THE CORRELATION OF TRUE BOILING POINT AND

EQUILIBRIUM FLASH VAPORIZATION CURVES

FOR SOME CANADIAN CRUDE OILS

by
WALTER HAYDUK

A THESIS SUBMITTED IN PARTIAL FULFILMENT OF

THE REQUIREMENTS FOR THE DEGREE OF

MASTER OF APPLIED SCIENCE

i n t h e Department

of

Chemical E n g i n e e r i n g

We a c c e p t t h i s t h e s i s as c o n f o r m i n g t o

the standard r e q u i r e d from candidates f o r

t h e degree o f MASTER OF APPLIED SCIENCE

Members o f t h e Department o f

Chemical E n g i n e e r i n g

THE UNIVERSITY OF BRITISH COLUMBIA

October, 1955.
ABSTRACT

An Ofchmer r e c i r c u l a t i n g s t i l l and a s t a n d a r d

packed column f r a c t i o n a t i n g u n i t were us«d i n d e t e r -

m i n i n g t h e e q u i l i b r i u m f l a s h v a p o r i z a t i o n and t r u e

b o i l i n g p o i n t c u r v e s r e s p e c t i v e l y , f o r e i g h t samples

o f crude o i l s from p r o d u c i n g o i l - f i e l d s i n A l b e r t a .

The EFV curves, a t 10 mm. a b s o l u t e p r e s s u r e were a l s o

o b t a i n e d f o r t h e s e samples.

Determinations a t atmospheric p r e s s u r e were

used f o r m o d i f y i n g Okamoto and Van W i n k l e ' s correl-

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

f r o m t h e TBP c u r v e s , f o r a p p l i c a t i o n t o crude oils.

The c o r r e l a t i o n r e l a t e s t h e 50 p e r c e n t p o i n t s and

the s l o p e s o f t h e two c u r v e s . I n s p i t e o f i t s s i m p l -

i c i t y , i t r e s u l t s i n p r e d i c t e d c u r v e s o f good a c c u r a c y .

I t i s b e l i e v e d t h a t t h i s method i s s u i t a b l e f o r a

l a r g e number o f crudes and can g i v e dependable phase

equilibrium data.
ACKNOWLEDGEMENTS

A p p r e c i a t i o n i s expressed f o r

t h e s u g g e s t i o n s and guidance g i v e n by

Dr. L. W. S h e r a i l t under whose s u p e r -

v i s i o n t h i s r e s e a r c h was p e r f o r m e d .

Acknowledgement i s a l s o made t o t h e

I m p e r i a l O i l Company o f Canada and t h e

S t a n d a r d O i l Company o f Canada who

s u p p l i e d t h e samples.
 TABLE OF CONTENTS

Page
I, INTRODUCTION 1 #

II. PREVIOUS CORRELATIONS 3.

III. APPARATUS 5.
(a) TBP Still
(b) EFV S t i l l

(c) Temperature Measurement

IV. SAMPLES AND MATERIALS X 6 #

V. PROCEDURE 20.

(a) TBP Still

(b) EFV S t i l l

(c) C a l i b r a t i o n o f TBP column

VI. RESULTS 29.

•VII. DISCUSSION OF RESULTS 5 6 #

VIII. BIBLIOGRAPHY 6 1 #
 TABLES

Page

T a b l e I N u m e r i c a l Data f o r TBP and EFT E x p e r i m e n t a l

Points 51

T a b l e I I N u m e r i c a l Data f o r TBP and EFV C o r r e l a t i o n s 55

ILLUSTRATIONS

1. Diagram o f TBP S t i l l , F i g . 1. 6

2. Diagram o f EFV S t i l l , F i g . 2. 10

3. C a l i b r a t i o n c u r v e f o r thermometers, F i g . 3. 14

4. Cox c h a r t , F i g . 4. 23

5. McCabe-Thiele Method f o r TBP column

E f f i c i e n c y , F i g . 5. 28

6. C o r r e l a t i o n o f TBP and EFV 50 p e r c e n t points.,

Fig. 6. 30

7. C o r r e l a t i o n o f TBP and EFV s l o p e s , F i g . 7. 31

8. A t m o s p h e r i c and 10 mm. EFV c u r v e s , F i g . 8a-8h. 32

9. Phase Diagrams f o r crude o i l samples, F i g . 9. 41

10. A t m o s p h e r i c TBP and EFV c u r v e s , F i g . l O a - l O h . 43

 1.

