SOLVENT EXTRACTION OF LOW MOLECULAR WEIGHT HYDROCARBONS

Citation preview

DOCTORAL D IS S E R T A T IO N SERIES

TITLE

So)mnt Extraction oflow Molecular A

AUTHOR

Glenn Herbokhtimer ^ dee. 194-2

UNIVERSITY. DEGREE

Jbmsi/lvania Sidle College

7V> 7.) / f j .U

PUBLICATION NO. 1! M ! |

M

l

1

mu

mini

I

mi

^

UNIVERSITY MICROFILMS

/M

ANN

ARBOR

■

MICHIGAN

T he P e n n s y l v a n i a S t a t e C o lle g e The G r a d u a t e S c h o o l D e p a r t m e n t o f C h e m ic a l E n g i n e e r i n g

S o lv e n t E x t r a c tio n of Low M o le c u la r W e ig h t H y d r o c a r b o n s

A D is s e rta tio n by

•

G le n n H e r b o l s h e i m e r

S u b m itte d i n P a r t i a l F u l f i l l m e n t o f t h e R e q u i r e m e n ts f o r t h e D e g re e o f D o c to r o f P h i l o s o p h y

D e c e m b e r, 194-2

SOLVENT EXTRACTION OF ' LOW MOLECULAR WEIGHT HYDROCARBONS

ACKNOWLEDGMENT The a u t h o r w i s 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 t o D r. M. R. F e n s k e , who s u g g e s t e d a n d d i r e c t e d t h i s w o r k , f o r h i s c o n t i n u e d i n t e r e s t a n d g u id a n c e .

The n u m ero u s h e l p f u l s u g g e s t i o n s a n d c o n s t r u c t i v e c r i t i c i s m s o f D r. G. H . Cummings w e re i n v a l u a b l e t o t h e a u t h o r .

The a s s i s t a n c e o f M r. R. A. R u s k , M r. W. L . B ro u s e a n d t h e v a r i o u s o t h e r m em bers o f t h e P e t r o l e u m R e f i n i n g L a b o r a t o r y w hose w i l l i n g c o o p e r a t i o n a i d e d m a t e r i a l l y i n t h e c o m p l e t i o n o f t h i s p ro b le m i s a l s o

g r a t e f u l l y a c k n o w le d g e d .

TABLE OF CONTENTS Page I. II.

III.

INTRODUCTION A.

P r e v i o u s W ork

1

B.

Aim o f P r e s e n t I n v e s t i g a t i o n

5

C.

T r i a n g u l a r D ia g ra m s a n d S e l e c t i v i t y F a c t o r , B e t a

6

D.

H y d r o c a r b o n s a n d S o l v e n t s U sed

9

SOLUBILITY DATA A.

IV .

i

SUMMARY

A p p a ra tu s an d P ro c e d u re 1.

A tm o s p h e r ic P r e s s u r e

12

2.

P r e s s u r e s A bove A tm o s p h e r ic

15

B.

R e s u lts and D is c u s s io n

17

C.

C o n c l u s io n s

55

TERNARY EQUILIBRIUM RELATIONSHIPS A.

A p p a ra tu s an d P ro c e d u re

57

B.

R e s u lts and D is c u s s io n

62

1.

2.

.3 .

4-.

T h e S y s te m s : M e t h y l c y e l o h e x a n e n -H e p ta n e -S o lv e n t

63

E f f e c t o f T e m p e r a tu r e o n T e r n a r y S o l u b i l i t y C u rv e s

88

T h e S y s te m s : T o lu e n e -M e th y lc y c lo h e x a n e -S o lv e n t

100

T he S y s te m s : T rim e th y le th y le n e n -P e n ta n e -S o lv e n t

119

DISCUSSION OF RELATIVE SOLVENT SELECTIVITY A.

C o m p a ris o n o f S e l e c t i v i t y o f S o l v e n t s f o r N a p h th e n e - P a r a f f in an d A ro m a tic N a p h th e n e S y s te m s

14-0

TABLE OF CONTENTS (continued) Page B.

V I. V II.

CONCLUSIONS

14-3 1^6

APPENDIX A.

S o l u b i l i t y A p p a ra tu s

14-3

B.

E q u i l i b r i u m A p p a r a tu s

155

C.

E x p e rim e n ta l P ro c e d u re 1.

S o l u b i l i t y D e te rm in a tio n s

160

2.

T e rn a ry E q u ilib riu m D e te rm in a tio n s

162

D.

D a ta S h e e t a n d C a l c u l a t i o n s

168

E.

S o l v e n t s U sed

170

F.

H y d r o c a r b o n s U sed

175

G.

F r a c t i o n a t i n g C olum n (2 0 mm. i n s i d e d i a m e t e r )

179

H.

T a b l e s o f D a ta ( P r o p e r t i e s o f H y d r o c a r b o n • M ix tu re s )

I 83

C a l i b r a t i o n C u rv e s

I 99

I. V III.

C o m p a ris o n o f S e l e c t i v i t y o f S o l v e n t s f o r O l e f i n - P a r a f f i n and. A r o m a tic - N a p h th e n e S y s te m s

BIBLIOGRAPHY

208

L IS T OF FIGURES F i g u r e No.

Page

1.

S o l u b i l i t y A p p a ra tu s (a tm o s p h e r ic p r e s s u r e )

_

13

2.

S o l u b i l i t y A p p a ra tu s ( p r e s s u r e s ab o v e a tm o s p h e ric )

16

3.

H y d ro c a r b o n S o l u b i l i t y i n A c e t o n i t r i l e

18

A.

H y d ro c a r b o n S o l u b i l i t y i n A c e t o n i t r i l e lo g a rith m ic )

( s e m i19

5-

H y d ro c a r b o n S o l u b i l i t y i n A c e t o n y l a c e t o n e

23

6.

H y d ro c a r b o n S o l u b i l i t y i n A c e t o n y l a c e t o n e ( s e m i lo g a rith m ic )

24

7.

H y d ro c a rb o n S o l u b i l i t y i n A n i l i n e

28

8.

H y d ro c a rb o n S o l u b i l i t y i n A n i l i n e

9.

H y d ro c a r b o n S o l u b i l i t y i n F u r f u r a l

33

H y d ro c a r b o n S o l u b i l i t y i n F u r f u r a l ( s e m i lo g a rith m ic ) '

34

11.

H y d ro c a r b o n S o l u b i l i t y i n M e th y l A lc o h o l

38

12.

H y d r o c a r b o n S o l u b i l i t y i n M e th y l A lc o h o l ( s e m i lo g a rith m ic )

39

13.

H y d ro c a r b o n S o l u b i l i t y i n M e th y l C a r b i t o l

42

14.

H y d ro c a r b o n S o l u b i l i t y i n M e th y l C a r b i t o l ( s e m i lo g a rith m ic )

43

15.

H y d ro c a r b o n S o l u b i l i t y i n M e th y l C e l l o s o l v e

47

16.

H y d ro c a r b o n S o l u b i l i t y i n M e th y l C e l l o s o l v e l o g a r i th m ie )

10.

(s e m i-lo g a rith m ic )

17.

H y d ro c arb o n S o l u b i l i t y i n P h e n y l C e llo s o lv e

18.

H y d ro c arb o n S o l u b i l i t y i n P h e n y l C e llo s o lv e lo g a rith m ic )

29

(s e m i4.8 51 (s e m i52

19.

E q u i l i b r i u m A p p a r a t u s ( t e r n a r y s y s te m s )

53

20a.

A n a ly tic a l F la s k

£>q

20b.

D e n s ity F la s k

£,g

LIST OF FIGURES (continued) Page

F i g u r e N o. 21.

T he S y s te m :

M e th y l c y c lo h e x a n e —n - H e p t a n e - A c e t o n i t r i l e

64

22.

T he S y s te m :

M e th y l c y c lo h e x a n e —n - H e p t a n e - A c e t o n y l a c e t o n e

66

231

T he S y s te m :

M e th y lc y c lo h e x a n e -n -H e p ta n e -A n ilin e

6o

24.

The S y s te m :

M e th y lc y c lo h e x a n e -n -H e p ta n e -F u rfu ra l

70

25.

T he S y s te m :

M e th y l c y c lo h e x a n e - n - H e p ta n e - M e th y l A lc o h o l

72

26.

The S y s te m :

M e th y l c y c lo h e x a n e - n - H e p t a n e - M e th y l C a r b i t o l

74

27.

T he S y s te m :

M e tliy lc y c lo h e x a n e - n - H e p ta n e ~ M e th y l C e l l o s o l v e

76

28.

T he S y s te m :

M e th y lc y c lo h e x a n e -n -H e p ta n e -P h e n y l C e llo s o lv e

78

29.

C o r r e l a t i o n o f B e ta W ith S o l u b i l i t y F u n c t i o n s f o r M e th y l— c y c l o h e x a n e - n - H e p t a n e S y s te m

86

30.

The S y s te m :

M e th y lc y c lo h e x a n e - n -H e p ta n e - A n ilin e a t 1 0 .0 ° C .

89

31.

T he S y s te m :

M e t h y l c y c l o h e x a n e - n - i l e p t a n e - A n i l i n e a t 2 5 .0 ° C .

91

32.

The S y s te m :

M e t h y l c y c l o h e x a n e - n - I I e p t a n e - A n i l i n e a t 3 9 .0 ° C .

93

33.

The S y s te m :

M e t h y l c y c l o h e x a n e - n - I I e p t a n e - A n i l i n e a t 5 0 .0 ° C .

95

34.

The S y s te m : M e th y l c y c 1 o h e x an e -n ~ H e p t a n e - A n i l i n e , F o u r I s o t h e r m a l S o l u b i l i t y C u rv e s

97

C o r r e l a t i o n o f B e ta W ith S o l u b i l i t y o f H y d r o c a r b o n i n E x t r a c t P h a s e f o r t h e S y s te m M e t h y l c y c l o h e x a n e - n H e p t a n e - A n i l i n e a t 1 0 . 0 , 2 5 . 0 , 3 9 . 0 a n d 5 0 .0 ° C .

99

35.

36.

The S y s te m :

T o lu e n e - M e th y lc y c lo h e x a n e - A c e t o n i t r i l e

101

37.

The S y s te m :

T o lu e n e -M e t h y l c y c l o h e x a n e - A c e t o n y l a c e t o n e

103

38.

T he S y s te m :

T o lu e n e -M e th y lc y c lo h e x a n e -A n ilin e

105

39.

The S y s te m :

T o lu e n e - M e t h y l c y c l o h e x a n e - F u r f u r a l

107

40.

The S y s te m :

T o lu e n e -M e th y lc y c lo h e x a n e -M e th y l C a r b i t o l

109

41.

The S y s te m :

T o l u e n e - M e th y l c y c lo h e x a n e - M e t h y l C e l l o s o l v e

111

42.

T he S y s te m :

T o lu e n e -M e t h y l c y c l o h e x a n e - P h e n y l C e l l o s o l v e

113

L IST OF FIGURES ( c o n t i n u e d ) F i g u r e N o. 43.

Page

C o r r e l a t i o n o f B e ta W ith H y d r o c a r b o n S o l u b i l i t y f o r . T o l u e n e - M e th y l c y c lo h e x a n e S y s te m

115

44.

T he S y s te m :

T r i m e t h y l e t h y l e n e - n - P e n ta n e - A c e t o n i t r l i e

120

45.

The S y s te m :

T rim e th y le th y le n e -n -P e n ta n e -A c e to n y la c e to n e

122

46.

T he S y s te m :

T rim e th y le th y le n e -n -P e n ta n e -A n ilin e

124

47.

The S y s te m :

T rim e th y le th y le n e -n -P e n ta n e -F u rfu ra l

126

48.

The S y s te m :

T rim e th y le th y le n e -n -P e n ta n e -M e th y l C a r b ito l

128

49.

The S y s te m :

T rim e th y le th y le n e -n -P e n ta n e -M e th y l C e llo s o lv e

130

50.

The S y s te m :

T rim e th y le th y le n e -n -P e n ta n e -P h e n y l C e llo s o lv e

132

51.

C o r r e l a t i o n o f B e ta W ith H y d r o c a r b o n S o l u b i l i t y f o r T r i m e t h y l e t h y l e n e - n - P e n t a n e S y s te m

134-

C o r r e l a t i o n o f B e ta W ith S o l u b i l i t y F u n c t i o n s f o r T rim e th y le th y le n e -n -P e n ta n e

138

D e t a i l e d D ra w in g o f S o l u b i l i t y A p p a r a t u s ( a t m o s p h e r i c p re ssu re )

149

D e t a i l e d D ra w in g o f S o l u b i l i t y A p p a r a t u s ( p r e s s u r e above a tm o s p h e ric )

154.

52.

53.

54-. 55.

D e t a i l e d D ra w in g o f E q u i l i b r i u m T ube

'

56.

S c h e m a tic D ra w in g o f F r a c t i o n a t i n g C olum n

158

57.

D e t a i l e d D ra w in g o f F r a c t i o n a t i n g C olum n

180

156

58.

C a lib ra tio n

o f 5—J u n c t i o n T h e rm o c o u p le

200

59.

C a lib ra tio n

o f E q u ilib riu m

204

60.

C a lib ra tio n

o f D e n s ity F la s k R

206

61 .

C a lib ra tio n

o f D e n s ity F la s k X

207

Tube

LIST OF TABLES T a b le No.

Pa ge

1.

A c e t o n i t r i l e - H y d r o c a r b o n M i s c i b i l i t y T e m p e r a tu r e s

20

2.

A c e t o n y la c e to n e - H y d r o c a r b o n M i s c i b i l i t y T e m p e r a t u r e s

25

3.

A n i l i n e - H y d r o c a r b o n M i s c i b i l i t y T e m p e r a tu r e s

30

4..

F u r f u r a l - H y d r o c a r b o n M i s c i b i l i t y T e m p e r a tu r e s

35

5.

M e th y l A lc o h o l- H y d r o c a r b o n M i s c i b i l i t y T e m p e r a t u r e s

4-O

6.

M e th y l C a r b i t o l - H y d r o c a r b o n M i s c i b i l i t y T e m p e r a t u r e s

44-

7.

M e th y l C e l l o s o l v e - H y d r o c a r b o n M i s c i b i l i t y T e m p e r a tu r e s

49

8.

P h e n y l C e llo s o lv e -H y d ro c a rb o n M i s c i b i l i t y T e m p e ra tu re s

53

9.

10.

Summary o f D a ta : M e th y l c y c l o h e x a n e - n - H e p t a n e A c e to n itrile

65

Summary o f D a ta : M e th y lc y c lo h e x a n e -n -H e p ta n e A c e to n y la c e to n e

67

11.

Summary o f D a t a :

M e th y lc y c lo h e x a n e -n -H e p ta n e -A n ilin e

69

12.

Summary o f D a ta ;

M e th y l c y c l o h e x a n e - n —H e p t a n e - F u r f u r a l

71

13.

Summary o f D a t a : A lc o h o l

Me t h y l c y c lo h e x a n e - n - H e p t a n e - M e th y l-

Summary o f D a t a : C a rb ito l

M e t h y l c y c lo h e x a n e - n - H e p ta n e - M e th y l

Summary o f D a t a : C e llo s o lv e

M e t h y l c y c l o h e x a n e - n - H e p ta n e - M e t h y l

Summary o f D a t a : C e llo s o lv e

M e th y lc y c lo h e x a n e -n -H e p ta n e -P h e n y l

14-.

15.

16.

17. 18. 19.

73

75

77

B e ta f o r t h e S y s te m s : S o lv e n t'

79 M e th y lc y c lo h e x a n e -n -H e p ta n e gO

C o m p o s itio n s o f E q u i l i b r i u m P h a s e s f o r M e t h y l c y c l o h e x a n e - S o l v e n t a n d n - H e p t a n e - S o l v e n t S y s te m s

84.

S o l u b i l i t y F u n c tio n s f o r M e th y lc y c lo h e x a n e -n -H e p ta n e .S y s te m

35

LIST OF TABLES (continued) Page

T a b le N o. 20.

21.

22.

23.

24.

25.

26.

27.

28.

29.

30.

31.

32.

33.

34. 35.

Sum m ary o f D a t a ; M e t h y l c y c l o h e x a n e - n - H e p t a n e A n i l i n e a t 1 0 .0 ° C .

90

Sum m ary o f D a t a ; M e t h y l c y c l o h e x a n e - n - I I e p t a n e A n i l i n e a t 2 5 .0 ° C .

92

Sum m ary o f D a t a : M e th y l c y c l o h e x a n e —n - E I e p ta n e A n i l i n e a t 3 9 .0 ° C .

94

Sum m ary o f D a t a ; M e th y l c y c l o h e x a n e —n - H e p t a n e A n i l i n e a t 5 0 .0 ° C .

96

Summary o f D a ta ; T o l u e n e - M e t h y l c y e l o h e x a n e A c e to n itrile

102

Summ ary o f D a ta ; T o lu e n e -M e t h y l c y c l o h e x a n e A c e to n y la c e to n e

104

Summ ary o f D a t a ; A n ilin e

T o lu e n e -M e t h y l c y c l o h e x a n e -

106

Sum m ary o f D a ta : F u rfu ra l

T o lu e n e -M e th y lc y c lo h e x a n e 108

Sum m ary o f D a t a : T o lu e n e -M e th y lc y c lo h e x a n e M e th y l C a r b i t o l

110

Sum m ary o f D a t a : T o lu e n e -M e th y lc y c lo h e x a n e — M e th y l C e l l o s o l v e

112

Sum m ary o f D a t a : T o lu e n e -M e th y lc y c lo h e x a n e P h en y l C e llo s o lv e

114

H y d ro c a rb o n S o l u b i l i t y a t P l a i t P o in t f o r T o lu e n e M e th y l c y c lo h e x a n e S y s te m

117

B e t a f o r t h e S y s te m s : S o lv e n t

117

Sum m ary o f D a t a ; A c e to n itrile

T o lu e n e -M e th y lc y c lo h e x a n e -

T rim e th y le th y le n e -n -P e n ta n e 121

Sum m ary o f D a t a ; T r i m e t l i y l e t h y l e n e - n - P e n t a n e A c e to n y la c e to n e

123

Sum m ary o f D a ta ; A n ilin e

125

T rim e th y le th y le n e -n -P e n ta n e -

LIST OF TABLES (continued) T a b le 36. 37.

38=

39.

4-0.

41.

42*

43*

44-.

45.

No.

? a ge

■

Summary o f D a ta :

T rim e th y le th y le n e -n -P e n ta n e -F u rfu ra l

Summary o f D a ta : C a rb ito l

T rim e tn y le th y le n e -n -P e n ta h e -M e th y l

Summary o f D a ta : C e llo s o lv e

T rim e th y le th y le n e -n -P e n ta n e -M e th y l

Summary o f D a ta : C e llo s o lv e

T r im e th y le th y le n e -n -P e n ta n e -P h e n y l

127

129

131

B e ta f o r t h e S y s te m s : S o lv e n t

133 T r i me t h y l e t h y l e n e - n - P e n t a n e 136

C o m p o s itio n s o f E q u i l i b r i u m P h a s e s f o r T r i m e t h y l e t h y l e n e - S o l v e n t a n d n - P e n t a n e - S o l v e n t S y s te m s

137

S o lu b i lity F u n c tio n s f o r T r im e th y le th y le n e -n -P e n ta n e S y ste m

137

C o m p a riso n o f S o l v e n t S e l e c t i v i t y f o r N a p h th e n e P a r a f f i n a n d A r o r a a tic - N a p h th e n e S y s te m s

14-0

C o m p a riso n o f S o l v e n t S e l e c t i v i t y f o r O l e f i n P a r a f f i n a n d A r o m a tic - N a p h th e n e S y s te m s

143

L i q u i d s U sed t o Remove S o l v e n t s f r o m H y d r o c a r b o n s

165

4 4 u _ _ P r o p e r t i e s o f Me t h y l c y c lo h e x a n e - n - I i e p t ^ e T l x t iu ' e s

I 84

47.

189

P r o p e r t i e s o f T o l u e n e - M e th y l c y c lo h e x a n e M i x t u r e s

4 6 . . P r o p e r t i e s o f T r im e th y le th y le n e - n - P e n ta n e M ix tu re s

195

I.

SUMMARY

T he s o l u b i l i t y o f e a c h o f s ix . h y d r o c a r b o n s , n - p e n t a n e , t r i m e t h y l e t h y l e n e , n—h e p t a n e , m e t h y l c y c l o h e x a n e , t o l u e n e a n d iso~» p r o p y lb e n z e n e h a s b e e n d e t e r m i n e d i n e a c h o f t h e f o l l o w i n g s o l ­ v e n ts :

a c e t o n i t r i l e , a c e t o n y l a c e t o n e , a n i l i n e , f u r f u r a l , m e th y l

a l c o h o l , m e th y l c a r b i t o l , m e th y l c e l l o s o l v e , a n d p h e n y l c e l l o s o l v e * T he c o m p o s i tio n s r a n g e d fr o m a p p r o x i m a t e l y 8 p e r c e n t t o 9 2 p e r c e n t b y w e ig h t o f h y d r o c a r b o n *

A t th e lo w e r p e r c e n ta g e s o f h y d ro c a rb o n c e n t f o r m ost s y s te m s ) t h e l o g a r ith m

(b e lo w 2 0 p e r

o f th e s o l u b i l i t y i s a l i n e a r

f u n c tio n o f th e r e c ip r o c a l o f th e a b s o lu te te m p e ra tu re and th u s e x t r a p o l a t i o n o f t h e c u rv e becom es p o s s i b l e .

The d a t a w h ic h w e re o b t a i n e d f o r t h e s o l u b i l i t y o f n— h e x a n e i n a n i l i n e w e re c o m p a re d w i t h s i m i l a r d a t a r e p o r t e d i n t h e lite ra tu re

a n d a c o n s i d e r a b l e d i s c r e p a n c y w as e v i d e n t .

The e a r l i e r

d a t a i s u n d o u b te d ly i n e r r o r , p r o b a b l y a s a r e s u l t o f t h e u s e o f im p u r e n - h e x a n e b y t h e s e i n v e s t i g a t o r s .

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

i n th e o r d e r o f in c r e a s in g

s e le c tiv ity fo r

e a c h b i n a r y h y d r o c a r b o n s y s te m i n t h e f o l l o w i n g , t a b l e s .

ii METHYLCYCLOHEXANE-n—HEPTANE

S o lv e n t

E x tra c tio n T e m p .» ° C .

Maximum D e g r e e o f S e p a ra tio n O bt a t In d ic a te d

B e ta * (A v e ra g e )

- 2 0 .0

1 .2 2

C o m p le te

A c e to n itrile

4 0 .0

1 .2 6

C o m p le te

M e th y l C e l l o s o l v e

1 0 .0

1 .2 8

C o m p le te

A c e to n y la c e to n e

3 0 .0

1 .3 C

C o m p le te

M e th y l C a r b i t o l

6 0 .0

1 .3 2

C o m p le te

F u rfu ra l

6 0 .0

1 .3 5

C o m p le te

A n ilin e

3 9 .0

1 .3 7

C o m p le te

P henyl C e llo s o lv e

5 0 .0

1 .3 9

C o m p le te

M e th y l A lc o h o l

* L im its o f p u re h y d ro c a rb o n s o l u b i l i t y M e th y l c y c lo h e x a n e : 1 5 - 7 t o 3 5 .3 n - H e p ta n e : S . 4 t o 1 1 . 4

in

s o lv e n ts

TOLUEN E-METHYLCYCLOHEXAHE

S o lv e n t

E x tra c tio n T e m p ., ° C .

B e ta ( a t 20% H yc. S o l 8y . )

Maximum D e g re e o f S e p a r a tio n O b ta in a b le a t I n d i c a t e d T e m p .__

P h en y l C e llo s o lv e

0.0

3 .1

41.0

M e th y l C a r b i t o l

0 ,0

3 .3

5 5 .0

M e th y l C e l l o s o l v e

-

2 0 .0

4 .2

3 3 .0

A n ilin e

-

10.0

4 .5

5 1 .0

F u rfu ra l

+ 10.0

5 .0

5 7 .0

A c e to n itrile

+ 10.0

6 .3

5 7 .0

A c e to n y la c e to n e

-

10.0

6.6

5 3 .0

iii

TRIMETHYLETHYLENE-n—PENTANE

S o lv e n t

E x tra c tio n T e m p ., ° C .

B e ta ( a t 20$ H y c . S o l 'y . )

Maximum D e g r e e o f S e p a ra tio n O b ta in a b le a t I n d i c a t e d Temp,.

M e th y l C a r b i t o l

3 0 .0

1 .3 3

C o m p le te

P h en y l C e llo s o lv e

3 0 .0

1 .3 7

C o m p le te

A n ilin e

3 0 .0

1 .4 0

79*0

- 2 0 .0

1 .4 6

8 2 .0

2 5 .0

1 .5 7

C o m p le te

‘ 0 .0

1 .5 3

9 4 .0

0 .0

1 .8 0

C o m p le te

M e th y l C e l l o s o l v e F u rfu ra l A c e to n y la c e to n e A c e to n itrile

F o r t h e g ro u p o f s o l v e n t s s tu d ie d t h e v a lu e s o f b e t a ,

th e

s e l e c t i v i t y f a c t o r , v a r y fro m 1 * 2 2 t o 1 . 3 9 f o r t h e h y d r o c a r b o n s y s te m m e t h y l e y c l o h e x a n e - r t - h e p t a n e , fro m 1 * 3 3 t o 1 . 3 0 f o r t h e s y s te m t r i m e t h y l - * e t h y l e n e - n - p e n t a n e , a n d fro m 3 * 1 t o 6 * 6 f o r t h e s y s te m t o l u e n e - m e t h y l c y c lo h e x a n e .

T he s e l e c t i v i t y f a c t o r , b e t a , may v a r y f r o m a fe w p e r c e n t ( m e th y lc y c lo h e x a n e - n —h e p t a n e s e p a r a t i o n ) t o s e v e r a l h u n d r e d p e r c e n t (to lu e n e -m e th y lc y c lo h e x a n e an d tr im e th y le n e - n - p e n ta n e s e p a r a tio n ) w ith th e change o f h y d ro c a rb o n s o l u b i l i t y i n th e e x t r a c t p h a s e .

T h i s se e m s

to be d e p e n d e n t o n b o th th e s o l v e n t and h y d ro c a rb o n s y s te m s .

C o r r e l a t i o n s h a v e b e e n o b t a i n e d b e tw e e n t h e s e l e c t i v i t y f a c to r , b e ta , and s e v e ra l fu n c tio n s b ased on th e h y d ro c a rb o n s i n th e s o lv e n t.

s o l u b i l i t y o f th e p u re

The s i m p l e s t o f t h e s e w as t h e d i f f e r e n c e

in c r i t i c a l s o lu tio n te m p e ra tu re o f th e l e s s

s o l u b l e a n d t h e m o re s o l u b l e

h y d ro c a rb o n i n th e s o lv e n t. ra tio

T he d i f f e r e n c e i n s o l u b i l i t i e s a n d t h e

o f t h e s o l u b i l i t i e s o f t h e tw o h y d r o c a r b o n s i n t h e s o l v e n t may

a ls o b e u sed to p r e d i c t b e t a . th e r a t i o

A f o u r t h f u n c t i o n w as t h e p r o d u c t o f

o f th e h y d ro c a rb o n s o l u b i l i t i e s m u ltip lie d by th e r a t i o

th e s o l u b i l i t i e s o f th e s o lv e n t i n th e h y d ro c a rb o n s.

of

II.

A.

INTRODUCTION

PREVIOUS WORK The s e p a r a t i o n o f t h e c o m p o n e n ts o f a l i q u i d m i x t u r e m ay

h e a t t a i n e d b y a n y o n e o f a v a r i e t y o f m e th o d s . fra c tio n a l d is tilla tio n ,

F o r e x a m p le ,

f r a c tio n a l c r y s t a l l i s a t i o n , a d s o rp tio n ,

c h e m i c a l c o m b i n a t i o n , a n d s o l v e n t e x t r a c t i o n a r e som e o f t h e m o re u s e f u l m e th o d s .

S i n c e t h e l a s t m e n tio n e d o f t h e s e h a s r e c e i v e d

re la tiv e ly l i t t l e

a tte n tio n as f a r as i t s

a p p lic a tio n to

r a t i o n o f lo w m o l e c u l a r w e i g h t h y d r o c a r b o n s i s

th e sep a­

c o n c e r n e d , i t w as

ch o sen f o r f u r th e r in v e s tig a tio n . T he e a r l i e s t i n v e s t i g a t i o n o f t h e c o m p o s i t i o n s o f t h e tw o .c o n ju g a t e l i q u i d p h a s e s w h ic h s e p a r a t e d fr o m a t h r e e c o m p o n e n t m i x t u r e was m ade b y T u c h s c h m id t a n d F o l l e n i u s

( 2 3 ) i n 1 8 7 1 o n t h e s y s te m w a t e r —

a l c o h o l —c a r b o n b i s u l f i d e * The w o rk o f W. D. B o n n e r ( 1 ) p u b l i s h e d i n 1 9 1 0 c o n t a i n s d a t a fo r f if t y

s y s t e m s , e a c h c o n s i s t i n g o f w a t e r a n d tw o o r g a n i c l i q u i d s ,

in c lu d in g h y d ro c a rb o n s , su ch a s n - h e p ta n e , n -h e x a n e , and x y le n e s . d e te rm in e d th e b in o d a l c u rv e s , p l a i t p o i n t s , and t i e s y s te m .

He

lin e s f o r each

T he d a t a , h o w e v e r , a r e p l o t t e d o n r e c t a n g u l a r c o o r d i n a t e s ,

r a t h e r th a n on t r i a n g u l a r d ia g ra m s .

He a l s o i n c l u d e s a l i s t o f t h e

t e r n a r y s y s te m s i n v e s t i g a t e d p r e v i o u s t o 1 9 1 0 , t o g e t h e r w i t h t h e a u t h o r and r e f e r e n c e f o r e a c h o f th e s e s y s te m s . S in c e 1 9 1 0 , n u m e ro u s o t h e r w o r k e r s h a v e s t u d i e d v a r i o u s t e r n a ­ r y s y s te m s .

J.

C. S m ith (1 9 ) h a s m ade a r a t h e r c o m p le te l i t e r a t u r e

v e y o f t h e w ork d o n e b e tw e e n 1 9 1 0 a n d 194-2.

He l i s t s

su r­

t h e s y s te m s ( a n d

2

r e f e r e n c e s ) f o r w h ic h t h e l i m i t i n g s o l u b i l i t y c u r v e ( b i n o d a l c u r v e ) an d t h e t i e

l i n e s a r e given®

A d i s c u s s i o n o f t h e m e th o d o f co n ­

s t r u c t i o n , r e p r e s e n t a t i o n , a n d i n t e r p r e t a t i o n o f s o l u b i l i t y d ia g r a m s f o r te x * n a ry l i q u i d s y s te m s i s a l s o i n c l u d e d . E l g i n (1 7 ) a l s o h a s t a b u l a t e d some o f t h e t e r n a r y s y s te m s (a n d r e f e r e n c e s ) f o r w h ic h d a t a h a v e b e e n p u b l i s h e d . c lu d e s r e f e r e n c e s t o

H is l i s t i n ­

s t u d i e s w h ic h i n v o l v e d c o n t i n u o u s o r b a t c h e x ­

t r a c t i o n s , i n a d d i t i o n t o t h o s e w h ic h p r e s e n t o n l y b i n o d a l c u r v e s a n d tie lin e s .

H ie m o s t r e c e n t a n d p r o b a b l y t h e m o s t c o m p le te m e th o d s o f

c a l c u l a t i o n f o r e x t r a c t i o n o p e r a t i o n s , e i t h e r c o n tin u o u s o r b a tc h , a r e a ls o d is c u s s e d by t h i s a u th o r. I n t h e p a s t m o s t o f t h e t e r n a r y s y s te m s f o r w h ic h e q u i l i b r i u m d a t a h a v e b e e n o b t a i n e d , i n c l u d e d w a t e r a s o n e c o m p o n e n t.

T he o t h e r

two c o m p o n e n ts w e re u s u a l l y o r g a n i c c o m p o u n d s, o n e o f w h ic h w as com­ p l e t e l y m is c ib le and th e o th e r o n ly p a r t i a l l y m is c ib le w ith w a te r . The s y s te m s w a t e r - e t h y l a l c o h o l —e t h y l e t h e r a n d w a t e r - a c e t i c a c i d — b e n z e n e f o r w h ic h d a t a h a v e b e e n p u b l i s h e d b y v a r i o u s a u t h o r s , a r e tw o e x a m p le s o f t h i s t y p e . Some i n t e r e s t i n g s y s te m s c o n t a i n i n g o n e i n o r g a n i c com pound have a ls o been s tu d ie d .

G ib b y o b t a i n e d d a t a f o r t h e s y s te m w a t e r —

acetone-K O H ( 7 ) a n d a l s o f o r t h e w a t e r - n itr o b e n s e n e - H p S O ^ W a te r-p h en o l-K O H a n d —NaOH w e re i n v e s t i g a t e d b y M eurs ( 1 5 ) .

s y s te m ( 6 ) . R eb u rn

a n d S h e a r e r ( I S ) r e p o r t e d d a t a f o r HC1, HBr a n d H I w i t h w a t e r a n d is o b u ta n o l. I n a d d i t i o n t o t h e s e , some n o n - a q u e o u s s y s te m s h a v e b e e n in v e s tig a te d .

