0 .3 0 0 0 .4 0 0 0 .5 0 0 0 ,6 0 0 0 .70 0 0 .8 00 0 .9 0 0 1 .0 0 0

R e f r a c t i v e In d e x c is 1 .4 4 8 3 1 .4 4 1 2 1 .4 3 3 8 1 .4 2 5 3 1 .4 1 6 3 1 .4 0 6 1 1 .3 9 4 2 1 .3 8 0 1 1 .3 6 5 3 1 .3 4 8 2 1 .3 2 8 7

tra n s 1 .4 4 5 5 1 ,4 3 8 0 1 .4 3 0 2 1 .4 a 9 1 .4 1 2 8 1 .4 0 2 7 1 .3 9 0 9 1 .3 7 7 7 1 .3 6 2 9 1 .3 4 7 0 1 .3 2 8 7

52

T a b le 3 R e fr a c tiv e I n d ic e s f o r B in ary S o lu t io n s o f c i s - o r t r a n s D ie h l o ro e t h y l ene w ith M e t h y la l, T etra h y d r o fu r a n , and I s o ­ p r o p y l E ther a t 20^0*

Mole F r a c tio n c is - D io h lo r o e th y le n e

M eth y la l

0 .0 0 .1 0 0 0 .2 0 0 0.3 00 0 .4 0 0 0.500 0 .6 0 0 0 .7 00 0 .8 0 0 0. 9 0 0 1 .0 0 0

R e fr a c tiv e Index 20 %) T etra h y d ro fu ra n I s o p r o p y l E th er 1 .4 0 6 9 1 .4 1 1 7 1 .4 1 6 1

1.36 80

1.3535 1.3630 1.3720 1.3815 1.3909 1.4003 1.4095 1.4190 1.4284 1 .4 3 8 6 1 .4 4 8 3

1 .4 2 4 9 1 .4 2 9 1 1 .4 3 3 2 1 .4 3 7 2 1 .4 4 1 0 1 .4 4 7 0 1 .4 4 8 3

1 .3 7 3 4 1 .3 7 9 0 1 .3 8 5 2 1.3918 1.3989 1 .4 0 6 4 1 .4 1 4 5 1 .4 2 3 5 1.4352 1 .4 4 8 3

1 .3 5 3 5 1 .3 6 2 2 1 .3 7 1 0 1.3800 1.3890 1 .3 9 7 9 1.4071 1 .4 1 6 2 1 .4 2 5 5 1 .4 3 5 3 1 .4 4 5 5

1 .4 0 6 9 1 .4 1 1 4 1 .4 1 5 7 1 .4 1 9 9 1 .4 2 3 9 1 .4 2 7 8 1 .4 3 1 5 1 .4 3 5 1 1 .4 3 8 5 1 .4 4 1 9 1 .4 4 5 5

1.3680 1 .3 7 3 5 1.3789 1 .3 8 4 8 1.3913 1 .3 9 8 5 1.4063 1 .4 1 4 5 1.4233 1 .4 3 3 4 1 .4 4 5 5

1.4206

t r a n s - D ic h io r o e t h y lene 0 .0 0 .1 0 0 0 .2 0 0 0 .3 00 0 .4 0 0 0. 500 0. 6 0 0 0 .7 0 0 0.80 0 0 .9 0 0 1 .0 0 0

53

T able 4 R e f r a c t iv e I n d ic e s f o r B in a ry S o lu t io n s o f c i s - o r t r a n s D ic h lo r o e th y le n e w ith E th y l F orm ate, M ethyl A c e t a t e , A ceto n e and 2-B utanone a t 20°C . Mole F r a c tio n c i s - D lc h lo r o e t h y l ene 0 .0 0 .1 0 0 0 .2 0 0 0 .3 0 0 0 .4 0 0 0 .5 0 0 0 .6 0 0 0 .7 0 0 0.800 0.9 0 0 1 .0 0 0

E th y l Form ate

M ethyl A c e ta t e A ceton e

2-B utanone

1 .3 5 9 8 1 .3 6 8 4 1 .3 7 6 7 1 .3 8 5 2 1 .3 9 3 6 1 .4 0 2 4 1 .4 1 1 4 1 .4 2 0 6 1 .4 2 9 5 1 .4 3 8 7 1 .4 4 8 3

1 .3 6 1 4 1 .3 6 9 8 1 .3 7 8 1 1 .3 8 6 4 1 .3 9 4 9 1 .4 0 3 2 1 .4 1 2 0 i.4 a o 1 .4 3 0 2 1 .4 3 9 2 1 .4 4 8 3

1 .3 5 8 6 1 .3 6 8 6 1 .3 7 8 1 1 .3 8 7 2 1 .3 9 6 5 1 .4 0 5 8 1 .4 1 4 6 1 .4 2 3 3 1 .4 3 1 8 1 .4 4 0 1 1 .4 4 8 3

1 .3 7 8 5 1 .3 8 4 9 1 .3 9 1 4 1 .3 9 8 0 1 .4 0 4 6 1 .4 1 1 2 1 .4 1 8 2 1 .4 2 5 6 1 .4 3 3 0 1 .4 4 0 5 1 .4 4 8 3

1 .3 5 9 8 1 .3 6 8 0 1 .3 7 6 2 1 .3 8 4 3 1 .3 9 2 7 1.4010 1 .4 0 9 5 1 .4 1 8 4 1 .4 2 7 2 1.4362 1 .4 4 5 5

1.3614 1 .3 6 9 6 1 .3 7 7 6 1 .3 8 5 8 1 .3 9 4 2 1.4026 1 .4 1 1 1 1.4194 1.4281 1 .4 3 6 7 1 .4 4 5 5

1 .3 5 8 6 1.3678 1 .3 7 6 7 1 .3 8 5 7 1 .3 9 4 8 1.4035 1 .4 1 2 0 1.4203 1 .4 2 8 7 1.4369 1 .4 4 5 5