I . INTRODUCTION

Such o p e r a t i o n s as t h e v a p o r i z a t i o n and c o n d e n s a t i o n

of hydrocarbon m i x t u r e s a r e b a s i c i n t h e p r o d u c t i o n and

r e f i n i n g of petroleum. I t i s o f t e n necessary t o p r e d i c t vapor-

l i q u i d phase e q u i l i b r i u m c o n d i t i o n s i n p r o c e s s d e s i g n c a l c u t

l a t i o n s and i n a n a l y z i n g commercial o p e r a t i o n s . The a b i l i t y

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

mixture, or the operating conditions t o give desired y i e l d s

of c e r t a i n f r a c t i o n s , i s o f prime economic i m p o r t a n c e . For

t h e s o l u t i o n o f problems concerned w i t h t h e phase e q u i l i b r i a

of complex h y d r o c a r b o n m i x t u r e s , e m p i r i c a l methods based on

t h e common l a b o r a t o r y , d i s t i l l a t i o n s , m u s t s t i l l be used.

Petroleum d i s t i l l a t i o n processes i m v a r i a b l y entail

the p r e h e a t i n g o f t h e s t o c k o r crude w i t h subsequent flashing

i n t h e d i s t i l l a t i o n column. Calculations f o r the conditions

of t e m p e r a t u r e and p r e s s u r e r e q u i r e d t o g i v e a p a r t i c u l a r

residuum a r e s i m p l i f i e d by t h e use o f e q u i l i b r i u m flash£ v a p o r -

i z a t i o n (EFV) c u r v e s . These c o n s i s t o f p l o t s showing isobaric

curves of percent v a p o r i z e d versus t h e v a p o r - l i q u i d equilibrium

temperature. The s m a l l l a b o r a t o r y EFV s t i l l d e s i g n e d by

Othmer (15) has proven t o be s u c c e s s f u l f o r o b t a i n i n g EFV c u r v e s

at subatmospheric p r e s s u r e s . S i n c e subatmospheric p r e s s u r e s
r

are g e n e r a l i n p e t r o l e u m r e f i n i n g , t h e EFV c u r v e s a r e w i d e l y

applicable. Because t h e s e s t i l l s a r e n o t as yfct s t a n d a r d

l a b o r a t o r y equipment and because o f t h e e x p e r i e m e n t a l d i f f i c u l t i e s

i n v o l v e d , EFV curves a r e u s u a l l y p r e d i c t e d from t h e more

common t r u e b o i l i n g p o i n t (TBP) and A.S.T.M. d i s t i l l a t i o n

curves. C o r r e l a t i o n s f o r p r e d i c t i n g EFV c u r v e s which can be

a p p l i e d t o petroleum f r a c t i o n s are u n s a t i s f a c t o r y f o r crudes.

A s u i t a b l e c o r r e l a t i o n f o r crudes was t h e s u b j e c t o f t h i s

investigation. Because t h e A.S.T.M. d i s t i l l a t i o n i s n o t v e r y

reproducible and i s d i f f i c u l t t o complete f o r c r u d e s , t h e TBP

d i s t i l l a t i o n was chosen as b e i n g t h e more s u i t a b l e f o r

correlating purposes.
 3.

I I . PREVIOUS CORRELATIONS

Two t y p e s o f e m p i r i c a l c o r r e l a t i o n s a p p l y i n g g e n e r a l l y

t o petroleum f r a c t i o n s are a v a i l a b l e i n the l i t e r a t u r e f o r

p r e d i c t i n g t h e EFV curve a t a t m o s p h e r i c p r e s s u r e . One t y p e

uses t h e i n t e r s e c t i o n p o i n t and t h e s l o p e s o f t h e f l a s h and

A.S.T.M. o r TBP c u r v e s , and t h e o t h e r uses t h e 50 p e r c e n t b o i l i n g

p o i n t s and s l o p e s . I n t h e method proposed by Piroomov and

Beiswenger (17) t h e f l a s h c u r v e was assumed t o be a s t r a i g h t

l i n e and was l o c a t e d by e s t i m a t i n g t h e p o i n t o f i n t e r s e c t i o n and

i t s s l o p e from t h e smoothed A.S.T.M. o r TBP d i s t i l l a t i o n s . In

t h e method proposed by N e l s o n and Souders (11) and m o d i f i e d by

. K a t z and Brown (9) t h e EFV c u r v e was a l s o assumed t o be a

s t r a i g h t l i n e and was p r e d i c t e d by e s t i m a t i n g i t s 50 p e r c e n t

p o i n t and s l o p e from t h e 50 p e r c e n t p o i n t and 10-70 p e r c e n t

s l o p e o f t h e A.S.T.M. o r TBP d i s t i l l a t i o n s . Experiment aLL

EFV d a t a i n d i c a t e t h a t t h e l i n e s a r e not a c t u a l l y straight

a l t h o u g h t h e c u r v a t u r e f o r a l a r g e p o r t i o n o f t h e curve i s

s l i g h t (16). I n t h e method p r e s e n t e d by P a c k i e (16) and r e v i s e d

by E d m i s t e r and P o l l o c k (4) t h i s d e p a r t u r e from a s t r a i g h t line

was t a k e n i n t o c o n s i d e r a t i o n .