T r im b le a n d F r a z e r ( 2 2 ) o b t a i n e d e q u i l i b r i u m d a t a f o r

3 a c e t o n e - e t h y l e n e g l y c o l m i x t u r e s w it h b e n z e n e , b ro m o b e n z e n e , c h l o r o b en zen e, n itr o b e n z e n e , to lu e n e and x y le n e .

E th a n o l-b e n z e n e -g ly c e ro l

r e l a t i o n s h i p s w e re d e te r m in e d b y M cDonald (14-)»

The o n l y d a t a pub-*

l i s h e d f o r b i n a r y h y d ro c a r b o n - s o l v e n t s y s te m s a r e t h o s e o f V a r t e r e s s i a n an d F e n sk e (24-) a n d T egge ( 2 1 ) . The p r o c e s s o f s o l v e n t e x t r a c t i o n h a s b e e n w i d e l y u s e d i n t h e p e tr o le u m i n d u s t r y f o r t h e im p ro v e m e n t o f c e r t a i n p h y s i c a l p r o p e r t i e s o f lu b ric a tin g o i l s .

H ow ever, f o r a co m p lex m i x t u r e o f c o m p o n e n ts w h ic h

c an n o t be i d e n t i f i e d ,

su c h a s i s p r e s e n t i n a l u b r i c a t i n g o i l , t h e p h a s e

e q u i l i b r i a c a n n o t b e r e p r e s e n t e d i n te r m s o f p u r e c o m p o n e n ts . o i l - s o l v e n t s y s te m s some p h y s i c a l p r o p e r t y o f t h e o i l ,

F o r th e s e

such a s th e

v is c o s ity - g r a v ity c o n s ta n t, i s re p re s e n te d on th e s id e o f th e t r i a n g u la r d ia g ra m o p p o s i t e t h e s o l v e n t v e r t e x . m eth o d m ore o r l e s s s u c c e s s f u l l y .

H u n te r a n d N ash (1 0 ) h a v e u s e d t h i s

I t h a s b e e n s u g g e s t e d t h a t some o t h e r

p h y s i c a l p r o p e r t i e s m ig h t b e u s e d a n d t h e m e th o d a p p l i e d t o o t h e r c o m p le x l i q u i d - s o l v e n t s y s te m s .

H o w ev er, i t m u st b e re m e m b ered t h a t o n l y l i m i t e d

g e n e r a l i z a t i o n s c a n b e d ra w n fro m s u c h e x p e r i m e n t a l d a t a o n c o m p le x s y s te m s . A num ber o f common o r g a n i c l i q u i d s h a v e b e e n u s e d c o m m e r c i a lly f o r th e e x tr a c tio n o f lu b r ic a tin g o i l .

Some o f t h o s e m o st w id e ly u s e d

a r e f u r f u r a l , n i t r o b e n z e n e , c h l o r e x , p h e n o l, a n d a m i x tu r e o f c r e s y l i c a c i d an d p ro p a n e (D u o s o l p r o c e s s ) .

T h e se p r o c e s s e s h a v e b e e n d i s c u s s e d

t o some e x t e n t i n v a r i o u s p u b l i c a t i o n s . The l o g i c a l a p p ro a c h t o a p ro b le m o f t h i s t y p e w o u ld b e t o o b t a i n d a t a f o r a num ber o f t e r n a r y s y s te m s co m p o sed o f p u r e c o n s t i t u e n t s .

Ar

W ith t h e s e d a t a a s a b a s i s , c o n c l u s i o n s c o u ld t h e n b e d raw n w ith r e ­ s p e c t to t h e r e s u l t s t o be e x p e c te d when a co m p lex m ix tu r e w as e x ­ tra c te d .

F o r t u n a t e l y , su c h a s i t u a t i o n e x i s t s i n t h e c a s e o f h y d r o ­

carb o n s in th e g a s o lin e ra n g e .

By c a r e f u l f r a c t i o n a t i o n an d c h e m ic a l

a n a ly s is i t h a s been p o s s ib le to i d e n t i f y a t l e a s t a p o r tio n o f th e h y d ro c a rb o n s w h ic h a r e p r e s e n t i n t h e g a s o l i n e f r a c t i o n o f p e t r o l e u m , a n d a l s o t o e s t i m a t e t h e p e r c e n t a g e o f t h e s e c o m p o n e n ts p r e s e n t i n %---t h e m ix tu r e . E ven w ith t h e s e f a v o r a b l e c i r c u m s t a n c e s no one seem s t o h a v e i n v e s t i g a t e d t h i s p ro b le m w ith t h e e x c e p t i o n o f V a r t e r e s s i a n an d F e n sk e (2 4 ) a n d Tegge ( 2 1 ) .

The f i r s t a u t h o r s r e p o r t t h e e q u i l i b r i u m

d a t a f o r t h e t e r n a r y s y s te m a n i l i n e - n - h e p t a n e - m e t h y l c y c l o h e x a n e , and com pare t h e e f f i c i e n c y o f s e p a r a t i o n o f t h e s e tw o h y d r o c a r b o n s , b y e x tr a c tio n , u s in g a n ilin e a s th e s o lv e n t, and by d i s t i l l a t i o n .

The

c o m p a riso n i s made th r o u g h t h e n u m e r ic a l s o l u t i o n , b a s e d o n e x p e r i m e n t a l d a t a , o f a d e f i n i t e p ro b le m .

T h e se r e s u l t s i n d i c a t e t h a t e x t r a c t i o n i s

t h e m ore e f f i c i e n t m ethod o f s e p a r a t i n g t h e s e tw o h y d r o c a r b o n s . T egge s t u d i e d t h e e q u i l i b r i u m r e l a t i o n s h i p s b e tw e e n s e v e r a l p u r e b i n a r y h y d r o c a r b o n m ix t u r e s a n d s u l f u r d i o x i d e .

The h y d r o c a r b o n s

c o v e r e d a r a n g e i n m o le c u la r w e ig h t an d m o le c u la r ty p e '.' in c lu d e d

H is s y s te m s

t r i m e t h y l e t h y l e n e - n - h e p t a n e , m e t h y l c y c l o h e x a n e - t o l u e n e , m e th y l

n a p h t h a l e n e - c e t a n e , an d is o p r o p y l b e n z e n e - n - h e x a n e .

5

B.

AIM OF PRESENT WORK The p ro b le m s e l e c t e d f o r t h i s i n v e s t i g a t i o n w as a c o n t i n u ­

a t i o n o f t h e s tu d y o f s o l v e n t e x t r a c t i o n a s a m eans o f s e p a r a t i n g t h e lo w e r m o le c u la r w e ig h t h y d r o c a r b o n s .

The m a in o b j e c t w as t o

o b t a i n some ty p e o f c o r r e l a t i o n b e tw e e n t h e s e l e c t i v i t y o f a s o l v e n t f o r a g iv e n h y d r o c a r b o n s y s te m a n d t h e s o l u b i l i t y o f t h e s e p u r e h y d ro ­ c a rb o n s i n t h e s o l v e n t . The wox-lc w as t o b e b a s e d o n s e v e r a l ty p e s o l v e n t s , s u c h a s a n a l c o h o l , a n a ld e h y d e , a k e t o n e , e t c . , t o g e t h e r w ith d e f i n i t e b i n a r y h y d ro c a rb o n s y s te m s r e p r e s e n t i n g t h e v a r i o u s t y p e s , s u c h a s p a r a f f i n ­ o le f in , n a p h th e n e -p a ra ffin , e tc . F i r s t , t h e s o l u b i l i t y - t e m p e r a t u r e r e l a t i o n s h i p s w e re t o b e d e te r m in e d f o r t h e v a r i o u s h y d r o c a r b o n s i n e a c h o f t h e s e l e c t e d s o l v e n t s . F o llo w in g t h i s , t h e t e r n a r y r e l a t i o n s h i p s an d s e l e c t i v i t y o f e a c h s o l v e n t f o r t h e d i f f e r e n t b i n a r y h y d r o c a r b o n m i x t u r e s w e re t o b e d e te r m in e d . From t h e s e d a t a t h e s e l e c t i v i t y - s o l u b i l i t y c o r r e l a t i o n m e n tio n e d above w as t o b e m ade.

I t . w a s f e l t t h a t t h i s ty p e o f c o r r e l a t i o n w o u ld b e

v e r y v a l u a b l e s i n c e s o l u b i l i t y d a t a a r e much m ore r e a d i l y o b t a i n e d t h a n a re th e te r n a r y e q u ilib riu m r e l a t i o n s h i p s .

6

C.

TRIANGULAR DIAGRAMS AND SELECTIVITY FACTOR, BETA The m ethod o f p r e s e n t i n g t h e d a t a o b t a i n e d f o r t h e s e v a r i o u s

t e r n a r y s y s te m s was i n t r o d u c e d b y S to k e s i n 1 3 9 1 ( 2 0 ) .

I t in v o lv e s

th e p l o t t i n g o f d a t a o n t r i a n g u l a r d ia g r a m s r a t h e r t h a n u s i n g r e c t a n g u ­ l a r c o o r d in a te s *

T h is m eth o d h a s b e e n u s e d b y m o st a u t h o r s b e c a u s e o f

i t s e a s e o f i n t e r p i 'e t a t i o n . The g e o m e t r i c a l p r o p e r t i e s o f e q u i l a t e r a l t r i a n g l e s a r e d i s ­ c u s s e d i n d e t a i l b y J . C. E L g in i n P e r r y ’ s ” C'hem. E n g . H andbook” ( 1 7 ) , by E v an s (4-), an d o t h e r a u t h o r s ( 9 )

(2 1 ).

A fe w g e n e r a l r e m a r k s , h o w e v e r, s h o u ld b e i n c l u d e d a t t h i s p o in t.

The e q u i l i b r i u m d a t a w h ic h w e re o b t a i n e d a t c o n s t a n t te m p e ra ­

tu r e and p r e s s u r e a r e p l o t t e d on e q u i l a t e r a l t r i a n g l e s .

E ach o f t h e

v e r t i c e s r e p r e s e n t s o n e o f t h e c o m p o n e n ts i n t h e p u r e s t a t e j a n y p o i n t o n a s i d e r e p r e s e n t s a b i n a r y m ix tu r e j an d a n y p o i n t w i t h i n t h e t r i ­ a n g le r e p r e s e n t s a t e r n a r y m i x t u r e .

The am o u n t o f co m p o n en t A p r e s e n t

i n a n y m ix tu r e i s p r o p o r t i o n a l t o t h e l e n g t h o f t h e p e r p e n d i c u l a r d raw n fro m t h e s i d e o p p o s i t e t h e v e r t e x r e p r e s e n t i n g p u r e A t o t h e p o i n t r e p r e s e n t i n g t h e c o m p o s itio n i n q u e s t i o n . The sum o f t h e s e 3 p e r p e n d i c u l a r s t o t h e s i d e s fro m a n y p o in t i s eq u al to th e a l t i t u d e o f th e t r i a n g l e , o r 100 p e r c e n t.

A ll

d a t a p l o t t e d t h r o u g h o u t t h i s w ork w i l l b e o n w e ig h t p e r c e n t b a s i s . Any o t h e r b a s i s s u c h a s m ole p e r c e n t o r v olum e p e r c e n t may b e u s e d i f th e s e a re a d d itiv e f o r a l l c o m p o s itio n s . The s e l e c t i v i t y f a c t o r , b e t a , y 3 , i s a n a lo g o u s t o t h e r e l a ­ t i v e v o l a t i l i t y f a c t o r , a lp h a , i n d i s t i l l a t i o n , and c o n s e q u e n tly i s a

7 m e asu re o f t h e e a s e o f s e p a r a t i o n o f t h e tw o c o m p o n e n ts b y e x t r a c t i o n w ith t h e t h i r d c o m p o n e n t.

B e ta , th e n , i s th e p r o p o r t i o n a l i t y f a c t o r

b e tw e e n t h e r a t i o o f t h e m ore s o l u b l e t o t h e l e s s s o l u b l e c o m p o n en t i n o n e p h a s e t o t h a t same r a t i o l i b r i u m w ith i t .

i n t h e o t h e r p h a s e , w h ic h i s i n e q u i ­

T h u s , f o r t h e b i n a r y s y s te m r a e th y l c y c lo h e x a n e - n -

h e p ta n e Y

(M .C .H .)

_

Q

Y (n -h e p ta n e )

X (M .C .H . ) ^ X (n -h e p ta n e )

w here Y = m o le p e r c e n t i n e x t r a c t p h a s e X = m o le p e r c e n t i n r a f f i n a t e p h a s e

T h is e q u a t i o n w i l l b e v a l i d i f t h e h y d r o c a r b o n c o m p o s itio n on a s o l v e n t - f r e e o r a n o v e r a l l b a s i s i s u s e d .

T h i s m u st b e t r u e s i n c e

o n ly t h e r a t i o o f t h e a m o u n ts o f t h e tw o h y d r o c a r b o n s p r e s e n t i s i n ­ v o lv e d an d t h i s , o f c o u r s e , d o e s n o t c h a n g e w hen t h e s o l v e n t i s re m o v e d . V a r t e r e s s i a n a n d F e n s k e (2/+) d i s c u s s t h i s f a c t o r f u r t h e r a n d show how i t may b e u s e d i n t h e s o l u t i o n o f t h e i r p r o b le m .

For th e ir

s y s te m a n d

c o n d i t i o n s o f o p e r a t i o n , b e t a w as n e a r l y c o n s t a n t a n d t h e y

assu m ed a n

a v e r a g e v a l u e t o h o ld o v e r t h e e n t i r e d i a g r a m .

I f th is

is

t r u e , t h e n a r e l a t i o n s h i p b e tw e e n t h e c o m p o s itio n o f h y d r o c a r b o n i n e x t r a c t and r a f f i n a t e p h a se i s a v a i l a b l e i n th e above e q u a tio n and a n e q u i l i b r i u m c u rv e may b e d raw n w h ic h i s l a t i o n w o rk .

s im ila r to t h a t used in d i s t i l ­

H ow ever, b e t a i s n o t n e c e s s a r i l y c o n s t a n t f o r a g iv e n

s y s te m a t a f i x e d t e m p e r a t u r e , b u t may v a r y a s much a s a h u n d r e d f o l d . The a b o v e a u t h o r s a l s o d i s c u s s t h e p h y s i c a l s i g n i f i c a n c e o f b e t a and. i t s r e l a t i o n s h i p t o H a o u l t ’ s la w a n d to o s m o tic p r e s s u r e .

S in c e t h e f a c t o r b e t a i s a d i r e c t m e a s u re o f t h e s e l e c t i v i t y o f a g iv e n s o l v e n t , i t i s

t h i s q u a n t i t y w h ic h w i l l b e o f g r e a t e s t

v a lu e when t h e t e r n a r y e q u i l i b r i u m d a t a a r e o b t a i n e d .

C o rre la tio n s

b e tw e e n b e t a an d s o l u b i l i t y d a t a w h ic h may b e u s e f u l i n p r e d i c t i n g t h e s e l e c t i v i t y o f v a r io u s s o lv e n ts w i l l be in c lu d e d .

9 D.

HYDROCARBONS AND SOLVENTS SELECTED I n t h i s e a r l y i n v e s t i g a t i o n o f s o l v e n t e x t r a c t i o n o f t h e lo w -

m o le c u la r w e ig h t h y d r o c a r b o n s , i t was n e c e s s a r y t o s e l e c t c o m p o n e n ts w hich r e p r e s e n t e d a s many t y p e s o f h y d r o c a r b o n s an d s o l v e n t s a s p o s s ib le .

From t h e d a t a o b t a i n e d on su c h s y s te m s g e n e r a l i z e d co n ­

c l u s i o n s may b e draw n a s t o t h e ty p e o f s o l v e n t w h ic h may b e m o s t s e l e c t i v e f o r a m ix tu r e o f c e r t a i n h y d r o c a r b o n t y p e s . W ith t h i s i n m in d , s i x h y d r o c a r b o n s i n t h e g a s o l i n e r a n g e w ere c h o s e n w h ic h r e p r e s e n t e d t h e t h r e e f o l l o w i n g b i n a r y m i x t u r e s : p a r a f f i n - o l e f i n , p a r a f f i n - n a p h t h e n e an d n a p h t h e n e - a r o m a t i c ,

The

s y ste m n - p e n t a n e - t r i m e t h y l e t h y l e n e ( 2- m e t h y l - b u t e n e - 2 ) r e p r e s e n t e d th e f i r s t ;

n - h e p ta n e - m e th y lc y c lo h e x a n e r e p r e s e n t e d t h e s e c o n d ; an d

m e th y lc y c lo h e x a n e w ith t o l u e n e o r i s o p r o p y lb e n z e n e r e p r e s e n t e d t h e l a s t s y s te m .

B o th co m p o n en ts o f e a c h b i n a r y h y d r o c a r b o n m ix t u r e

c o n ta in e d t h e same num ber o f c a r b o n a to m s ; i . e . ,

5 i n th e c a s e o f th e

f i r s t s y s te m and 7 f o r e a c h o f t h e o t h e r tw o ( t o l u e n e w as u s e d w ith m e th y lc y c lo h e x a n e ) .

T h e se p a r t i c u l a r h y d r o c a r b o n s 'w e r e - c h o s e n b e c a u s e

th e y w ere a v a i l a b l e a t a r e l a t i v e l y lo w c o s t a n d b e c a u s e t h e y w e re c o m p a r a tiv e ly e a s y to p u r i f y .

(The m e th o d s o f p u r i f i c a t i o n w i l l be

fo u n d i n A p p e n d ix F . ) The e i g h t s o l v e n t s u s e d d u r i n g t h e c o u r s e o f t h i s I n v e s t i ­ g a t i o n 'were s e l e c t e d t o r e p r e s e n t t h e v a r i o u s t y p e s o f o r g a n i c com pounds. I n a d d i t i o n , s e v e r a l o t h e r f a c t o r s h a d t o b e c o n s i d e r e d w hen t h e s e ­ l e c t i o n was m ade.

F i r s t , a l l th e h y d ro c a rb o n s h ad to be r e l a t i v e l y

s o l u b l e i n t h e s o l v e n t , b e lo w a p r e s s u r e o f 1 25 l b s . / s q . i n .

Second, a t

10

l e a s t one co m p o n en t o f e a c h b i n a r y s y s te m h a d t o b e p a r t i a l l y im ­ m i s c i b l e j t h a t i s , i f b o th c o m p o n en ts w ere c o m p le t e ly m i s c i b l e w i t h t h e s o l v e n t a t t h e lo w e r te m p e r a t u r e l i m i t , no s e p a r a t i o n couLd b e o b ta in e d .

The s o l v e n t s c h o s e n w e re r e l a t i v e l y n o n - t o x i c . M e th y l a l c o h o l w as s e l e c t e d , a s t h e a l c o h o l .

S in c e t h e

h y d ro c a rb o n s w e re q u i t e s o l u b l e i n t h i s s o l v e n t , t h e y w o u ld p r o b a b l y h a v e b e e n much to o s o l u b l e i n t h e h i g h e r m em bers o f t h e s e r i e s . The a ld e h y d e u s e d w as f u r f u r a l .

T h is i s a r e l a t i v e l y

s t a b l e compound an d h a s b e e n u s e d e x t e n s i v e l y i n c o m m e rc ia l i n s t a l ­ l a t i o n s f o r th e s o lv e n t e x tr a c tio n o f l u b r i c a t i n g o i l .

C o m p a riso n

o f t h e s e l e c t i v i t y o f t h i s s o l v e n t f o r h i g h an d lo w m o l e c u l a r w e ig h t h y d r o c a r b o n s w i l l t h u s b e made a v a i l a b l e . As a r e p r e s e n t a t i v e o f 'th e c y a n id e t y p e , a c e t o n i t r i l e m e th y l c y a n id e ) w as u s e d .

(o r

I t h a d b e e n u s e d p r e v i o u s l y b y M air an d

S t r e i f f o f t h e N a t i o n a l B u re a u o f S ta n d a r d s ( 1 3 ) .

T h ey u s e d i t a s

a s o l v e n t t o rem ove t h e a r o m a t ic h y d ro c a rb o n s fro m k e r o s e n e . A n i l i n e was s e l e c t e d a s t h e a m in e s i n c e t h e e q u i l i b r i u m r e l a t i o n s h i p s f o r t h e n - h e p ta n e —m e th y lc y c lo h e x a n e s y s te m h a d b e e n o b t a i n e d b y V a r t e r e s s i a n a n d E e n sk e ( 2 4 ) .

The s e l e c t i v i t y f o r o t h e r

b i n a r y h y d r o c a r b o n s y s te m s c o u ld t h e n b e co m p ared w i t h t h a t o b t a i n e d

•

p re v io u s ly . Some s o l v e n t s o f h i g h e r m o l e c u la r w e ig h t w e re a l s o u s e d . The d ik e t o n e , a c e to n y lg ic e to n e , w as r e l a t i v e l y h i g h b o i l i n g a n d h a d th e p ro p e r s o l u b i l i t y c h a r a c t e r i s t i c s .

A l l t h e h y d r o c a r b o n s w e re much

to o s o l u b l e i n a c e to n e t o p e r m i t i t s u s e ..

11

M e th y l c e l l o s o lv e h a s b e e n r a t h e r w id e ly u s e d a s a s o l v e n t and was u s e d i n t h i s i n v e s t i g a t i o n *

I t c o n t a i n s a h y d ro x y g ro u p a s

w e ll a s a n e t h e r l i n k a g e . M e th y l c a r b i t o l , t h e . m e th y l e t h e r o f d i e t h y l e n e g l y c o l , w as a c o n s i d e r a b l y h i g h e r m o le c u la r w e i g h t , h i g h e r b o i l i n g s o l v e n t o f a ty p e s i m i l a r t o m e th y l c e l l o s o l v e .

T h is a n d t h e f o l l o w i n g s o l v e n t

w e re s e l e c t e d t o i n d i c a t e i n w h a t r e s p e c t t h e s i z e o f t h e s o l v e n t m o le c u le m ig h t e f f e c t i t s

s e le c tiv ity c h a ra c te ris tic s .

The h i g h e s t m o le c u la r w e i g h t , h i g h e s t b o i l i n g com pound i n ­ v e s t i g a t e d was p h e n y l c e l l o s o l v e .

I t i s o f t h e sam e g e n e r a l t y p e a s

t h e two s o l v e n t s m e n tio n e d p r e v i o u s l y .

S in c e t h i s i s t h e p h e n y l e t h e r

o f e t h y l e n e g l y c o l an d m e th y l c e l l o s o l v e i s t h e m e th y l e t h e r , a com­ p a r i s o n o f t h e e f f e c t o f t h e s e tw o g ro u p s o n t h e s o l v e n t s e l e c t i v i t y may b e p o s s i b l e . The s o u rc e a n d p u r i f i c a t i o n o f e a c h o f t h e s e s o l v e n t s i s d e s c r ib e d I n A p p en d ix E.

12 H I.

A.

SOLUBILITY DATA

APPARATUS AMD PROCEDURE 1.

A tm o s p h e ric P r e s s u r e . The a p p a r a t u s w h ic h was u s e d t o d e te r m in e t h e s o l u b i l i t i e s

o f t h e v a r i o u s s o l v e n t s a t a tm o s p h e r i c p r e s s u r e , i s

show n i n F i g u r e 1*

The s o l v e n t a n d h y d r o c a r b o n w e re w e ig h e d i n t o a g l a s s tu b e w h ic h w as 1 in c h i n d ia m e te r a n d 7 i n c h e s i n l e n g t h .

T h is m i x t u r e was s t i r r e d

b y a s o le n o i d o p e r a t e d s t i r r e r w h ile t h e s o l u t i o n w as h e a t e d o r c o o le d I a s was n e c e s s a r y . T h ro u g h t h e u s e o f t h e s o l e n o i d , t h e g l a s s t u b e c o u ld be c l o s e d b y a g ro u n d g l a s s s t o p p e r w h ic h p r e v e n t e d a n y l o s s o f e i t h e r com ponent d u r i n g t h e d e t e r m i n a t i o n .

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

b y a l i m i t s w itc h w h ic h i n t u r n w as o p e n e d a n d c l o s e d b y a cam w h ic h was f a s t e n e d t o t h e s h a f t o f a v a r i a b l e s p e e d m o to r . The tu b e c o n t a i n i n g t h e s o l v e n t - h y d r o c a r b o n m ix tu r e w as s u r r o u n d e d by a g l a s s j a c k e t w h ic h p e r m i t t e d t h e e v e n h e a t i n g o r c o o l i n g o f t h e s a m p le .

T he h e a t i n g w as a c c o m p lis h e d b y a p p l y i n g a g a s f la m e t o

th e g la s s ja c k e t.

TOien t h e s a m p le s h a d t o b e c o o le d b e lo w room te m p e r a ­

t u r e a b a t h o f d r y i c e an d a c e to n e w as p r e p a r e d a n d t h e j a c k e t e d s a m p le im m ersed i n t h i s b a t h .

The t e m p e r a t u r e o f t h e s a m p le w as m e a s u re d b y

a n A n sc h u tz th e rm o m e te r g r a d u a te d i n l / 5 ° C . A f t e r m a k in g some t r i a l d e t e r m i n a t i o n s i t w as fo u n d t h a t a sa m p le w i t h a t o t a l volum e o f 17 c c . m ixed by t h e s t i r r e r .

(+0 . 3 c c . ) c o u ld b e t h o r o u g h l y

A t t h e same tim e t h i s v o lu m e o f sa m p le p e r m i t t e d

a r e a s o n a b l e am ount o f e a c h co m p o n en t t o b e p r e s e n t ( f o r e a c h d e t e r ­ m i n a tio n ) o v e r t h e r a n g e i n v e s t i g a t e d .

The v o lu m e o f s o l v e n t a n d h y d r o ­

c a r b o n n e c e s s a r y t o g iv e a p r e - d e t e r m i n e d c o m p o s itio n w as p i p e t t e d i n t o

F i g u r e No. 1 SOLUBILITY APPARATUS (A tm o s p h e ric P r e s s u r e )

u

t h e tu b e *

By w e ig h in g t h e t u b e o n a n a n a l y t i c a l b a l a n c e b e f o r e an d

a f t e r e a c h a d d i t i o n , t h e c o m p o s itio n w as d e te r m in e d t o w i t h i n + 0 .0 1 w e ig h t p e r c e n t .

A c o r k c o v e r e d w i t h t i n f o i l was u s e d a s a s t o p p e r

d u r i n g t h e tim e t h e s a m p le s w e re b e in g w e ig h e d . The t e m p e r a t u r e o f t h e s a m p le s w as m e a s u re d t o w i t h i n + 0 .1 ° C . b y t h e c a l i b r a t e d A n sc h u tz th e rm o m e te r.

The t e m p e r a t u r e o f

c o m p le te m i s c i b i l i t y o n h e a t i n g a n d t h e t e m p e r a t u r e a t w h ic h t h e f i r s t c l o u d i n e s s a p p e a r e d o n c o o lin g w e re r e c o r d e d .

E ach sam p le was h e a t e d

and c o o le d s e v e r a l tim e s a n d t h e t e m p e r a t u r e s r e c o r d e d e a c h t i m e . F o r m o st o f t h e s a m p le s t h e s e t e m p e r a t u r e s c h e c k e d e a c h o t h e r t o w i t h i n 0 .1 ° C .

H ow ever, w hen a lo w p e r c e n t a g e o f e i t h e r c o m p o n en t w as p r e s e n t

t h e te m p e r a t u r e a t w h ich c o m p le te m i s c i b i l i t y o c c u r r e d w as s e v e r a l t e n t h s o f a d e g r e e , o r m o re , h i g h e r t h a n t h e c lo u d p o i n t t e m p e r a t u r e . I t w as a l s o o b s e r v e d t h a t o n h e a t i n g an d c o o l i n g a g i v e n sa m p le t h e m i s c i b i l i t y t e m p e r a t u r e s v a r i e d b u t t h e c lo u d p o i n t t e m p e r a t u r e s c h e c k e d e a c h o t h e r t o 0 .1 ° C .

I f a n y o f t h e sam p le h a d v a p o r i z e d w h ile h e a t i n g

an d c a u s e d t h e d i f f e r e n c e i n m i s c i b i l i t y t e m p e r a t u r e s t h e n i t w o u ld h a v e b e e n e x p e c te d t h a t t h i s m a t e r i a l w o u ld h a v e c o n d e n s e d o n t h e w a l l s a n d a l s o c a u s e d a v a r i a t i o n i n c lo u d p o i n t t e m p e r a t u r e .

S in c e t h e c lo u d

p o i n t te m p e r a t u r e s r e m a in e d c o n s t a n t i t i s r e a s o n a b l y c e r t a i n t h a t t h i s was n o t t h e c a s e , b u t r a t h e r t h a t a n a p p r e c i a b l e l e n g t h o f tim e w as r e q u i r e d f o r t h e s m a ll am ount o f t h e o n e co m p o n en t t o d i s s o l v e i n t h e s e c o n d c o m p o n e n t.

T h is i n d i c a t e d t h a t t h e c lo u d p o i n t t e m p e r a t u r e w as

t h e c o r r e c t t e m p e r a t u r e and t h e r e f o r e i t w as t h e o n e r e p o r t e d .

The

m i s c i b i l i t y t e m p e r a t u r e s w h ic h a r e f o llo w e d b y a v a l u e i n p a r e n t h e s e s w e re d i f f i c u l t t o d e te r m in e an d a r e o n ly a c c u r a t e w i t h i n t h e l i m i t s in d ic a te d .

15

2.

P r e s s u r e s Above A tm o s p h e ric . The m i s c i b i l i t y te m p e r a t u r e o f n u m ero u s s a m p le s w as ab o v e

t h a t o f t h e b o i l i n g p o i n t o f one o f t h e c o m p o n e n ts .

T h e se r e q u i r e d a

c o n t a i n e r , shown i n F ig u r e 2 , w h ic h c o u ld w i t h s t a n d s u f f i c i e n t p r e s ­ s u r e to k e e p t h e l i q u i d s fro m b o i l i n g .

A h e a v y - w a lle d P y r e x g l a s s

tu b e w hich was s e c u r e l y f a s t e n e d b e tw e e n two e n d - p l a t e s was u s e d i n p l a c e o f t h e g l a s s tu b e m e n tio n e d i n t h e f i r s t s e c t i o n .

Two p i e c e s

o f s t a i n l e s s s t e e l t u b i n g w e re s i l v e r - s o l d e r e d t o t h e t o p e n d - p l a t e ; one e x te n d e d down i n t o t h e t u b e an d s e r v e d a s a th e rm o c o u p le w e l l ; th e sec o n d w as u s e d a s a p r e s s u r e g ag e c o n n e c t i o n .

The s t i r r i n g

m echanism w as s i m i l a r t o t h a t u s e d b e f o r e , w i th t h e e x c e p t i o n t h a t t h e s t i r r e r e x te n d e d up i n t o a c o p p e r tu b e w h ic h w as a l s o s i l v e r s o ld e r e d t o t h e u p p e r e n d - p l a t e . F o u r l e g s w ere f a s t e n e d t o t h e lo w e r e n d - p l a t e .

The a s ­

sem bled a p p a r a t u s was h e a te d b y im m e rs io n i n a b a t h o f M e ru so l w h ic h was h e a te d b y a g a s f la m e .

The c o n t a i n e r w as a t h r e e - l i t e r P y r e x

b e a k e r w h ic h w as f i l l e d to w i t h i n l / 2 i n c h o f t h e t o p .

The M e ru so l

was s t i r r e d b y a m o to r s t i r r e r d u r i n g t h e d e t e r m i n a t i o n . S in c e t h e g l a s s p r e s s u r e t u b e was to o s m a l l t o p e r m it t h e u s e o f a n A n sc h u tz th e rm o m e te r t o m e a s u re t h e t e m p e r a t u r e o f t h e s a m p le , a n i n d i r e c t m ethod h a d t o b e u s e d .

The t e m p e r a t u r e o f t h e M e ru so l b a t h

w as m e asu re d b y a n A n sc h u tz th e r m o m e te r , an d a t t h e same tim e t h e te m p e r­ a t u r e d i f f e r e n c e b e tw e e n t h e b a th an d sam p le w as m e a s u re d b y m eans o f a d i f f e r e n t i a l th e rm o c o u p le w h ic h was c o n n e c te d t o a d e f l e c t i o n g a lv an o m e ­ te r.

One j u n c t i o n o f t h e th e rm o c o u p le w as p l a c e d i n t h e b a t h and t h e

o t h e r e x te n d e d i n t o t h e s a m p le .

The c o m p le te d e s c r i p t i o n o f t h e s e tw o

t u b e s and a u x i l i a r y e q u ip m e n t i s g iv e n i n S e c t i o n A o f t h e A p p e n d ix .

F ig u r e No. 2 SOLUBILITY APPARATUS ( P r e s s u r e s ab o v e A tm o s p h e r ic )

17

I n u s i n g t h e p r e s s u r e t u b e a 22 c c . sa m p le was u s e d .