1 .3 7 8 5 1 .3 8 4 6 1.3910 1.3973 1.4038 1 .4 1 0 1 1.4168 1.4233 1.4300 1 .4 3 7 4 1 .4 4 5 5

tr a n s - D lc h lo r o e th y l ene 0 .0 0 .1 0 0 0 .2 0 0 0 .3 0 0 0 .4 0 0 0.5 0 0 0.6 00 0 .7 0 0 0.800 0 .9 0 0 1 .0 0 0

54

T a b le 5 D ata on B in a ry A z e o tr o p e s o f c i s - D ie h lo r o e th y le n e and tr g in s -D ic h lo r o e th y le n e w ith M ethyl A lc o h o l A z eo tr o p e o f CH^OS w ith c i s-D ic h lo r o tr a n s -DlchlorO' e th y le n e eth ylan a 5 1 .5 ° C . B o ilin g P o in t a t 7 6 0 .0 mm. A verage C h lo r in e C ontent 62.3% Mole F r a c tio n o f D ic h lo r o 0 .6 5 4 e th y le n e from C h lo rin e A n a ly si s Mole F r a c tio n o f D ic h lo r o 0 .6 5 1 e th y le n e from R e f r a c t iv e Index Mole F r a c tio n o f D ic h lo r o e t h y l­ 0 .6 5 0 ene from X - 2 Curve

4 l.9 ° C . 66.5%

0.768 0.769 0 .7 6 9

Tabla 6 V apor-L iqu id E q u ilib r iu m D ata fat* System c i s -D i ch i oro e t h y l eneM ethyl A lc o h o l a t 7 6 0 ,0 Mm. Temp., ®0. 6 4 .6 6 3 .3 61.8 60.6 5 8 .0 5 6 .9 5 6 .0 5 4 .5 5 3 .7 5 3 .1 5 2 .6 5 2 .4 5 2 .0 5 1 .8 5 1 .5 5 1 .8 5 1 .9 5 2 .3 5 2 .9 5 5 .4 5 6 .3 57.8 6 0 .3

M ole F r a c tio n c ls - D lc h lo r o a t h y le n a V apor, y j L iq u id , X]^ 0 .0 0.029 0 .0 4 8 0 .0 7 0 0.136 0.169 0.196 0.259 0 .3 1 4 0 .3 6 5 0.400 0,426 0.513 0 .5 7 1 0 .6 5 1 0.705 0.774 0 .8 5 0 0.916 0.986 0.996 o .m

1.000

0 .0 0.089 0.137 0 .1 8 7 0 .3 3 1 0 .3 7 1 0.391 0 .4 5 4 0.504 0 .5 3 9 0 .5 5 9 0.576 0 . 6 09 0 .6 3 4 0 .6 5 1 0 .6 5 5 0 .6 7 6 0.708 0.740 0 .8 4 0 0.873 0.939 1.000

55

T a b le 7 V a p o r-L iq u id E q u i lib r iu m D a ta f o r System t r a n s - D i c h lo r o e th y le n e - M e th y l A lc o h o l a t 760 .0 Mm, T em p., °C ,

M ole F r a c t i o n t r a n s - D i e h l o r o e t h y l e n e L iq u id , V a p o r, y^ 0.0 0.007 0 .0 2 1 0.028 0 .0 5 8 0.112 0.134 0.187 0 .2 4 6 0.294 0 .3 4 3 0.438 0 .5 6 0 0 .7 1 0 0.737 0.769 0.886 0.965 0.987 0.996 1.000

6 4 .6 6 3 .4 60.9 60,5 5 6 .5 52.3 5 1 .1 4 8 .1 4 6 .0 4 4 .8 4 4 .3 4 3 .0 4 2 .4 4 2 .0 42.0 4 1 .9 4 2 .3 4 3 .1 4 4 .8 4 6 .0 4 8 .3

0.0 0 .0 5 1 0.138 0.168 0.304 0 .4 5 2 0 .4 8 5 0 .5 3 8 0 .5 9 3 0 .6 5 3 0.680 0 .7 2 8 0 .7 3 3 0 .7 5 8 0.760 0 .7 6 9 0.790 0.830 0.906 0.944 1 .0 0 0

T a b le 8 Smoothed E q u i lib r iu m D a ta and A c t i v i t y C o e f f i c i e n t s f o r System c i s - D ic h lo r o e th y le n e - M e th y l A lc o h o l a t 7 6 0 ,0 Mm. T em p., °C . 64.7 61.6 5 9 .2 55.9 5 3 .8 5 2 .7 5 2 .0 5 1 .7

M ole F r a c t i o n c i s D ie h lo r o e th y le n e L i q u i d , x^ V a p o r, y^ 0,0 0.050 0.100 0.200 0.300 0.400 0.500 0.600

0.0 0,145 0 .2 5 6 0.400 0.490 0.560 0.607 0.639

A c tiv ity C o e ffic ie n ts D ie h lo r o e th y le n e A lc o h o l 2.80 2 .7 6 2 .6 4 2 .3 1 2.07 1.81 1.61 1 .4 3

1.00 1.03 1.04 1.08 l.l5 1.22 1 .3 4 1 .5 6

56

T ab le 8 , c o n t 'd Tgm p.,

5 1 .6 5 1 .9 5 2 .7 5 3 .6 5 4 .9 5 5 .8 5 6 .8 6 0 .3

M ole F r a c tio n t r a n s D ie h l o ro e th y l e ne L iq u id , V apor, 0.700 0.800 0.900 0 .9 5 0 0 .9 8 0 0 .9 9 0 0 .9 9 5 1 .0 0 0

0 .6 5 4 0 .6 8 3 0 .7 2 9 0 .7 7 5 0 .8 2 5 0 .8 5 3 0.876 1.000

A c tiv ity D ie h l oro et] 1.26 1.13 1.05 1 .0 2

A lc o h o l 2 .0 0 2 .7 1 4 .4 9 7 .1 5

1 3.2 mm am

1 .0 0

2 1 .3 3 4 .4

38.0

T a b le 9 Smoothed E q u ilib r iu m D ata and A c t i v i t y C o e f f i c i e n t s f o r System tr a n s -D ie h lo r o e th y le n e -M e th y l A lc o h o l a t 7 6 0 .0 Mm. Temp. , °c. 6 4 .7 5 7 .4 5 3 .0 47 .6 4 4 .7 4 3 .4 4 2 .5 4 2 .2 4 2 .0 4 1 .9 42*2 4 2 .8 4 4 .0 4 5 .2 4 8 .3