None o f t h e e x i s t i n g methods o f . c o r r e l a t i o n a r e

constructed t o apply s p e c i f i c a l l y f o r crudes. The E d m i s t e r

and P o l l o c k c o r r e l a t i o n , f o r example, uses t h e TBP s l o p e s as

parameters on a p l o t o f TBP 50 p e r c e n t v e r s u s t h e d i f f e r e n c e

i n TBP and EFV 50 p e r c e n t p o i n t s . The s l o p e s , however, have

t o o s m a l l a range t o account f o r t h e s t e e p s l o p e s o f TBP c u r v e s

 4.

f o r crudes. As a r e s u l t a s i m p l i f i e d c o r r e l a t i o n by Okamoto

and Van W i n k l e (14)^which shows g e n e r a l relationships

between TBP and EFV c u r v e s , has been chosen as a b a s i s f o r

the present c o r r e l a t i o n . I n t h i s c o r r e l a t i o n the' EFV 50 p e r c e n t

p o i n t i s determined from the TBP 50 p e r c e n t points, and t h e 10-70

p e r c e n t s l o p e i f r o m t h e TBP. 10-70 p e r c e n t s l o p e . The v a l u e s

f o r t h e crude o i l s a r e compared d i r e c t l y w i t h t h e c o r r e l a t i o n

of Okamoto and Van W i n k l e .

 5

III. APPARATUS

(a) True B o i l i n g P o i n t S t i l l

The TBP apparatus c o n s i s t s of an a l l - g l a s s analytical

d i s t i l l a t i o n u n i t w i t h an e f f i c i e n t f r a c t i o n a t i n g column

s u i t a b l e f o r crude e v a l u a t i o n . Accessories include a

l i q u i d - d i v i d i n g s t i l l - h e a d f o r convenient r e f l u x control,

a vacuum u n i t w i t h a p r e s s u r e c o n t r o l l e r and d r y - i c e t r a p ,

a mercury manometer, and a m a n i f o l d p e r m i t t i n g s e p a r a t e

e v a c u a t i o n o f t h e d i s t i l l a t e r e c e i v e r d u r i n g vacuum

operation. F i g u r e 1 shows the arrangement o f t h e apparatus.

A g l a s - c o l h e a t e r p r o v i d e s t h e n e c e s s a r y heat i n p u t t o

t h e s t i l l - p o t ; f o r r e d u c i n g t h e l a r g e heat l o s s a t t h e

h i g h temperatures used, a u x i l i a r y r i b b o n h e a t e r s covered

w i t h i n s u l a t i o n e n c l o s e t h e column and s t i l l - h e a d . The

u n i t i s compact and simple i n o p e r a t i o n , d e s i g n e d to

o p e r a t e w i t h a minimum amount o f a t t e n t i o n .

The column i s a s t a n d a r d type 1 - i n c h s i l v e r e d vacuum-

j a c k e t e d column packed t o h e i g h t o f 22 i n c h e s w i t h 1/8

inch glass helices. Twelve e x p a n s i o n b e l l o w s a l o n g the

outer j a c k e t permit the necessary expansion f o r the h i g h

temperatures encountered i n crude d i s t i l l a t i o n . The

performance o f t h e column when c a l c u l a t e d by t h e McCabie

and T h i e l e method (10) u s i n g a benzene-carbon t e t r a c h l o r i d e

t e s t m i x t u r e , i s 11.4 theoretical plates. T h i s performance

corresponds t o o p e r a t i o n a t a t m o s p h e r i c pressure, at

t o t a l r e f l u x , and a d i s t i l l a t i o n r a t e o f about 1500 ml.

REFLUX TIMER V"
s
POTENTIOMETER
 7.

p e r hour, the r a t e n o r m a l l y used. The column i n c o n j u n c t i o n

w i t h the r e f l u x c o n t r o l s t i l l - h e a d has an a v a i l a b l e f e e d

c a p a c i t y c o n s i d e r a b l y h i g h e r than t h a t used i n t h e s e d e t e r -

m i n a t i o n s ; however, f o r convenience, r e l a t i v e l y s m a l l samples,

(2 l i t r e s ) were d i s t i l l e d . At 10 mm. p r e s s u r e no significant

d i f f e r e n c e i n column o p e r a t i o n was obsejrved. In a l l respects

t h e column o p e r a t e d s u c c e s s f u l l y .