T h is

f i l l e d t h e t u b e t o su c h a n e x t e n t t h a t t h e am o u n t o f v a p o r p r e s e n t i n t h e s p a c e a b o v e t h e l i q u i d c o u ld b e n e g l e c t e d .

C a re was t a k e n , h o w e v e r,

t h a t s u f f i c i e n t s p a c e was p r e s e n t t o a l lo w f o r t h e e x p a n s io n o f t h e l i q u i d on h e a tin g . The s o l v e n t s a n d h y d r o c a r b o n s w e re p u r i f i e d a c c o r d i n g t o t h e p r o c e d u r e s o u t l i n e d i n S e c t i o n s E a n d F o f t h e A p p e n d ix .

I t w as co n ­

s id e r e d e s s e n t i a l t h a t th e s e m a te r ia ls be i n a s p u re a s t a t e a s p o s s ib le . I n t h i s w ay, a c c u r a t e and r e p r o d u c i b l e r e s u l t s w e re o b t a i n e d . The d a t a o b t a i n e d f o r t h e s o l u b i l i t y o f t h e s e v e r a l h y d ro ­ c a rb o n s i n e a c h s o l v e n t w e re p l o t t e d , f i r s t , a s w e ig h t p e r c e n t h y d ro ­ c a r b o n v e r s u s t h e m i s c i b i l i t y t e m p e r a t u r e , and. s e c o n d , a s t h e r e c i p r o c a l o f th e m i s c i b i l i t y te m p e ra tu re , i n d e g re e s a b s o lu te ( ° K .) , v e r s u s th e lo g a r i t h m o f t h e w e ig h t p e r c e n t h y d r o c a r b o n . B.

RESULTS AND DISCUSSION 1.

A c e to n itrile The o r d e r o f i n c r e a s i n g s o l u b i l i t y f o r t h e s i x h y d r o c a r b o n s i n

a c e t o n i t r i l e i s a s fo llo w s :

n - h e p t a n e , m e t h y lc y c lo h e x a n e , n - p e n t a n e a n d

t r i m e t h y l e t h y l e n e , w i t h t o l u e n e a n d is o p r o p y lb e n z e n e b e in g m i s c i b l e i n a l l p r o p o r t i o n s down t o t h e f r e e z i n g p o i n t o f t h e m i x t u r e ( a b o u t -4-3 t o —5 0 °C . f o r e q u a l v o lu m e s o f s o l v e n t a n d h y d r o c a r b o n ) .

The c u r v e s f o r

t h e f o u r h y d r o c a r b o n s , F ig u r e 3 , a r e t h e u s u a l t y p e w hen p l o t t e d o n a s o l u b i l i t y v e r s u s te m p e r a t u r e d ia g r a m .

The f i r s t t h r e e l i s t e d h a v e

c r i t i c a l s o l u t i o n t e m p e r a t u r e s o f 3 3 . 3 ° C . , 7 S .5 ° C ., a n d 6 7 .5 ° C . r e s p e c t i v e ­ ly .

The f o u r t h , t r i m e t h y l e t h y l e n e i s much m ore s o l u b l e , h a v in g a c r i t i c a l

s o l u t i o n te m p e r a t u r e o f a b o u t 1 2 .2 ° C .

18

F ig u r e No. 3 HYDROCARBON SOLUBILITY IN ACETONITRILE

•o-

le thyicjji

T em perature,

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20

60

80

Weight Per Cent Solubility

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Weight Per Cent S o lu b ilit y , Hydrocarbon in A c e to n itr ile to

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SOLUBILITY Of HYDROCARBONS IN ACETONITRILE

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Table No. 1 ACETONI TRILE-HY DEOCARBON MISCIBILITY. TEMPERATURES P ressu re lb ./in .2

W e ig h t p a r c e n t H y d ro c a r b o n

M i s c i b i l i t y T e m p e r a tu r e °C . l / OK~- 'y 1 ° 3

M e th y lc y c lo h e x a n e

— —

13 IS 20 20 15 12

9 .1 5 1 6 .1 5 2 4 .1 2 3 5 .6 9 49. 26(e q . v o l.) 6 4 .2 5 7 4 .6 7 8 5 .4 6 9 0 .4 2

9 .2 3 6 .7 5 5 .0 7 0 .1 7 7 .1 7 8 .5 7 8 .0 7 1 .8 63.0

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

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

3 .4 7 6 3 .2 8 0 2 .9 5 1 2.862 2 .8 0 9 2 .8 0 3 2 .8 1 3 2 .8 8 1 2.9 -4 4

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

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

n - H s p ta n e

— —

.

19 23 23 25 18 16

7 .0 0 1 0 .3 2 2 3 -1 9 3 2 .5 3 4 7 .1 0 (e q . v o l .) 6 3 .0 3 7 3 .9 0 8 5 .5 5 8 9 .5 2 n -P e n ta n e

12 28 37 40 37 30 20

9 .9 7 1 9 .6 9 3 2 .4 0 4 4 * 0 9 (e q . v o l .) 5 9 .0 8 7 3 .1 8 8 5 .1 4 9 1 .1 7

( C o n c lu d e d on n e x t p a g e )

21 T a b le No. 1 ACETONITRILE—HYDROCARBON M ISGIBILITY TEMPERATURES (C o n c lu d e d ) P ressu re lb ./in . 2

W e ig h t p e r c e n t Hy d r o c a r b o n

M i s c i b i l i t y T e m p e r a tu r e °C . l/° K . x 103

T rim e th y le th y le n e 1 2 . IB fro z e -4 7 - 3 1 .0 1 9 .9 9 - 8 .8 3 0 .1 9 4 2 .8 1 ( e q - v o l .) + 5 . 7 5 9 .4 2 1 1 .2 1 2 .0 '7 3 .4 2 8 3 .1 2 6 .1 - 6 .5 9 2 .9 4 T o lu e n e 5 2 .5 8 ( e q . v o l . )

fro z e -5 0

Is o p ro p y lb e n z e n e 5 2 .4 3 (e q . v o l . )

fro z e -4 -8

—

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

22

The c u r v e s f o r t h e s e sam e h y d r o c a r b o n s a n d s o l v e n t a r e p l o t t e d a s l / ° K . v e r s u s l o g a r i t h m o f t h e s o l u b i l i t y a n d show n i n F i g u r e 4-.

T h e s e c u r v e s h a v e s i m i l a r s l o p e s a t s o l u b i l i t i e s b e lo w

a p p r o x i m a t e l y 50 p e r c e n t *

A t e v e n l o w e r c o n c e n t r a t i o n s , b e lo w 1 5

p e r c e n t h y d ro c a rb o n , th e l i n e s a r e v e r y n e a r ly s t r a i g h t so t h a t e x t r a p o l a t i o n i s p o s s i b l e w hen a t l e a s t tw o p o i n t s o n t h i s p o r t i o n o f t h e c u r v e a r e k n ow n.

F o r e x a m p le , t h e c u r v e f o r n - h e p t a n e may b e

e x tr a p o la t e d s in c e th e e x p e rim e n ta l m i s c i b i l i t y te m p e ra tu re s h av e b e e n d e te rm in e d a t 1 0 p e r c e n t an d 7 p e r c e n t h y d ro c a rb o n an d th e s e p o i n ts lie

on th e s t r a i g h t l i n e p o r tio n on th e c u rv e s .

The s t r a i g h t l i n e

p o r t i o n o f t h e t r i m e t h y l e t h y l e n e c u r v e h a s a lo w e r s l o p e , t h a t i s , t h e ch an g e in s o l u b i l i t y i s l e s s f o r a g iv e n d if f e r e n c e i n te m p e r a tu re . C o m p le te d a t a a r e g i v e n i n T a b le 1 . 2.

A c e to n y la c e to n e The s o l u b i l i t i e s o f o n l y t h r e e h y d r o c a r b o n s , n - h e p t a n e , n -

p e n t a n e a n d m e t h y lc v c lo h e x a n e w e re d e t e r m i n e d o v e r t h e r a n g e fro m 1 0 t o 90 p e r c e n t . T a b le 2 , w i t h t h e s o l u b i l i t y i n c r e a s i n g i n t h e o r d e r g iv e n .

E q u a l v o lu m e s o f t r i m e t h y l e t h y l e n e a n d s o l v e n t h a d a m i s c i b i l i t y

t e m p e r a t u r e o f - 1 2 . 7 ° C . w h ic h w as so lo w t h a t t h e r e m a i n d e r o f t h e c u r v e w as n o t d e t e r m i n e d .

When m i x t u r e s o f e q u a l v o lu m e s o f t o l u e n e a n d s o l ­

v e n t w e re c o o le d t h e m i x t u r e f r o z e a t - 2 5 ° C . J

50 v o lu m e p e r c e n t i s o ­

p r o p y l b e n z e n e i n s o l v e n t f r o z e a t - 1 9 ° C. The c r i t i c a l s o l u t i o n t e m p e r a t u r e s , a s r e a d fr o m t h e c u r v e s o f F i g u r e 5 a r e n - h e p t a n e 7 0 . C P C ., n - p e n t a n e 6 0 . 0 ° C . , a n d m e t h y l c y e l o h e x a n e 5 0 .6 ° C .

I t w i l l be n o te d t h a t n - p e n ta n e i s l e s s

s o lu b le i n

a c e to n y la c e to n e th a n m e th y lc y c lo h e x a n e , •w h ile t h i s o r d e r i s r e v e r s e d

F ig u r e No. 5 HYDROCARBON SOLUBILITY IN ACETONYLACETONE

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Figure No. 6 24

Solubility, Hydrocarbon

in Acetonylacetone

SOLUBILITY OF HYDROCARBONS IN ACETONYLACETONE (CH3C0CH2CH2C0CH3)

Weight

Per

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Table No. 2 ACETONYLACETONE-HYDKOCAKBON M ISC IB IL ITY TEMPERATURES

P ressu re lb ./in 2

V .'eig h t p e r c e n t H y d ro c a rb o n

M is c ib ility °C .

T e m p e r a tu r e l / ° K . .x IQ 3

M e th y lc y c lo h e x a n e 9 .9 8 1 3 .1 8 1 6 .1 9 1 8 .6 7 3 0 .4 7 4 4 .3 9 ( e q . v o l .) 5 3 .3 3 6 3 .8 2 7 3 .6 3 8 2 ,9 7 8 9 .7 0

C r y s ta ls a t -1 0 .8 ° 1 C ry s ta ls a t -8 to ■ 2 0 . S(jKD.2) 3 .4 0 1 3 .3 3 0 2 7 .1 4 3 .9 3 .1 5 4 3 .0 9 5 4 9 .9 3 .0 9 0 5 0 .4 5 0 .3 3 .0 9 1 4 8 .2 3 .1 1 1 4 1 .4 3 .1 7 9 3 .3 0 0 2 9 .8

n —H e p ta n e 1 0 .0 1 1 7 .5 3 2 7 .9 8 4 1 .7 8 ( e q . v o l .) 5 1 .8 0 6 3 .0 3 75*44 8 4 .3 5 9 1 .1 1

2 6 .4 5 0 .0 6 4 .7 6 9 .8 7 0 .0 6 9 .3 63 .6 5 2 ,6 3 5 .8

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

2 .0 ( + 0 .3 ) 3 8 .0 5 2 .5 5 9 .0 6 0 .0 5 9 .8 5 7 .7 4 9 .9 2 6 .0

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

n -P e n ta n e ---

11 18 24 25 25 24 16 —

9 .3 1 1 8 .8 4 2 7 .4 1 3 8 .6 8 ( e q . v o l .) 4 9 .0 9 5 9 .9 5 6 8 .8 0 7 9 .3 8 9 1 .1 5

( C o n c lu d e d o n n e x t p a g e )

26 Table No. 2 ACETONYLACETONE-HYDROCARBON M ISC IB IL IT Y TEMPERATURES ( C o n c lu d e d ) P ressu re lb ./in . 3

W e ig h t p e r c e n t H y d ro c a r b o n

M i s c i b i l i t y T e m p e ra tu re °C . l / ° K ♦ x IQ 3

T rim e th y le th y le n e 4 - 0 .9 6 ( e q . v o l . )

-1 2 .7

T o lu e n e 4 7 .1 5 ( e q . v o l .)

f r o z e -2 5

Is o p ro p y lb e n z e n e 4 7 .0 0 ( e q i v o l . )

f r o z e -1 9

3 -.8 3 9

27

f o r th e s o l u b i l i t i e s i n th e f i r s t h e p ta n e i s

s o lv e n t,

a c e to n itrile .

T he n -

a g a i n t h e l e a s t s o l u b l e a n d t h e t r i m e t h y l e t h y l e n e i s much

m o re s o l u b l e t h a n a n y o f t h e s e t h r e e . P lo ttin g

th e s e d a ta a s l/° K . v s . lo g a rith m

o f th e s o lu ­

b i l i t y , F i g u r e 6 , t h e c u r v e s h a v e s i m i l a r s l o p e s b e lo w 5 0 p e r c e n t s o lu b ility .

They a l s o

seem t o i n d i c a t e t h a t b e lo w a p p r o x i m a t e l y 1 5

p e r c e n t s o l u b i l i t y th e c u rv e s t r a i g h t e n s o u t an d p e r m its e x t r a p o l a t i o n . Due t o t h e r e l a t i v e l y h i g h f r e e z i n g p o i n t o f t h e s o l v e n t , - 9 ° C . t h e m i s c i b i l i t y te m p e r a tu r e s f o r m e th y lc y c lo h e x a n e c o u l d .n o t b e d e te r m in e d b e lo w 1 6 w e i g h t p e r c e n t s o l u b i l i t y . 3.

A n ilin e T he s o l u b i l i t y d a t a f o r t h e h y d r o c a r b o n s n - p e n t a n e , n -

h e p ta n e , n -h e x a n e , m e th y lc y c lo h e x a n e , and t r i m e th y l e th y le n e i n a n i l i n e (lis te d

i n T a b le 3 ) a r e p l o t t e d i n F i g u r e s 7 a n d 8 .

The s o l u b i l i t i e s

o f th e th r e e p a r a f f in s in v e s tig a te d a r e v e ry n e a r ly th e

sa m e ; m e th y l ­

c y c l o h e x a n e a g a i n i s m o re s o l u b l e a n d t r i m e t h y l e t h y l e n e i s s o lu b le o f th e s e f i v e .

th e m ost

T o lu e n e a n d i s o p r o p y i b e n z e n e a r e c o m p l e t e l y

m i s c i b l e down t o t h e f r e e z i n g p o i n t s o f t h e 50 v o lu m e p e r c e n t m i x t u r e s w h ic h w e re —3 0 a n d —1 5 ° C . , r e s p e c t i v e l y . The d a t a f o r t h e

s o lu b ility

o f a n ilin e in th e th re e p a r a f f in

h y d ro c a rb o n s (o r h y d ro c a rb o n s o l u b i l i t y

g r e a t e r t h a n 50 p e r c e n t ) i s

show n i n F i g u r e S b y t h e b r o k e n l i n e .

T h e s e s o l u b i l i t i e s a r e so n e a r l y

t h e sam e t h a t a s i n g l e

re p re se n t a ll

c u rv e s e r v e s to

th re e .

T h is i s

th e

o n l y s o l v e n t s t u d i e d f o r w h ic h t h e d i f f e r e n c e i n m o l e c u l a r w e i g h t r e s u l t s in

su ch a s m a ll d i f f e r e n c e

in

s o l u b i l i t y o f a ty p e h y d ro c a rb o n .

It

e m p h a s iz e s v e r y c l e a r l y t h e b a s i c d i f f e r e n c e b e tw e e n s o l v e n t e x t r a c t i o n

28

F ig u re

N o. 7

HYDROCARBON SOLUBILITY IN ANILINE

80

Temperature, °C

AO

+20

Trim©-

I P E fR O L iC U tf B E F t a l R S

L A B 0 R A 7 >RY

TH$ PEWMaYlrVAtt)* BL* 0

20

:. s i i , t e

$oLu

r e « l in d r /w 11

-J - AWWST+fJ*-

60 W eig h t P e r C e n t S o l u b i l i t y

-f 80

100

Weight Per Cent Solubility, Hydrocarbon in Aniline

ro

Vo

fO

09

o

V O o

oa

o

oa

O

t-3 •O

01

X

O

i >;

8

(C6 H5NH2 )

X

Figure No.

-So/T

H* :

SOLUBILITY O F HYDROCARBONS IN ANILINE

XS

$

Table No. 3 ANILINE-HYDROCARBON M ISC IB ILITY TEMPERATURES

P ressu re lb ./in . 2

W e ig h t p e r c e n t H y d ro c arb o n

M i s c i b i l i t y T e m p e r a tu r e °c. 1 /° K . x 1 0 3

M e th y l c y c lo h e x a n e

;

8 .3 7 1 5 .3 9 2 4 .7 8 3 3 .3 2 4 2 .8 5 ( e q . v o l .) 6 0 .3 2 7 0 .5 2 7 9 -3 2 8 7 .0 6 9 3 .9 3

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

-

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

n —H e p ta n e 3 .2 4 4 .8 0 7 .0 9 1 3 -3 1 2 5 .2 7 4 0 .0 0 ( e q . v o l .) 60.00 7 0 .8 8 9 2 .5 4

- 1 .4 + 1 5 .1 2 8 .1 5 0 .8 6 6 .3 6 9 -4 6 8 .0 6 3 -5 2 4 .3

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

3 3 .3 5 7 .0 6 7 .2 7 0 .4 7 0 .5 6 8 .8 62.0 4 8 .1 3 3 .4

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

n —P e n t a n e /A

0 22 30 34 33 32 25 16 7

9 .8 2 1 8 .1 0 2 7 .2 7 3 8 .0 6 (e q . v o l .) 5 0 .2 3 6 2 .2 4 7 3 .8 0 8 4 .0 7 9 0 .0 3

( C o n c lu d e d on n e x t p a g e )

31 Table No. 3 ANILINE-HYDROCARBON M ISCIBILITY TLiViPEiiATURES ( C o n clu d ed .) P ressu re lb ./in .2

W e ig h t' p e r c e n t H y d ro c a r b o n

M i s c i b i l i t y T e m p e r a tu r e °C . l / ° K . .x IQ^3

T rim e t h y l e t h y l en e 1 1 .1 3 1 8 .3 2 2 8 .2 6 4-0.23 ( eq . v o l . ) 5 1 .2 6 6 2 .5 2 7 3 .9 6 3 4 .1 4 9 1 .0 5

- 1 8 .8 - 1 .2 + 9 .7 1 2 .8 1 2 .2 1 0 .2 +4 • 8 - 7 .6 - 19 .0

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

T o lu e n e 4 5 * 9 l(e q . v o l.)

f r o z e —30

I s o p ro p y lb e n z en e 4 5 .7 7 ( e q . v o l .)

f r o z e -1 5

n -H e x a n e 6 .5 1 1 3 .4 7 2 4 .8 3 3 9 * 7 4 (e q . v o l .) 5 4 .2 4 6 4 .1 8 7 6 .1 4 8 3 .0 5 9 3 .0 3

2 0 .3 4 7 .5 6 4 -1 68.3 6 8 .2 6 6 .1 5 8 .5 4 9 .5 2 2 .1

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

32

and d i s t i l l a t i o n ;

th e f i r s t s e p a r a te s a c c o rd in g to m o le c u la r ty p e ,

w h ile t h e s e c o n d e f f e c t s a s e p a r a t i o n o n t h e b a s i s o f m o l e c u l a r w e ig h t (b o ilin g p o in t) . T he l o g a r i t h m i c p l o t o f t h e d a t a f o r n - h e p t a n e f a l l s o n a s t r a i g h t l i n e , w i t h i n e x p e r i m e n t a l e r r o r , f o r t h e lo w e r p e r c e n t a g e s o f h y d ro c a rb o n . The s o l u b i l i t y d a t a o b t a i n e d f o r n - h e x a n e i n a n i l i n e w e re c o m p ared w ith s i m i l a r d a t a w h ic h w e re r e p o r t e d b y K e y e s a n d H i l d e b r a n d (1 2 ) i n 1917.

T hese a u th o r s i n d i c a t e a h ig h e r s o l u b i l i t y a t a g iv e n

te m p e r a t u r e t h a n t h a t fo u n d i n t h i s

s tu d y .

F o r e x a m p le , t h e i r c r i t i c a l

s o l u t i o n t e m p e r a t u r e i s r e c o r d e d a s 5 9 .6 ° C . a s c o m p a re d t o 6 8 .7 ° C . t a k e n fro m t h e c u r v e i n F i g u r e 7 . 6 9 .0 ° C .

The a c c e p t e d l i t e r a t u r e v a l u e a t p r e s e n t i s

T h e se i n v e s t i g a t o r s u s e d n - h e x a n e w h ic h h a d b e e n s e p a r a t e d fro m

a p e tr o le u m f r a c t i o n a n d h a d b e e n p u r i f i e d o n l y b y s e v e r a l s im p le d i s t i l ­ la tio n s .

The m a t e r i a l w h ic h t h e y u s e d p r o b a b l y c o n t a i n e d a s m a l l am o u n t

o f benzene a s im p u r ity s in c e i t

i s d i f f i c u l t to

s e p a r a te t h i s a ro m a tic

fro m n - h e x a n e , e s p e c i a l l y b y s im p le d i s t i l l a t i o n .

T h e i r m e th o d o f o b ­

t a i n i n g m i s c i b i l i t y t e m p e r a t u r e s w as s i m i l a r t o t h a t u s e d b y o t h e r w o r k e r s a n d t h e y seem ed t o b e a b l e t o

c h e c k t h e i r own r e s u l t s .

T h e re fo re i t

see m s

t h a t t h e i r d i s c r e p a n c y w as p r o b a b l y d u e t o t h e u s e o f im p u re n - h e x a n e r a t h e r t h a n t o a n y e r r o r i n t h e i r m e th o d o f d e t e r m i n a t i o n . 4-.

F u rfu ra l The tw o p a r a f f i n s , n - h e p t a n e a n d n - p e n t a n e , a r e t h e l e a s t s o l u ­

b l e i n f u r f u r a l w i t h m e th y lc y c lo h e x a n e a n d t r i m e t h y l e t h y l e n e f a l l i n g n e x t in th a t o rd e r.

The tw o a r o m a t i c s , t o l u e n e a n d i s o p r o p y l b e n z e n e , w e re

F ig u re

N o. 9

HYDROCARBON SOLUBILITY IN FURFURAL

100

80

Temperature,

°C

ISa- ihyicy' jlohex^uae

+20

•20

jpe;tr*Qletjgj :&£££$ The :Penns jrlvjani i :S|fcat e : G o ll e g e JSta teHCcti: t e g e y - Pnransy ivajaia ~ —r A ugiiat; 1 5 , 1 9 ^ 2 ' .j o

20

AO

60

W eig h t P e r C en t S o l u b i l i t y

80

100

Weight Per Cent S o lu b ilit y , Hydrocarbon in Furfural 2.60

to

£

2.80 3.00 3.20 3.40

"TO"

1/°K. 3.60

x 10 3

O O

SOLUBILITY OF HYDROCARBONS IN

«+•

3*80

O

f ig u r e No. 10

ITY Of HYDROCARBONS IN FURFURAL

(C4 H3 OCHO)

J !eda xlLi iim-BflJ !i jig. Laftbn .toiy » t ( rC< >111>ge '■he ; . ... i >t«l r& t^ o lle g ^ , J.UglLBt l t e ! ' : . ' r •••-

3.60

40 1 /°K .

x

103

4 .0 0

4 .2 0

4 .6 0

Table No. 4 F U

P l b

r e .

s

s

/

i n

u

K F U

R

r e

A L - H

W

. 2

M

e

Y D

R

O

C A R B O N

e

i g

h

t

p

e

r

H

y

d

r o

c

a

r b

t h

y

l c

l o

h

y

c

c

e

o

e

n

I S

C

I B

t

I L

M

a

n

1 2 .6 3 2 0 .7 0 3 0 . 8^ 3 9 * 8 8 (e q . 4 8 .5 3 6 0 .4 1 7 0 .3 6 7 9 .2 9 8 8 .7 3 9 3 .0 6

I T

i s

_____

n

x

M

Y

c

° C

T E M

i b

P E R A T U R E S

i l i t y

.

e

m

p

l / °

T

K

.

e

r a

t u

x

e

v

o

l . )

3 5 .6 5 7 .0 6 8.6 7 1 .9 7 2 .5 7 2 .5 7 0 .2 64.8 5 0 .4 3 6 .1

3 .2 3 8 3.028 2 .926 2 .898 2 .8 9 3 2 .8 9 3 2 .9 1 2 2 .9 5 9 3 .0 9 0 3 .2 3 3

31 .6 51.6 6 5.8 8 9 .3 9 3 .5 9 4 .0 92 .0 83 .2 6 1 .0 ±0 .2 3 9 .7 ± 0 .2

3.281 3 -0 7 9 2 .9 5 0 2 .7 5 9 2 .7 2 7 2 .7 2 3 2 .7 3 8 2 .8 0 6 2 .9 9 2 3 .1 9 6

n —H e p ta n e 6 .4 4 9 .5 7 1 2 .9 5 2 6.08 3 7 .3 6 (e q . 5 0 .5 1 6 2 .7 5 7 6 .3 1 8 8 .1 4 9 3 .3 1

v

o

l . )

'

n —P e n t a n e 10 33 52 60 62 58 50 32 13

■

1 0 .0 5 1 7 .2 0 2 5 .3 1 3 4 * 7 6 (e q . 4 7 .6 3 5 9 .8 8 7 1 .2 9 8 1 .5 1 9 0 .5 8 ( C

o

n

c

l u

d

e

d

v

o

o n

3 8.8 6 8 .7 8 4 -2 9 0 .8 9 1 .6 9 0 .0 8 3 .2 6 8 .3 4 3 -6

l . )

n

e

x

t

p

a

g

3 -2 0 5 2 .9 2 5 2 .7 9 8 2 .7 4 7 2 ; 741 2 .7 5 3 2 .8 0 6 2 .9 2 8 3 .1 5 7 e

)

I Q

r e

3

Table No. 4 FURFURAL—HYDROCARBON M IS C IB IL IT Y TEMPERATURES ( C o n c lu d e d )

P l b

r e

s

s

.

/

i n

u

r e

W

. 2

e H

T

r i m

i g

h

y d

e

t

p

r o

t h

e c

y

l e

r a

c r b

t h

e o

y

n

t

M

n

l e

i s

c ° C

n

i l i t y

e

m

p

l / °

T

K

.

e

r a x

e

1 0 ; 01 1 8 ; 53 2 '7 ;9 5 3 6 ;1 0 (e q . v o l .) 4 8 ; 45 5 8 ;7 5 6 8 .8 0 SO; 1 6 9 0 ; 76 T o lu e n e 4 2 .7 8 ( e q .

i b

. _______________

- 3 5 - 0 ( ± 0 .3 ) + 0 .6 19*6 2 6 ;8 2 8 ;9 28; 6 2 6 ;0 +16; 7 - 3 .6

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

v o l.)

C ry s ta ls a p o e a re d a t -5 5 °C .

4 2 ;6 4 (e q ; v o li)

C r y s ta ls a p p e a re d a t -4 -8 ° C.

Is o p ro p y lb e n z e n e

t u I Q

r e

3

37

m

i s

c

c

r y

s

h

i p

a

b

s

f u

s

i b

l e

a s

t a

l s

a

b e t w

o

r a

l u

t e

l .

l o

p

p

e e n

t e

m

T h e

5.

e

M

r e

t h

e

e

r a

t h

a

y

—55

a s

a

p

d

e

w

d

l o

t a

l

.

A

g

T

h e s e

a

r i t h

t u

r e

f o

a

r e

g

i v

o

l

l c

o

h

—A8°C..

a n d

c

m

r

t h

e

n

u

r v

o

f

e

i n

e

s

t h

l o

T

a

e

w

l s

s

e

a

r e

b

r

l e

s

o

e

i n

o

s

p

l u

o

U

c

d

b

l u

t i v

i c

a

e

t e

i l i t y

b

a n d

;

a

t

a

s

t r a

a n d

i l i t i e

p

l y

l o

s

o

t t e

d

t h

t h

e

f

h

i n

y

e

s

e

i g

h

r e

c

t e

m

t - l i n

i p

c

r b

o

r o

c

a

F

i g

u

r e

s

e

e

r o

d

p

r a

r e

a

l

t u

r e

l a

t i o

f

t h

o

n

i n

9

a n d

f u

s

n

e

r ­

10.

T h ree o f th e s i x h y d ro c a rb o n s , tr i m e th y l e th y le n e , to lu e n e and i s o p r o p y l b e n z e n e w e re m i s c i b l e w i t h t h e m e th y l a l c o h o l a t l e a s t a s lo w a s -6 0 °C .

The o t h e r t h r e e w e re a l s o v e r y s o l u b l e i n t h i s s o l v e n t , n—

p e n ta n e b e in g th e m ost s o l u b l e .

M e th y lc y c lo h e x a n e w as so m e w h a t l e s s

s o lu b le and n -h e p ta n e h ad th e lo w e s t s o l u b i l i t y .

F o r i n s t a n c e , a.s c a n

b e s e e n fro m T a b le 5 a n d F i g u r e s 1 1 . a n d 1 2 , a t - 2 0 ° C . , t h e s o l u b i l i t i e s w e re :

n - p e n t a n e 2 7 .0 p e r c e n t , m e th y lc y c lo h e x a n e 1 7 . 5 rp e r c e n t a n d n—

h e p t a n e 1 2 .5 p e r c e n t .

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

m e th y l a l c o h o l e x h i b i t t h e s t r a i g h t - l i n e r e l a t i o n s h i p o n t h e s e m i lo g a rith m ic p l o t o v e r th e w id e s t ra n g e o f any o f th e e ig h t s o lv e n ts s tu d ie d ; th a t i s ,

t h e p o i n t s b e lo w 30 p e r c e n t s o l u b i l i t y f a l l v e r y

n e a r ly on th e s t r a i g h t l i n e . A n o th e r p e c u l i a r i t y i s

n o te d i n t h e lo w s o l u b i l i t y o f t h e

s o l v e n t , m e th y l a l c o h o l , i n t h e h y d r o c a r b o n s . t e m p e r a t u r e w h ic h i s

T he c r i t i c a l s o l u t i o n

u s u a l l y n e a r a c o m p o s i t i o n o f 50 w e ig h t p e r c e n t , ,

i s a t a p p ro x im a te ly 70 w e ig h t p e r c e n t h y d ro c a rb o n f o r t h i s

s o lv e n t.

The s t e e p n e s s o f t h e b r o k e n c u r v e s i n F i g u r e 1 2 ( s o l u b i l i t y o f m e th y l a lc o h o l in h y d ro c a rb o n ) in d ic a te s th e ra p id d e c re a s e i n s o l u b i l i t y a s

­

F ig u r e

No. 11

HYDROCARBON SOLUBILITY IN METHYL ALCOHOL

•Of lieth; rlcycl< xhexane

+20

Temperature,

°C

’eirjbana

S o l s t i iL R e f i ling Tniborat. ary.. ! Thi i Penn 3ylvan .a :£5ta- 3e College jtjtj t-te:Co: iLege,' P s im a rust :i; >, 194

0

20

60 W e ig h t P e r C en t S o l u b i l i t y

80

100

F igure No. 12 SOLUBILITY OF HYDROCARBONS IN METHYL ALCOHOL

80

60

AO

30

20

15

10 8

6

A 3

2

1

3.00

3 .2 0

3.60

3 .8 0 l/° K . x 103

A.00

(C

Figure No. 12 39 )LUBILITY OF HYDROCARBONS IN METHYL ALCOHOL

(CH30H)

\

W iiiliiilrtilH

3.60

3.80 l/° K . x 103

A.OO

Table No. 5 M

E T H

Y L

A L C O

H O

L - H Y D R O

C A R B O

N

M

I S

!,ve i g h t p e r c e n t H y d ro c a r b o n

C

I B

I L

I T

Y

T E M

P E R A T U R E S

M i s c i b i l i t y T e m p e ra tu re °C . l / ° K . x IQ 3

M e th y lc y c lo h e x a n e 2 1 .6 1 3 5 -9 0 4-9• 0 8 ( e q . v o l . ) 5 7 .3 8 6 6 .3 2 7 0 .6 2 9 0 .6 0

- 6 .6 + 2 4 -.6 3 9 .1 4 3 -1 4 4 -.0 4 4 -1 3 3 -4

■

3 .7 5 1 3 .3 5 8 3 -2 0 2 3 -1 6 2 3 .1 5 3 3 -1 5 2 .3 .2 6 2

n —H e p t a n e

-

9 .9 1 1 4 .-5 5 1 8 .2 2 2 4 -7 4 3 1 .0 0 4 6 .3 0 ( e q . v o l.) 5 7 .6 3 7 1 .6 8 7 6 .4 7 8 6 .0 9 9 1 .8 0

- 3 3 .6 -1 1 .3 + 1 .5 + 1 9 .4 3 1 .9 4 7 .2 5 0 .3 5 0 .6 5 0 .4 4 4 -7 , 3 3 .9

4 .1 7 4 3 .3 1 8 3 .6 4 0 3 -4 1 8 3 .2 7 8 3 -1 2 1 3 .0 9 1 3 .08 8 3 -0 9 0 3 .1 4 6 3 -2 5 6

- 6 4 .0 0 n c;

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

n —P e n t a n e 1 2 .0 2 2 3 -4 7 3 3 .3 9 4 4 « 1 4 -(eq . v o l . ) 5 5 .6 9 69 • 6 1 8 2 .0 2 8 6 .7 6 9 1 .8 3 T

r i m

e

t h

- 7 .4 + 6 .3 1 3 .6 1 5 -4 1 5 .0 1 2 .3 5 -4 y

l e

t h

y

l e

n

4 5 « 5 6 (e q . v o l .)

e

b e l o w —6 0 ° C .