Mole F r a c tio n t r a n s D ie h l 0 ro e th y 1 en e L iq u id , x^ V apor, 0 .0 0.050 0 .1 0 0 0 .2 0 0 0.300 0.4 0 0 0.500 0,600 0 .7 0 0 0.800 0.900 0,950 0.980 0.990 1 ,0 0 0

0 .0 0 .2 7 7 0 .4 2 4 0.560 0 .6 4 8 0.709 0.730 0.740 0 .7 5 5 0.774 0 .7 9 4 0.819 0.862 0.916 1.000

A c t iv it y C o e ffic ie n ts D ic h lo r o e th y le n e A lc o h o l 4 .7 5 4 .1 2 3 .6 4 2.90 2 .4 8 2 .1 5 1.81 1 .5 3 1 .3 5 1 .2 2 1 .1 0 1.05 mam•

m#

1 .0 0

1 .0 0 1.03 1.04 1 .1 4 1.19 1.21 1.40 1.70 2 .1 5 2 .9 9 5 .3 9 9.23 16.6 19.2 22.5

57

T a b le 10 A c t i v i t y C o e f f i c i e n t s C a l c u l a t e d From A z e o tr o p ic D a ta f o r S y s­ tem c i s - D ic h i o r o e t h y l e n e - E t h y l A lc o h o l U sin g Van L a a r E q u a tio n s . X-Y R e l a t i o n s h i p s C a l c u l a t e d From A c t i v i t y C o e f f i c i e n t s . Mole F r a c t i o n c i s - D i c h l o r o e th y le n e L iq u id Vapor y^^ 0 .0 0 .0 5 0 0 .1 0 0 0 .2 0 0 0.3 0 0 0 .4 0 0 0 .5 0 0 0 .6 0 0 0.700 0 .8 0 0 0.902 0.950 1.000

0 .0 0 .1 3 5 0 .2 3 2 0 .4 1 2 0 .5 5 1 0.661 0 .7 3 6 0 .7 9 8 0 .8 5 0 0 .8 8 2 0.902 0.910 1.000

A c tiv ity C o e ffic ie n ts D ic h lo r o e th y le n e E th an ol 1 .4 8 1 .4 8 1 .4 7 1 .4 5 1 .4 2 1 .4 0 1 .3 6 1 .3 2 1 .2 6 1.18 1.08 1.03 1.00

1 .0 0 1 .0 0 1 .0 0 1 .0 0 1 .0 1 1 .0 2 1 .0 4 1 .0 9 1,18 1 .4 3 2.4 1 4.56 19.05

T a b le 11 A c t i v i t y C o e f f i c i e n t s C a l c u l a te d From A z e o tr o p ic D a ta f o r System t r a n s - D i e h l o r o e th y le n e - E th y l A lc o h o l U sin g Van L a a r E q u a tio n s .

X-Y R e l a t i o n s h i p s C a l c u la te d from A c t i v i t y

C o e ffic ie n ts . M ole F r a c t i o n t r a n s - D i c h i o r o e th y le n e L iq u id x^ V apor y^ 0 .0 0.050 0 .1 0 0 0 .2 0 0 0 .3 0 0 0 .4 0 0 0.5 00 0 .6 0 0 0 .7 0 0 0 .8 00 0 .90 0 0 .9 40 1 .0 0 0

0 .0 0.169 0.293 0.491 0.611 0.706 0 .7 7 3 0 .8 4 4 0 .8 9 1 0.916 0.935 0.940 1 .0 0

A c tiv ity C o e ffic ie n ts D ic h lo r o e th y le n e E th a n o l 1 .4 5 1 .4 1 1 .4 0 1.36 1.24 1.18 1 .1 3 1.09 1.05 1 .0 2 1 .0 1 1.08 1 .0 0

1 .0 0 1 .0 0 1 .0 0 1 .0 0 1 .0 1 1 .0 1 1 .0 2 1.05 1 .1 2 1.30 2 .2 2 4.19 1 3 5 .0

58

T able 12 V ap or-L iq u id E q u ilib r iu m D ata f o r System c i s -D ic h lo r o e th y le n e M eth y la l a t 760*0 Mm. Temp. , °0.

Mole F r a c tio n M eth y la l L iq u id ,X j V apor,y^ 0.0 0.020 0 .0 4 8 0 .1 0 4 0.180 0.267 0.366 0.437 0 ,5 1 3 0 .5 8 1 0 .6 5 3 0 .7 3 7 0.810 0.918 0.983 1 .0 0 0

60.3 60.1 5 9 .9 5 9 .4 5 8 .3 5 7 .0 5 5 .3 5 4 .0 5 2 .4 5 0 .9 4 9 .4 4 7 .5 4 5 .9 4 3 .8 4 2 .8 4 2 .6

0.0 0 .0 2 5 0,062 0.130 0.237 0 .3 4 9 0 ,4 8 1 0 .5 6 7 0 .6 5 2 0.727 0.790 0 .8 5 9 0.909 0.967 0 .9 9 8 1 .0 0 0

T a b le 13 V apor-L iqu id E q u ilib r iu m D ata f o r System tr a n s -D ie h lo r o e th y le n e M eth ylal a t 7 6 0 . 0 Mm. Tem p., ®G,

Mole F r a c tio n M eth y la l L i q u i d , V a p o r , y ^

48.3

0.0

0 .0

4 8 .3 4 8 .4 4 8 .5 4 8 .5 4 8 .5 4 8 .6 4 8 .6 4 8 .5 4 8 .5 4 8 .4 4 8 .3 4 8 .2 4 8 .0 4 7 .4

0 .0 3 0 0 .0 8 9 0 .1 4 0 0 .1 8 3 0 .2 1 2 0 .2 3 1 0 .2 5 1 0 .2 7 4 0 .3 0 4 0 .3 3 1 0 .3 5 6 0 ,3 8 8 0 ,4 2 8 0 .5 0 1

0 .0 2 7 0 .0 8 0 0.128 0 .1 7 5 0 .2 0 4 0 .2 2 5 0 .2 5 0 0 .2 7 7 0 .3 1 1 0 .3 4 4 0 .3 7 5 0 .4 1 2 0 .4 5 5 0 .5 4 2

59

T ab le 1 3 , o o n t'd Temp. , ®C.