An a u t o m a t i c l i q u i d - d i v i d i n g s t i l l - h e a d (manu-

f a c t u r e d by t h e G l a s s E n g i n e e r i n g L a b o r a t o r i e s , San C a r l o s ,

C a l i f o r n i a ) (3) a c t i v a t e d by a s o l e n o i d , a l o n g w i t h a w a t e r -

c o o l e d condenser, p r o v i d e s any d e s i r e d r e f l u x r a t i o . The

s t i l l - h e a d i s so c o n s t r u c t e d t h a t t h e vapor s t r e a m r i s i n g f r o m

the column f l o w s p a s t a g r o u n d - j o i n t p a r t i a l - i m m e r s i o n

thermometer, t h e n d i r e c t l y t o the condenser. The condensate

f l o w s down t h r o u g h the s t i l l - h e a d by a d i f f e r e n t r o u t e ,

p a s s i n g t h r o u g h a s m a l l t i p p i n g f u n n e l which n o r m a l l y directs

t h e l i q u i d stream t o the c e n t r e o f t h e column p a c k i n g .

Contained i n t h e t i p p i n g f u n n e l i s a p i e c e of s o f t i r o n w h i c h

can be a t t r a c t e d by a s o l e n o i d o u t s i d e the s t i l l - h e a d . When

so a t t r a c t e d the f u n n e l d i r e c t s the l i q u i d s t r e a m t h r o u g h a

vapor t r a p t o the product r e c e i v e r . The solenoid i s activated

by an e l e c t r o n i c t i m e r w h i c h s u p p l i e s power f o r t h r e e seconds

at a time. R e f l u x c o n t r o l i s e f f e c t e d by changing t h e on-off

time r a t i o of the t i m e r and assuming t h a t t h i s corresponds to

the l i q u i d r e f l u x r a t i o o b t a i n e d . T e s t s have i n d i c a t e d t h a t

the r e f l u x r a t i o - c o n t r o l l e r g i v e s a somewhat h i g h e r r e f l u x
 8.

r a t i o t h a n i n d i c a t e d by t h e t i m e r ( 3 ) ; however, t h i s does

n o t s i g n i f i c a n t l y e f f e c t t h e o p e r a t i o n o f t h e column.

The vacuum u n i t i n c l u d e d an o i l - f i l l e d fore-pump-

t y p e , vacuum pump, a surge t a n k , a C a r t e s i a n - t y p e manostat,

and a d r y - i c e t r a p connected i n s e r i e s . The surge t a n k was

equipped w i t h a needle v a l v e t o a l l o w an approximate

p r e s s u r e adjustment t o a v a l u e somewhat l o w e r t h a n r e q u i r e d

i n t h e u n i t ; t h e p r e s s u r e was m a i n t a i n e d p r e c i s e l y by t h e

manostat. The d r y - i c e t r a p was used i n t h e main e v a c u a t i n g

l i n e t o p r e v e n t t h e escape o f l i g h t f r a c t i o n s . The p r e s s u r e

i n t h e u n i t was measured by a mercury manometer c o n n e c t e d

t o t h e vacuum l i n e from t h e condenser.

 9.

(b)Equltibrium Flash:Vaporization Still

The most s u c c e s s f u l l a b o r a t o r y v a p o r - l i q u i d

e q u i l i b r i u m s t i l l s almost i n v a r i a b l y employ condensate r e -

circulation. The vapor i n e q u i l i b r i u m w i t h t h e b o i l i n g liquid

is passed i n t o a condenser, and t h e condensate i s c o l l e c t e d i n

a r e s e r v o i r from which i t i s r e c i r c u l a t e d back i n t o t h e b o i l i n g

liquid. When t h e e n t i r e s t i l l has r e a c h e d a s t e a d y s t a t e ,

the s a t u r a t e d v a p o r r i s i n g from t h e b o i l i n g l i q u i d i s o f t h e

same c o m p o s i t i o n as t h e r e c i r c u l a t i n g condensate, and i s a t

the same t e m p e r a t u r e as t h e b o i l i n g l i q u i d . The v a p o r - l i q u i d still

d e s i g n e d by Othmer.^(l$)) f o r t h e d e t e r m i n a t i o n o f EFV c u r v e s o f

crudes and p e t r o l e u m f r a c t i o n s e n t a i l s two b a s i c m o d i f i c a t i o n s :

a method o f v a r y i n g t h e volume o f condensate h e l d up i n t h e

r e s e r v o i r , and o f a c c u r a t e l y d e t e r m i n i n g t h i s volume w i t h o u t

interrupting the operation of the s t i l l . A graduated r e s e r v o i r

w i t h a c a p i l l a r y stopcock i n the r e c y c l e l i n e e f f e c t i v e l y solve

these problems. The Othmer s t i l l a l o n g w i t h a u x i l i a r y e q u i p -

ment i n c l u d i n g a vacuum pump, surge t a n k , d r y - i c e t r a p and

manometer, i s shown i n F i g u r e 2.

The s t i l l
; c o n s i s t s of a complete.pyrex g l a s s u n i t :

a 500 m l . s t i l l - p o t , vapor-arm, p r i m a r y condenser, g r a d u a t e d

r e c e i v e r , and r e f l u x l i n e . Nichrome r e s i s t a n c e h e a t e r s p r o v i d e

e x t e r n a l h e a t i n g t o t h e s t i l l - p o t , vapor-arm, and r e f l u x line;

these s e c t i o n s are a l s o i n s u l a t e d w i t h asbestos l a g g i n g coated

w i t h aluminum p a i n t t o p r e v e n t e x c e s s heat l o s s by r a d i a t i o n .
4
 11.