T o lu e n e 5 2 .2 4 ( e q . v o l . )

b e lo w - 6 0 ° C .

Is o p ro p y lb e n a e n e 5 2 .1 0 ( e q . v o l . )

b e lo ? / —6 0 ° C .

A1 th e te m p e ra tu re i s lo w e re d .

T h is i s

c u r v e s , w h ic h

show t h a t a l a r g e

c a u s e a g iv e n

change o f s o l u b i l i t y

6.

i n d i r e c t c o n tr a s t to th e

s o lid

ch an g e i n te m p e ra tu re i s n e c e s s a r y to of

h y d ro c a rb o n i n th e s o lv e n t,

M e th y l C a r b i t o l T he s h a p e s o f t h e h y d r o c a r b o n s o l u b i l i t y

a r e th e m ost u n u s u a l o f th e e n t i r e

g ro u p .

c u rv e s i n t h i s

s o lv e n t

T he d a t a a r e p l o t t e d i n

F i g u r e s 13 a n d 14. a n d t a b u l a t e d i n T a b l e 6 .

T h ese do n o t r e a c h th e

c r i t i c a l s o l u t i o n te m p e r a tu r e a t th e n o rm a l c o n c e n t r a t i o n , a p p r o x im a te ly 50 w e ig h t p e r c e n t h y d r o c a r b o n f o r m o s t m i x t u r e s , b u t see m t o h a v e a n in f le c tio n p o in t a t ab o u t t h i s

c o m p o s itio n .

I t v;as o n l y f o r n - h e p t a n e

a n d m e th y lc y c lo h e x a n e t h a t a maximum p o i n t i n t h e s o l u b i l i t y v s . t e m p e r a ­ tu re

( ° C . ) c u r v e s w as f o u n d , a n d t h e s e

cam e a t a b o u t 7 7 p e r c e n t a n d 8 8

p e r c e n t h y d ro c a rb o n , r e s p e c tiv e ly . For

n -p e n ta n e a p r e s s u r e o f

ta in e d a t a h y d ro c a rb o n

c o n c e n tra tio n

125 l b s . p e r s q .i n .

g a g e w as o b ­

o f 63 p e r c e n t . T h i s p r e s s u r e h a d

b e e n f i x e d a s t h e maximum a t w h ic h t h e a p p a r a t u s c o u l d b e o p e r a t e d s a f e l y . The a s s e m b le d a p p a r a t u s w a s t e s t e d a t 2 0 0 l b s . p e r s q . i n . t e m p e r a t u r e b e f o r e i t w as u s e d .

g a g e a t ro o m

The m i s c i b i l i t y te m p e r a tu r e f o r th e

s a m p le c o n t a i n i n g 84- p e r c e n t t r i m e t h y l e t h y l e n e w as q u i t e d i f f i c u l t t o d e t e r m i n e a n d t h e r e f o r e no maximum f o r t h i s

c u r v e w as f o u n d .

T he i s o p r o p y l b e n z e n e w as t h e m o s t a b n o r m a l o f a l l t h e h y d r o ­ c arb o n s.

M ien a d d i n g t h e i s o p r o p y l b e n z e n e t o t h e s o l v e n t a t ro o m t e m p e r ­

a t u r e , t h e tw o w e re m i s c i b l e u n t i l a c o m p o s i t i o n o f a b o u t 9 2 w e i g h t p e r c e n t h y d r o c a r b o n w as o b t a i n e d . c lo u d in e s s a p p e a re d i n th e

On f u r t h e r a d d i t i o n o f h y d r o c a r b o n a

s a m p le a n d t h e p o i n t s w e re d e t e r m i n e d a s

F ig u r e No. 13 140

HYDROCARBON SOLUBILITY IN METHYL CARBITOL

120

100

Temperature, °C

80

-bic^iej &na:

Ui

60

40

+20

K*

0

T* -2 0

T;i ? £ T ; >■0 U * » W H f * 1 fW~-8WTfcT*«JW M I PgwtetU ^ W .... i i M W ti'fe '+ W 3

0

20

n rp

r!

•: ’

I:

;

40 60 W eigh t P er C ent S o l u b i l i t y

80

100

Weight Per Cent Solubility, Hydro carbon in Methyl Carbitol

Figure No. 14 SOLUBILITY OF HYDROCARBONS IN METHYL CARBITOL

1/°K. x 10

(CH3C

Figure No. 14 [TY OF HYDROCARBONS IN METHYL CARBITOL (GH3OCH2CH2OCH2CH2OH)

43

:'etrol rum;Re:Injjig Laborutoiy ibislPaiasyiviini^ Siat^ Cullfege iState ioileg fenisyj.Taid.a|

r+;>o 3.20

3.40

3.60 1/°K. x 103

3.80

4.00

A. 20

4.40

4.60

-44T a b le N o. 6 M

P l b

E T H Y L

r e

s

s

u

r e

.

/

i

n

. 2

C

A

R

W

— — . — — . — — —

21 23 22

I T O

e

e t h

L — H Y D R O C A R B O N

i g

h

t

p

e

r

y

d

r o

c

a

r b

H

M

— .

B

y

l c

y

c

l o

h

c

e

o

e

n

M

I S

t

M

x

a

n

—

23 25 28 36 38 38 ' 36

i s

I L

c

I T

i b

Y

T

°C .

l/° K .

o

n

c

l u

d

e

e

m

p

e

r a

- 1 8 .1 + 1 8 .5 5 2 .8 6 5 .2 7 1 .5 7 9 .1 8 3 .8 9 3 -9 1 0 4 .2 1 1 0 .2 1 0 7 .7 , • , 9 1 .0 ( ± 0 .3 )

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

4 7 .7 6 1 .5 7 8 .4 9 5 .8 1 0 6 .9 1 1 2 .6 1 1 8 .5 1 2 6 .3 1 3 0 .3 1 2 9 .0 1 2 4 .5 ( ± 0 .3 )

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

d

o n

n

e

x

3 7 .0 7 6 .4 9 4 -0 1 0 2 .7 1 1 2 .4 1 2 2 .4 above 124

t

p

a

g

e

)

t u

r e

x IQ 3

-

9 .8 6 1 7 .9 9 2 6 .6 8 3 7 .6 2 ( e q . v o l .) 4 9 .5 9 6 2 .9 3 8 5 .2 8

( C

P E R A T U R E S

i l i t y

n —P e n t a n e 11 45 73 78 100 123 125

T E M

e

8 .0 3 1 0 .3 9 1 4 .2 6 1 9 .8 7 3 0 .3 0 3 9 -7 4 (e q . v o l.) 5 2 .4 7 6 4 .3 2 7 4 .8 0 8 3 .7 9 8 9 .3 1

—

I B

n

6 .1 9 1 0 .0 3 1 9 .1 7 2 5 .6 1 3 1 .2 6 4 3 .3 7 ( e q . v o l- ,) 5 4 .4 2 6 9 .5 2 7 9 .0 6 3 7 .4 9 9 1 .2 1 9 6 .6 6 n —H e p ta n e

—

C

3 -2 2 4 2 -8 6 0 2 .7 2 3 2 .6 60 2 .5 9 3 2 .5 2 8

15 T a b le N o. 6 v tE T H Y L

C

A

R

B

I T O

L — H Y D R O C A R B O N

M

I S

C

I B

I L

I T

Y

T E M

P E R A T U R E S

( C o n c lu d e d ) P ressu re lb ./in 2

W e ig h t p e r c e n t H y d ro c a r b on

M i s c i b i l i t y T e m p e ra tu re °C . l / ° K . x IQ 3

T r im e t h y l e t h y l e n e — — — .

6 10 12 22 62

9 -6 5 1 8 .2 8 2 5 .8 0 3 2 .2 9 3 8 . 9 7 ( e q '. v o l . ) 5 8 .7 5 7 0 .9 2 8 1 .1 7

- 1 7 .7 - 1 .0 2 0 .6 3 1 .1 3 7 .5 1 9 -7 5 9 .1 9 1 .5 ( ± 0 .5 )

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

b e lo w —5 6 ° C. -1 8 .8 + 1 9 .1 3 8 .6 3 8 .7

3 .9 3 1 3 .1 2 1 3 -2 0 7 3-206

• Is o p ro p y lb e n z e n e 7 7 .8 2 8 7 .1 5 9 1 .7 1 9 1 .1 8 9 6 .7 1 T o lu e n e 1 5 .6 6 ( e q . v o l .)

b e lo w —6 5 ° C .

4-6

I n

d

i c

a

t e

d

.

S a m p le s w i t h l e s s h y d r o c a r b o n w e r e m i s c i b l e a s lo w a s - 6 0 ° C . ;

sa m p le s w i th h i g h e r p e r c e n t a g e s o f h y d r o c a r b o n t h a n t h e l a s t o n e p l o t t e d d id E

q

u

n

a

o

l

t

show a r e p r o d u c i b l e m i s c i b i l i t y

(o r im m is c ib ility )

v o lu m e s o f t o l u e n e a n d m e t h y l c a r b i t o l w e r e m i s c i b l e b e lo w —6 5 ° C . A c o m p a ris o n o f t h e l o g a r i t h m i c p l o t ,

F i g u r e 14-, w i t h t h e

s i m i l a r o n e f o r m e th y l a l c o h o l ,

F ig u re 1 2 ,

tw o c o m p o u n d s h a v e som e s i m i l a r

s o lv e n t p r o p e r tie s .

p o rtio n s o f th e th a t Is ,

s o lu b ility

seem s to

in d ic a te

a t lo w s o l u b i l i t i e s ,

a m uch l a r g e r s o lu b ility .

tw o s o l v e n t s ,

change In te m p e ra tu re i s

In

a d d itio n ,

te m p e ra tu re f o r e a c h h y d ro c a rb o n h a s b e e n s h i f t e d

h y d r o c a ir b o n p e r c e n t a g e s , b e t w e e n 7 5 a n d 9 0 p e r c e n t ; te m p e ra tu re o f th e h y d ro c a rb o n s i n

t h a t th e s e

The s t r a i g h t - l i n e

c u r v e s a r e m uch f l a t t e r . f o r t h e s e

q u ire d f o r - a g iv e n change I n tio n

te m p e ra tu re .

th e to

c ritic a l

re ­ s o lu ­

th e h ig h e r

th e c r i t i c a l

s o lu tio n

th e o t h e r s o l v e n t s w as a t a p p r o x im a te ly

50 w e ig h t p e r c e n t h y d r o c a r b o n . 7*

M e th y l C e l l o s o l v e ' T h is s o l v e n t seem s t o

h a v e th e n o rm a l s o l u b i l i t y

a s c an be s e e n fro m F ig u r e s 15 an d 1 6 .

The l e a s t

s o lu b le i s

w ith n -p e n ta n e an d m e th y lc y c lo h e x a n e b e in g i n c r e a s i n g l y v o lu m e p e r c e n t m i x t u r e o f t r i m e t h y l e t h y l e n e

in

c h a ra c te ris tic s

th e

n -h e p ta n e ,

s o lu b le .

A 50

s o l v e n t w as im m is c ib le

b e lo w —3 6 . 5 ° C. w h ic h w a s s o lo w t h a t no f u r t h e r d e t e r m i n a t i o n s w e r e m a d e . E q u a l v o lu m e m i x t u r e s o f t h e th e

a ro m a tic s ,

to lu e n e

an d is o p r o p y lb e n z e n e , w ith

s o l v e n t f r o z e a t —6 0 ° C . w i t h n o s e p a r a t i o n o f a s e c o n d l i q u i d

above t h a t te m p e ra tu re . T a b le 7 .

The d a t a f o r t h i s

p h ase

s o lv e n t w ill be fo u n d i n

U7

F ig u r e N o. 15 HYDROCARBON SOLUBILITY IN METHYL CELLOSOLVE

+20

Temperature, °C

M eth y l c y c lo l-

20

T r i a e t h y l e t h y l e cie ■10

p e t PoUetBi --ftepaa fcB^rLafcoratopy j j v a h i aa. Srtat es : C o llje g e The Pettns fjrllvani S t a t e C o l teg ie, ftugjtiati :15,::3.j?42

-60 0

20

60 Weight Per Cent Solubility

80

100

Weight Per Cent Solubility, Hydrocarbon in Methyl Cellosolve to

o

oa

I— 1

o

T OO

V jJ o

o

S

8

SOLUBILITY OF HYDROCARBONS IN METHYL CELLOSOLVE

o

•-3

M I-1 O

(CH30CH2CH20H)

fO o

v_o

CO CKJ

O

49 Table No. 7 METHYL CELLO SOLVE—HY DRO CARBON .M ISC IB IL IT Y TEMPERATURES W e ig h t p e r c e n t H y d ro c a rb o n _

M i s c i b i l i t y T e m p e ra tu re °C . l / ° K . x IQ 3

M e th y lc y c lo h e x a n e 1 1 .1 1 2 1 .6 9 31*46 4 4 .5 9 (e q . v o l.) 6 3 .3 2 7 7 .5 3 8 9 .16

•

-2 1 .0 ( ± 0 .3 ) + 7 .3 1 9 .O 2 3 .8 2 4 .6 2 2 .7 1 3 .2

3 -9 6 5 3 .5 5 9 3 .422 3*367 3-358 3 .3 8 0 3 .4 9 2

n —H e p t a n e 9 .9 5 1 5 .6 1 2 8 .1 5 41*5 2 (e q . v o l.) 6 0 .9 3 ; 8 0 .7 9 9 0 .3 6 n —P e n t a n e 1 2 .4 0 2 0 .2 8 3 1 .4 9 3 9 .3 2 ( e q . v o l .) 5 9 .9 4 7 6 .7 8 8 9 .3 8

5 .8 2 4 -8 4 2 .3 4 6 .5 4 6 .8 3 9 .9 2 6 .0

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

- 7 .1 + 1 4 -6 2 7 .2 3 0 .1 3 1 .3 2 7 .8 1 6 .0

3 .7 5 8 3 .4 7 5 3 .3 2 9 3 ,2 9 7 3 .2 8 4 3 .3 2 2 3 .460

T rim e th y le th y le n e 4 0 .7 5 ( e q . v o l.)

- 3 6 .5 ( + 0 .5 )

T o lu e n e 4 7 .3 4 (e q . v o l .)

fro ze

—6 0 ° C .

fro ze

-6 0 °C .

Is o p ro p y lb e n z e n e 4 7 .2 Q ( e q . v o l . )

•

4 .2 2 5

50

8.

P henyl C e llo s o lv e The d a t a f o r t h e h y d r o c a r b o n s o l u b i l i t i e s

a re p lo tte d fin s

in p h en y l c e llo s o lv e

i n F i g u r e s 1'7 a n d 1 8 a n d r e p o r t e d i n T a b l e 8 .

a g a in a r e th e l e a s t s o lu b le w ith

T he tw o p a r a f ­

th e n -p e n ta n e b e in g l e s s

s o lu b le

ab o v e 26 w e ig h t p e r c e n t h y d ro c a rb o n an d th e n - h e p ta n e b e in g l e s s b e lo w t h i s

c o m p o s itio n .

m e th y le th y le n e . m ix tu re s ,

N ex t i n o r d e r a r e m e th y lc y c lo h e x a n e an d t r i —

The t o l u e n e an d is o p r o p y lb e n z e n e ,

s o lid ifie d

in

5 0 v o lu m e p e r c e n t

a t —2 0 ° C . a n d —2 ° C . , r e s p e c t i v e l y .

T he c u r v e s i n F i g u r e 1 8 i l l u s t r a t e re la tio n s h ip

s o lu b le

b e tw e e n l / ° K .

and th e lo g a rith m

lo w e r h y d ro c a rb o n s o l u b i l i t i e s .

v e ry c le a r ly o f th e

th e l i n e a r

s o lu b ility

a t th e

F ig u re

N o. 17

HYDROCARBON SOLUBILITY IN PHENYL CELLOSOLVE

100

Temperature, °C

80

+20

p

20

^

t r

o

i : e

j 4

i a

;

The-' ?eh n sy sjb at a ■C o l l fegal- •Pkobi A iigu at 15> 1 9& Z !; 0

20

60 Weight Per Cent Solubility AO

80

100

figure No. 18 52

SOLUBILITY Of HYDROCARBONS IN PHENYL CELLOSOLVE (C ^O C H j CHj OH) 100 80

60

40

30

20

15

■

4 \

10 8

5

6

4

3

in Hycroterlon

2

Teapeirat iKXr i

80;

6b

1

3.20

3.40

l/°K. x 103

3.80

4.00

Table No. 8 PHENYL CELLOSOLVE-HYJJROCARBON M ISC IB IL ITY TEMPERATURES

P ressu re lb ./in .2

w e ig h t p e r c e n t H y d ro c a rb o n

f. ' I i s c i b i l i t y T e m p e r a tu r e °C . 1 /° K . x 1 0 3

M e th y lc y c lo h e x a n e S. 17 1 7 .3 3 2 9 .2 5 42 .'13 ( eq . v o l . ) 5 0 .4 8 6 3 .2 7 7 4 -8 0 8 4 .9 7 9 1 .4 7

- 2 .3 + 3 2 .4 4 7 .4 5 2 .2 5 2 .6 5 2 .5 50.6 4 A -5 34--8

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

4 0 .2 6 2 .8 8 4 .6 9 2 .7 9 4 .6 94*4 9 0 .7 7 9 .0 6 1 .3

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

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

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

n - H e p ta n e 7 -9 5 1 2 .1 9 2 1 .7 3 3 0 .8 9 3 9 -4 4 (e q . v o l.) 5 5 .3 9 7 0 .3 1 8 2 .6 3 9 0 .8 7 n —P e n t a n e 16 47 73 76 72 58 25

1 0 .9 5 2 3 .1 0 3 6 .2 8 (e q . v o l .) 4 9 .1 6 6 6 .3 8 7 7 .8 5 8 9 .6 3

( C o n c lu d e d o n n e x t p a g e )

54T a b l e N o. 8 PHENYL. CELLO SOL VE—HYDROCARBON M IS C IB IL IT Y TEMPERATURES ( C o n c lu d e d )

P ressu re lb .P in .

W e ig h t p e r c e n t Hydr o c a r b on __

M is c ib ility °C .

T e m p e ra tu re l/° K . x 103 •

T rim e th y le th y le n e S ..40 fro z e -1 9 1 2 .6 5 —1 0 . 1 1 5 .5 3 - 0 .2 2 7 .7 1 + 2 4 .6 3 3 .4 2 ( e q . v o l .) 3 1 .3 5 1 .8 8 3 2 .8 6 3 .2 7 3 2 .0 7 4 -8 1 2 7 .7 8 5 .9 1 1 7 .2 9 2 .3 1 3 .6 T o lu e n e 4 3 -9 1 (e q . v o l.)

fro z e -2 0 °C .

Is o p ro p y lb e n z e n e 4 3 -7 6 (e q . v o l.)

f r o z e —2 ° C .

3*801 3 .6 6 3 3 .3 5 8 3 .2 7 9 3*263 3 .2 7 7 3 -3 2 3 3 -4 4 4 3 .6 1 3

55 C.

CONCLUSIONS E v en th o u g h t h i s i n v e s t i g a t i o n w as l i m i t e d

to

th e d e te r m in a tio n

o f t h e s o l u b i l i t y o f s i x h y d r o c a r b o n s i n e i g h t o r g a n i c c o m p o u n d s , w h ic h serv ed a s s o l v e n t s ,

t h e d a t a se e m t o

in d ic a te

th a t c e rta in d e f in ite

con­

c l u s i o n s m ay b e d r a w n . The f i r s t a n d m o st g e n e r a l c o n c lu s io n i s carb o n s o l u b i l i t i e s ,

t h a t f o r lo w h y d r o ­

b e lo w 2 0 w e i g h t p e r c e n t i n m o s t c a s e s , , t h e d a t a

f a l l o n a s t r a i g h t l i n e w hen t h e l o g a r i t h m

o f th e

s o lu b ility is

p lo tte d

v e rsu s th e r e c i p r o c a l o f th e a b s o lu te te m p e r a tu r e . S e c o n d , th e a ro m a tic h y d ro c a rb o n s w e re m is c ib le i n t h e l i q u i d p h a s e t o a t l e a s t —6 0 ° C ., w h e n s a m p l e s c o n t a i n i n g

5 0 v o lu m e p e r c e n t

h y d ro c a rb o n w e re u s e d .

I n som e c a s e s , w h en t h e

h ig h f r e e z i n g p o i n t , i t

s e p a r a t e d fro m th e m ix tu r e a s a s o l i d p h a s e .

The o l e f i n ,

s o lv e n t had a r e l a t i v e l y

t r i m e t h y l e t h y l e n e , w a s t h e m o s t s o l u b l e a n d n —h e p t a n e w as

th e l e a s t s o lu b le o f th e re m a in in g f o u r h y d r o c a r b o n s . In

s ix o f th e

n -p e n ta n e ; i n

s o l v e n t s m e t h y l c y c l o h e x a n e w a s m o re s o l u b l e t h a n

t h e r e m a i n i n g tw o , a c e t o n i t r i l e

an d m e th y l a lc o h o l ,

o r d e r w as r e v e r s e d , w i t h n - p e n t a n e b e i n g t h e m o re s o l u b l e o n e . le a d s to c arb o n i n

th e th ir d

c o n c lu s io n ; n a m e ly , t h a t th e s o l u b i l i t y

th is

T h is

o f a h y d ro ­

t h e s e tw o l o w e r m o l e c u l a r w e i g h t s o l v e n t s d e p e n d s o n t h e

o f th e h y d ro c a rb o n m o le c u le r a t h e r th a n o n th e ty p e o f m o le c u le .

s iz e T hus,

t h e tw o 7 —c a r b o n m o l e c u l e s , o n e a p a r a f f i n a n d t h e o t h e r a n a p h t h e n e h a v e m o re n e a r l y t h e

sam e s o l u b i l i t y

a n a 5 c a r b o n a to m s r e s p e c t i v e l y . th e m i s c i b i l i t y

t h a n d o t h e tw o p a r a f f i n s , o f 7

F u r t h e r e v id e n c e o f t h i s i s

fo u n d i n

t e m p e r a t u r e s w h ic h w e r e d e t e r m i n e d f o r e a u i —v o lu m e

m ix tu re s o f e a c h o f t h e

s i x h y d r o c a r b o n s w ith a c e to n e an d w e re a s f o ll o w s :

56 n -h e p ta n e - 2 0 ° C .,

m e th y lc y c lo h e x a n e - 2 6 ° C . , n -p e rx ta n e - 3 8 ° C . , a n d t h e

r e m a in in g t h r e e w e r e b e lo w - 6 0 ° C . is e x h ib ite d i n

th re e

k e to n e ( a c e t o n i t r i l e ,

S in c e t h i s

ty p e s o f s o lv e n t s ,

sam e o r d e r o f s o l u b i l i t y

a c y a n id e , a n a lc o h o l, and a

m e th y l a lc o h o l a n d a c e to n e , r e s p e c t i v e l y )

i t m ust

be a r e s u l t o f t h e i r lo w m o l e c u l a r w e i g h t , £ ± , 3 2 , a n d 58 r e s p e c t i v e l y . T hese r e s u l t s

seem t o i n d i c a t e

t h a t f o r t h e lo w m o l e c u l a r w e i g h t

s o l v e n t s t h e s e l e c t i v i t y m ay b e i n f l u e n c e d d iffe re n c e in h y d ro c a rb o n s iz e .

T hat is ,

lo w e r m o l e c u l a r w e i g h t s o l v e n t s t o

to a c o n s id e ra b le e x te n t b y a it

e f f e c t s e p a r a t i o n s o f m o le c u le s o f th e

sam e t y p e , b u t d i f f e r e n t m o l e c u l a r w e i g h t s . fe c tiv e fo r th is

m ay b e p o s s i b l e t o u s e t h e

T h e y m ay b e e v e n m o re e f ­

t y p e o f s e p a r a t i o n t h a n f o r t h e s e p a r a t i o n o f tw o h y d r o ­

carb o n s o f d i f f e r e n t ty p e s .

T h is t r e n d i s

a l c o h o l , f o r w h ic h t h e

c ritic a l

35°C . lo w e r th a n i t

f o r n—h e p t a n e .

is

m o st m a rk e d f o r t h e m e th y l

s o l u t i o n te m p e ra tu re o f n -p e n ta n e i s I n m ost o th e r s o lv e n ts th e c r i t i ­

c a l s o lu tio n te m p e ra tu re s f o r th e p a r a f f i n h y d ro c a rb o n s d i f f e r by o n ly a fe w d e g r e e s a n d f o r a n i l i n e t h e e n t i r e

c u rv e s f o r th e

th re e p a ra ffin s a re

a lm o s t i d e n t i c a l . I n c o n tr a s t to

th e above g e n e r a liz a tio n ,

a lm o s t i d e n t i c a l s o l u b i l i t i e s in p henyl c e llo s o lv e .

in a n ilin e

F o r b o th o f th e

th e p a r a f f in s have

and v e ry s im ila r s o l u b i l i t i e s

s o lv e n ts , th e

s o l u b i l i t y c u rv e f o r

n - p e n t a n e c r o s s e s t h a t f o r n —h e p t a n e a t a p p r o x i m a t e l y 2 6 o r 2 7 w e i g h t p e r c e n t h y d ro c a rb o n . m ore s o l u b l e ;

T h i s m e a n s t h a t b e lo w t h i s

above t h i s

c o m p o s i t i o n , n —p e n t a n e i s

p o i n t t h e n —p e n t a n e i s l e s s

c o rre s p o n d in g ly h ig h e r c r i t i c a l s o l u t i o n te m p e ra tu re .

s o lu b le and h a s a S in c e t h i s

o c cu rs

o n l y f o r t h e s e tw o s o l v e n t s , a n d t h e y a r e t h e o n e s w h ic h c o n t a i n a p h e n y l g r o u p , C5H5- ,

th is

p e c u lia rity

in

s o l u b i l i t y m ay b e d u e t o

th is

g ro u p .

57 IV . A.

TERNARY EQUILIBRIUM RELATIONSHIPS

APPARATUS AND PROCEDURE T he a p p a r a t u s u s e d t o d e t e r m i n e t h e e q u i l i b r i u m

v a rio u s t e r n a r y

s y s te m s i s

sh o w n i n F i g u r e 19«

d a ta f o r th e

The t h r e e

c o m p o n e n ts w e r e

brought t o e q u i l i b r i u m i n a P y r e x g l a s s t u b e 1—1 / 2 i n c h e s i n d i a m e t e r a n d 12 i n c h e s i n l e n g t h . t u r n w as f a s t e n e d p h a s e s , w as h e l d

T h is tu b e w as f a s t e n e d

to a d r i l l p r e s s . by th e d r i l l

to

a f l a n g e p l a t e w h ic h i n

The s t i r r e r ,

w h ic h a g i t a t e d

t h e tw o

ch u ck and p a s s e d th ro u g h a s t u f f i n g

w h ic h w as b r a z e d t o t h e f l a n g e t o p .

box

The c h a r g in g an d s a m p lin g tu b e s a n d

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

th e tu b e .

The

t e m p e r a t u r e o f t h e m i x t u r e w a s d e t e r m i n e d b y a 5—j u n c t i o n t h e r m o c o u p l e c o n n e c te d t o

a m illiv o ltm e te r.

To t h e r e m a i n i n g o u t l e t w e r e c o n n e c t e d a

p re s s u re g a g e , a p r e s s u r e r e l i e f v a lv e an d a c o m p re sse d a i r l i n e . Two b a t h s w e r e p r o v i d e d f o r m a i n t a i n i n g t h e e q u i l i b r i u m a t a c o n s ta n t te m p e ra tu re .

O ne o f t h e s e w a s a w a t e r b a t h u s e d f o r

t e m p e r a t u r e s a b o v e ro o m t e m p e r a t u r e ;

t h e o t h e r w a s a d r y —i c e —a c e t o n e b a t h

w h ic h w as u s e d f o r t h e l o w e r t e m p e r a t u r e s . fro m b u r e t t e s a l s o

m ix tu re

T he h y d r o c a r b o n s w e r e c h a r g e d

im m e r s e d i n a w a t e r b a t h w h ic h w a s k e p t a t 2 0 .0 9 C . b y

a n im m e r s io n h e a t e r w h ic h w a s o p e r a t e d b y a r e g u l a t o r a n d r e l a y h o o k u p . The s o l v e n t w a s c h a r g e d b y w e i g h t f r o m a s m a l l f l a s k . a p p a ra tu s i s

d e s c rib e d i n

d e ta il in

The c o m p le te

t h e A p p e n d ix , S e c t i o n B.

T h e s o l v e n t s a n d h y d r o c a r b o n s u s e d w e r e t h e sam e o n e s a s w e re u sed i n t h e

s o lu b ility

s t u d i e s , w h ic h w e r e d i s c u s s e d i n

th e p re v io u s

s e c tio n . P r e l i m i n a r y c a l c u l a t i o n s w e re m ade f o r e a c h r u n t o th e a m o u n t o f e a c h c o m p o n e n t t o b e u s e d .

d e te rm in e

T he h y d ro c a rb o n s w e re th e n

58 F i g u r e N o. 19 EQUILIBRIUM APPARATUS

59 fo rc e d fro m th e a i r and th e

s to ra g e b u r e tte s in to

th e

e q u ilib riu m

s o l v e n t a d d e d fro m a t a r e d f l a s k .

tu b e b y c o m p re sse d

T he m i x t u r e w a s s t i r r e d

fo r a t l e a s t 15 m in u te s a f t e r i t h a d r e a c h e d th e d e s i r e d in d ic a te d by th e m illiv o ltm e te r re a d in g . s e ttle

te m p e ra tu re , a s

T he m i x t u r e w a s t h e n a l l o w e d t o

f o r a t l e a s t 15 m in u te s , o r u n t i l th e p h a se s h ad s e p a r a te d r e l a ­

tiv e ly w e ll. B e f o r e t a k i n g o f f t h e s a m p l e s , t h e v o lu m e s o f t h e e x t r a c t a n d r a f f i n a t e p h a s e s w e re d e te r m in e d fro m t h e b riu m t u b e .

s c a le re a d in g s on th e e q u i l i ­

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

th e e x t r a c t p h a s e a n d t h e o t h e r i n t o

th e r a f f i n a t e .

O n ly p o r t i o n s o f

each p h a s e w e re w ith d ra w n f o r a n a l y s i s a n d t h e s e w e re re m o v e d w ith e x tr e m e c a r e t o p r e v e n t c o n t a m i n a t i o n o f o n e p h a s e b y t h e o t h e r . s a m p le s o f e a c h p h a s e w e r e f o r c e d i n t o a f t e r th e h o ld u p i n

th e li n e s had been d is c a rd e d .

serv ed a s c h e c k s on th e a n a ly s is . in to

a ta re d

ta re d fla s k s

d e n s ity f la s k

A th ird

Two

sh o w n i n F i g u r e 2 0 a T h e s e tw o s a m p l e s

s a m p le o f e a c h p h a s e w a s t a k e n

show n i n F i g u r e 2 0 b .

A fte r th e s e

s a m p le s i n

th e d e n s i t y f l a s k s h a d b e e n k e p t a t t h e te m p e r a tu r e o f t h e r u n f o r a h a lf h o u r th e

s c a l e r e a d i n g w as r e c o r d e d a n d t h e f l a s k s w e i g h e d .

F ro m

th e s e d a t a t h e d e n s i t i e s w e re c a l c u l a t e d . The v o lu m e tr ic f l a s k s

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

w ere r e w e i g h e d t o d e t e r m i n e t h e t o t a l w e i g h t o f e a c h s a m p l e .

T he s o l v e n t

i n e a c h s a m p l e w a s t h e n re m o v e d f r o m t h e h y d r o c a r b o n b y a d d i n g a s u i t a b l e l i q u i d w h ic h w o rild d i s s o l v e s o lv e n ts ,

th e s o lv e n t.

su c h a s m e th y l c e l l o s o l v e ;

re m o v e d f u r f u r a l a n d a c e t o n y l a c e t o n e j

W a te r w a s u s e d f o r som e o f t h e

a 1 5 p e r c e n t s o l u t i o n o f NaHS03 a n d m e t h y l a l c o h o l w a s re m o v e d w i t h

Figure No. 20

(a ) A n a l y t i c a l F la s k s

(b ) D e n s ity F la s k

S'

61

a 5 P e r c e n t s o l u t i o n of* C a C l2 s e t c . s o l v e n t - f r e e h y d r o c a r b o n w as f l o a t e d th e f l a s k

( a s e c t i o n o f a 50 c c .