M< L iq u id ,! , 0 .5 8 0 0 .6 7 3 0 .7 5 6 0 .8 5 2 0 .9 3 3 0 .9 8 3 1 .0 0 0

4 6 .9 4 6 .2 4 5 .3 4 4 .2 4 3 .1 4 2 .7 4 2 .6

V ap o r,y . 0 .6 3 3 0 .7 2 9 0 .8 1 1 0 .8 9 4 0 .9 5 5 0 .9 0 9 1 .0 0 0

T a b le 1 4 V a p o r-L iq u id E q u ilib r iu m D a ta f o r System c i s -D i c h i o ro e t h y l ene T e tr a h y d r o f u r a n a t 7 6 0 .0 Mm.

°C , 6 6 .1 6 6 .4 6 6 .9 6 7 .1 6 7 .8 6 8 .5 6 8 .9 6 9 .3 69.7 69.7 6 9 .8 6 9 .8 69.7 6 9 .4 68.9 6 8 .0 67.0 66.3 64.9 6 3 .6 62.4 6 1 .6 60.3

M ole F r a c t i o n c i s - D i c h l o r o e th y le n e V a p o r, y. L iq u id ,! , 0 .0 0.018 0.045 0.083 0.136 0 .1 8 5 0.232 0.2 8 1 0 .3 1 3 0 .3 5 7 0 .3 7 3 0.392 0.421 0 .4 4 7 0 .4 9 7 0 .5 5 2 0.627 0.695 0 .7 7 5 0 .8 4 3 0.909 0.9 81 1 .0 0 0

0 .0 0 .0 1 0 0.030 0.055 0.096 0 .1 5 0 0.203 0 .2 5 9 0.297 0.350 0.368 0 .3 9 5 0 .4 2 7 0.466 0.5 26 0.609 0.697 0.768 0 .8 5 1 0.907 0.943 0.945 1.000

60

T a b le 15 V a p o r-L lq u id E q u i lib r iu m D a ta f o r S ystem t r a n s - D ic h lo r o e th v le n e * T e tr a h y d r o f u r a n a t 7 6 0 .0 Mm. Tg m p ..

M ole F r a c t i o n tr a n s - -D ic h lo ro e th y le n e L iq u id ,! , V a p o r, y.

6 6 .1 6 6 .1 6 6 .0 6 5 .9 6 5 .4 6 4 .4 6 2 .5 6 1 .3 60.1 5 7 .5 5 5 .6 5 3 .8 5 2 .6 5 0 .9 4 9 .5 4 8 .3

0 .0 0 .0 1 6 0 .0 4 5 0 .0 8 5 0.160 0.266 0.376 0 .4 5 4 0 .5 0 6 0 .5 9 7 0.683 0 .7 5 1 0.828 0.903 0.967 1 .0 0 0

0 .0 0. 01 6 0.047 0.092 0 .1 8 1 0.329 0 .4 7 2 0.576 0.619 0.736 0 .8 01 0 .8 5 3 0.905 0.948 0.978 1.000

T a b le l 6 V a p o r-L iq u id E q u ilib r iu m D a ta f o r S ystem c i s - D ic h lo r o e t h y l e n e I s o p r o p y l E th e r a t 7 6 0 .0 Mm. T em p., °0. 6 8 .0 67.6 67.4 67.2 66.9 6 6 .4 6 5 .9 6 5 .4 6 5 .0 6 4 .4 63.5 62.2 61.5 6 0 .3

M ole F r a c t i o n c i s - - D ic h lo ro e th y le n e V ap o r,y . L i q u id , 0 ,0 0.058 0. 1 1 6 0.176 0 .2 4 5 0.329 0 .3 9 9 0.460 0 .5 3 4 0.618 0.697 0.828 0.903 1 .0 0

0 .0 0 .0 6 3 0.129 0.198 0 .2 7 0 0.378 0.450 0.521 0.604 0 .6 8 4 0.767 0.877 0.932 1.00

61

T able 1? V a p o r-L iq u id E q u i lib r iu m D a ta f o r System t r a n s - P ic h io r o e th y le n e I s o p r o p y l E t h e r a t 7 6 0 .0 Mm. Tgm p., C.

M ole F r a c t i o n t r a n s - D ic h lo r o e th y le n e L iq u id , V apor,y_

68.0 66.9 6 5 .9 6 5 .0 63.1 6 1 .1 5 9 .5 5 8 .0 5 6 .1 5 5 .6 5 3 .4 5 3 .3 5 1 .6 50.7 4 9 .4 4 8 .3

0.0 0.063 0.110 0,160 0 ,2 4 8 0 .3 4 1 0 .4 1 7 0 .4 7 4 0.576 0 .^ 8 8 0 .7 0 6 0.769 0.805 0 .8 5 7 0.942 1 .0 0

0.0 0 .0 9 9 0 .1 7 2 0 .2 4 2 0 .3 5 8 0 .4 6 4 0 .5 6 0 0.624 0.725 0 .7 3 4 0 .8 3 6 0 .8 8 1 0.902 0.928 0 .9 7 1 1 .0 0

T a b le l 8 Smoothed E q u ilib r iu m D a ta an d A c t i v i t y C o e f f i c i e n t s f o r S ys­ tem c i s - D i c h l o r o e t h y l e n e - M e t h y l a l a t 7 6 0 .0 Mm. Temp. , OC. 6 0 .3 5 9 .8 59.4 5 8 .1 5 6 .5 5 4 .7 52.6 5 0 .5 4 8 .3 4 6 .1 4 4 .1 4 3 .3 4 2 .6