An i n t e r n a l nichrome r e s i s t a n c e h e a t e r e f f e c t s smooth b o i l i n g ,

w i t h o u t bumping o f o r s u p e r h e a t i n g o f even s m a l l liquid

volumes.

The bottom s e c t i o n of the s t i l l - p o t i s f a b r i c a t e d

w i t h a s m a l l e r bubble so that the d e p t h of l i q u i d i s sufficient

f o r h e a t i n g and a c c u r a t e l y measuring t h e t e m p e r a t u r e when

most of t h e change i s i n the condensate r e s e r v o i r . The vapor-

arm i s o f a s i z e determined by two r e q u i r e m e n t s : t h a t t h e

p r e s s u r e drop o f t h e vapor p a s s i n g t o t h e r e s e r v o i r s h o u l d be

n e g l i g i b l e , and t h a t t h e t o t a l volume o f t h e v a p o r i n t h e

f r e e space o f t h e s t i l l - p o t and vapor-arm s h o u l d be s m a l l enough

t o i n t r o d u c e n e g l i g i b l e e r r o r i n t h e l i q u i d volume measurement.

The p r e s s u r e drop a c r o s s the vapor-arm depends on t h e v a p o r -

i z a t i o n r a t e w h i c h , a t low p r e s s u r e s (10 mm), can be c o n s i d e r a b l e ;

f o r t h i s reason a uniform slow d i s t i l l a t i o n r a t e i s i m p e r a t i v e .

The e r r o r i n t r o d u c e d by n e g l e c t i n g t h e amount of vapor i n t h e

s t i l l i n measuring t h e condensate volume c o r r e s p o n d s t o l e s s

t h a n 5 n i l . o f condensate d u r i n g adverse c o n d i t i o n s ( 1 5 ) . A
c o r r e c t i o n can be a p p l i e d i n v e r y p r e c i s e work; however, t h i s

i s u s u a l l y not n e c e s s a r y s i n c e i t i s d t h e o r d e r o f a c c u r a c y

for r e a d i n g the volume i n t h e r e s e r v o i r . A t reduced p r e s s u r e s ,

t h i s e r r o r g r e a t l y d e c r e a s e s i n magnitude.

The condenser i s c o n s t r u c t e d i n two p a r t s f o r h a n d l i n g

crudes o r heavy f r a c t i o n s . The p r i m a r y condenser can be

o p e r a t e d a t a temperature j u s t s u f f i c i e n t t o condense t h e h i g h e r

b o i l i n g p o r t i o n o f the vapors and s t i l l a l l o w t h e condensate

 t o f l o w f r e e l y down the w a l l s w i t h o u t f r e e z i n g out t h e waxy

.material. The more v o l a t i l e p o r t i o n i s condensed i n the

secondary condenser c o o l e d t o a l o w e r t e m p e r a t u r e . Since a

'small p o r t i o n o f t h e crude o i l s c o n s i s t s o f a h i g h l y v o l a t i l e

f r a c t i o n , t h e d r y - i c e t r a p s e r v e s as an a u x i l i a r y condenser;

d u r i n g 10 mm. p r e s s u r e o p e r a t i o n w i t h l i g h t crudes as much

as 25 m l . o f condensate was c o n s i s t e n t l y c o l l e c t e d i n t h e t r a p .

The volume was c a r e f u l l y measured and added t o t h a t i n t h e

r e s e r v o i r ; i t was i m p r a c t i c a l t o attempt t o keep t h i s volatile

f r a c t i o n i n the r e s e r v o i r because i t b o i l e d a t t h e r e s e r v o i r

temperature.

The p r e s s u r e i n t h e u n i t was measured by an a b s o l u t e

manometer and m a i n t a i n e d at a c o n s t a n t v a l u e by a C a r t e s i a n -

t y p e manostat.

(c) Temperature Measurement

Three d e v i c e s a r e commonly used f o r measuring

t e m p e r a t u r e s , t h e mercury thermometer, t h e r m o c o u p l e , and

r e s i s t a n c e thermometer. The mercury thermometer i s a v a i l a b l e

f o r use e i t h e r as a t o t a l - i m m e r s i o n o r a p a r t i a l - i m m e r s i o n

thermometer. I n b o t h cases s i m i l a r problems a r e p r e s e n t e d i f

v e r y p r e c i s e t e m p e r a t u r e measurement of t h e v a p o r phase i n a

vapor-liquid equilibrium determination i s required. It is

d i f f i c u l t t o construct a s t i l l - h e a d or s t i l l - p o t that allows

adequate c i r c u l a t i o n of t h e vapor o r l i q u i d around t h e s e c t i o n

o f the thermometer s p e c i f i e d f o r immersion. The partial-

immersion thermometer u s u a l l y c r e a t e s a vapor p o c k e t where

 13.

i t e n t e r s t h e s t i l l - h e a d ; t h e emergent stem i s a l s o exposed

to v a r i a b l e temperatures. These problems l i m i t t h e use o f

mercury thermometers i n v e r y p r e c i s e work.