( S e e A p p e n d ix , S e c t i o n C) up in to

th e

T he

c a lib r a te d neck o f

b u r e tte had b een s e a le d to

th e b a se

o f a 1 0 0 c c . v o l u m e t r i c f l a s k ) w h e r e t h e v o lu m e c o u l d b e r e a d .

The

d e n s i t y a n d c o m p o s itio n o f t h e h y d ro c a rb o n w e re d e te r m in e d fro m t h e re fra c tiv e

in d e x a s m e a s u re d o n a n A b b e -ty p e S p e n c e r r e f r a c t o m e t e r .

T a b l e s 4-6, 4 7 , a n d 4 8 w h ic h c o r r e l a t e d

t h e s e p r o p e r t i e s w e re u s e d .

From t h e d a t a t h u s o b t a i n e d t h e c o m p o s i t i o n o f e a c h p h a s e a n d t h e s e le c tiv ity fa c to r,

b e t a , w e re c a l c u l a t e d .

T he w e i g h t o f e a c h p h a s e

w as c a l c u l a t e d f r o m t h e v o lu m e a n d d e n s i t y m e a s u r e m e n t s , a n d f i n a l l y a m a t e r i a l b a l a n c e w a s m ade a n d c o m p a r e d w i t h t h e o r i g i n a l w e i g h t o f e a c h com ponent c h a r g e d . The d a t a o b t a i n e d f o r e a c h t e r n a r y

s y s te m w e re p l o t t e d

on a

t r i a n g u l a r d ia g ra m , w ith th e u p p e r v e r t e x r e p r e s e n t i n g th e m o st s o lu b le h y d ro c a rb o n , th e lo w e r l e f t h a n d v e r t e x th e l e a s t s o lu b le h y d ro c a rb o n an d th e lo w e r r i g h t h a n d v e r t e x t h e

s o lv e n t.

The is o t h e r m a l s o l u b i l i t y

c u r v e d ra w n t h r o u g h t h e p o i n t s s e p a r a t e d t h e h o m o g e n e o u s a n d h e t e r o ­ g e n e o u s a r e a s o f t h e d i a g r a m a n d t h e t i e —l i n e s re p re s e n tin g th e

c o n n e c te d th e p o i n t s

c o m p o s itio n s o f th e c o n ju g a te p h a s e s .

w e re o n a w e i g h t b a s i s .

A ll c o m p o s itio n s

62 B.

RESULTS AND DISCUSSION T e rn a ry e q u ilib r iu m

r e l a t i o n s h i p s w e re d e te r m in e d f o r e ac h o f

th e th r e e b i n a r y h y d r o c a r b o n s y s te m s , m e th y lc y c lo h e x a n e - n - h e p ta n e , to lu e n e -m e th y lc y c lo h e x a n e an d t r i m e th y l e th y le n e - n - p e n ta n e , each o n e o f t h e s o l v e n t s ,

e x c e p t m e th y l a l c o h o l .

to g e th e r w ith

T he i m m i s c i b i l i t y

t e m p e r a t u r e s f o r t h e l a s t tw o b i n a r y h y d r o c a r b o n s y s t e m s i n m e t h y l a l c o h o l w e r e so low ' t h a t n o e q u i l i b r i u m

d a t a c o u ld b e o b t a i n e d f o r t h e s e

s y s te m s . T h e m a in o b j e c t o f t h i s e a r l i e r , w as to

c o m p a re t h e

o r d e r t o do t h i s ,

it

in v e s tig a tio n , as h as been s ta te d

s e le c tiv ity

w as n e c e s s a r y t o

v a r i a b l e s , w h ic h a f f e c t s e l e c t i v i t y ,

o f v a r io u s ty p e s o l v e n t s .

In

e l i m i n a t e a s m any o f t h e o t h e r as p o s s ib le .

by T e g g e ( 2 1 ) , t h a t f o r s o m e s y s t e m s , t h e

I t h a s b e e n sh o w n

s e le c tiv ity

fa c to r,

b e ta ,

v a rie s c o n s id e r a b ly w ith a ch an g e i n h y d ro c a rb o n s o l u b i l i t y . T h is s o l u b i l i t y

is

d e p e n d e n t on th e te m p e ra tu re and a ls o on

th e c o m p o s itio n o f t h e o r i g i n a l h y d ro c a rb o n c h a r g e .

As t h e t e m p e r a t u r e

i s i n c r e a s e d , a g i v e n h y d r o c a r b o n m i x t u r e w i l l b e co m e m o re a n d m o re s o lu b le .

A s s u m in g t h a t t h e

te m p e ra tu re be h e ld

s o l u b i l i t y m ay s t i l l b e i n c r e a s e d s o lu b le h y d ro c a rb o n i n

c o n s ta n t,

by in c r e a s in g th e

th e h y d ro c a rb o n

a m o u n t o f t h e m o re •

th e c h a rg e .

F rom a k n o w le d g e o f t h e

s o l u b i l i t y o f e ac h p u re h y d ro c a rb o n

i n t h e s o l v e n t , w h ic h h a d b e e n d e t e r m i n e d d u r i n g t h e f i r s t p a r t o f t h e in v e s tig a tio n , th e re s u lte d

t e m p e r a t u r e a t w h ic h a g i v e n h y d r o c a r b o n s o l u b i l i t y

c o u ld b e e s t i m a t e d r e a d i l y .

T h is w as o n ly p o s s i b l e , h o w e v e r,

f o r t h o s e s y s t e m s o f w h ic h b o t h h y d r o c a r b o n s w e r e o n l y p a r t i a l l y m i s c i — b le w ith th e s o l v e n t ,

f o r e x a m p l e , m e t h y l c y c l o h e x a n e —n —h e p t a n e —

63 a c e to n itrx le .

In

th e

c a se o f th o s e

s y s t e m s i n w h ic h t o l u e n e w a s o n e

o f th e c o m p o n e n ts, no su ch e s t i m a t i o n an d s o l v e n t w e r e c o m p l e t e l y m i s c i b l e . t e m p e r a t u r e w as s e l e c t e d

c o u l d b e m ad e s i n c e t h e t o l u e n e W henever p o s s i b l e , a n e x t r a c t i o n

su ch t h a t th e h y d ro c a rb o n s o l u b i l i t y i n

th e

e x t r a c t p h a s e w o u ld b e 1 5 w e i g h t p e r c e n t w h en t h e o r i g i n a l h y d r o c a r b o n c h a r g e c o n t a i n e d e q u a l w e i g h t s o f e a c h c o m p o n e n t. .

1.

T he S y s t e m s :

M e t h y l c y c l o h e x a n e —n —H e p t a n e - S o l v e n t

O ne s e r i e s o f e q u i l i b r i u m t u r e w as m ade fo x ' e a c h o f t h e m ix tu re .

In a d d itio n ,

d e te r m in a tio n s a t c o n s ta n t te m p e ra ­

e i g h t s o lv e n ts w ith t h i s

b in a ry h y d ro c a rb o n

t h e e f f e c t o f - t e m p e r a t u r e o n a t e r n a r y s y s t e m w as

s t u d i e d b y m a k in g a s e r i e s o f r u n s , u s i n g a n i l i n e o f th e fo llo w in g te m p e ra tu re s :

1 0 .0 ,

a s th e s o lv e n t, a t each

2 5 . 0 , 3 9 . 0 , a n d 5 0 .0 ° C .

a r e p l o t t e d o n t r i a n g u l a r d i a g r a m s a s sh o w n i n F i g u r e s 2 1 t o s iv e . ta b le

T he p e r t i n e n t d a t a a r e

T hese d a ta in c lu ­

28,

s u m m a r iz e d i n T a b l e s 9 t o 1 6 , w h e r e e a c h

c o n ta in s th e d a ta f o r one is o th e rm a l s e r i e s . F i v e r u n s w e r e m ade f o r

e ach o f th e e ig h t s o lv e n ts w ith th e

o r i g i n a l h y d ro c a rb o n c h a rg e s h a v in g th e fo llo w in g c o m p o s itio n s : 50, 75 and 100 p e r c e n t n - h e p ta n e . e a c h r u n w as e q u a l t o

th e t o t a l w e ig h t o f h y d ro c a rb o n c h a rg e d .

to

th e d a ta i n

T he s o l v e n t s a r e l i s t e d ity ;

i.e.,

m e th y l a lc o h o l h a s th e

In

th is

T s .b le 1 7 . th e o rd e r o f I n c r e a s in g

s e le c tiv ­

s m a lle s t a v e ra g e v a lu e o f b e ta ,

1 .2 2 ,

T he t e m p e r a ­

s e r i e s o f r u n s fo x ’ e a c h s o l v e n t w a s m ade i s

t h e s e c o n d c d lu m n o f t h e t a b l e .

The

s y s te m m ay b e

and p h e n y l c e l l o s o l v e h a s th e l a r g e s t a v e r a g e v a l u e , 1 .3 9 . t u r e a t w h ic h t h e

25,

T he w e i g h t o f s o l v e n t c h a r g e d f o r

s e l e c t i v i t y o f th e v a r io u s s o lv e n ts w ith r e s p e c t to c o m p a re d b y r e f e r e n c e

0,

g iv e n i n

T h e s o l u b i l i t y o f t h e h y d r o c a i 'b o n i n

1 0 0, \ Methylcyclohexane

Run No.

B eta

Weight % Solubility Hyc. in Ext.

Phase D en sity a t 40.0°C . R a ff. E x t. Figure Mo. 21

38-H 30-H 29-H

1 .2 9 1 .2 4 1 .2 4

/ ‘>-H

1 5 .7 15.2 14.2 1 3 .0 11.2

0 .7 5 6 0.7 3 8 0 .7 H 0.6 9 5 0.6 7 9

0.764 0.755 0.754 0.756 0.753

The System 'METHYLCYCLOHEXANE-n-HEPTANEACET0NITRILE

(C o m p o sitio n s on W eight B a s is ) T em p eratu re

4 0 .0 °C .

A tm o sp h eric P r e s s u r e

7 P e tro le u m R e fin in g L a b o ra to ry The P e n n s y lv a n ia S ta te C o lleg e S t a t e C o lle g e , P e n n s y lv a n ia J u ly 2 7 , 1942

s

n-Heptane

7

Acetonitrile 100

O '-

t-

65

T a b le No. 9 SUMMARY OF DA T A fwHEPTANE

«, ME T H Y L C Y C L OH E X A N E

RUN NUMBER

TEMPERATURE,

38-H

°C.

$

i

Y.'T.

ST.

U)

2 ME T H YLCYCLOHEXANE ORIGINAL RAFFINATE ( A ) IB) EXT RACT I As (b;

i

HYDROCARBOf l I N ORIGINAL RAFFINATE ( f t ) IB) EXT RACT (AJ

IN

£

AT TEMPERATURE

OF

RUM

1 5 .2

40 — 12.3 11.3 II.! 1.00

49.1 43.2 43.2

25.8

2 5 .2

55*5 53*5

29.5 29.5

V/T. OF ME T HYLCYCLOHEXANE CHARGED ( C M . ) WT. OF METHYLCYCLOHEXAME RECOVERED ( G M . ) V/T. OF M- H E P T A N E CHARGED ( G M . ) A T . OF Ma H e PTAME RECOVERED ( G M . ) * A T . OF A C E T O N I T R I L E CHARGED ( G K . ) HIT. OF ACET0N1 T R I L E RECOVERED ( G M . ) * TOTAL WEI GHT CHARGED ( G M . ) TOTAL V/EIGHT RECOVERED ( Gf . U) *

AND

1.00

1 3 .0 1.00

0 .0 0 .0 0 .0 0.0 0 .0

1 0 0 .0 1 0 0 .0 1 0 0 .0 IC- 0 . 0 1 0 0 .0

73*7 73*7 78.5 73.3

5 0 .0

50 .0

50 .0

5 0 .0

5 0 .0

95*5 95*7 15.8

94.4 95.0 14.2 14.2

94.0

93.9 91.2

15.6

f94 . 9 95*0 15.2 15.2

50.0

50.0

5 0 .0

4.5 4.3 34.2 34.4

5.1 5.0 84.8 84,8

5.6 5.0

0.756 0.764

74.8

25*2

93.3 13.0

11.3

13.0

11.1

5 0 .0 6.0 6 .1

5 0.0 6* I 8 .8

35.8

37.0

88.7

8 5 .8

8 7 .0

8 8 .9

*

0.758 0.755

0.714 0.754

0.695 0.756

0

,61

0 . 7:

69.3

49.3 67.3

54.4 68.0

55.7 65.3

58.8 64.1

38.7 49.4

39.9 48.3

11.1 11.4

0 .0 0.0 44.0

45.8

OF PHASE ( G M . ) RAFFINATE EXTRACT

A

40 1.24 14.6 13-0

1 5 .6

40 1.24 15.9 14.2 14.2 1.00

( dJ)

VOLUME OF PHASE ( c c . ) RAFFINATE EXT RACT

OF

18.9 15.2

40 1.29 17 . 5 15.2

PHAS E

RAFFINATE EXT RACT

AVERAGE

39-K

HYDROCARBOf l

( b)

4EIGHT

3 1-H

PHASE

AC ETC NI TR ILE IN ORIGINAL RAFFINATE ( A ) ( b) E XT RACT (AJ

DE NS I T Y

29-H

I .00

(B) HT,

ACETCNITRILE

30-H

40

BETA * ST. Y I E L D OF HYDROCARBON AC E X T R A C T * S O L U B I L I T Y I N E XT RACT P H A S E ( 6) S C L V E N T - T O - Q I L RAT i f i BY / . E I G H T

-

54.6

36.4

58.8

52.9

5 0 .8

51.3

44.0 41 . 4 0.0 0.0

33.1 31.5 11.0 10.8 44.0

23.0

43.9 46.1 87.9 87.6

44.9 88.0 87.2

21.5 22.9 22.5 45.6 46.1

33.0 31.7 44.0 45.3 88.1 38.1

9U 5

90.1

42.3 44.0 45.9 88.0 88.2

E SAMPLES

PETROLEUM R E F I N I N G L A B OR AT OR Y . THE P E H f l S Y L V AMI A S T A T E COLL EGE STATE COLLECE, PENNSYLVANIA JUNE

30,

1942

100 , x Methylcyclohexane

Run No. 47-H 33-H 32-H 34-H 48-H

B eta —

1 .3 0 1 .3 0 1 .2 9 -

W eight % S o lu b ility Hyc. i n E x t. 1 8 .9 1 5 .8 1 3 .7 1 1 .6 1 0 .2

D e n s itv P hase a t 3 0 .0 °C . R aff. E x t. 0 .7 8 4 0 .7 6 0 0 .7 4 0 0 .7 1 6 0 .6 9 6

0 .9 2 2 0 .9 2 5 0 ,9 1 7 0 .9 2 3 0 .9 3 8

F ig u re No. 22

The System

METIffLCYCLOHEXANB-n-HEPTANE ACET0N7LACET0NE

(C o m p o sitio n s on W eight B asis.) T em p eratu re

3 0 .0 °C .

A tm ospheric P r e s s u r e

P e tro le u m R e fin in g L a b o ra to ry The P e n n s y lv a n ia S ta t e C o lleg e S t a t e C o lle g e , P e n n s y lv a n ia J u l y 2 7 , 1942

n-Heptane

Acetonylacetone

100

• Tv

67

Table No. 10 SUMMARY C F DA TA n-HEPTANE

-

ME T M Y L C Y C L D H E X A N E

RUN HUMBER

TEMPERATURE, BETA * HT. i Y IE L D ?. S O L U B I L I T Y

°C. OF

SOLVENT-TO-CiL

Vf T.

*

EXTRACT R ATIO

;:E I G H T

15.9 15.7 I .0 0 1

13.7 13.7 I.OC

11 . 5 I I .6

75.2 74.2

49.0

25*6

47.9 47.5 54.4 54.4

24.7

5 0 .0 39. e

5 0.0 89 .8

IM (A)

(A)

EXTRACT

B1 (A}

1. 2 9 12 .2

1 0 .8 10.1 1 0 .2 1.00

1. 0 0

0 .0 0.0 0 .0 0.0 0 .0

24.7 29.8 29 . e

PHASE

IN

AT T E M P E R A T U R E RAFFINATE

90.0

__

19.0 18.8

15.9

5 0 .0 1 0 .2 1 0 .0

5 0 .0 10 .2

81.0 81.?

84.1 84.5

50 .0 90 .8 90 .6 13.7 13.7

15.7

5 0 .0

5 0 .0 8 8 .0 90.9 11.5

92.2 92.8 10 . 1

1 1. 6

1 0 .2

5 0 .0 1 2 ,0

5 0 .0

PHASE

OF

RUN

50 .0 9.? 9.4

__

7.8 7.2

9.1 88.5 88.4

86.3 86.3

89.9

89 .8

(DI)

0.784

0.760

0.740

0.716

0.6 9 6

0 .9 2 2

0.925

0.917

0.923

0.938

(c c .)

481? 54.1

51.7 53.1

54.2 51.8

57.9

6 0 .6

50.1

49.5

RAFFINATE

38.2 49.9

39.3 49.1

40.1

EXTRACT

41.5 46.2

42.2 46.4

33.1 32.3

22 .0 2 1 .0

RAFFINATE EXTRACT OF

PHASE

(C M .)

WT .

OF

METH Y L C Y CLOU EX ANE

CHARGED

T/ T.

OF

METHYLCYCLOHEXANE

RECOVERED

HT.

OF

H-HEPTAME

CHARGED

(G M .)

T.'T,

OF

N-HEPTANE

RECOVERED

WT.

OF

ACETONYL ACETONE

CHARGED

HT.

OF

ACETONYLACETONE

RECOVERED

TOTAL

WEIGHT

CHARGED

TOTAL

WEIGHT

RECOVERED

*

30.

I0C .0

EXTRACT

REIGHT

30.

(bj

(A)

PHASE

30. 1.30 14.8

79.0 79.0

ORIGINAL RAFFINATE

OF

30. l.jo 17-6

(A)

(B)

VOLUME

50.

(B)

% ACETONYLACETONE

DENSITY

48-H

1 0 0 .0 1 0 0 .0 I 0 0 .0

(B) BT.

34-K

HYDROCARBON

LB] EXTRACT

32*K

ICO.O

HYDROCARBON ORIGINAL RAFFINATE

IN

35-H

19.0 IE . 8 1. O C

I A)

EXTRACT

J

BY

AC£ T 0 N Y L A C ETONE

4 7 -K

21.4

*

PHASE

METHYl. CYCLOHEXASiE ORIGINAL RAFFINATE

BT.

Xo E X T R A C T

HYDROCARBON

IN

-

AVERAGE

OF

A

AND

(G M .)

(C M .) (GM •

>

44.0

(C-M.) (GM.)

0 .0 0 .0

*

(G M .) (GM .)

43.7

*

44.0 44.4 3 8 .C 38.1

11. 0 10.7 44.0 45.^

88.1 88.4

47.5

.

22.0 21.9 43.9 44.7 87*9 87.6

0.0 0 .0

1 1.CiIO. 8 53.0 51.7 44.0

45.7 44.0

45.2

44.9

8 8 .0

8 8 .0 8 8 .6

44.0

87.7

B SAMPLES PETROLEUM THE

STATE JUNE

REF I M A G

PENNSYLVANIA COLLEGE,

30,

1942

L ABORAT ORY

STATE

COLLEGE

PENNSYLVANIA

100 M

Run No.

9-H 13-H 12-H 14-H 11-H

Beta

Weight % S o lu b ilit y Hyc. in Ext. 35-3

1 .2 9 1 .3 5 1 .4 6 -

2 0 .1

1 5 .4 1 0 .7 8 .4

Phase D ensity a t 39.0°C . Ext. R aff.

o.sa 0.771 0 .7 4 2 0.717 0.695

0 .8 9 6

0.939 0.948 0 .9 6 2

Methyl cy cl ohexan e

b

F ig u re No. 23

The System METHYLCYCLOHEXANEn-HEPTANE-ANILINE

0.967 (Compositions on Weight B asis) Temperature

3 9 . 0 ° C.

Atmospheric Pressure

Petroleum R efining Laboratory The Pennsylvania S tate College S tate C ollege, Pennsylvania July 27, 1942

n-Heptane

A niline

0

100

69

Table No. 11 SUMMARY n-HEPTANE

-

T L MP T . P A T U R L t YIELD

OF

•/■ S O L U B I L I T Y SOI ITT.

°C.

A * f

H Y DR OC A RB ON

IN

VENT-TO -O IL ?'

EXTRACT RATIO

EXT R A C T

?

EXTRACT

i

A N I L I N E IN ORIGINAL R A F F I MATE. EXTRACT

DENSITY

AT

E XT R A CT (

+

I!-.

HEIGHT

1. 0 0

39 1.34

15 .0 14.9 1

j

1. 0 0

14 - H

♦*

~

7 .8 8 .3 8.4 1.00

2 5 .2

2 1 .8 2 1 .2 21.3 I . 00

100.0

31.9

0.0 0.0 0.0 0.0

55-0

31.9

0.0

100.0

50.0

5 0 .0

80.0 80.4

83.3 82.8 14.9

5 0 .0 8? . l

50 .0 8 8 .8 89 . I

5 0 .0 8 3 .0

8.3 8.4

2 1 .2

24.5

B

ICO.O

74.2

4?.6

24.3

(A)

100.0 100.0

78.8

55-0

78.8

5 0 .0 66. S 67.1

100.0 ICO.O 100.0

PHASE

(A) IB ) ( a) b

I S —H 31

39 —

1. 4 6 10.1 10.6 1C.8 1. 0 0

49.1 47.6

IN

ll-K

3V

74.5 74.2

)

35.2

82.7

*5-9

86.7 I C .6 1C. 8

5 0 .0

50 .0

5 0 .0

5 0 .0

12.9

II . 2

17.0

15.6

16.7 17.2

13.3

10.9

79.2 80.0

85.1 84.1

89.4

91.7 91.6

17.3 78.8

2 0 .2 2 0 .0

35.4

21.3

PH AS E

5 0 .0 2 0 .0

5 0 .0 ( A) (e) (A)

32.9 64.6

(

64.8

b

33.?

)

TEMPERATURE

OF

RUN

(D *) 0.82 !

0.7M2T

0.771 0.959

0.896

0.948

89.8

0.717

0.695 0.967

0 .9 6 2

(or;.}

78.7

0.808 0.957

RAF F I MATt

55.4

62.0

67.9

71.2

76.1

2V.}

EXTRACT

58.6

55.6

52.0

b g . s

48.7

54.1

45.5 52.6

47.8 50.4

50.4

51.1 47.9

5 2 .9 47.1

48.4

49.3

50.5 49.1

37.9 36.4

2 5 .2

12.6

0.0

50.9

24.1

12.4

0.0

0.0

25.3

38.0

0.0

12.7 12.0

25.3

5 0 .9 4 9.0

50.5 49.8

48.9

5 0 .5 49.1

101.0

IC I.I

50.5 1C I.0

37.1 50 .5 4 9 .5

5 0 .6 51.1 5 0 .5

51.1 0.0

I C I .1

IC I.I

IC I.O

98.2

99-7

99.0

IC O.O

100.2

OF

PHASE

(GM.)

EXT R A CT KT.

OF

MF T H Y L C Y C L O H E X A N f :

CHA R GE D

NT.

OF

METFYLCYCLOHCXANF.

RECOVERED (G M .}

U .

OF

n-HEPTANE

IVT. AT.

OF OF

n -H E P T A K E RECOVERED ( G M . } + A N I L I N E CHARGED ( G M . )

NT.

OF

ANIL INI,

CHARGED

RECOVERED

TOTAL

WE I G H T

CHARGED

TOTAL

WEI GHT

RECOVERED

*

12-H

H Y DROCARBON

R AF F 1 K A T E

**

2 0 .0 2 0 .2 2 0 .0 1.00

35.2

RAF F I MATE EXTRACT

V O L U M E OF P H A S E

56.8

(e)

W EIGHT

BY

39 1.29

55.4

ANILINE

I5-.H

59 — )

a

-

ICO.O IC O.O

( ITT.

WE T F Y L C Y C L O H F . X A K E

(A)

H Y DROCARBON OR 1 G I F At. RAFFINATE

AS

PH AS E

MF T UYl . C YCI - OU r . XAN F OR ICi I MAI. RAFF|MATE

•AT.

DATA

9-H

RUN NUMBER

LET fT.

OF

AVERAGE- OF

A AND

D E T c R M I N A T I CM OF

E

(G M .} *

(GM.)

(GM.) ( C M . )"

98. 1

(G M .)*

50.5

51.8

0.0

SAMPLES.

SOLUBILITY

OF

ME THY LC TCI . 0 H E X A N E

IN

ANILINE

AT

3 I.0 °C .

(S 7 .8 °F .; PETROLEUM R E F I N I N G LABORATORY TFT. P E N N S Y L V A N I A S T A T E C O L L E G E STATE

COLLEGE,

FEBRUARY

i,

PENNSYLVANIA

IS4I

100 /.\ Methylcyclohexane

Run No.

Beta

Weight % S o lu b ility Hyc. in Ext.

mO-H

2 1 .1

36-H 1 .3 5 ' *>—t* 1.33 37-H 1 .3 3 41-H

17.8 1 4 .8 1 2 .6 1 0 .6

Phase D ensity a t 6 0 ,.0°C. R a ff. Ext. 0 .796 0.765 0.744 0 .7 1 4 0.690

F ig u re No.

1.013 1 .0 3 0

The System

1.0 4 4 1 .0 4 2

1 .056

METHYLCYCLOHEXANEn-HEPTANE-FURFURAL (Compositions on Weight B asis) Temperature

60.0°C.

A tm osoheric P r e s s u r e

Petroleum R efining Laboratory The Pennsylvania S ta te College S ta te C ollege, Pennsylvania July 27, 1942

n-Heptane

Furfural

71

Table No. 12 SUMMARY n-HEPTANE

-

OF

DA TA

ME T H Y L C Y C L O H E X A N E

FURFURAL

R1IIJ HUMBER

40-K

36 - H

35 - H

37-H

41-H

TEMPER A TURE , ° 0 . BETA * ST. YI E. LO OF HYDROCARBON AS S O L U B I L I T Y i N EXT RACT PHASE

60

60 1 .3 5

60 1 .3 3 14.7

60

60

i

i

S O L V E N T - ' 0 - 0 11. P. ATi C

V. T .

Jf ME T H Y L C Y C L 01I CXANE ORIGINAL RAFFINATE ( a )

EXTRACT p'.j

V'E | GHT

IN

% HYDROCARBON

100.0 10 0 . . 0 100.0 100.0 100.0

EXT RACT

i

FURFURAL

IN

ORIGINAL RAFFINATE

(a)

AT T E MP E R AT U R E RAFFINATE EXTRACT

VOLUME OF PHAGE

WEI GHT

OF

RUN

(O*) 4

14.8 14.8 1.00

7 5 .0 73 .6

49.5 47.8

73.6 79.0 79.0

47-8 54.9

12.5 1. 0 0

31.1 31-1

0 .0 0.0 0.0 0.0 0.0

25.3 24.7 24.7

54.9

5 0 .0

5 0 .0

5 0.0

5 0 .0

5 0 .0

79.7 30.8 21 . 6 20.6

65.? 35.0

84.0 84.4 14.8 14.8

35.1 85.3 12.6 12.5

86.0 86.4 10.6

50 .0

5 0 .0 16 . e

5 0 .0

5 0 .0

5 0 .0

20 .x

16.0

19.? 78. 4 79.4

17.0 82.1 82.2

1 5 .6 85.?

14.9 14.7 87.4 87.5

14.0 15.6 89.4

i? -9 17.8

0.796 1.015

0.765 1.030

"•

10.5

35.2

0.744 1.044

89.5

0.690

0 . 7 14 1.0 4 2

1. 0 5 6

(CO.)

5 6 .0

RAFF I N ATE EXTRACT

52.? 46.5

44.5

OF PHAS E ( C M „ ) RAFFINATE E XT RACT

b l.5

62.8

'+7.1

1 +5. 8

1+1).0

53.1 32.7 I 1. 0 1 1.1 1 +6 . 0 44.8 88.1 83.6

V' T. OF M E T H Y L C Y C L O H E X A N E CHARGED ( C M . ) WT. OF M E T H Y L C Y C L O H E X A N E RECOVERED ( G M . ) WT. OF M - H E P T A H E CHARGED ( C M . ) V.'T. OF N - H E P T A N E R ECOVERED ( G M . ) * WT. OF FUR F UR A L CHARGED ((>■’•’ . ) '•'•'T. C-F FURF URAL F.ECOVEFi GD ( G V . ) * ' I OTAL H E I G H T CH ARCED GM. ) TOTAL WEI GH T F’ ECOVERED ( C M . ) *

(

!|3.2 0.0 0.0 l +l +.O 45.4 88.0 88.6

57.4 41. 8

61.7 41 . e

64.7 40.8

42.? 43.6

44.1 43.6

43.1

22.0

11.0 11.0

20.7 22.0

44.6

0.0 0.0 44.0 45.0 44.0 44.7 88.0

3 5.0 3 2.1

21.7 44.0 45.9 33.0

44.0 44.6 88.0

86.5

37.7

87-7 ;:

-t f, 7ir' — *

— 10 . 4 10.6 10.5 1.00

12.5 12.6

PHAS E

EXT RACT

DENSITY

18.5 17.9 I7.8 1. 0 0

IM PHASE

OR I G I H A L RAFFINATE

WT.

22.6 21.6 20.6 1.00

1.58

HYDROCARBON

hS ( a) (8)

EXTRACT

WT•

BY

~-

:_r=

AVERAGE OF A AND B SAMPLES PETROLEUM R E F I N I N G LABORATORY THE P E M M S YL V A h ! A STATE COLLEGE STATE COLLEGE, P E H H S Y L V A N f A JUIIE

30,

19 4 ?

100 Methyl cyclonexan**

Density

Weight %

Run No.

Beta

55—H 53-H 1.19 52-H 1 .2 0 5A-H 1 .2 6 —

S o lu b ility Hyc. i n E xt. 1 6 .1 1 5 .5 U .2 1 3 .2 11. A

a t -20 .0°C . R a ff. E xt. 0.811 0 .791 0 .7 6 6 0.7A4 0.727

0.831 0 .8 2 6 0.825 0.817 0.820

F ig u re No. 25

The System METHYLCYCLOHEXANEn-HEPTANE-METHYL ALCOHOL

(C o m p o sitio n s on W eight B a s is ) T em p eratu re -2 0 .0 ° C . A tm ospheric P r e s s u r e

P etroleum R efin in g L aboratory The P en n sy lv an ia S ta te College S ta te C o lleg e, P ennsylvania J u ly 2 7 , 19A2

n-Heptane />• 0

M ethyl Alcohol TJ

73

Table Ho. 1 3 SUMMARY n-HEPTANE

-

$

-20 EXTRACT (A)

*

-‘J O L V E N T - T O - O ! L

RATiO

BY

METHYLCYCLOHGXAN-

IN

16 . 0 1 .0 0

(

EXTRACT

{ . A!

a

100.0 100.0 100.0 100.0 100,0

)

(B5

( b) .'IT.

2 HYDROCARBON l ! i OR 131 HAL RAFF I HATE I A )

>

IN

AT T E MP E R AT U R E R A F F i l l ATE EXTRACT

VOLUME OF P H A S E R A F F I.'I ATE EXTRACT WEI GHT

OF RUN

14.!

-20 .2 6

—-

15.!

12.3

1 3 .2 1 3 .2

11.5 1 1. 4 1.00

1. 0 0

48.? 48.4 43.4

25-9

25 .0 25.9 29.6 29.6

52.9 52.9

50.0 96.3 97.4

50.0 93.0

50.0 97.9 97.3 14.!

15*5 »5*5

14.3

50.0

50.0

50 .0

2 .7 2.1 35.3 84.0

3.2 2.6

2.1 2.7 85.9 35.7

84.5 84.5

0.31 1 0.331

0.0 0.0 0.0 O.Q 0,0

5 0.0

97.9 15.2 13.2

97.9 93.0 11.3 1 1.4

50.0 2.0 2.1 86.8 86.3

50.0 2.1 2.0 88.? 83.6

0.?66 0.325

0.791 0.326

0.744 0.317

0.727 0.820

{r.o.)

OF PHAS E ( G M . ) R A F F I MATE EXTRACT

*

43.3 63.2

45.6 63.2

43.6 62.5

61

50.5 .?

6 0 .2

35.5 52.5

36.1

5 2.2

37.2 5! *6

37.6 50.4

39.1 49.4

44.0

53.0

22.0

43*2 0.0 0.0

32.3 t I .0

11.0 I I . 2 33.0

0 .0

44.0 44.3 80. 0 38.0

44.0 45.1 38.0

21.5 22.0 22.2 44.1 45.1 38.! 38.8

.1 I AVERAGE OF

I

(oj)

VIT. OF M E T H Y L G Y C L O H E X A H E CHARGED ( G M . ) y/ T. OF ME T H Y L C Y C L OH E X A H E RECOVERED ( G W . ) t "T. OF N i H E P T A M E CHARGED ( C M . ) WT. OF I I - H E P T A N E RECOVERED ( C M . ) «* S T . OF ME T H Y L ALCOHOL CHARGED ( G M . ) S T . OF ME T H Y L ALCOHOL RECOVERED ( G M . ) * TOTAL VIE | GHT CHARGED ( G M . ) TOTAL WE I GH T RECOVERED ( G M . ) *

*

14.3 1.00

-20

PHASE

( bj DENSITY

15*5 15.5 1.00

77.4

97.9 16.2 16.0

(A)

METHYL ALCOHOL ORIGINAL RAFFINATE ( a ) (b) EXTRACT IA l

-2 0 1.20 1 6 .6

75.0. 74.2 74.2 77.4

50.0 97.5

( b) ST.