A c tiv ity C o e ffic ie n ts M ole F r a c t i o n M e th y la l D ie h lo ro e th y le n e V a p o r,y ^ M e th y la l L i q u id ,x ^ 0 .0 0.050 0 .1 0 0 0 .2 0 0 0.300 0.400 0.500 0.600 0.700 0.800 0.900 0.950 1 .0 0 0

0 .0 0.062 0.127 0.262 0.394 0.522 0 .6 4 0 0 .7 4 5 0 .8 3 1 0.902 0.958 0 .9 8 1 1 .0 0 0

0 .6 3 0 0 .6 6 2 0 .6 9 3 0.742 0.786 0.834 0.8 8 1 0.920 0 .9 4 8 0.974 0.990 0.990 1 .0 0 0

1.00 0 .9 9 3 0 .9 9 6 0 .9 8 5 0 .9 7 8 0 .9 5 8 0 .9 3 4 0 .8 91 0 .8 4 8 0.798 0 .7 3 5 0.686 0.600

62

T a b le 19 Sm oothed E q u i lib r iu m D a ta and A c t i v i t y C o e f f i c i e n t s f o r S ystem t r a n s - D i c h l o r o e t h y l e n e - M e th y la l a t 7 6 0 ,0 Mm. Temp. ,

°c.

4 8 .3 4 8 .3 4 8 .4 4 8 .5 4 0 .6 4 8 .5 4 8 .1 4 7 .5 4 6 .8 45.9 4 4 .7 4 3 .5 4 3 .0 42.6

M ole F r a c t i o n M e th y la l L i q u id ,x ^ V apor ,y ^ 0 .0 0.050 0 .1 0 0 0 .2 0 0 0.250 0.300 0.400 0.500 0 .6 0 0 0 .7 0 0 0 .8 0 0 0.900 0.950 1 .0 0 0

0 .0 0 .0 4 2 0.089 0.192 0.250 0.308 0.424 0 .5 4 1 0 .6 5 3 0 .7 5 5 0 .8 4 8 0.932 0.968 1 .0 0 0

A c tiv ity C o e ffic ie n ts Di c h i o r o e th y le n e M e th y la l 0 .6 4 0 0.673 0.708 0 .7 6 2

————— 0.815 0 .8 5 3 0,894 0.920 0.935 0.968 0.988 0.985 1 .0 0

1 .0 0 1 .0 2 1 .0 2 1 .0 1 ———— 0 .9 9 5 0.980 0.959 0.925 0.892 0.870 0 .8 1 1 0.772 0.740

T a b le 20 Sm oothed E q u i lib r iu m D a ta an d A c t i v i t y C o e f f i c i e n t s f o r S ystem c i s - D i c h l o r o e t h y l e n e - T e t r a h y d r o f u r a n a t 7 6 0 .0 Mm, T em p., ®C.

66.1 66.8 67.5 68.6 69.5 m

6 8 .8 67.2 6 6 .1 ÔX .6

60.3

M ole F r a c t i o n c i s D ic h lo r o e th y le n e Liquid,V apor,y^ 0.0 0 .0 5 0 0 .1 0 0 0 .2 0 0 0.300 0.386 0.400 0.500 0.600 0.700 0.800 0.900 0.950 1 .0 0 0

0 .0 0.032 0,069 0.164 0.282 0.386 0.404 0 .5 3 5 0.667 0.776 0 .8 7 3 0.942 0 .9 7 1 1 .0 0 0

A c tiv ity C o e ffic ie n ts D ic h lo r o e th y le n e T e tr a h y d r o f u r a n 0 .4 8 0 0 .5 1 2 0 .5 4 3 0.622 0.692 ————— 0 .7 3 5 0 .7 9 9 0.878 0.907 0 .9 4 8 0.965 0 .9 7 5 1 .0 0

1 .0 0 0.995 0.997 0 .9 7 1 0.925 ————— 0 .8 8 5 0 .8 5 0 0 .8 0 4 0 .7 4 6 0.672 0 .6 5 2 0.673 0.670

63

T ab le 21 Sm oothed E q u ilib r iu m D a ta and A c t i v i t y C o e f f i c i e n t s f o r System t r a n s - D l o h l o r o e t h y l e n e - T e t r a h y d r o f u r a n a t 7 6 0 .0 Mm. Temp. , °c. 66.1 6 5 .9 6 5 .7 6 5 .0 6 3 .9 62.2 60.2 5 7 .6 5 5 .2 5 3 .1 5 0 .9 4 9 .7 4 8 .3

M ole F r a c t i o n t r a n s D ie h l o ro e th y le n e L i q u id , V a p o r,y ^ 0.0 0.050 0.100 0.200 0.300 0.400 0.500 0.600 0 .7 0 0 0.800 0.900 0 .9 5 0 1.000

0.0 0 .0 5 5 0 .1 0 9 0 .2 3 4 0 .3 7 2 0 .5 0 1 0.621 0 .7 3 0 0 .8 1 7 0.886 0 .9 4 6 0 .9 7 4 1.000

A c tiv ity C o e ffic ie n ts D ic h lo r o e th y le n e T e t r a h y d r o f u r an 0.600 0 .6 4 3 0 .6 4 2 0 .7 0 2 0 .7 6 8 0 .8 1 7 0 .8 6 1 0 .9 1 6 0 .9 4 4 0 .9 5 9 0 .9 7 3 1.00 1.00

1.00 1.00 1.00 0 .9 9 3 0.960 0.942 0.916 0.892 0.872 0 .8 7 7 0.890 0.909 0.920

T a b le 22 Sm oothed E q u i lib r iu m D a ta and A c t i v i t y C o e f f i c i e n t s f o r S ystem c i s - D i c h l o r o e t h y l e n e - I s o p r o p y l E th e r a t 7 6 0 .0 Mm. Temp. , ®c. 68.0 6 7 .7 67.5 6 7 .0 6 6 .5 6 5 .9 6 5 .2 6 4 .4 63.5 62.5 61.5 60.9 60.3

M ole F r a c t i o n c i s D ic h lo r o e th y le n e V a p o r,y ^ L i q u id ,x ^ 0.0 0.050 0 .1 0 0 0 .2 0 0 0.300 0.400 0.500 0.600 0.700 0 .8 0 0 0.900 0 .9 5 0 1 ,0 0 0