B o t h t h e thermocouple and r e s i s t a n c e thermometer

can g i v e n h i g h l y a c c u r a t e t e m p e r a t u r e measurements. Although

the r e s i s t a n c e thermometer o f f e r s t h e g r e a t e s t a c c u r a c y a s

w e l l as maximum r e l i a b i l i t y and r e p r o d u c i b i l i t y , t h e t h e r m o c o u p l e

i s o f more g e n e r a l use because i t i s l e s s b u l k y , has l i t t l e

temperature l a g , and r e q u i r e s t h e use o f o n l y a p o t e n t i o m e t e r .

The r e s i s t a n c e thermometer i s e s p e c i a l l y s u i t a b l e f o r c a l i b r a t i n g

purposes.

I n b o t h t h e TBP and EFV d e t e r m i n a t i o n s p a r t i a l -

immersion thermometers were used t o measure t h e v a p o r - l i q u i d

e q u i l i b r i u m temperatures. The a c c u r a c y d e s i r e d , * 1.0°F, i n

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

when t h e s e thermometers were c a l i b r a t e d a g a i n s t t h e N a t i o n a l

Bureau o f S t a n d a r d s No. 169314; r e s i s t a n c e thermometer. The

c a l i b r a t i o n c u r v e s appear i n F i g u r e 3. The thermometers were

used i n p r e f e r e n c e t o t h e r m o c o u p l e s because t h e o r i g i n a l

d e s i g n s o f both u n i t s i n c l u d e d g r o u n d - j o i n t p a r t i a l - i m m e r s i o n

thermometers. These were c o n v e n i e n t - because o f ease i n

r e a d i n g t h r o u g h o u t t h e whole range o f t e m p e r a t u r e s e n c o u n t e r e d .

I n t h e EFV a p p a r a t u s a s p e c i a l advantage o f t h e u s e

of a p a r t i a l - i m m e r s i o n thermometer was t h a t t h e l i q u i d temper-

ature i n the s t i l l c o u l d be watched and checked r e a d i l y w h i l e

a d j u s t m e n t s were made t o t h e h e a t e r s . Other temperatures

c o u l d be measured by t h e r m o c o u p l e s l o c a t e d a t v a r i o u s p o i n t s
CALIBRATION OF THERMOMETERS
 15.

o f t h e s t i l l - p o t , vapor-arm and r e c y c l e l i n e a t t h e g l a s s -

insulation interface. By means o f a m u l t i p l e - s w i t c h and Leeds

and N o r t h r u p t y p e K p o t e n t i o m e t e r , t h e t e m p e r a t u r e a t any

p o i n t r e q u i r e d c o u l d be o b t a i n e d . An a u x i l i a r y thermometer

was p l a c e d i n t h e vapor-arm thermometer w e l l by w h i c h a check

on t h e e x t e n t o f s u p e r h e a t i n g c o u l d be made.

The TBP u n i t r e q u i r e d a p a r t i a l - i m m e r s i o n thermometer

s p e c i f i e d t o f i t the s t i l l - h e a d ; the s t i l l - h e a d i s designed

t o reduce t h e thermometer e r r o r due t o poor v a p o r c i r c u l a t i o n .

The thermometer i s centred i n t h e vapor-stream a l l o w i n g a

maximum amount o f c o n t a c t . Another thermometer was used t o

g i v e an approximate i n d i c a t i o n o f t h e t e m p e r a t u r e o f t h e

ribbon heater surrounding the s t i l l - h e a d . The crude charge

t e m p e r a t u r e was measured by means o f an i r o n - c o n s t a n t a n thermo-

couple and p o t e n t i o m e t e r . T h i s thermocouple was used o n l y as

an approximate check f o r k e e p i n g t h e charge temperature below

650°F and, t h e r e f o r e , was n o t c a l i b r a t e d .

 16.