1-19 18.4

56-H

PHAS E

B EXTRACT

54-1!

HYDROCARBON

OS I G I T A L RAFF I. TATE

,/ 2 —II

-20

19.2 I d. 2

iVE I GHT

ALCOHOL

55-B

—

(B)

3

METHYL

55-H

TEMPERAT D T E , ® C . BETA * ST. Y I E L D OF HYDROCARBON AS 3 Q L U E I I . ! TV IW E X T R A C T P H A S E

ST.

DATA

ME T H Y L C Y C L O H E X A N E -

NUfl '!UMBER

i

OF

A AMD 6 SAMPLES

*1*

1 0 .9

88.3 * ,L*

“

r c i ,7

—

32.3 44.0 44.5 88.0 ■ 88.0

x*

7'

53.3

0.0 44.0 43.9 44.0 44.6 88.0 88.5

z-zz~-

PET ROLEUM R E F l l l i N G LABORAT ORY THE P E N N S Y L V A N I A S T A T E C OL L EGE STATE COL L EGE , P EN N S Y L V A N I A JUNE T O , 1 9 H2

A / M ethvl cv c l o ;.exane / • • •\ A --7 \ f./ . .'A — 4/. . \ /.v ■ / v - . A 100

Run No.

Beta

— 44-H 46-H 1 .3 0 42-H 1 .3 1 45-H 1 .3 4 43-H . -

Phase Density Weight % S o lu b ility a t 60 • 0°C . Hyc. in E x t. R a ff. E x t. 2 1 .0 1 6 .6 1 3 .1 1 1 .4 9 .0

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

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

Figure No. 26

The System METHYLCYCLOHEXANE-n-HEPTANEMETHYL CARBITOL

(C o m p o sitio n s on W eight B a s is ) T em p eratu re

6 0 .0 °C .

A tm ospheric P r e s s u r e

iO / _ _ v

n-Heptane

P e tro leu m R e fin in g L a b o ra to ry The P e n n s y lv a n ia S ta te C o lle g e S ta te C o lle g e , P e n n sy lv a n ia J u ly 2 7 , 19-42

Methyl C a rb ito l 'O

75

Table i-]o. 1/. SUMMARY' n- Wi C? TAf l E

OF

_ Mc 'THYLCYT. OHEXAME

M3-H

60

60

60

2 i .!

60 1. 3 0 (S .! 16.5

1.54 11.9 12.0

20.9

1 6 .6

1.31 13.? 13.2 13.0 1.00

75*2 ?M »2 74. 2

1)9.5 1)3.! 1) 3. 1

2 5 .6 2 5 .0 25 .0

79.0 79.0

5l).9 5* 4.9

30.9

5 0 .0

5 0 .0

88.6 33.3

90-1

35.0

50.0 3?.6 37.3 16.5

13.2

90.5 12.0

91.6

2 1 .1 20.9

16.6

13.0

10.9

8.9

50.0

50.0

50.0

15*0

59.0 I2.!| 12.2 03.5 8 3 . >1

9.9 9.5 38.0 39.!

50.0 8.6 S.M

78.9 79.1

1 I . 1) ! I .2 86.3 87.0

S3.3

*

( b) S O L V E R T - T 0 - 9 IL

WT.

RATI J

EXT RACT

% HYDRO CAR ROM 0RJ3IH.AL RAFF SKATE EXT RACT

WT.

I 00.0

I 00.0

H

100.9

(AJ

I 00.0

W

I00.0

Ifl

OEMS I T T

AT

50.0 30. 3

{ Af

B

15.2

>8

(A'

TEMPERATURE

OF

HUN

(D t )

*

0.775 0.558

0.7V3 0.944

50.7

OF PHAS E ( G M . ) R A F F } ATE

U

33.0

L0.2

E XT R AC T

49.7

47 «9

MM. O

33.1 32.5 11 . 0 10.8 i)l). 0 1)L.3

OF METH YL CY CL ONE X AM £ OF ME T H Y L C Y C L O H E X A N E

CHARGED ( G M . ) RECOVERED ( G i l . )

AVERAGE OF A AMD B SAMPLES

1*3.5 0.0 0.0 MM. O

*

45.2 38.0

38. ?

0.719 0.9'43

5M.5

50.3 53.0

I f T . OF N - H E P T A N E CHARGED ( G M . ) F T . OF N - H E P T A M E RE COVE RE D ( G M . ) « WT. OF METHYL C A R B M O L CHARGED ( G M . ) K T , OF METHYL C A R B I T O L R E COVE R E D ( G M . ) TOTAL WEI GHT CHARGED ( G M . ) TOTAL WEI GHT RECOVERED ( G M . ) *

*

30.9

0.0 0.0 0.0 0.0 0.0

5 0 .0 91.4 9 .0

IM PHASE

VOLUME OF PHASE ( c u . } RAFFINATE E XT R AC T

WT. WT.

10.9 1.00

PHASE

F A F F I MATE E XT RACT

K EI GHT

I .00

9.3 9.0 8.9 1.00

I M HYDRO OAR SOM

(Al

>. METHYL CARD 1 TOL O R I G I N AL RAFFINATE ( a ' EXTRACT

I .0 0

WEI GHT

% ME T HYLRYGLOHEXAME OR ! 01 IT AL '• AFF ! NA TE

WT.

ST

CARBITOL

45-H

*8.

i

METHYL

- )2-H

BETA

S T . 3 Y I E L D OF HYDROCAPB ON AS E X T R A C T S O L U R t l . l f f if) EXTRACT PHASE ( a )

-

4 6 -H

RUM HUMBER T E MP E R A T U R E ,

DA TA

57.9 U 3.7

88.1 30. i

0.697 0.957

6 0 .6 47.6

U I.6 L6.2

M2.2

22.0 21.1 22.0 21.3 1)3.3 M L.9 87.3 87.8

11.1 II.! 33-0 32.2 MM. O MM.5 88.! S?.8

45.6

91.0 91.1

0 .6 7 8 0.965

65.5 47.1

M 3.! M5.5 0.0 0.0 MM. O 43.5 44.1 45.1 83.1 88.6

.

PETROLEUM R E F ( M l KG L A B ORAT ORY THE P E N N S Y L V A N I A S T A T E C OL L EGE STATE COLLEGE, PENNSY LVAN IA J U N E 3 0 , 19 ^ 2

100 /,

Weight %

Run No. 60-H 58-H 57-H 59-H 61-H

B eta —

1 .2 6 1 .3 0 1 .2 9 -

S o lu b ility H yc. i n E x t. 2 2 .3 1 8 .0 1 5 .2 1 2 .7 1 0 .A

Methylcyclohexane

Phase Density

a t 1 0 .0 ° C . R a ff. E x t.

P ip u re No. 2",

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

The System METHYLCYCLOHEYANE-n-HEP TANE~ METHYL CELLOSOLVE

(C o m p o sitio n s on W eight B a s is )

60 L

y_

/\

T em p eratu re

1 0 .0 ° C .

A tm o sp h eric P r e s s u r e

P e tro le u m R e f in in g L a b o ra to ry The P e n n s y lv a n ia S t a t e C o lle g e S t a t e C o lle g e , P e n n s y lv a n ia J u ly 2 7 , 1942

n -H ep tane

/ \ •y .\ 100

M ethyl C e llo s o lv e

77

Pablo Ho. 15 SUMMARY

OF

DATA

CLOHEXAi lE

RUN N U MBER 'tem perature,

*0.

BET A *

i

S O L V E N T - ! i ) - 0 1L

BT.

$

RATIO

*

'

13V ’WEI GHT

METHYLC YCLOK' EKAf l E ORIGINAL RAFF f IT ATE ( a )

t

10

HYDROCARBON I N on I 3 1 N AL. RAFFINATE f A E XT RACT

50.0 89-1 39.9 22.2 22.4

(A)

CE L L O S OL V E

ORIGINAL RAFFINATE EXT RACT

IN

5JMHI __________

59-H

6 1—11

10

10

10

1.29 13.9 12.6 12.0 1. 0 0

11*1 10.4 10.5 1.00

1.30

18.0 13.1 1.00

I?.! 15.2 15.3 1.00

74.7 73.9 73-9 78,2 73.2

43.0 48.1 48.1 54.6 54.6

5 0 .0

50.0 92.4 92.6

ae*>*

2 6 .2 2 5 .0 2 5 -0 30.!

30.1

0.0 0.0 0.0 0.0 0.0

50.0 (a) B IAS

AT T EMPERAT URE RAFFINATE E XT RACT

10.9 10.1 77.3 77.6 OF

90.7 90.9 18.0 18.!

15.? 15.3

5 0 .0

5 0.0

93.9 93.5 12.6 12.8

93.5 93.9 10.4

50.0 6.1 6.5 87.4 37.2

50.0 6.'5 6.1 89.6

10.5

PHAS E

(b) DENSITY

1.26 20.6

____________

PHAS E

(B) 2 METHYL

2?.0 22.2 22.4 1.00

100.0 100,0 100.0

(A)

)

1ST.

10

100.0 I 00.9

IB) WT.

5 3 —rl

C E L L OS OL V E

I M HYDRO CAR BOM

(81 EXT RACT

METHYL

6 0 —H —

ST. ' Y I E L D OF HYDRO CAE? 0 0 AS E X T R A C T !*> S O L U B I L I T Y . H E X T R A C T P H A S F . | A j

-

RUN

50.0 9.3 9.1 82.0

50.0 7.6 7.4 84.3

81.9

84.7

89.$

( dJ ) 0.303 0.930

0.775 0.929

o.?54 0.954

0.751 0.959

0.714 0.959

VOLUME OF PHASE ( c c . ) RAFFINATE E XT RACT

44.3 57.2

49.0

5 2.0

54.3

53 - 0

55.6 51.2

53.1 49.9

WEI GHT OF PHASE ( G M . ) RAFFINATE EXT RACT

35-6 55.8

37.9 50.4

39.2 49.5

40.6 43.1

41 . 5 46.3

44.0

33*0

22.0

11 . 0

0.0

45.3 0.0 0.0 43-9 *45.0 37.9 33.3

32.5 I II .0 44.0 44.3 38.0 88.3

2 1 .6

11.3 35.0 32.9 44.0

0.9 44.0 43.3 4 4 .9

44.5

44.5

WT.

OF ME T H Y L C Y C L OH E X A N E CHARGED

IVT. WT. VIT . WT. WT. TOTAL TOTAL

OF ME T H Y L C Y C L OH E X A N E RECOVERED ( G M . ) * OF n - h e p t a n e CHARGED ( G M . ) OF N - H E P T A N E R E CO V E R E D ( G : f l . ) * OF METHYL C E L L O S O L V E CHARGED ( G M . ) OF METHYL C E L L O S O L V E RE COVE RE D ( G M . ) WEI GH T CHARGED ( G M . ) WEI GHT RECOVERED ( G M . ) *

*

AVERAGE OF A AND B SAMPLES

(GM.)

l.o

22.0 22.3 44.1 44.9

88.1

88.0

88.9

88.7

8 8 .0 88.3

PETROLEUM R E F I N I N G L A B OR AT OR Y T HE P E N N S Y L V A N I A S T A T E COLL EGE STATE COLLEGE, P E N N S Y L V A N I A J UNE

30,

1942

100 / Weight %

Run No. 66-H 64-K 63-H 65-H 67-If

B eta

1 .3 7 1 .3 9 1 .4 1 —

P hase D e n s ity a t 5 0 .0 °C . R a ff. E x t.

S o lu b il: t y Hyc. i n E x t. 3 2 .9 2 0 .1 1 4 .8 1 1 .2 8 .6

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

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

Methylcyclohexane

A

/ 'W v A - A

Figure No.

, v • • ■A -

-A

80 .

28

The System 7 ; ^ A

^ r ~ A

\ / \ y . A\. /

v / V

-

-

METHYLCYCLOUEXANE-n-HEPTANE PHENYL CELLOSOLVE

(C o m p o sitio n s on W eight B a s is )

6o /---

>\

/

T e m p e ra tu re

5 0 .0 °C .

A tm o so h eric P r e s s u r e

P e tro le u m R e f in in g L a b o ra to ry ' The P e n n s y lv a n ia S t a t e C oller< S t a t e C o lle g e , P e n n s y lv a n ia J u ly 2 7 , 1942

/

n -H ep tane

y 7. . X. \ 7

7

x'.V. A 'A l A 100

P h en y l C e llo s o lv e

79

Table b o . 16 SUMMARY r i —H E P T A N E

-

OF

DATA

METHYLCYCLOHEXANE

-

PHENYL

CELLOSOLVE

RUN NUMBER

66-H

64-H

63-H

65-H

67-H

TE MP E R AT U R E, ° C . BET A * YIT. g Y I E L D OF HYDROCARBON AS E X T R A C T S O L U B I L I T Y IN EXTRACT PHASE ( a )

50

50

50 U 59 16.3

50 1.41

50

U3? 22.9

2 0.1 20.1

14.9 14.7

—+

41.3 32.7 53.0

'4

(b) SOLVENT-TQ-OIL

tVT.

RATIO

g ME T H Y L C Y C L OH E X A N E ORIGINAL RAFFINATE EXTRACT

WT.

$

HYDROCARBON ORIGINAL RAFFINATE EXTRACT

i'.'T.

BY

1. 0 0

WEI GHT

IN

(a) vB) ( a) (B) IN

AT T E MP E R AT U R E

OF

R UN

(

dJ

TOTAL TOTAL

74.7 75.9 73.9 79.5 79.5

49.3 48.4 43.4

25.9 25.0

5 6.6 56 .6

32.0 32.0

50.0

5 0.0

50.0

5 0.0

5 0 .0

74.5 74.3

36.1 36.1

89.5 39.2

32.7 33.0

20 .1 20.1

14.9 14.7

91.5 91.5 11.2

92.6 92.3 8.7

11 . 5

8.5

50.0 25.5 25.2 67.3 67.0

5 0.0

5 0.0

50.0

50 .0

13.9 13.9 79.9 79,9

10.5 10.3 35.1 85.3

3.5 8 .5 38.3

7 .4 7.2

0.313 0.952

VOLUME OF PHAS E ( c o . ) RAFFINATE EXTRACT

OF OF OF OF OF OF

1 0 0 .0 1 0 0 .0 1 0 0 .0 1 0 0 .0 13 0 . 0

2 5 .0

0 .0 0 .0 0 .0 0.3

0 .0

OF P H A S E ( G M . ) RAFFINATE EXT RACT ME T H Y L C Y C L OH E X A N E CHARGED ( G M . ) ME T H Y L C Y C L OH E X A N E RE COVE RE D ( G M . ) N - H E P T A N E CHARGED ( G M . ) N - H E P T A N E RECOVERED ( G M . ) * PHENYL C E L L O S O L V E CHARGED ( G M . ) PHENYL C E L L O S O L V E RE COVE RE D ( GM. ) WEI GHT CHARGED ( G M . ) v v e i g H T RECOVERED ( G M ' . )

AVERAGE OF A AND 8 SAMPLES

*

8 8 .7

91.3 91.5

)

R A F F I I I ATE EXTRACT

WT. V/T. NT. Vi T. U’T . S/T,

1.0 0

PHASE

IB)

WEI GHT

11.3 I . 00

PHAS E

g PHENYL C E L L O S O L V E ORIGINAL R A F F II I ATE (b) f Al EXTRACT

DENSITY

1.00

— 9.0 8.7 3.5

HYDROCARBON

(A) (B) (A) (b) IN

I . 00

1 2.0 1 1 .2

*

0.997

0.729 I »020

0.70?

1 .032

0.682 1.041

6U?

40.? 53.6

51.5 50.1

55*5 47.4

59.1 45-5

33.! 55.2

39.3 49.9

40.3 43..3

4 !.3 47.9

42. I 46.2

44.0

33.0

2 2.0

II. 0

42,9

33.0 I I .0 11.9 44.0

21.5

11.5 33.0

0.9 0.9 44.0 43.9

0 .0 0 .0 *

0.764

44.1 45.4 38. 1 83.1

45.2 38.9 89.2

2 2.0 21.7 43.9 45.4 87.9

8 8 .6

32.3 44.1 45.2 38.1 88.3

44.4

43.9 45.3 87.9 33.3

P E T R OL E U M R E F I N I N G L A B OR A T OR Y THE P E N N S Y L V A N I A S T A T E C OL L EGE STATE COLLEGE, PENNSYLVANIA JUNE 5 0 , 19 42

Table No. 17 SELECTIVITY FACTOR, BETA, FOR THE SYSTEM METHTLCYCLOHEXBiE-n-KEPTAHE

S o lv e n t

Temp. °C.

Wt. % S o l 'y H yc. i n E x tra c t#

9 cc* 'v

R*

X*

C

*

1 .4 1

1 .4 1

6 .7

+ 4 -0 .0

1 .2 6

4 .5

1 .4 0

1 .4 5

5 .2

1 0 .0

1 .2 8

1 1 .9

2 .1 4

2 .0 4

2 2 .3

3 0 .0

1.30

8 .7

1 .8 5

1 .8 0

1 9 .3

6 0 .0

1 .3 2

1 2 .0

2 .3 4

2.1 6

2 0 .0

60 .0

1 .3 5

1 0 .5

1 .9 9

1 .8 5

2 1 .4

3 9 .0

1 .3 7

2 6 .9

4 .2 0

3 .1 6

2 9 .7

5 0 .0

1 .3 9

2 4 .3

3 .8 3

3 .0 8

4 2 .4

e

l

l v

.

4 .7

l

C

° C

1 . 22

e

y l

. ,

- 2 0 .0

n e

i t o

p

e

* D e fin itio n o f fu n c tio n s S = ( w t. % M .C .H . -

w t . % n - h e p t a n e ) e x -tr a c t

r - f vrfc» % M .C .H . \ \w t. % n - h e p t a n e / e x t r a c t X

__ \ \ w t . % n —h e p t a n e / e x t r a c t

x / w t. % M .C .H . \ \w t. % n -h e p ta n e / r a f f i n a t e

C = ( C .S .T . o f n —h e p t a n e ) — ( C .S .T . o f M .C .K .) T he f i r s t o f t h e f u n c t i o n s m e n tio n e d a b o v e , t h e d i f f e r e n c e i n s o l u b i l i t y o f t h e tw o h y d r o c a r b o n s i s

show n a s l i n e S .

T he p o i n t s f o r

m e th y l c e l l o s o l v e a n d f u r f u r a l l i e o n

o p p o s ite s id e s o f

th e l i n e , w ith

b e t a f o r f u r f u r a l h a v i n g a v a l u e 0 .0 4 - u n i t s t o o l a r g e a n d m e th y l

F ig u r e N o. 29 86

CORRELATION OF BETA WITH SOLUBILITY FUNCTIONS (H y d ro c a rb o n S y s te m : Fey:

S

M e t h y l c y c lo h e x a n e - n - H e p ta n e )

(W t./o M .C .H . - Wt.% n - H e p ta n e ) ex t .

\ ^ Q ______ I Wt .% M .C .H . I W t.% n - H e p t a n e / e x t . x

_______fw t.% M .C .H . \ /W t.jo M .C .H . \ \Wt. % n - H e p ta n ej e x t * Uv t . % n - H e p ta n e j r a f f .

C a

( C .S .T . o f n - H e p ta n e - C .S .T . o f M .C .H .)

8 0 .0 6 0 .0

—I O -P •H

I

i— \ i—I o

AO.Q

•H •H

rH

o rH

3 0 .0

I—I •H

20.0

-p

rH

1 0 .0 8 .0 6 .0

S

o

l u

b

i l i t y

F

u n c t i o n s

•H

4 .0 3 .0

2 .0 PETROLEUM R E F I N I N G LABORATORY THE P E N N S Y L V A N I A S T A T E COLLEGE STATE COLLEGE,PPENNSYLVAN I A OCTOBER 2 6 , 19 ^ 2 ,

1 .0 1.20

r .3 o

1 *-° B e ta

87

c e llo s o lv e 0*04- u n i t s "too s n a i l "to f a l l o n t h e 1 1 n s . show t h e l a r g e s t d e v i a t i o n s fro m t h i s

T h e s e "two s o l v e n t s

s tra ig h t lin e .

I n c u r v e R a r e show n r a t i o s o f t h e s e tw o s o l u b i l i t i e s p l o t t e d v e rs u s th e c o rre s p o n d in g v a lu e s o f b e ta . l i n e w ith th e e x c e p tio n o f f u r f u r a l , a b o u t 0 .0 5 u n i t s

T hese p o in ts l i e

n e a r e r th e

f o r w h ic h t h e v a l u e o f b e t a i s

to o l a r g e .

The t h i r d

fu n c tio n -m e n tio n e d above i s

W ith t h e e x c e p t i o n o f f u r f u r a l a g a i n , l a t i o n o f t h e fo u r* .

th is

show n a s c u r v e X.

seem s t o b e t h e b e s t co i’r e -

B e t a f o r f u r f u r a l l i e s 0 . 0 6 u n i t s fro m t h e c u r v e ,

b u t th e o th e r s a r e w i th in 0 .0 2 u n i t s .

T h u s , i t w o u ld seem, t h a t b y

s im p ly d e t e r m i n i n g t h e c o m p o s i t i o n o f t h e tw o c o n j u g a t e p h a s e s f o r each p u re h y d r o c a r b o n - s o lv e n t s y s te m , a t l e a s t a r e a s o n a b le e s ti m a te o f t h e s e l e c t i v i t y o f t h e s o l v e n t may b e m a d e.

O f c o u r s e , a s date*, f o r m ore

s o l v e n t s a r e o b t a i n e d t h i s g e n e r a l i z a t i o n may h a v e t o b e m o d i f i e d . C u rv e C , t h e u p p e r o n e o n t h i s f i g u r e , b e tw e e n b e t a a n d t h e l o g a r i t h m

sh o w s t h e c o r r e l a t i o n

o f th e d iff e r e n c e in

c r i t i c a l s o lu tio n

t e m p e r a t u r e s o f t h e tw o h y d r o c a r b o n s i n a g i v e n s o l v e n t . m e th y l c e l l o s o l v e a n d a c e t o n i t r i l e

The tw o s o l v e n t s

shov? t h e g r e a t e s t d e v i a t i o n fro m t h e

s t r a i g h t l i n e , w ith b e t a f o r a c e t o n i t r i l e l y i n g a b o u t 0 .0 5 u n i t s to r i g h t o f th e l i n e

a n d b e ta , f o r m e th y l c e l l o s o l v e f a l l i n g

d is ta n c e to th e l e f t o f th e l i n e .

F u r f u r a l a g a in l i e s

th e

a b o u t t h e sam e

to th e r i g h t o f

th e l i n e , o n ly a b o u t 0 .0 2 u n i t s , h o w e v e r. I f we c o n s i d e r t h e s t r a i g h t l i n e s f o r e a c h p a r t i c u l a r f u n c t i o n a s r e p r e s e n t i n g t h e a v e r a g e v a lu e s o f b e ta to be e x p e c te d f o r a n y g iv e n v a lu e o f th e f u n c t i o n , th e v a r i o u s s o l v e n t s .

c e rta in

c o n c l u s i o n s may b e d ra w n v ? ith r e s p e c t t o

100 .

Run No.

7-H 5-H 3-H X-H 6-H

B e ta

W eight % S o lu b ility H yc. i n E x t.

P hase at R aff.

1 .5 8 1 .6 5 1 .7 6

9 .9 8*6 6 .8 X .7 3.X

0 .7 8 7 0 .7 6 9 0.7X 8 0 .7 2 2 0 .7 0 3

—

Methylcyclohexane

F ig u re No. 30

0 .9 9 9

1.002

The System

1 .0 0 7 1 .0 H 1 .0 1 8

METHYLCYCLOHEXANEn-HEPTME-ANILINE (C o m p o sitio n s on W eight B a s is ) T em p eratu re

1 0 .0 ° C.

A tm o sp h eric P r e s s u r e

P e tro le u m R e f in in g L a b o ra to ry The P e n n s y lv a n ia S t a t e C ollege S t a t e C o lle g e , P e n n s y lv a n ia J u ly 2 7 , 19X2

n-H eptane

0

A n ilin e 00 O

90

T

a

b

l e

SUMMARY n —H R P ' i a ML -

N

o .

CF

2 0

DATA'

YE T H Y L C S ' C' L O h f . XA.’ .'L --------------------- --------■------ -

RUN

NUMBER

7-M

i ; KPLRA iU R R ,

10

*

beta

itt.

3C.

%yit.Lo

SOLUBILITY

or-

hydrocarbon

|M E X T R A C T

as

extract

*

(/,)

(e) E Ol _ y t V.T.

; ~T 0 _ Q ! U R A T I O

BY

" r METHYLCYCLOHEX/VNil

9.7 1.0

.VL1ULT IN

9-9 10 . 0

/

i

PCICIHT

_

_

/ z i L 10

8.3 3.2 9.0 1.0 1

7.0 6.5 7.1 i .01

4-K 10 1.76

6-11 10 —

4.9 4.5

3.2 3.4

4.5 1.0!

5.4 I . 0c

HYOROC/.fiaOi: 79.3

EXTRACT

(A )

I0C.0 100.0

?9.o 79.0

59.2 57.8

57.8

B5.7

69.3 69.3

49 . R 34.2

49.6 54.5

8 5 .7

26. I £ 4 . 9

24.g 56.9 56.9

0.0 0.0 0.0 0.0 0.0

PHASE

3 0.0

94,2

( L7

AM I L I H E I t P H A S E ORIGINAL R A F F i I TA TL ( A T

94.4

9.7

3.2 9.0

50 .0

5 0 .2

50.2

50.3

5 0.0

5-8

5.5

4.7 4.7 95.3 95 -1

4.5 4.7

5 .S

h)

5 .a

(A )

90 .0

(-/

90.3

AT T E M P E R A T U R E R A F F ! MATE LXTFAC1

OF RUN

(B *) "

GF F H A S F ( c c . ) R A F F IN A T l EXTRACT OF P H A S E ( C M . ) R A F F I NATE EXTRACT

T, ' T. O F M E T H Y L C Y C L O H E X A N E C H A R G E D ( C i ! , ' . } V . T. O F M E T H Y L C Y C L O H E X A N E R E C O V E R E D ( G K . ) < U I . OF n - H E f ’ TARE C H A RG ED ( G M . ) i.T. OF n -H E P T A N C R E C O V E R E D ( G M . } » IV T . O F A N I L I N F C H A R G E D ( G M . ) I V ' I . O F All I L I M E R E C O V E R E D ( GI . T. ) * ! i.*T/.L W E I G H T C l I A P G E D ( G U . T 'TOTAL F L I G H T R E C O V E R E D { G M . } *

5 0.0 95 .5 95 .3

7 .1

49.7 95-3 95-3 4.5 . 4.9

94.?

10.0

(A)

OF A AND

*■*•••

1. 6 5

100.0

* AVERAGE

~ r : ' "l-'l.— '-V-

1 .3 8

I 00.0

EXTRACT

VOLUME

10

)

a

H Y D R O C A R B O N tj. O R H i I MAE RAFF I M A H ( A )

DENSITY

5-H

(

EXTRACT

IVT .

--

Of: | G 1 AiAL RAF P I MATE

I 00.0 f t ,

ANILINE

0.737 0 . 9 99

5.6 91.6

9l.o 0.769

I .002

94.4

6. [}

5.6 93.5 92.9 0.743 1.007

0.722

I.Ob

3.4

96.6 9 6 .6

0.705 I .018

39.4 50.9

62.1

64.0

67.0

74.4

50.5

51.1

51.3

47.1

46.8

47.8 5 1.0

47.9

48.4

50 .8

51.5

52.1

52.3 47.9

50.5 48.3

4 0 . Ci

30 .0

39.4

28.5

12.4 12.4

0.0 0.0

10.1 10.1

2 0 .1 2 0 .2

50.5

50.5

5 0 .8

43.3

1 01 . 0

IC O .6 98.8

50.5 50.7 100.6

51.3 100.4

99.4

100.5

9 7 .6

37.5 36.2 50.5

0.0 0.0 5 0 .6 51 .5 50.5 48.7 1 01 . 1 100.2

B SAMPLES. P ET R OL E U M R E F I N I N G L A B OR AT OR Y THE P E N N S Y L V A N ! A S T A T E C OL L EGE S T A T E C O L L E G E , PL MR BY L V / i. I A FEBRUARY I , 19 4 1

100

Run No.

10-H 2Q-H 21-H 22-H 23-H 8-H

Weight % Solubility Hyc. in Ext.

Beta

1 6 .8 1 3 .2

1 -4 9 1 .5 4 1 .5 1 1 .5 6

10.2 8 .6 6 .6 5 .6

P h ase D e n s ity a t 2 5 .0 °C . R a ff. E x t. 0 .7 8 7 0 .7 7 8 0 .7 5 3 0 .7 3 9 0 .7 1 9 0 .6 3 7

A

Methylcyclohexane

Figure No. 3-

The System

O.964 0 .9 8 0 0 .9 8 0 0 .9 9 1 0 .9 9 5 0 .9 9 2

METHYLCI CLOHEXANEn-HEPTANE-ANILINE (C o m p o sitio n s on W eight B a s is ) T em p eratu re

25»0°C.

A tm o sp h eric P r e s s u r e

X

n-Heptane

P e tro le u m R e fin in g L a b o ra to ry The P e n n s y lv a n ia S t a t e C o lle g e S t a t e C o lle g e , P e n n sy lv a n ia J u ly 2 7 , 1942

A n ilin e

0 100

sO H

92

T a b le N o. 21 SUMMARY n-HEPTANE

-

OF

DA TA

ME T H Y L C Y C L O H E X A N E

-

ANILINE

RUN NUMBER

10 - H

20-H

21 ~H

22-H

25-H

TEMPERATURE, ° c . BETA * V.'T. Y I E L D OF HYDROCARBON E XT RACT S O L U B I L I T Y I N E X T R A C T PHAS E ( a )

25

25

25

25 1.SI 8 .6 8.7 a. s 1 .01

25

20.2

--

%

I

__ I

(B) S O L V E N T - T O - O 1L R A T I O WT.

f

BY

ME THY L CY CL OHE XA NE ORIGINAL RAFF I N F T E ( a )

16.7 1.00

WEIGHT IN

10 0 . 0 10 0 . 0 10 0 . 0 10 0 . 0 10 0 . 0

(b) . HYDf i OCAhbON I N ORIGINAL RAFFINATE ( A )

WT.

EXTRACT

Vr' i ;

i

ANILINE

IN

ORIGINAL RAFFINATE EXTRACT

DENSITY

VOLUME

V.EIGHT

50 .0 87.?

10 .6

79.6 79.3 79.5 85.1 85.1

59-8 58. 1 58. 1 68. 0 68.0

39*6 38.5 38.5 98. s 98. 8

99.9 88.2 88.2

99.6 88.8 90 .L 9.9 10.6

99.0 90. R 90.6 8.7

50.9 11.2 9.6 90.1 89.9

(B) (A)

87.5 16.8

(b)

16.7

13*9 13.0

9-9

1 0.6 1.01

25 —

6.7

5.9

6 .5 6 .6

5-5

1.0 0

5 .6 1 . oc

1 9 .6 19-6 27.6 27.6

0.0 0.0 0.0 0.0 O.Q

50 .0

50.1

T2 .7 12.5 8?.?

1 1.8 11.8 86.6 87.0

50 ,0

50 .0

90. 9

93-0

9 1 .0

3.5

6.5 6.6

92.3 5.5 5.6

50 .2

50 .0

5 0 .0

9.6 9.9

9.6 9.0

7.0

91.? 91.5

95.5 93-9

99 .5

PHAGE (a) >B < ( A) ( 3)

.

RUN

(D?) ‘‘

83.3

0.78?

0.778

0.755

0.739

0.7 1 9

0.- 904

0.980

0.98Q

0.991

0.995

OF PHASE ( c c . ) RAFFINATE EXTRACT OF PHASE ( G M . ) RAFFINATE EXTRACT

K T . OF ME T H Y L C Y C L OH E X A N E CHARGED ( G M . ) Yi T. OF M E T H Y L C Y C L O H E X A N E RECOVERED ( G K . ) « VST. OF n - H E P T A l Y E CHARGED ( G M . ) WT. OF n - M E P T A N E RECOVERED ( G M . ) * i n . OF AMI L I M E CHARGED ( G M . ) A T . OF A N I L I N E RECOVERED ( GM. I * TOTAL VIE I GET CHARGED ( G M . ) TOTAL WE I GH T RECOVERED ( G M . ) *

CF

15-9 15-H 13.0 1.00

1 -5 6

PHASE

AT T E MP E R A T U B E OF RAFFINATE E XT RACT

AVERAGE

-I- 5 M

HYDROCARBON

B (a)

EXTRACT

6 .S

1. 9 9

8 -H

A AND

65.0

68. J.

71.9

70.0

55-1

52.5

51 .8

90.7

98.8 98.9

96.9

53.?