0.0 0.054 0 .1 1 0 0 .2 2 7 0.342 0.452 0.562 0.669 0.768 0 .8 5 3 0.930 0.965 1.000

A c tiv ity C o e ffic ie n ts E th e r D ic h l o r o e th y l e n e 0.800 0.834 0 .8 5 6 0.8 96 0 ,9 1 7 0.922 0 .9 3 9 0.960 0,973 0.982 0 .9 8 4 0.979 1 .0 0

1.00 1.00 1 .0 0 0,998 0.988 0.976 0 .9 5 8 0.934 0.900 0 ,8 8 8 0.875 0 .8 8 5 0.920

64

T ab le 23 Smoothed E q u ilib r iu m D ata and A c t i v i t y C o e f f i c i e n t s f o r System t r a n s - D ie h lo r o e t h y le n e - I s o p r o p y l E ther a t 7 6 0 ,0 Mm, T em p., °C . 68.0 6 7 .1 66.2 6 4 .1 6 2 .0 5 9 .8 5 7 .6 5 5 .4 5 3 .4 5 1 .7 5 0 .0 4 9 .1 4 8 .3

M ole F r a c t i o n t r a n s D ic h lo r o e th y le n e V a p o r,y ^ L iq u id , 0.0 0 .0 7 8 0 .1 5 4 0 .2 9 5 0 .4 2 2 0 .5 4 0 0 .6 5 0 0 .7 4 6 0 .8 2 9 0 .8 9 8 0 .9 5 2 0 .9 7 5 1 .0 0 0

0.0 0.050 0.100 0 .2 0 0 0.300 0 .4 0 0 0 .5 0 0 0 .6 0 0 0.700 0 .8 0 0 0.900 0 .9 5 0 1 .0 0 0

A c tiv ity C o e ffic ie n ts D ic h l o r o e t h y l e n e E th e r 0,820 0 .8 4 9 0 . 86o 0 .8 7 8 0 .8 9 6 0 .9 2 3 0 .9 5 8 0 .9 8 1 1 .0 0 1 ,0 1 0 .9 9 6 0.996 1 .0 0

1.00 0,998 1.00 0.998 1 .0 0 1 .0 0 0.998 0.973 0.944 0,902 0.892 0 .9 5 6 0.950

T a b le 24 V a p o r-L iq u id E q u ilib r iu m D a ta f o r System c i s - D ic h lo r o e th y le n e E th y l F o rm a te a t 7 6 0 ,0 Mm. Temp. , c. 60.3 6 0 .3 60,3 6 0 .1 59.7 59.2 5 8 .8 5 8 .6 58.2 5 7 .7 5 7 .1 5 6 ,7 56.4 5 5 .8 5 5 .3 5 4 .4 5 4 .0 53.9

M ole F r a c t i o n E th y l F o rm ate L iq u id ,x ^ V a p o r,y ^ 0 .0 0 .0 1 2 0.039 0 .1 2 0 0.194 0.283 0 .3 6 3 0,425 0,505 0.579 0 .6 4 8 0.718 0,783 0 .8 4 0 0 .8 8 6 0,955 0.993 1.000

0 .0 0 .0 1 4 0.043 0.129 0 .2 1 3 0 .3 1 3 0.398 0 .4 6 3 0 .5 4 8 0.624 0 .7 0 0 0.765 0.825 0.877 0.919 0.970 0 .9 9 8 1 .0 0 0

65

T ab le 25 V fto o r-L lg u ld E a u illb r iu m D a ta f o r S ystem t r a n s - D l o h l o r o e t h y l e n f E th y l F o rm a te a t 7 5 0 .0 Mm. Tamp. , °C .

M ole F r a c t i o n t r a n s - D lo h lo r o e th y ] L iq u id ,! , V apor,y-^ 0 .0 0 .0 5 0 0 .1 1 0 0.167 0.228 0.312 0.387 0 .4 5 1 0.525 0.619 0 .6 9 1 0 .7 5 8 0.829 0 .8 5 1 0.934 0.974 1 .0 0 0

5 3 .9 5 3 .7 5 3 .5 5 3 .0 5 2 .5 5 1 .9 5 1 .3 5 0 .9 5 0 .5 4 9 .9 4 9 .5 4 9 .3 4 9 .0 4 8 .9 4 8 .5 4 8 .5 4 8 .3

0 .0 0.067 0 .1 4 0 0.208 0.282 0 .3 6 9 0 .4 4 8 0 .5 1 2 0 .5 8 3 0.662 0 .7 2 7 0 .7 8 4 0 .8 4 9 0 .8 6 8 0.938 0 .9 7 6 1.000

T a b le 26 V a p o r-L iq u id E q u i lib r iu m D a ta f o r S ystem c l s - D l c h l o r o e t h y l e n e -M e th y l A c e ta te a t 7 6 0 .0 Mm. Temp . , °0. 5 0 .3 5 0 .6 61.0 61.2 6 1 .3 6 1 .4 6 1 .5 61.6 6 1 .7 6 1 .7 6 1 .7 6 1 .6 6 1 .5

M ole F r a c t i o n M eth y l A c e ta te V a p o r,y ^ L iq u id , 0 .0 0.031 0 .0 7 2 0 .1 1 2 0 .1 4 7 0.198 0.224 0.276 0 .2 9 6 0 .3 2 6 0.347 0.375 0.395

0 .0 0 .0 2 7 0.062 0.099 0 .1 3 3 0.183 0.213 0.266 0.291 0 .3 2 6 0 .3 5 1 0.383 0.408

66

T a b le 2 6 , c o n t 'd Temp. , °0.