IV. SAMPLES AND MATERIALS

(a) Crude O i l Samples

E i g h t samples o f A l b e r t a crude o i l were

analyzed. Assurance was g i v e n t h a t t h e samples

were drawn t o g i v e r e p r e s e n t a t i v e composite samples

of t h e o i l - f i e l d o r p i p e l i n e . Storage i n a c o o l

place avoided excessive vapor l o s s . Relevant i n f o r

m a t i o n about t h e samples i s l i s t e d below:

API G r a v i t y
1. Pembina crude - r e p r e s e n t a t i v e sample
from Pembina P i p e l i n e s t r e a m d e l -

i v e r e d i n 10 g a l l o n drum August

16, 1955, by I m p e r i a l O i l Company

Limited. 38.0

2. W i z a r d Lake crude - r e p r e s e n t a t i v e sample

from b a t t e r y r e c e i v i n g crude from

s e v e r a l producing w e l l s i n the Wizard

Lake f i e l d d e l i v e r e d i n 10 g a l l o n

drum August 16, 1955, by I m p e r i a l

O i l Company L i m i t e d . 37.5

3. Leduc-Woodbend crude - r e p r e s e n t a t i v e
sample from I m p e r i a l P i p e L i n e Leduc

g a t h e r i n g system d e l i v e r e d i n 10 g a l l o n

drum August 16, 1955, by I m p e r i a l O i l

Company L i m i t e d . 40.1
 API G r a v i t y
4. Texaco P i p e l i n e crude - r e p r e s e n t a t i v e

sample o f crude m i x t u r e from Texaco

P i p e L i n e b a t t e r y as R e c e i v e d t h r o u g h

Trans-Mountain P i p e L i n e , d e l i v e r e d

i n 5 g a l l o n can J u l y , 1955, by S t a n d a r d

O i l Company L i m i t e d . 40.6

5. Redwater crude - r e p r e s e n t a t i v e sample o f

crude from I m p e r i a l P i p e L i n e Redwater

system as r e c e i v e d t h r o u g h Trans M o u n t a i n

P i p e l i n e , d e l i v e r e d i n 5 g a l l o n can J u l y ,

1955, hy S t a n d a r d O i l Company L i m i t e d . 35»5

6« S t e t t l e r crude - r e p r e s e n t a t i v e sample o f crude

from S t e t t l e r f i e l d d e l i v e r e d i n 5 g a l l o n

can i n 1952, by I m p e r i a l O i l Company

Limited. 28.8

7. Joseph Lake crude - r e p r e s e n t a t i v e sample o f

crude from Joseph Lake f i e l d d e l i v e r e d

i n 5 g a l l o n c a n i n 1952 by I m p e r i a l O i l

Company L i m i t e d . 37*3

8. Golden S p i k e crude - representative sample

of crude from Golden S p i k e f i e l d delivered

i n 5 g a l l o n can i n 1952 by I m p e r i a l O i l

Company L i m i t e d . 38.9

S i n c e b o t h t h e TBP and EFV curves were t o be d e t e r m i n e d

on a volume p e r c e n t b a s i s , a c c u r a t e measurement o f t h e

volume o f crude charge t o t h e s t i l l s was r e q u i r e d . The

 18.

charge p o r t i o n s t o t h e TBP and EFV s t i l l s were 2000 m l . and

500 m l . , r e s p e c t i v e l y . S i n c e the samples were a t an approx-

imate t e m p e r a t u r e of 60°F and not v e r y v i s c o u s , t h e y were

poured d i r e c t l y i n t o a g r a d u a t e d c y l i n d e r o f a p p r o p r i a t e

s i z e t o a l e v e l somewhat h i g h e r t h a n the volume t o be

delivered. When the g r a d u a t e was emptied and o i l a l l o w e d

t o d r a i n t o t h e bott©m'f the r e m a i n i n g volume c o u l d be

estimated. By p r a c t i c e t h e volume of charge r e q u i r e d c o u l d

be r e a d i l y o b t a i n e d by t h i s method.

(b) Benzene and Carbon T e t r a c h l o r i d e

'A. t e s t m i x t u r e of benzene-carbon t e t r a c h l o r i d e

was used t o determine t h e e f f i c i e n c y o f the TBP distillation

column. P u r i f i c a t i o n was required to obtain a r e f r a c t i v e

i n d e x f o r the benzene w h i c h compared f a v o u r a b l y w i t h p u b l i s h e d

results. A commercially pure grade o f benzene was supplied

by t h e N i c h o l s C h e m i c a l Company. Thiophene was removed by

shaking a mixture of benzene and concentrated sulfuric acid

i n a large separating funnel. The o p e r a t i o n was repeated

w i t h new p o r t i o n s of a c i d u n t i l no t h i o p h e n e d i s c o l o r a t i o n

appeared. The concentrated a c i d would a l s o remove most o f t h e

w a t e r i f i t was present. A f t e r c a r e f u l s e p a r a t i o n of the

a c i d l a y e r the thiophene-free benzene was placed i n a clean 2 1.

d i s t i l l a t i o n f l a s k o v e r sodium r i b b o n and a l l o w e d t o s t a n d f o r

a day. The t o p of the f l a s k was closed with a drying funnel

of c a l c i u m o x i d e a l l o w i n g f r e e e v o l u t i o n o f hydrogen.
 19,

Distillation f o r f i n a l p u r i f i c a t i o n was performed i n a packed

column o f 14 e q u i v a l e n t p l a t e s p r e v i o u s l y used f o r p u r i f i c a t i o n

purposes (19). The column was c a r e f u l l y cleaned w i t h acetone

and d r i e d . Distillation of the benzene was c a r r i e d out over

sodium a t a r e f l u x r a t i o o f 30:1. The i n i t i a l 200 ml. p o r t i o n

was d i s c a r d e d a f t e r which about 1 1. o f pure benzene o f b o i l i n g

p o i n t 80.4 °C was o b t a i n e d f o r t e s t i n g purposes.