5 2 .0

50.9 51 . 8

51 • ? 51.6

5 0 .5

90.9 90.0 10.2

3 0 .0

20.2

■ 29.1 20.2 20.0 50.9

IG.7 50.3 30.9

10.2 10. 1 90.8

__

1 0 1 .0 --

0.697 0-992

51!. 5 98.6

0.0 0.0 5 0 .3

99.9

62 .5

—

__

7-7

9-9 50.9 51.9 101.3 1G 1 . 6

51 .8 I d . 1 100.9

59.9 50.9 52.9 101.9 102.9

50.9 52.1 101 . 9 102.2

0.0 0.0

50 .6 97 .9 5 0 .5 99.? 101 . 1 97.2

B S AMPL ES PE TRGLE.-JM F-CF I C I N G L A B OR AT OR Y THE P E N N S Y L V A N I A S T A T E C OL L EGE STATE C OL L EG E , P EN N SY LV AN IA FEBRUARY

28,

1991

\

Methylcyclohexane

/— Run No.

9-H 13-H 12-H U -H 11-H

B eta

W eight % S o lu b ility Hyc. i n E x t.

P hase D e n sity a t 3 9 .CPC. R aff. E x t. 0 .8 2 1 0 .7 7 1 0 .7 4 2 0 .7 1 7 0 .6 9 5

35-3 1 .2 9 1 .3 5 1.4-6

20.1 1 5 .4 1 0 .7 8 .4

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

/•:\ > \ X r-r,-.;.— X / . \ / . ■. / /• ■a /■__ \/_j_ • \ / r . r\ . . / . : . . a / •. x : / ; \ : / ; x ' / , \ 8 0 —a ~-

Figure No. 32

The System i 7 :--V \ ;\ / \ . y . - \ ' / \ / \ 7 -.\. / . \ _________ • ■' / • • • •■/___ ■y • ■ y ■ \ / \ ’v ’v r/ \ /. \ 7 f 1----- -y—

METHYLCYCLOHEXANEn-HEPTANE-ANILINE (C o m p o sitio n s on W eight B a s is ) T em perature

3 9 •0 ° C.

A tm ospheric P r e s s u r e

P etro leu m R e fin in g L a b o ra to ry The P e n n s y lv a n ia S ta te C o lleg e S ta te C o lle g e , P e n n sy lv a n ia J u ly 2 7 , 1942

Xv

sO XO

n -IIep tan e

A n ilin e 100

T a b le No. 2 2 SUMMARY OF DATA n-HEPTANE -

RUN

METHYLCYCLOHEXANE -

A N IL IN E

number

9 -H

15-H

12-H

14-H

1 1-H

19-H

temperature, ° c

39 — 3 6 .8 3 5 .4 35 -2 1 .0 0

39 1.2 9

39 1. 4 6

39

31 * *

2 0 .0 1. 0 0

39 1.3 4 15 .O 14 .9 • 5*9 1 .0 0

10 0.0 10 0.0 10 0.0 10 0.0 10 0.0

7 4 .5 7 4 .2 74 .2 7 8 .8 7 8 .8

HYDROCARBON IN PHASE ORIGINAL RAFFINATE (A ) (b) EXTRACT (A ) (B)

50 .0 6 6 .8 67 .1 55-4 35-2

A N IL INE IN PHASE ORIGINAL RAFFINATE (a) (b EXTRACT (A ) (B)

50.0 33-2 32 -9 6 4 .6 6 4 .8

. BETA * WT. t YIELD OF HYDROCARBON AS EXTRACT * % SOLUBILITY IN EXTRACT PHASE ( a ) ( b) SOLVENT-TO-O1L RATIO BY WEIGHT ST.

WT.

WT.

t

%

1

METHYLCYCLOHEXANE IN HYDROCARBON ORIGINAL RAFFINATE (A ) (B ) EXTRACT (A ) ( b)

20.0 20.2

_ _

10.1 10.6

7 -8

21 . 8

8.3

10 .8 1. 0 0

8 .4 1.0 0

2 1 .2 2 1 .3 1.00

49. 1 47.6 47.6 55.0 55.0

2 5 .2 2 4 .3 2 4 .3 3 1 .9 3 1 .9

0 .0 0 .0 0 .0 0 .0 0.0

5 0 .0 8 0 .0 8 0 .4 2 0 .2 2 0 .0

50.0 83.3

50.0

50.0

50.0

8 2 .8 ' 1 4 .9 • 5-9

87.1 8 6 .7 10 .6 10 .8

8 8 .8 89.I 8 .3 8 .4

8 3 .0 8 2 .7 21 . 2 2 1 .3

50 .0 2 0 .0 1 9 .6 7 9 -8 8 0 .0

50.0

50.0

50.0

50.0

16 .7 . • 7.2 85.I 84.1

1 2 .9 • 3 -5 8 9 .4 8 9 .2

11 .2 10 .9 9 1 .7 9 1 .6

17 .0 • 7 .5 7 8 .8 7 8 .7

10 0.0 10 0.0 10 0.0 10 0.0 10 0.0

DENSITY AT TEMPERATURE OF RUN ( d J ) RAFFINATE EXTRACT VOLUME OF PHASE ( C C . ) RAFFINATE EXTRACT WEIGHT OF PHASE (G M .) RAFFINATE EXTRACT WT. OF METHYLCYCLOHEXANE CHARGED ( G M . ) WT. OF METHYLCYCLOHEXANE RECOVERED ( G M . ) * WT. OF n-HEPTANE CHARGED ( G M .) WT. OF n-HEPTANE RECOVERED ( G M . ) * WT. OF A N IL INE CHARGED ( G M .) WT. OF A N IL INE RECOVERED ( G M . ) * TOTAL WEIGHT CHARGED (GM. ) TOTAL WEIGHT RECOVERED ( G M . ) *

*

0 .8 2 1 0 .8 9 6

0.771 0-939

0 .7 4 2 0 .9 4 8

0.7 17 0 -9 62

0 .6 9 5 0 .9 6 7

0 .8 08 0 .9 5 7

55 -4 5 8 .6

6 2 .0 5 3 -6

6 7 .9

52.0

71 .2 49 .8

76 .1 4 8 .7

59-9 54. 1

45-5

4 7 .8 50 .4

5 0 .4 4 9 .3

5 1 .1 47 -9

5 2 .9 47-1

4 8 .4

3 7 -9 36 .4 1 2 -7 12.0 5 0 .5 4 9 .8 10 1.1 98 .2

25.2 24 .1 25 .5 2 5 .3 5 0 .5 50 .3 1 0 1.3 9 9 .7

12 .6 12.4 3 8 .0 37-1 5 0 .5 49 -5 101 .1 9 9 .0

0 .0 0 .0

5 0 .5 51.1 0.0 0 .0

52.6 50 .5 49 .1 0 .0 0 .0

50.5 49.0 101.0 98 .1

50.6 5 1 -1

50.5 4 8 .9 10 1.1 1 0 0.0

51.8

50.5 49.1 10 1 . 0 10 0.2

AVERAGE OF,A AND B SAMPLES.

* * DETERMINATION OF SO LUBILITY OF METHYLCYCLOHEXANE IN A N IL IN E AT 3 I . 0 ° C .

(8 7 .8 °F .)

PETROLEUM REFINING LABORATORY THE PENNSYLVANIA STATE COLLEGE STATE COLLEGE, PENNSYLVANIA FEBRUARY I , 19 4 1

100 Methylcyclohexane /•\ /■ ■ " A /■ \ Run No.

17-H 16-H 15-H 18-H

Beta

1 .0 5 1 .2 0 1 .2 7

Weight % ' Solubility Hyc. in Ext. 3 6 .4 2 3 .3 1 6 .0

12.2

Phase Density at 50.0°C. Raff. Ext. 0 .8 1 6 0 .7 6 5 0 .7 5 4 0 .7 0 9

4 /•• V /

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

^

Figure No. 33

A

- \ '/ A The System

x / v ./a A ---A y\ /‘ • \- \/ /•• ■-•\> 'V\ // **\ \// /•'■ 'V / ' - A / ' V / ■

METHYLCYCLOHEXANEn-HEPTANE-ANILINE

•-/'

(C o m p o sitio n s on W eight B a s is ) ■A 60 k~

_ A / 1

T em p eratu re

5 0 .0 °C .

A tm o sp h eric P r e s s u r e

T fvA A A / T A T vA -a P e tro leu m R e fin in g L a b o ra to ry The P e n n s y lv a n ia S t a te C o lleg e S t a t e C o lle g e , P e n n sy lv a n ia J u ly 2 7 , 1942

/V

n -H ep tane 0

/\.

Y

•\7 - • A

A n ilin e

,o

96

Table No. 29 SUMMARY a - H E M AKE -

RUN

7 C ME L ft

SO I. V F N 7 —T 0 - 0 i L V.'T .

f

Fi A T ! I 1 BY

ME T i l Y L C Y C l . C H E X A L E

DATA

METHYLCYCLflHEXAKE -

NU MB E R

!■1 U R t , °C. BIT A * ? , r , % Y I E L D OV H Y DR OC A R B ON AS f. S O L U B I L I T Y I N E X T R A C T P H A S E

OF

E XT R AC T

WEI GHT

I 7-FT 50

50

I .05 5 0 .1

1.20 22.0

5 7 ’. 0

25.4

55-0

23.1

0.9V

6 6 .0 (A )

IfS . 5 47.?

6 6 .>(

52.

66. 4

i

H Y E ROC- A FUTON ORIGINAL R A F F I f ATE

IN

50.5 2

60.

b(

61.1 57.0

U f

A N I L I N E if. ORIGINAL RAFFINATE EXTRACT

3 5 .B

(a) (d) ( a)

WEI GHT

WT. W7. WT. FT.

V I. ST.

TEMPERATURE

6m. 2 OF

4

OF M E T H Y L C Y C L O H E X A N E CHARGED ( G M . ) OF M E T H Y L C Y C L O H E X A N E R ECOVERED ( C - M . J * OF r , - H E P T A N E CHARGED ( G M . ) OF n - H F P T A N F R E C O V E R E D ( G M . ) » OF A N I L I N E C H A R G E D ( G M . ) OF A N I L I N E R E C O V E R E D ( C M . ) *

CHARGED

(C..Y-.) RECOVERED ( G M . ) *

. . -- ----- - ---------- ---- „ ^

* AVERAGE O F

A

0.99

0.99

2 5. s 24.9

0.0 0.0

2 4 .°

0 .0

29.7 29.7

0.0 0.0

50 .1

50.1

79.9 30.7 16.2

82 .5 82.9

15.8

12.2

49.9

23 .u 23.1

12.1

_ __ _ _ _ _ _ _ _ _ _ __ (_ ,_ _ _ __ _ _ _ „ _ _ _ _ _ AND

76.6

15.3 83.8

49.9 17.5 17.1 87.9

7 6 .9

84.2

87.8

26 .4

2 0 .!

ft U14 ( o ' 1 ) 0.316 0.880

59.5 42.9

WEI GHT

15.8

1C.8

12.1 12.2

50.1

25.9

OF PHAS E ( C M . ' 1 R A F F I NA TE E XT RACT

TOTA L

16.2

50

73.6 7*i. I

30.9

73.0 48.7

WEI CUT

L 52.4

4 9 .9

OF P H A S E { c c . l RAFFINATE EXTRACT

TOTAL

1)/ 9

49.5 39 . 8 63.0

RAFFINATE E XT RACT VOLUME

14.5

18-H

PHASE

IB i D i: Fi F I T Y AT

15-B 50 l.?7

PHASE

(a'

EXTRACT

I .00

65.5

65.5

EXTRACT

ITT.

I6-h

I N HYDROCARBON

ORIGINAL

RAFF IR A T E

A N I LI NE

0.765 0.916

69 .c

0.754

0.7C 9 0.942

0.945

73-3 48.7

77.7 47.6

48.1

55*3 46.0

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B SAMPLES. PETROLEUM R E F I N I N G LABORATORY THE P E N N S Y L V A N I A S T A T E C OL L EGE STATE C O L L E G E , P EN K SY L VA N I A FEBRUARY I , 1541

100 . \M e th y lc y c lo h w c a n e

EFFECT OF TEMPERATUR ON SOLUBILITY CURVES

The System METKYLCYCLOT! F M En-HEPTA!E-AN ILINF. (Compositions cn freight Basis) Tem peratures: 1 0 .0 , 2 39-0 and 50.0°C

Key to Tie Line

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P ressure

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Petroleum R efining Laboratory The Pennsylvania S ta te College S ta te C ollege, Pennsylvania J u ly 27, 19A2"

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F i g u r e No. 35 V

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Run No. 75-H 74-H 71-H 73-H 72-H

Beta 2 .3 3 2 .8 4 3 .7 2 5.94 —

Weight % S o lu b ilit y Hyc. in Ext. 50.7 4 5 .4 3 6 .9 21.3 8 .4

Phase D ensity a t 10.0°C . R a ff. Ext. 0 .8 1 8 0 .8 1 3 0 .8 1 2 0 .7 9 6 0 .7 8 8

Figure No. 36

0 .8 1 8 0 .817 0.819 0.809 0 .8 0 0

The System TOLUENE-METHYLCYCLOHEXANEACETONITRILE

(C o m p o sitio n s on W eight B a s is ) T e m p e ra tu re

1 0 ,0 ° C .

A tm o so h eric P r e s s u r e

P e tro le u m R e f in in g L a b o ra to ry The P e n n s y lv a n ia S t a t e C o lle g e S t a t e C o lle g e , P e n n s y lv a n ia J u ly 2 7 , 1942

M eth y lc y clo ­ hexane

A c e to n itrile

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SUMMARY O r vclgiisx

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RATIO

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HYDROCARBON 10 PHAS E ORIGINAL ■ RA F FI NA TE ( A ) . (B> EXT RACT f Ai

75-H

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RAFFINATE

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D E NS I T Y AT TEMPERATURE RAFFINATE EXTRACT

J J

OF

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49.3 49.3

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(CC.)

50 .2

RAFFINATE EXTRACT WEI GHT OF P H A S E , RAFFfNATE EXTRACT

3.72 45.3 37.0 36.3 0.81

PHASE

ORIGINAL

VOLUME OF P H A S E ,

aceto nitrile

2-H

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EXT RACT

WT.
*

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32.3

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45.5 90.6

8 8 .5

99.7

42.7 44.0 45.9 83.0 83.6

5 6 .2

--------------------- . . .

AVERAGE OF A AND 13 SAMPLES

48.7 59.6

39.3 32.3

32.5 44.0

27.5 23.6 88.3 80.3

48.3

25.9 33.0 33-1 28.7 29.6 88.1 88.6

. .............------------------ —

P ET R OL E U M R E F I N I N G L A B OR A T OR Y THE P E N N S Y L V A N I A ST A T E C OLL EGE CTATE C OL L EG E , P E N N S Y L V A N I A

JULY

16 ,

1942

1 0 0 Toluene

Run. No. 76-H 77-H 82-41

Weight % S o l u b i l i ty B eta . Hyc. i n E x t. 2.23 6 .4 8 —

45.3 20.7 7 .5

Phase D ensity a t --10.0°C. R a ff. E x t. 0 .8 5 6 0 .8 2 4 0 .8 0 8

figure No. 37

0.929 0.967 0.988

The System

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-1 0 .0 ° C .

A tm ospheric P r e s s u r e

P e tro leu m R e f in in g L a b o ra to ry The P e n n s y lv a n ia S ta te C o lle g e S t a t e C o lle g e , P e n n s y lv a n ia J u ly 2 7 , 1942

Methylcyclo­ hexane 100

Acetony1aceto n e

eO

V.0

A

104-

Table No. 25 SUMMARY OF DATA ■YETHYL.OYCLOHEX ANE -

TOLUENE ..

82-H

RUM NUMBER

TEMPERATURE, BETA *

SOLVI-NT-TO-Oil.

RATIO

' AT. ? TOLUCWE I N ORIGINAL RAFFINATE

EXTRACT

BY W E IG H T

,

I .00

a

1. 0 0

!0 2. 2 5 3245.

Q 45. 7 0 .? 2

HYDROCARBON

0 .0 0 .0 0 .0 0 .0

2 1 .7 1 2 .5 1 2 .3 4 7 .6

3 7 .6 31.3 3t . * 50. 4 5 0 . *1

o.o fA)

m

YfT• ? HYDROCARBON I N ORIGINAL RAFFINATE ( a ) IB ) E XT RACT (A) (B)

5 0 .0

5 0 .0

6 5 .9

95 .7 96 .0

39.6 91.1

79.5 80.0

7 . 1!

20.5

7.6 IN

5 0 .0

50.O 10 . i;

4.?

I b)

4.0 92.6 92.4

CENSI TY AT T E MP E R AT U R E RAFFINATE EXT RACT VOLUME O F P H A S E , RAFFINATE EXTRACT

(C-C.

WEIGHT CF P H A S E , RAFFINATE EXTRACT

(GM.)

OF R U N ,

WT. WT. ' WT . WT. WT.

*+5.9

*45.7 34.1

20 .5

8.9

20.0

79.5 79 .2”

54.! 54.3

dI

OF TOLUENE CHARGED ( G M . ) OF TOLUENE R E CQVE P ED ( G M . ) * O F ME T H Y L C Y C L OH E X A N E CHARGED ( G M . ) O F ME T H Y L C Y C L OH E X A N E RE COVE RE D ( C M . ) O F ACETONYL. ACETONE CHARGED ( C M . ) ’ WT . OF A C E T ON Y L A C E T O N E R E COVE R E D ( G M . ) * TOTAL WEI GHT CHARGED ( G M . ) TOTAL WEI GHT R ECOVERED ( G I A . ) *

8

20.S

PHASE

(Ai ( b)

A AND

47.6

PHASE

ACETONYLACETONE ORIGINAL RAFFINATE ( A )

AVERAGE CF

2 6 .1

2 0 .5 20.

76-H -

6.4t?

7. 1 * 7.6

( b)

*

-10

a.

*

(A)

EXT RACT

77-H

-! Q

° C .

BT.j S Y I E L D OF HYDROCARBON AS E X T R A C T ? S O L U B I L I T Y IM EXTRACT PHASE | / » j

WT . ?

ACETONYLACETONE

0.808 0.988

*

0.824 0.967

0.856 0.929

50.3 48.4

40.1

57.0

57.3

45.5

40.6 47.8

33.0 55-4

48.8

0.0 0.0 44.0 42.5 44.0 45.9 38.0 88.4

9-7 9.2 34.3 32.2 44.0 4?.0 38.0 33 .L

42.3 22.5 22.0 37.2 36.3 30.9 32.8 90.6 91.1

SAMPLES P E T R O L E U M R E F I N I N G L A B OR AT OR Y THE P E N N S Y L V A N I A S T A T E COLLEGE STATE COLL EGE, P E N N S Y LV AN IA JULY

16 ,

1942

lOO,

Run No. 68-H 70-H 69-h

Beta 1 .5 7 4 .9 8 -

Weight % S o lu b ilit y Hyc. in E xt. 4 6 .6 1 7 .6 5 .4

Phase D en sity a t --10.0°C . R a ff. E xt. 0 .8 9 2 0 .8 3 5 0 .8 1 0

Figure No. 38

0 .9 4 6 1 .0 1 8 1.0 4 3

The System TOLUENE-METHYLCYCLOHEXANEANILINE

(Com positions on Weight B asis) Temperature

-1 0 .0 °C .

Atmospheric Pressure

Petroleum R efin in g Laboratory The Pennsylvania S ta te C ollege S ta te C o lle g e , Pennsylvania Ju ly 2 7 , 1942

Methylcyclo­ hexane

A n ilin e H O A iflH B

106 T a b le No. l 6 ■SUMMARY OF DATA METHYLCYCLOHEXANE -

RUM NUMBER

-»

°c,

BETA* S T . 5! Y I E L D OF HYDROCARBON AS E X T R A C T S O L U B I L I T Y I N EXTRACT PHASE ( A )

*

(B) SOLVENT-TO-OIL

TOLUENE

RATIO

IN

ORIGINAL RAFFINATE EX T R A C T

BY W E I G H T

(A) IS ) (A)

i ' / T . i HYDROCARBON I N OR I G I N A L RAFFINATE ( a )

io

5 .6 5 .4

I-5 7 ' 62.2 46.?

5.3 1.00

17.6 1.00

46.5 0.84

0 .0 0 .0 0 .0 0 .0 0 .0

2 2.0 15.1 15.1

35 .5 3 5.5

46.9 46.9

46.5 16.5

42.3

5 0 .0

50 .0

54.5

91.1 91.6 17.6 17.6

70.0 69.9 46.7 46.5

5 0 .0

50 .0 8.9

45.7 30.0

8 .3

50.1

(A)

5.1 4.4 94.6

82.4

53.3

( b)

94.7

82.4

53.5

PHASE ( a)

(

b)

DENSI T Y AT T E MP E RAT URE RAFT 1 HATE EXT RACT VOLUME OF P H A S E , RAFF ( H A T E E XT RACT

(CC.)

WEIGHT OF P H A S E , F A F F I MATE EXT RACT

(GM.1

uF. HUH,

D?

WT. OF TOLUEME CHARGED ( G M . ) WT. OF TOLUENE RECOVERED ( G M . ) * WT. OF M E T H Y L C Y C L O H E X A N E CHARGED ( C . M . } WT. OF M E T H Y L C Y C L O H E X A N E RECOVERED ( C M . ) WT. OF A N I L I N E CHARGED ( G M . ) S T . OF A N I L I N E RECOVERED ( G M . ) * total w e ig h t c h a r g e d ( cm) Total WEIGHT F E C OV E RE D ( C M . ) *

AVERAGE OF

-

4.93 20.7 17 . 6

94.9 95 .6 5.4 5.3

(A) (B)

EXT RACT

id

PHASE

I b)

WT . « A N I L I N E I N ORIGINAL RAFFINATE

-

o

68-H

HYDROCARBON

^B)

EXT RACT

70-H

- -

i

*

A N IL IN E

69-H

tem p e ra tu re ,

WT.*

TOLUENE -

A AND 0

*

0.81 0

0 .83 5

0 .89 2

1.043

1.018

0.946

5 3 .8 4 3 .L'

44.3

50 .8

31*0 73.8

43.6 45.5

57.0 51.7

27.7 69.8

0.0 0.0

9.7 9.u

22.1 22.0 30 .2

44.0

34,3

43.9 44.0 45.0

33.5 44.0

4 5 .8

8 8.0

33.0

29.9 44.0 45.6 96.3

88.9

33.7

97-5

S AMPL ES P E T R OL E U M R E F I N I N G L A B O R A T O R Y THE P E N N S Y L V A N I A S T A T E C OL L EGE STATE COLLEGE, PENNSY LVAN IA

JULY

S6,

1942

loo /.\ Toluene

Run No.

Beta

81-H 79-H 78-H 80-H

2 .0 7 3 .1 7 5 .3 0 -

Weight % Solubility Hyc. In Ext. 4-3.3 3 2 .3 1 8 .5 6 .8

Phase Density at 10.0°C. Raff. Ext. 0 .8 7 8 0.84-9 0 .8 1 8 0 .8 0 2

Figure No. ~9

/ ■\ / . » ■ / . /^ ;0 r% r-\

1 .0 0 0 1 .0 4 3 1 .0 9 1 1 .1 3 9

The System

so /•:-Y a A a a a ~ a a ■•\ • / _ -A A - ,a A j A _ A a

TOLUENE-METHYLCYCLOHEXANEFURFURAL

A y y / N / V / \ v a\ z^ • - ' / • \ / ■■*/ • \ / *\ / • • • \ / ./ • \ ■ \ Z w : \ / Z ; / ^ A v ^

(C o m p o sitio n s on W eight B a s is ) T em p eratu re

1 0 ,0 ° C .

A tm o sp h eric P r e s s u r e

■ y \;/y \ V

v

A

x '

- " A

P e tro le u m R e f in in g L a b o ra to ry The P e n n s y lv a n ia S ta te C o lle g e S t a t e C o lle g e , P e n n s y lv a n ia J u l y 2 7 , 194-2

40

y / . '. '. \ F u r f u r a l H O 100 -O JB k

Table No. 27 SUMMARY

OF DATA

M£ TH Yl. C Y CL 0 HE X AM E -

TO LUENE

-

FU R F UR A L

Rljfl NUMBER

80-H

73-H

79-H

81 - H

TEMPERATURE, ° C . BET A * WT. < Y I E L D OF HYDROCARBON AS E X T R A C T S O L U B I L I T Y I N E X T R A C T PHAS E | A j

10

10 5.30 21.7

10

10

3.1 7 2 7 .0

13.5 13.4

32.5 32.2

i

7.2 6.8

SOLVED T - T O - O I L

6.7 1.00

1VT.

RATIO

i> TOLUENE

BY

WE I GHT

IN ORIGINAL RAFF I NATE

HYDROCARBON

E XTRACT

(A)

0.0 0.0 0.0 0.0 0.0

(A)

IB)

'.VT.$ HYDROCARBON ORIGINAL RAFF I NATE

IN

1VT.5 FURFURAL I N PHAS E ORIGINAL RAFF I NA TE ( A ) ( b) EXT RACT (A) (B) D E N S I T Y AT TEMPERATURE OF R A F F I NATE E XT RACT

36 .6 23.6 28.6

44.6 37.3 37.3

47.5 47.5

55-9 55-9

55.7 55.7

50.0

50 .2

60 .0

6 1 .7

91.6 91 . 3 13.5 13.4

85-9 86.0

78.1 78.0

32.3 32.2

43.3 43.3

50,0

49.3 8.4 8.2

40.0 14.1 14.0

38.3 21 . 9 22.0

81.5 81 . 6

67*7 67.8

5 6 .7

9 5 o

56.7

R UM, 0.302

0.318

1.139

1.0 91

0.349 1. 0 4 3

0.378 1.0 0 0

(CO.) 52.3 40.9

45.4 47.6

52.2 42.3

49.5 43.3

42.3 46.6

37.1 51.9

44.3 44.1

43.5 43.3

0.0 0.0 44.1 43.4 44.0

9.3 9.6

19.4 13.9 33-4

23.7 25.4

(GM.)

W T . OF TOLUENE CHARGED ( G M . ) WT. OF TOLUENE RECOVERED ( G M . ) * WT. OF ME T H Y L C Y C L OH E X A N E CHARGED ( G M . ) WT. OF ME T H Y L C Y C L OH E XA N E RECOVERED ( G M . ) WT. OF FURF URAL CHARGED ( G M . ) WT. OF FURF URAL RECOVERED ( G M . ) * TOTAL WEI GHT CHARGED ( G M . ) TOTAL WEI GHT RECOVERED ( G M . ) *

*

22.2 [4.6 14.6

94-9 95.1 6.3 6.?

5.1 4.9 93.2

RAFF I N ATE EXTRACT WEI GHT OF P H A S E , RAFF I NATE E XT RACT

0.67

PHASE

EXTRACT

VOLUME OF P H A S E ,

0.99

2 .0 7 3. 5 * 4 43.3 43.3 0.62

45-5 88.1 83.9

54.5 54.0 44.0 45.4 88.3 39.0

33.5 35-2 36.1 88.0 83 .4

3 0 .0 29.6 33.4 54.3

87 .1 87.3

AVERAGE OF A AND B SAMPLES PETROLEUM R E F I N I N G LABORAT ORY THE P E N N S Y L V A N I A S T A T E COLL EGE STATE COLL EGE , P EN NS Y LV AN IA J U L Y l b , I 9 lI 2

100 / \

Run No. 86-H 84-H 83-H 85-H

B eta 1 .3 4 2 .6 9 4 .2 1 -

Weight % S o lu b ility Hyc. i n E x t. 5 0 .6 2 9 .9 1 7 .6 7 .0

M

Phase' Density a t 0 . 0°C. R a ff. E x t. 0 .8 8 7 0 .8 4 1 0 .8 2 0 0 .8 0 4

T o lu e n e

k

A y v:-/a / r —y — y y — A

0 .9 3 8 0 .9 7 9 1 .0 0 8 1 .0 3 3

Figure No. 40 \

80 /■ • \ / v / . /

A \ Y

V .

• / \'

The System a

TOLUENE-METHYLCYCLOHEXANEMETHYL CARBITOL

•AY/-

/:Y :Y V /A A Y -Y \ 60

, ■■ ■\ /

• ' \ / ■ ' X,/ • - V

\/-

(C o m p o sitio n s on W eight B a s is )

V

T em p eratu re

X.

\ • A- - / v 7 \ - • -A /■ A / v / - ’ / •

- ' A

' A - . / avA - A / A ’ /■ • X 7

/Y Y v y A A A ffl X A r X —

/V

-A

•/

■■■•■ y.

/ \

A

A tm o sn h eric P r e s s u r e

■A ■/ \ . a.

/ A :A ~ 7 A

- x / . v / '. - . x / f - A

\/.

7

/

\

■\

■

\

A'.-. /'■ />

V /--77“

A T A A T A A A A ta/

Methylcyclohexane

0 .0 ° C .

P e tro le u m R e f in in g L a b o ra to ry . The P e n n s y lv a n ia S t a t e C o lle g e S t a t e C o lle g e , P e n n s y lv a n ia J u ly 2 7 , 1942

/

M ethyl C a r b i to l H o vO

110

T a b le No. 23 SUMMARY OF DATA M E TH Y L CYCLOHEXAME -

°C.

•ilT . ? Y I E L D OF HYDROCARBON AS E X T R A C T % S O L U B I L I T Y I N E X T R A C T PHAS E | a | SOLVENT - T O - O ' L

RATIO

KT.S

HYDROCARBON

TOLUENE I N ORIGINAL RAFFINATE

BY

*

7.5 7.1 6 .9

I .0 0

‘ EIGHT

0.0 0.0 0.0 0.0 0.0

( a)

(8) EXTRACT

(A)

(B) ill.'}

HYDROCARBON I N ORIGINAL RAFFINATE ( a ) cb) EXTRACT CA)

WT. 3 METHYL C A R B I T O L ORIGINAL RAFFINATE ( a ) (B) EXT RACT (A)

83-H

84 -H

86-H

0

0

0

4.21

2.59

21 . 0

25.1 29.3

17.5 17.6

5 0 .0

1. 0 0

0.66

21.7

56.6

15.7 15.7 44.0 44.0

30.6 30.6 54.3 54.3

1.54 50.2 50.5 50.7

0 .56

48-3 45.3 45.3 53.2 53.2

5 0 .0

5 0 .0

60.1

97.4 97.6

93.9 94.3

86.9

7.1 6.9

17.5

1 7.6

5 0 .0

5 0 .0

2.4

5.2 82.5 82.4

64.2 71.4 71.6

85.? 29.3 30.0

50.5 50.7

39.9 13-2 14.3

55.3 28.6 28.4

70.2

49.5 49.3

I N PHASE

2.6

9 2 .9

(B) AT TEMPERATURE

95.1 OF RUN,

0.304 1.035

VOLUME OF P H A S E , RAFFINATE EXTRACT

(CC.)

WEIGHT OF P H A S E , RAFFINATE E XT RACT

(GM.)

6.1

70.0

d£

RAFFINATE EXTRACT

WT. OF TOLUENE CHARGED ( G M . ) WT. OF TOL UENE RECOVEREO ( G M . ) * WT. OF ME T H YLCYCLOHEXANE CHARGED ( G M . ) WT. OF METHY L CY CL OHE XA NE RECOVERED ( G M . ) WT. OF METHYL C A R B I T O L CHARGED ( G M ) YIT. OF METHYL C A R B I T O L RECOVERED ( G M . ) * TOTAL WEI GHT CHARGED ( GM ) TOTAL WEI GHT RECOVEREO ( G M . ) *

AVERAGE OF a

C A R B IT O L

PHASE

( b)

DENSI TY

METHYL

85-H

RUN N U M B E R TEMPERATURE, BETA *

TO LU E NE -

*

35.3 52.4

45.3

66.2

44.3

40.9

9.7 -9 .3 34.5

19.4 13.3 33.4

33.2

33.7 44.0 45.2 38.0

32.5 35 .1 37.0

88.2

8 8 .1

52.0

41.6 47.2

0.0 0.0

44.9

88.1 88.8

0.387 0.938

74.6 43.6

43.6

43.9 44.1

0.979

52.1 45.3

5U3 45*7

44.0

0.341

0.320 I .003

87.9

3 2 .6 35.6 55.4 58.5 39.1 107.1

107.1

AND B SAMPLE? PETROLEUM R E F I N I N G LABORATORY THE P E N N S Y L V A N I A S T A T E COLLEGE STATE COLLEGE, P EN NS YL V AN IA JULY

16,

1942

lO O

7/eight %

Run No.

Beta.

89-H 87-H

1 .5 3 3.3B

88— 11

S o lu b ility Hyc. i n E x t. 51.3 2 6 .9 1 1 .1

Phase

T o lu en e

/A /A

Density

/

a t - ■20.0°C. R a f f. E x t, 0 ,8 6 8 0 .8 2 9 0 .8 1 6

- .\

Figure No.