M ole F r a c t i o n M eth y l A c e ta te L iq u id , V a p o r,y ^

6 1 .4 61.2 60.8 60.2 5 9 .7 5 9 .2 5 8 .4 5 7 .6 5 7 .3 5 7 .2

0 .4 4 4 0 .5 1 1 0 .5 8 3 0 .6 5 1 0 .7 1 5 0 .7 7 2 0.880 0 .9 5 0 0.988 1.000

0 .4 6 5 0 .5 4 1 0.623 0 .6 9 6 0 .7 7 0 0.820 0 .9 0 7 0 .9 6 5 0 .9 9 3 1.000

T a b le 27 V a p o r-L lq u ld E q u i lib r iu m D a ta f o r System t r a n s -D lc h lo ro -* e th y le n e - M e th y l A c e ta te a t 7 6 0 .0 Mm. T em p ., 5 7 .2 5 7 .0 5 7 .0 5 6 .7 5 6 .4 5 5 .6 5 4 .8 5 4 .1 5 3 .1 5 2 .3 5 1 .3 5 0 .8 5 0 .1 4 9 .4 4 9 .1 4 8 .5 4 8 .3 4 8 .3

Mole F r a c t i o n t r a n s - D lc h i o r o e t h y l e n e L i q u id , x^ V a p o r, y. 0.0 0 .0 1 4 0.032 0.082 0 .1 3 1 0.222 0 .3 1 4 0 .3 9 2 0 .5 0 8 0 .6 0 2 0.690 0 .7 4 3 0.832 0 .9 0 3 0 .9 2 9 0 .9 7 1 0 .9 8 4 1.000

-

0.0 0 .0 1 7 0 .0 3 9 0.100 0 .1 5 5 0 .2 6 5 0 .3 6 8 0 .4 5 4 0 .5 8 1 0 .6 7 5 0 .7 6 3 0.808 0 .8 7 7 0 .9 2 9 0 .9 4 9 0 .9 7 8 0.990 1.000

67

T a b le 28 V a p o r-L lq u id E q u i lib r iu m D a ta f o r S ystem c l s -D lc h X o ro e th y le n e A c e to n e a t 7 6 0 ,0 Mm, Mole F r a c t i o n A c e to n e L iq u id ,!, V a p o r,

Tamp. , °C .

0 .0 0.023 0 .0 3 5 0.053 0.095 0.125 0.163 0.233 0.263 0.333 0.357 0 .3 9 3 0 .4 6 3 0.516 0 .5 4 8 0 .5 8 7 0.638 0.736 0 .7 9 9 0 .8 8 3 0.926 0.979 1 .0 0 0

6 0 .3 6 0 .6 6 0 .8 61.0 6 1 .3 61.4 61.5 61.7 61.8 61.9 61.8 61.6 61.3 61.0 60.8 6 0 .5 6 0 .2 5 9 .2 5 8 .6 5 7 .8 5 7 .1 5 6 .7 5 6 .4

0 .0 0.016 0.032 0.044 0.080 0 .1 1 0 0 .1 4 7 0.218 0 .2 5 1 0 .3 3 7 0.364 0.407 0.493 0 .5 5 3 0 .5 8 6 0 .6 4 0 0.697 0 .7 9 9 0 .8 4 5 0.915 0.950 0.987 1 .0 0 0

T a b le 29 V a p o r-L lq u ld E q u i lib r iu m D a ta f o r System t r a n s - D l c h i o r o e th y le n e - A c e t one a t 7 6 0 .0 Mm, T em p., 0.

M ole F r a c t i o n t r a n s - D ie h l o r o e t h y l e n e L i q u id , V a p o r, y-j^

56.4

0 .0

0.0

5 6 .3 5 6 .0 5 5 .8 5 5 .1 5 4 .8 54.2

0 .0 2 1 0 .0 4 0 0.070 0.130 0 .1 5 7 0.207

0 .0 3 2 0 .0 4 8 0 .0 9 1 0 .1 7 2 0.198 0 .2 6 5

68

T able 29> o o n t 'd Temp• , °G . 5 3 .5 5 2 .3 5 1 .4 5 1 .0 5 0 .1 4 9 .6 4 9 .1 4 8 .8 4 8 .5 4 8 .3 4 8 .3 4 8 .3

M ole F r a c t i o n t r a n s - D i c h l o r o e t h : L iq u id ) V a p o r,y ^ 0 .2 7 6 0 .3 9 0 0 .4 6 9 0 .5 3 7 0 ,6 5 5 0 .7 2 6 0 .7 8 7 0.866 0 .9 0 9 0 .9 5 6 0 .9 7 5 1.000

0 .3 4 6 0 .4 7 4 0 .5 4 7 0,620 0 .7 2 3 0 .7 7 6 0.820 0 .8 8 5 0.922 0.962 0 .9 7 6 1,000

T a b le 30 V a p o r-L iq u id E q u i lib r iu m D a ta f o r S y stem c i s - D i o h l o r e e t h y l e n e 2 -B u ta n o n e a t 7 6 0 .0 Mm. T em p ., °c. 7 9 .6 7 9 .6 7 9 .5 7 9 .4 7 9 .3 7 9 .2 7 9 .0 7 8 .6 7 8 .3 7 7 .9 7 7 .0 7 5 .9 7 4 .0 7 2 .1 7 0 .1 6 7 .6 6 5 .1 6 2 .6 6 l .6 6 0 .3

M ole F r a c t i o n c i s - D i e h lo r o e th y le n e L i q u id , V a p o r,y ^ 0.0 0 .0 0 5 0 .0 1 7 0 .0 4 2 0 .0 6 4 0 .0 8 1 0 .1 1 5 0 .1 4 8 0 .1 8 3 0 .2 4 2 0.298 0 .3 6 7 0.470 0.552 0 .6 3 4 0.730 0.830 0 .9 3 1 0 .9 5 6 1 .0 0 0

0.0 0 .0 0 6 0.018 0 .0 4 8 0.072 0.094 0 .1 3 4 6.180 0.228 0.302 0 .3 8 0 0 .4 7 7 0 .5 9 7 0 .6 8 8 0 .7 7 1 0 .8 5 0 0 .9 2 1 0 .9 7 5 0 .9 8 5 1.000

69

T a b le 31 V a p o r-L iq u id E q u i lib r iu m D a ta f o r S ystem t r a n s - D io h lo r o e t h y l 0n e - 2 - B u ta n o ne a t 7 6 0 .0 Mm. T em p., °c. 79.6 79.1 7 7 .3 74.9 72.9 7 0 .2 6 8 .4 6 6 .7 65.5 62.9 61.1 59.6 5 8 .1 5 6 .1 5 3 .9 5 1 .8 49.8 49.2 4 8 .3

M ole F r a c t i o n t r a n s - D l o h l o r o e t h y l e n e V apor,y^ L i q u id , 0.0 0 .0 1 5 0 .0 6 5 0.120 0.169 0.244 0 .2 8 5 0 .3 3 9 0 .3 7 1 0 .4 4 8 0.504 0.557 0,600 0.670 0.760 0 .8 5 3 0.943 0.973 1 .0 0 0

0.0 0.032 0.130 0 .2 4 2 0.329 0.442 0.507 0 .5 6 6 0.604 0 .6 8 5 0.728 0 .7 7 3 0.804 0 .8 5 5 0.900 0.938 0 .9 7 4 0.983 1 .0 0 0

T able 32 Sm oothed E q u i lib r iu m D ata and â c t i v i t y C o e f f i c i e n t s f o r S y s­ tem c i s - D i c h l o r o e t h y l e n e - E t h y l F o rm ate a t 7 6 0 .0 Mm. Temp. , °c. 6 0 .3 60.2 60.1 5 9 .7 5 9 .1 5 8 .6 5 8 .1 5 7 .5 5 6 .8 5 6 ,1 5 5 .1 5 4 .5 5 4 .0

M ole F r a c tio n E th y l Formate V apor,y^ L iq u id , 0.0 0.050 0.100 0.200 0.300 0.400 0.500 0.600 0 .7 0 0 0 .8 0 0 0.900 0.950 1 .0 0 0

0.0 0.053 0.107 0.218 0 .3 3 1 0.438 0,540 0 .6 4 6 0 .7 4 8 0 .8 4 2 0.930 0.968 1.000

A c tiv ity C o e ffic ie n ts E s te r D ie h io r o e t h y le n e

0 .0 3 0 0 .8 4 8 0.860 0.889 0 .9 1 6 0.931 0.933 0 .9 4 6 0 .9 6 1 0 .9 6 7 0.981 0.995 1 .0 0 0

1 .0 0 0 .9 9 0 0,990 0.989 0.987 0.989 0 .9 8 5 0.966 0 .9 3 7 0.903 0.826 0 ,7 7 6 0 .7 3 5

70

T a b le 33 Smoothed E qu ilib riu m . D ata and A c t i v i t y C o e f f i c i e n t s f o r System t r a n s- D ie h lo r o e t h y le n e - E t h y l Form ate a t 7 6 0 .0 Mm. T gm p., 54.0 5 3 .7 5 3 .5 52.8 52.0 5 1 .2 50 .5 50.0 49.5 49.1 4 8 .7 4 8 .5 4 8 .3

M ole F r a c t i o n t r a n s i- D ic h lo r o e th y le n e L iq u id , V a p o r,y ^ 0 .0 0 .0 0.050 0 .0 6 5 0.128 0 .1 0 0 0 .2 4 8 0 .2 0 0 0.300 0 .3 5 9 0 .4 6 2 0.400 0.500 0 .5 5 9 0 .6 0 0 0 .6 4 7 0 .7 3 4 0.700 0.821 0.800 0.910 0.900 0.954 0.950 1 .0 0 0 1 .0 0 0

A c tiv ity C o e ffic ie n ts D ie h l o r o e th y l e n e E s t e r 1 .0 0 0.992 0.979 0.975 0 .9 7 1 0.983 0.989 1 .0 0 1.04 1.05 1.09 1 .1 2 1 .1 4

1 .1 3 1 .1 1 1.10 1.09 1.07 1 .0 7 1.06 1.03 1.03 1 .0 1 1 .0 2 1 .0 2 1 .0 0

T a b le 34 Sm oothed E q u ilib r iu m D a ta and A c t i v i t y C o e f f i c i e n t s f o r System c is - D lc h lo r o e th y l o n e - M 3 t h y l A c e ta te a t 7 6 0 .0 Mm. Temp. ,

°c.

60.3 60.8 61.1 61.4 61.7 61.7 61.5 61.2 6 4 .2 5 9 .8 5 9 .0 5 8 .1 5 7 .7 5 7 .2

M ole F r a c t i o n M eth y l A c e ta te V a p o r,y ^ L i q u id , 0 .0 0.050 0 .1 0 0 0 .2 0 0 0.300 0 .3 2 6 0.400 0.500 0 .6 0 0 0 .7 0 0 0 .8 0 0 0.900 0.950 1 .0 0 0

0 .0 0.042 0 .0 8 7 0 .1 8 4 0.295 0.326 0 .4 1 3 0.528 0 .6 4 2 0 .7 5 1 0 .8 4 4 0.924 0 .9 6 4 1 .0 0 0

A c tiv ity C o e ffic ie n ts E s t e r D1c h io r o 0 th y le n e 0.710 0.738 0 .7 5 8 0 .7 9 9 0 .8 4 8 -? --0.897 0 .9 2 1 0.959 Ô .976 0.990 0.994 1 .0 0 1 .0 0

1 .0 0 0.977 0.975 0 .9 7 6 0.957 ----0.936 0.907 0 .8 8 3 0 .8 3 1 0 .8 0 5 0 .8 0 7 0.781 0,750

71

T a b le 35 Smoothed E q u ilib r iu m D ata and A c t i v i t y C o e f f i c i e n t s f o r System tr a n s -D ie h lo r o e th y le n e -M e t h y l A c e ta te a t 7 6 0 .0 Mm, Tgmp.,

1 :1

5 6 ,6 5 5 .9 5 5 .0 5 4 .0 5 3 .2 5 2 .3 5 1 .3 5 0 .4 4 9 .4 4 8 .8 4 8 .3

M ole F r a c t i o n t r a n s -D ie h lo ro * e th y le n e L i q u i d , V a p o r , y ^

A c tiv ity C o e ffic ie n ts D ie h lo r o e t h y l e n e E s t e r

0 .0 0.060 0 .1a 0.238 0.353 0.463 0 .5 7 3 0.674 0.768 0 .8 5 3 0.928 0.965 1 .0 0 0

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