0 .9 1 2 0 .9 5 7 0 .9 7 9

The System

v '

' V

'

\

'

TOLUENE-METHYLCYCLOHEXANEMETHYL CELLOSOLVE

•\ /

/A ^ A 2 A A /\

/\ '7 \•

\/

X /

/ ■> ' / V

x /

(C o m p o sitio n s on h e ig h t B a s is )

/'v ' A

V/. \ /

60 a/■ • /• A •- a • - - / \ /.■ V. /. \ 7 ;.\- v \ •/ • \ - / / . , / .

A Y/

'

■

T em p eratu re

•;7-Y y\ \ // \ \\ /-A/ •\\ / /\ \

A

■ A

A

v-' .A./-AV-

•

// A - 7 / - •A■y_/ - _ y

A

-2 0 .0 ° C .

A tm o sp h eric P r e s s u r e

T T -A ./ a . - A /\ v / \ V / \\ // ’\ // • "7 A

• • • /'
P e tro le u m R e fin in g L a b o ra to ry The P e n n s y lv a n ia S ta t e C o lle g e \ / . v \ S t a te C o lle g e , P e n n sy lv a n ia A — /\ J u ly 2 7 , 1942

i-1

Methylcyclohexane

100

M ethyl C e llo s o lv e

112

Table No. 29 SUMMARY OF DATA METHYLCYCLOHEXANE -

RUN NUMBER

t

(B) BY WE 13 HT

RATIO

n.4

HYOROCARBOII

IN

ORIGINAL R A F F I NA T E

EXTRACT

ORIGINAL R A F F I NA T E EXTRACT

\fT .i

EXTRACT

3 5 .8

0.0

89-H -20 1.53 37.4

27.0

5 1 .5

26.7 1.00

51.0 0.54

22.0 13.3 13.3 35.2

50.6 26.3 26.3 55.9

35.2

55.9

PHASE

(a) IB ) (A)

50.0 96. I 96.3 11.2

50.0 90.9 92.3 27.0

5 1 .5

(B)

10.9

26.7

51.0

50.0 3.9 3.2 88.3 89.1

5 0 .0

35.0 23.4 23.6 48.5 49.0

METHYL C E L L OS OL V E ORIGINAL RAFFI NATE

3.38

0.0 0.0 0.0 0.0

A) B) A)

IN

-20

10.9 1.00

B)

HYDROCARBON

87-H

-20 — 12.2 I I .2

U)

SOLVENT - T O - O J L

VT.i

METHYL CELLOSOLVE

88-H

TEMPERATURE, ° C . BETA* WT.< Y I E L D OF HYDROCARBON AS EXT RACT * S O L U B I L I T Y I N EXT RACT PHASE

TOLUENE

TOLUENE -

I N PHASE

(A). (B) (A) (B)

DENSI TY AT TEMPERATURE OF RUN, RAFFI NATE EXTRACT VOLUME OF P H A S E , RAFFI NATE c XTRACT

(CC„)

WEIGHT OF P H A S E , RAFFI NATE EXTRACT

(CM.)

65.0 76.6 76.4

9.1 7.7 73.0 75.3

ol

WT. OF TOLUENE CHARGED (G M .) WT. OF TOLUENE RECOVERED ( G M . ) * WT. OF METHYLGYCLOHEXANE CHARGED ( G M . ) WT. OF METHYLCYCLOHEXANE RECOVERED ( GM. ) WT. OF METHYL CE L L OS OL V E CHARGED ( G M . ) WT. OF METHYL C E L L OS OL V E RECOVERED ( G ! A . ) TOTAL WEI GHT CHARGED ( G M . ) TOTAL WEI GHT RECOVERED (G M .) *

0.316 0.979

* *

0.S29 0.957

0.368 0.912

48.4 49.5

35*5 61.2

53»0 45.7

39-5 48.5

29.4 58.6

46.0 41.7

0.0 0.0 44.0 43-5 44.0 44.5 88.0 38.0

9.7 9.3 34.3 35.4 44.1 45.3 83.1 83.0

17.6 i/ A * V/A '

a

’

/

V

\

f\

• / '

(C o m p o sitio n s on W eight B a s is )

■\ •/ ■A / A- ■/ ‘ '■ ■\ / ' A ’ -V......A . . . / . A• x ! / \ • V -/ \ .x / \ 7 - \ / •\ - / ' / ._ „ 7 -

T em p eratu re

3 0 .0 °C .

A tm o sp h eric P r e s s u r e

V/ . \ / ' '\ - ■ /

A -' A

a

. \ ,7 -a /---------\ y-----------y---------/ - - ' \ a ',/■ -— —-- -AV '.'7 \'a / \ ■a / . .

' v•■■y \

./V.

-A

/\ X V.

/

A - v : y ,

.

\ •/ .v / .

P e tro le u m R e fin in g L a b o ra to ry J ''\fa T \ ^ ne P e n n s y lv a n ia S ta t e C o lle g e ' V S t a t e C o lle g e , P e n n s y lv a n ia 'V a J u ly 27, 1942

-/ \ ,

aV '/ A; / \\ / // X\ / . : \ / ' X / ' \ K \ / - A 7AAA. \\ y . '

. A

‘A—At;

7r:"-7r.'—X r" 7 — ,V

/•

20 T A X ■.

V / .

X ' x 7 - : v / / ’7 ,

'7 7 7 / v - A / .

V

/

V

/

-

V ■A - - A ■A A - - A - -A .

n-Pentane

0 /--

.

A

a •

7A a v ^v T T v ^

A'/

y y a a \ a '■ ■ T — -^ r - f c r - y • X - ■/

X ■ ■/

A

^ \

v

-a

• • • A

A

• A

A

/ \

■ •

t

• / \

:.'

/ •

/.V .V/.

80

100

Aniline

125

Table No. 35 SUMMARY OF OATA N-PENTANE -

TR IMETHYLETHYLEHE -

ANIL I ME

RUN NUMBER

12 6 -H

lll-H

108-H

1 10-H

109-H

TEMPERATURE, ° C . BETA * ET. ? YIELD OF HYDROCARBON AS EXTRACT * i SOLUBILITY IN EXTRACT PHASE | A |

3 0 .0

3 0 .0 1 .2 6 2 6 .6 2 6 .R 2 6 .6 1 .0 0

3 0 .0 1 .*»9 I7 .*» 1 7 .1 1 7 .c 1 .0 0

3 0 .0 1 .6 7 1 1 .6 1 l.*4 1 1 .3 1 .0 0

3 0 .0 —-

5 0 .8 *48.L *48.*4 5 8 .3 5 8 .3

2 5 .5 2 3 .5 2 3 .3 3 3 .6 3 3 .6

5 0 .0

5 0 .0

5 0 .0

8 0 .2 7 9 .5 17 .1 1 7 .0

8 7 .3 8 6 .9 I I . *4 N .3

9 0 .6

5 6 .2 3 8 .6 3 8 .7

5 0 .0 6 9 .** 6 9 .1 2 6 .5 2 6 .6

5 1 .2 M 3 .8 *43.8 6 1 . *4 6 1 .3

5 0 .0 3 0 .6 3 0 .9 7 3 -5 73.*4

5 0 .0 1 9 .8

5 0 .0

50 .0

1 2 .7 1 3 .1 8 8 .6 8 8 .7

9.*4 9 .1

1.05

SOLVEKT-TO-Oll. RATIO BY WEIGHT

WT.

$

TR IMETHYLETHYLEHE IK HYDROCARBON ORIGINAL A' RAFFINATE

B

EXTRACT

A

(B) WT. f HYDROCARBON IN PHASE ORIGINAL RAFFINATE

f

5 6 .2

A N IL IN E IN PHASE ORIGINAL RAFFINATE ( a )

(Bl

EXTRACT

IA I

IB) DENSITY AT TEMPERATURE OF RUN, RAFFINATE EXTRACT

7 7 .0 7 7 .0 7 8 .3 7 8 .3

* l8 .e

EXTRACT

WT.

1 .0 8 m .6 3 8 .6 3 8 .7

7 0 .9 6 8 .3

6 8 .3 7 3 .1 7 3 *1

2 0 .5 8 2 .9 8 3 -0

7 .5 7.*4 7 .6 1 .0 0

0 .0

0 .0 0 .0 0 .0 0 .0

90 .9 7.*4 7 .6

92 .6 9 2 .*4

d{

0 .7 7 8 0 .8 3 9

0 .7 2 6 0 .8 8 6

0 .6 9 0 0.93*4

0 .6 6 8 0 .9 5 9

0 .6 5 1 0 .9 6 8

VOLUME OF PHASE, (C C .) RAFFINATE EXTRACT

5*1.7 5 6 .5

6 0 .*4 >49.6

6 2 .0 *47.8

6*4.2 *46.7

6 7 .1 **5 .5

HEIGHT OF PHASE (G M .) RAFFINATE EXTRACT

*4 2.6 *4?.*4

*45*5 **3«S

*42.8 *4*4.6

*42.5 *4*4.8

*45-7 *4*4.0

IT. OF T R I METHYLETHYLEHE CHARGED, (G M .) NT. OF TR I METHYLETHYLEHE RECOVERED, (G M .) WT. OF H-PENTANE CHARGED, (G M .) WT. OF ll-PEHTANE RECOVERED, (G M .) * WT. OF A N IL IN E CHARGED, (G M .) WT. OF A N IL IN E RECOVERED, ( G M .) * TOTAL WEIGHT CHARGED, (G M .) TOTAL WEIGHT RECOVERED, (G M .) *

5 3 .9 3 2 .8 1 0 .2 9 *5 *46.2 *47.7 9 0 .3 9 0 .0

3 0 .8

2 2 .0 2 1 .1 2 2 .0 2 0 .8 *4*4.0 *45.5 88. C 8?.*4

1 1 .0 10.14 3 5 .0 3 2 .1 *4*4.0 *45.2 88. C 8 7 .7

0 .0 0 .0 *4*4.0 >43.0 **5 .9 *4*4.7 8 7 .9 8 7 .7

* AVERAGE OF A AND B SAMPLES

2 9 .5 1 3 .2 1 2 .9 *4*4.0 *4 5.6 8 8 .0 8 7 .e

PETROLEUM REFINING LABORATORY THE PEHNSYLVANJA STATE COLLEGE STATE COLLEGE, PENNSYLVANIA AUGUST 2 5 . 15*12

100

Run he.

W eight % S o l u b i l i ty Hyc. in E x t.

B eta

97-H 96— H 1 .6 0 93-H 1 .8 6 94-H 2 .0 0 95-H

■31.-4 1 9 .2 1 3 .6 9 .4 6. 3

0.941 1 .022 1.065 1 .080

0 .6 4 9

1 .1 0 1

Trimet,hylet.hylene

/ x

/ \

A

Phase D ensity a t 25.0°C . R a ff. E xt. 0.7-48 0.701 0 .6 8 0 0 .659

/V

/•\ /■

8° /x —

.jyL..

-v . / . \ .

X/X

Figure Me. 47

The System TRIMETHYLETHYLENE-n- PENTANE FURFURAL (C om positions on Weight B asis) Tem perature

25.

A tm ospheric p re s s u re

P etroleum R efin in g L aboratory The P en n sy lv an ia S ta te C ollege S ta te C o lleg e, P ennsylvania J u ly 27, 1942

40 A A

ro

O '

n-Pentane

0

& M

127

T a b le No. 36 S U MMAR Y n-PENTANE

_

°C.

BETA *

SOLVENT-TO-OIL

PATIO

IN

IE (A, b)

% HYDROCARBON RAFFINATE EXTRACT

25.0

25*0 1.60 20.7 19.1 19.2 I .00

2R.0 1.86 14.6

25.0 2.00 9.3 9.4 9.4 1.00

2 5 .0

IO O .C

7 5 -1

100 . c

73.8 73.8 81 . 8 81 . 8

50.4 47.7 47.7 63.0 65.0

'25.5 23.7 23.7 38.1 38.1

0.0 0.0 0.0 0.0 0.0

IN

5 0 .0 92.6 92 .7 6 .5 6.3

100.0 100.0

$ FURFURAL

AT

50 .0

50. C

5 0 .0

5 0,0

7 0 .3

83.9 84.6

87.? 33.5

S

51.7 31.1

19.1 19.2

15.5 13-7

89.3 90.5 9.4 9.4

5 0 .0 2 9 .6 2 9 .7

80.0 16.1 15.4

50.0 12 . 1

5 0 .0 10.7

5 0 .0

H .7

9.5

63.3 63.9

30.9 30.8

8 6 .5

9 0.6 9 0 .6

7-3 93.7 93.7

IN

OF

RUM,

0.748 0.941

EXTRACT ■AT. WT.

OF OF

TRIMETHYLETHYLENE TR I M E T H Y L E T H Y L E N E

WT.

OF

! l _ PEf J TAMr :

OF

N-PENTANE

A T. WT.

OF OF

FURFURAL FURFURAL

RECEOVERED,

CHARGED,

TOTAL

WEI GHT

HE C O V E R E D ,

a

and

b

cm

0.649

0.659 1.080

1.065

I.IO I

6 6 .2

50.7 52.4

56.5 46.5

59.4 44.4

62.7 42.3

40.6

37.9 49.3

39.6

40.4

47.5

47.3

41.3 45.7

'4 5 .0 44.7

44.9

35.0

22.0 2 1 .!

I I .0

0.0 0.0

.0 1 0 .5

22.0

0.0

21 . 0

3U0

44.:

44.0

Nil.5

3 8 .1

88.0

37. 2

27 .1

44.0 45.6 38.0 37.?

4* 1.0

45.0

(GM .)

*

02.2 0 .0

(C V .)

(til.)

.) *

(C M .)

CHARGED? ( G M . ) RECOVERED, ( S M . )

WEI GHT

of

, ( RECOVERED,

charged

CHARGED,

TOTAL

AVERAGE

0.630

(GM.)

RAFFINATE

WT.

o.?oi 1.022

(flO .)

EXTRACT PHASE,

86.3

7.4

D»(

ll. M- TI I IAI ' c

' .VEIGHT 0 -

•

PHASE

TEMPERATURE

PHASE,

6.3 6.3 1.00

70.4

RAFFIMATE EXTRACT OF

6.4

(a1

EXTRACT

OEMS I T V

15.5 13.7 1.00

_ _

PHASE

ORIGINAL RAFFINATE

*

95-H

IO O .C

ORIGINAL

VOLUME

94-H

HYDROCARBON

IA

EXTRACT

WT .

93-H

31.7 31. i 1.00

WEIGHT

$ TRIMETHYLETHYLENE ORIGINAL R A F F ! I. ' ATE

VIT.

BY

FURFURAL

96-H

33.2

EXTRACT |a|

-

9 7 -H

—

VT» i Y I E L D OF H Y D R O C A R B O N AS i S O L U B I L I T Y IN EXTRACT PHASE

'AT.

DATA

TRIMETHYLETNYLENE

RUM NUMBER TEMPERATURE,

OF

’*

*

J2.I : i

10.4 33.0

33.0

44.0 42.7 44.1 45.0 38.1

B?. 0

87.?

45.6

samples

PETROLEUM THE

STATE

J ULY

REFINING

PENNSYLVANIA COLLEGE, 51

,

1942

LABORATORY

STATE

C OL L E GE

PENNSYLVANIA

lo o

Ay Trimethyle'thylene

Run No.

100-H 102-H 98-H 101-H 99-H

Beta

Weight $ Solubility Hyc. in Ext. 3 1 .3

1 .3 2 1 .5 1 1 .5 7

20.0 M -3 1 0 .7 7 .1

Phase Density at 30.0°C. Raff. Ext. 0 .72 9 0 .6 8 7 0 .6 6 4 0 .6 4 8 0 .6 3 2

0 .87 7 0 .9 25 0 .9 4 8 0 .9 65 .0.983

mm.

Figure No. 48

The System TRIMETHYLETHYLENE-n-PENTANEMETHYL CARBITOL . (C o m p ositio ns on Weight B a s is ) Tem perature

30.0°C .

Atm ospheric P r e s s u r e

P etro leu m R e f in in g L a b o ra to ry The P e n n s y lv a n ia S t a t e C ollege S t a t e C o lle g e , P e n n s y lv a n ia J u ly 27, 1942

H ro

00

n-Pentane

Methyl C a rb ito l

0 ]00

129

T a b le No. 37 SUMMARY.OF n —P fT iT A 'IE

-

tr

| M E T H Y L ,r T UYLG''lE

RUN H U M B E R

ETTA

°C.

w

- T O —0.1 L

TR I i.lETHYL E T H Y L E M E

C at

METHYL C A R B IT O L O RIGINAL R A F F ! MATE (ft)

VOLUTE OF P H A G E , RAFFINATE EXT RACT

(OC.'l

’. ( EI GHT OF P H A S E ,

(GM .)

ST.

TOTAL TOTAL

*

CHARGED,

.VEIGHT CHARGED,

(G'.l.) WEI GHT RE COVE RE D, ( G M . )

OF

50.0 —

1 .00

76 , ! 74.4 74.4 79.2 79.2

5 0 .0 84.6 84.6 20.0 19.9

5 0 .0

5 0 .0

2 7 . If 27.2 68.3 68.?

I '3 - b 15-9 30.0 80.!

0 .723

0.63?

0.877

0.925

15.6 14.4 14.2

1 .0 0

f.5 7 11 . 4

7.4 7.0 7.2

10 .6 10.7

1.00

1 . 00

58.3 53.3

24.4 25.0 25.0 51.3 51 . 3

0.0 0 .0 0.0 0.0 0.0

50.0 89.2 39.0 14 . 4 14.2

5 0 .0 95-5 93-9 10.6 10.?

5 0 .0 9 4 .0 95. i 7 .0

51. 1 43.0 98. 0

7.2

5U.0 10.8 If .0

5 0 .0

8 5 .6

39.4

85.3

89-5

50 .0 6.0

6.5 6* i

4-9 93-0 92.3

(GM.)

*

*

0.664 0.948

0.640 0.965

-

0 .6 5 2 0.935

55.6 53-2

59.2

6 1 .6

53.3

5 0 .6

43.7

36.5 51 . I

33.2 49.2

3 9 0 48.0

39.9 47.0

4 1 .5

44.0 42.5 0.0 0.0 44 . 0

33*0 31.3 ! 1.0 10.4 44.0

1 I .0 10.2

45. ! 88. 0 37.6

45.? 33.0 87.4

22.0 20.3 22.0 21 . ! 44.0 45.4 83.0

44.5 88.0

3?.3

86.9

0.0 0.0 44.0 42.6 44.0 44.3 38.0 37.4

50.

T R I M E T H Y L E T H Y L E N E RE COVE RE D, ( Gi=1.) N - P E M T A U E CHARGED, ( G M . ) M- P E N T A ME RECOVEREO, ( G M . ) * METHYL C A R B I T O L CHARGED, < CM * ) METHYL C A R B I T O L RE COVE RE D, ( D M .

AVERAGE

50.0

U51

OF RUM,

OF T R I l f l t T H Y L E T H Y L E N E

OF S T . OF » T . OF *-VT. OF HT. OF

50.0

1.52 22.if

IN PH A G E

E XTRACT

in.

;fi.o

19.9

51.2 31.3

(8) (A) I oi

AT T E M P E R A T U R E RAFFINATE IXTRACT

RAFFINATE

99-H

5i o

50.0 72.6 72. a

( b)

DENSITY

101 —H

PHASE

IB)

EXTRACT

98-H

I Pi H Y D R O C A R B O N

EXTRACT

EXTRACT

10 2 - H

2 0 .0

100.0 1 00.0 1 0 0 .0 1 00.0 1 00.0

HYDROC-TfiBOM IN ORIGINAL R A FF IN A T E (ft)

CA RBITO L

50 .o 51.2

1 .0 0

' I OH”

RATIO

OR ! G I 'IAL R A FF INA

$

00 ~H

—

EOLVEMT

AT.

METHYL

5 0 .0

•.VT. ? Y I E L D O F H Y O R O C \ R B 0 ! i A S E X T R A C T * S S 0 L U 8 I L I TV IN E X T R A C T P H A S E

?/T , $

-

I

TEMPERATURE,

V;t . i

DATA

!

35.0

3 2 .2 44.0

65.7 46.7

45.9

A AMD B SAMPLES PETROLEUM R E F I N I N G L ABOR ATI THE P E N N S Y L V A N I A STATE COLLEGE S T ' - T E COL L E GE , P E N N S Y L V A N I A J U L Y 3 1 , 19 4 2

100 \

Run No.

Beta

Weight % S o lu b ility Hyc. in Ext.

Phase D ensity a t -~20.0°C. R a ff. E xt.

T r im e th y le th y le n e

F igure No. 49

j / / ■ ,/tt :

■.5 0 .7 5

- 2 0 .0 1 .214 31 »** 30.T* 3 0 .7 0 .8 2

-2 0 .0 I . 1*7

7 9 .9 7 8 .5 7 8 .J 80. e 8 0 .8

7 2 .5 7 1 .2 7 1 .2 7 5 . *t 7 5 . *t

5 0 .U 1*8.0 1*8.0 5 7 .7 5 7 .7

5 7 .9 7 2 .3 7 2 .6 * » l.3 **• »5

5 5 .C 8 2 .5 8 2 .2 30.1* 3 0 .7

1*2.3 2 7 .7 2 7 .it 5 8 .7 5 8 .5

N 5 .0 1 7 .5 1 7 .8 6 9 .6 6 9 .3

2 2 .U

1 9 .0 1 8 .5 1 .0 0

1 9 .0 1 8 .S

5 0 .0 8 .5 8 .e 8 1 .0 8 1 .1

5 0 .0 **.7 *1.6 87.1* 8 ? .l*

5 0 .0 3 .3 3 -6

92.1 9 2.0

dJ

0 .7 6 1 0.8«t?

0 .7 2 9 0 .8 8 1

0.7 0 3 0 .9 1 9

0 .6 8 6 0.9** •*

0 .6 7 0 0 .9 6 2

VOLUME OF PHASE, (C C .) RAFFINATE EXTRACT

5 8 .1 53. S

5 2 .5 5 6 .3

5 6 .3

5 5 .9 5 2 .1

6 0 .9 1*9.2

WEIGHT OF PHASE, (G M .) RAFFINATE EXTRACT

•***.? *♦ 5 .6

3 8 .3 1*9.6

3 5 .9 5 1 .7

3 8 .3 1*9.2

N 0 .8 1*7.3

WT. OF TRIMETHYLETHYLEHE CHARGED, (G M .) WT. OF TRIMETHYLETHYLEHE RECOVERED, (G M .) * WT. OF N-PENTANE CHARGED, (G M .) WT. OF H-PEKTANE RECOVERED, (G M .) * WT. OF METHYL CELLOSOLVE CHARGED, (G M .) WT. OF METHYL CELLOLSOLVE RECOVERED, (G M .) * TOTAL WEIGHT CHARGED, (G M .) TOTAL WEIGHT RECOVERED, (G M .) *

L l . i* N o .5 10.1* 1 0 .5 5 7 .9 3 8 .8 8 9 .7 8 9 .8

3 5 .2 5 **.0 1 3 .2 1 2 .8 3 9 .6 1*1.1 8 8 .C 87. S

2 2 .C 2 1 .5 2 2 .0 2 1 .2 1*1*.0 1*1*.9 8 8 .0 8 7 .6

1 1 .0 1 0 .6 5 3 .0 5 2 .1 1*1*.0 1*1*. 8 8 8 .0 8 7 .5

0 .0 0 .0 1*1*.0 1*3 . 2 1*3.9 1*1* . 9 8 7 .9 8 8 .1

* AVERAGE 6F A AND B SAMPLES

51.1

PETROLEUM REFINING LABORATORY THE PENNSYLVANIA STATE COLLEGE STATE COLLEGE, PENNSYLVANIA AUGUST 2 5 , I9**2

10°/\ Trimethylethylene

/■'•A A': Run No.

124-H 122-H 121-H 123-H 125-H

Beta

—

1 . 39 1 . 51 1 . 58 -

Weight % S o lu b ility Hyc. i n E x t. 3 2 .1 1 9 .2 13-1 1 0 .0 7 .4

Phase D e n sity a t 30.0°C . R aff. E x t. 0 .731 0.679 0.65 8 0.645 0 .6 28

Figure No. 50

0 .9 17 0 .9 8 6 1 .014 1 .0 4 1 1 .0 57

The System TRIMETHYLETHYLENE-n-PENTANE PHENYL CELL0S0LVE (C om positions on Weight B a sis) Tem perature

30.0°C .

Atmospheric P r e s s u r e

Petroleum R e f in in g L a b o ra to ry The P e n n s y lv a n ia S t a t e C ollege S t a t e C o lle g e , P e n n s y lv a n ia J u l y 27, 1942

A

H V jJ

n-Pentane

Phenyl C e llo s o lv e

0 100

SUMMARY OF DATA N-PENTANE -

TEMPERATURE, BETA

TRIMETHYLETHYLENE -

30 .0

°C.

__

*

WT. ? YIELD OF HYDROCARBON AS EXTRACT SOLUBILITY IN EXTRACT PHASE ^A|

*

%

SOLVENT-TO-OIL RATIO BY WEIGHT

WT.

i

TRIMETHYLETHYLENE IN HYDROCARBON ORIGINAL RAFF IHATE ( a ) EXTRACT

(A

(B) IT .

%

HYDROCARBON IK PHASE ORIGINAL RAFFIHATE EXTRACT

IT .

i

PHENYL CELLOSOLVE

PHENYL CELLOSOLVE IN PHASE ORIGINAL RAFF I NATE ( a V EXTRACT

M (B )

DENSITY AT TEMPERATURE OF RUN, RAFFIHATE EXTRACT

3 8 .5 5 2 .2 3 2 .0 1 .0 0

1 0 0 .0 1 0 0 .0 1 0 0 .0 1 0 0 .0 1 0 0 .0

5 0 .0 1 -5 9 2 1 .7 1 9 .2 19 .1 1 .0 0

3 0 .0 1.51 IV .2 1 5 .3 1 2 .8 0 .9 9

30 .0 I . 58

7 5 .1 7M .»i 7 U .4 8 0 .2 8 0 .2

5 0 .8 4 6 .0 1*8.0 5 8 .3 5 8 .3

2 5 .? 2 4 .0 2 4 .0 3 3 -2 3 3 .2

0 .0 0 .0 0 .0 0 .0 • 0 .0

5 0 .5 92 . 5 9 3 .5 13*5 1 2 .8

5 0 .0 9 4 .6 9 5 .7 10. 1 9 .S

50 .0 9 5 .8

4 9 .5 7 -5 6 .5 8 6 .7 8 7 .2

5 0.0

5 0 .0

5 .4 4 .3 8 9 .S

4 .2 5 .6 9 2 .6 9 2 .7

5 0 .0

5 0 .0

7 5 .6 7 6 .6 3 2 .2 3 2 .0

8 8 .0

5 0 .0

5 0 .0

2 4 .4 2 3 .4 67. e 6 8 .0

1 2 .0 1 1 .9 8 0 .8

88 .3 1 9 .2 1 9 .1

80 .9

1 0 .8 10.1 9 .9 1 .0 0

7 .8 7 .4 7 .3 l.0 (

9 6 .4 7 .4 7 .3

90.1

d£

0 .7 3 1 0 .9 1 7

0 .6 7 9 0 .9 8 6

0 .6 5 8 1 .0 1 4

0 .6 2 8 1 .0 5 7

0 .6 4 5 1.041

VOLUME OF PHASE, (C C .) RAFFIHATE EXTRACT

4 8 .4 5 7 .6

5 5 .8 5 0 .3

6 0 .0 4711

6 1 .3 4 5 -7

WEIGHT OF PHASE, (G M .) RAFF I MATE EXTRACT

3 5 .4 5 2 .8

3 7 .9 4 9 .6

3 9 -5 4 7 .8

3 9 .5 4 7 .6

WT. > OF TRIHETHYLETHYLEME CHARGED, (G M .) WT. OF TRIMETHYLETHYLENE RECOVERED, (G M .) * WT. OF M_PENTa KE CHARGED, (G M .} WT. OF N-PENTANE RECOVERED, (G M .) • ST. OF PHENYL CELLOSOLVE CHARGED, (G M .) WT. OF PHENYL CELLOSOLVE RECOVERED, (G M .) • TOTAL WEIGHT CHARGED, (G K .) TOTAL WEIGHT RECOVERED, (G M .) *

4 4 .0 4 3 .8 0 .0 0 .0 4 4 .1 4 4 .4 8 8 .1 8 8 .2

3 3 .0 3 2 .5 1 1 .0 1 0 .? 4 4 .0 4 4 .? 8 8 .0 8 7 .5

22 . 0 2 1 .2 2 2 .0 2 1 .7 4 3 .6 4 4 .4 8 7 .6 8 ? .?

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

* AVERAGE OF A AND B SAMPLES

3 0 .0

6 5 *4 4 3 .6

'

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

PETROLEUM REFINING LABORATORY THE PENNSYLVANIA STATE COLLEGE STATE COLLEGE, PENNSYLVANIA AUGUST 2 5 , 1942

134 Figure No. 51 VARIATION OF BETA WITH HYDROCARBON SOLUBILITY ( H y d r o c a r b o n S y s te m :

T rim e th y le th y le n e -n -P e n ta n e )

Key t o S o l v e n t s 1. 2.. 3. 4• 5. 6. 7.

PETROLEUM R E F I N I N G LABORAT ORY THE P E N N S Y L V A N I A S T A T E COLLEGE

A c e to n itrile A c e to n y la c e to n e A n ilin e F u rfu ral M eth y l C a r b i t o l M eth y l C e l lo s o lv e Phenyl C e llo so lv e

STATE

2.8

2 .4 2.2

2.0

B eta

1 .8

1.6

1 .2

1.0

10

40 20 S o lu b ility Weight Per Cent Hydrocarbon Solubility

C OL L EGE , P E N N S Y L V A N I A ' OCTOBER 2 6 , 19*42

135 hydrocarbon s o l u b i l i t y a t b e ta = 1 .0 f o r th e s o lv e n t s a c e to n y la c e to n e , a n i l i n e , e n d m e t h y l c e l l o s o l v e w e r e o b t a i n e d fr o m t h e t e r n a r y d i a g r a m s . The t i e - l i n e s o n t h e t r i a n g u l a r d i a g r a m s w e re b i s e c t e d a n d t h e l i n e c o n n e c t i n g t h e s e p o i n t s was e x t e n d e d t i l l

it

c ro sse d th e s o l u b i l i t y

c u r v e , w h ic h w as t h e d e s i r e d s o l u b i l i t y . From t h e . s e d a t a i t

is

e v id e n t t h a t th e v a lu e s o f b e ta f o r a

sy ste m a r e n o t n e c e s s a r i l y c o n s t a n t ,

even th o u g h b o th h y d ro c a rb o n s a r e

o n ly p a r t i a l l y m i s c i b l e i n t h e s o l v e n t a t th e e q u ilib r iu m te m p e r a tu r e . (See F i g u r e s 4 i ,

4-7, 4-3 a n d 5 0 . )

T h i s was a l s o

t r u e f o r t h e sy ste m

m e t h y l c y c l o h e x a n e - n - h e p t a n e —a n i l i n e a s was p o i n t e d o u t e a r l i e r . A l s o , w h en t h e r e i s

a v a r i a t i o n o f b e ta w ith h y d ro c a rb o n

s o l u b i l i t y , i t may o r may n o t b e l i n e a r when t h e d a t a a r e p l o t t e d o n a s e m i-lo g a rith m ic p l o t .

T h is seem s to d epend on t h e s o l v e n t a s w e l l

a s on t h e p a r t i c u l a r h y d r o c a r b o n s w h ic h make u p t h e s y s t e m .

From t h e

d a t a w h ic h a r e a v a i l a b l e a t p r e s e n t no g e n e r a l c o n o l u s i o n s c a n be d raw n w ith r e s p e c t t o t h e r e l a t i o n b e tw e e n b e t a and h y d ro c a rb o n s o l u b i l i t y , , i n th e e x t r a c t p h a se .

H o w e v e r, w hen m ore s o l v e n t s a n d h y d r o c a r b o n

s y s te m s h a v e b e e n i n v e s t i g a t e d ,

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

I n T a b l e 4-0 t h e v a l u e s o f b e t a a r e l i s t e d w h ic h c o r r e s p o n d t o a h y d r o c a r b o n s u l u b i l i t y o f 20 w e i g h t p e r c e n t . fro m t h e c u r v e s f o r t h e s e v e r a l s o l v e n t s . o rd er o f in c re a s in g v a lu e s f o r b e ta ,

is

They- a r e t a b u l a t e d i n t h e

so t h a t c o m p a r i s o n s may be made w i t h

t h e o t h e r two h y d r o c a r b o n s y s t e m s s t u d i e d . w e ig h t h y d ro c a rb o n s t h e n i t r i l e

T h ese v a l u e s w ere t a k e n

F o r t h e s e lo w m o l e c u l a r

th e m ost s e l e c t i v e , w ith th e d ik e to n e

and t h e a l d e h y d e f o l l o w i n g w i t h l o w e r v a l u e s o f b e t a . l i s t e d , m e th y l c a r b i t o l h a s th e lo w e s t s e l e c t i v i t y .

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