The carbon t e t r a c h l o r i d e o b t a i n e d from the Baker and

Adamson Company was p u r i f i e d by d i s t i l l a t i o n o n l y . Distillation

at a r e f l u x r a t i o o f 30:1 gave carbon t e t r a c h l o r i d e of a

refractive index t h a t checked f a v o u r a b l y w i t h t h a t g i v e n i n

the literature. Refractive indices o b t a i n e d at 25°C were

1.4572 and 1.4980 f o r carbon t e t r a c h l o r i d e and benzene,

respectively, compared w i t h l i t e r a t u r e v a l u e s o f 1.45734 and

1.49794 ( 8 ) .
 20.

PROCEDURE

(a) TBP S t i l l

The o p e r a t i o n o f t h e TBP s t i l l was e s s e n t i a l l y

the same as t h a t o f any l a b o r a t o r y f r a c t i o n a t i n g u n i t .

A b a s i c d i f f e r e n c e , however, was t h a t two p r e s s u r e s

were used d u r i n g t h e d i s t i l l a t i o n o f c r u d e s : a t m o s p h e r i c

d i s t i l l a t i o n u n t i l t h e charge r e a c h e d a t e m p e r a t u r e o f

about 65O0F. a f t e r which t h e column was c o o l e d , t h e n

10 mm. p r e s s u r e u n t i l t h e t e m p e r a t u r e a g a i n r e a c h e d

about 6$0°F. Some comparable TBP s t i l l s f u r t h e r reduce

the p r e s s u r e t o 1 mm. b u t s i n c e t h i s p a r t i c u l a r a p p a r a t u s

was n o t d e s i g n e d f o r such l o w p r e s s u r e s , t h e d i s t i l l a t i o n

was t e r m i n a t e d a t 10 mm.

To b e g i n o p e r a t i o n s a t a t m o s p h e r i c p r e s s u r e , a f t e r

the s t i l l - p o t was charggd and a t t a c h e d t o t h e column,

c o o l i n g w a t e r was passed t h r o u g h t h e condensers,

powdered d r y - i c e p l a c e d i n t h e c o l d t r a p and t h e g l a s - c o l

h e a t e r was t u r n e d on. A normal procedure i n t h e o p e r a t i o n

of packed columns i s t o p r e f l o o d t h e column b e f o r e t h e

a c t u a l d i s t i l l a t i o n b e g i n s ; t h e purpose o f t h i s i s t o

c o m p l e t e l y wet t h e p a c k i n g s u r f a c e t o ensure maximum

column e f f i c i e n c y . F o r two r e a s o n s t h i s p r o c e d u r e was

not f o l l o w e d : t h e l i q u i d - d i v i d i n g s t i l l - h e a d has t o o

s m a l l a c a p a c i t y t o cause column f l o o d i n g and i s i t s e l f

flooded f i r s t . A l s o , i f f l o o d i n g was even approached

 21.

d u r i n g the i n i t i a l r e f l u x i n g o f a crude, too l a r g e a f r a c t i o n

would be l o s t t o the cold trap. As a r e s u l t , the normal

slow r a t e of r e f l u x i n g , 1500 t o 2000 ml. per h o u r , was

p e r m i t t e d t h r o u g h o u t the complete d i s t i l l a t i o n ; the possible

l o s s i n i n i t i a l column e f f i c i e n c y was c o n s i d e r e d to be not

significant.

A preliminary equilibrium period o f about h a l f an

h o u r was a l l o w e d b e f o r e any d i s t i l l a t e was drawn i n t o the

receiver. A f t e r t h i s time a t the normal r e f l u x i n g r a t e ,

the r e f l u x - t i m e r was set t o g i v e a r e f l u x - r a t i o o f 10:1. The

d i s t i l l a t e volume and c o r r e s p o n d i n g v a p o r t e m p e r a t u r e were

o b t a i n e d by r e a d i n g t h e thermometer, c l o s i n g t h e inlet

r e c e i v e r s t o p c o c k , and t h e n d r a i n i n g the d i s t i l l a t e i n t o a

250 ml. graduated c y l i n d e r . The still-pot temperature was

a l s o noted. To o b t a i n the i n i t i a l c o r r e c t volume distilled

r e a d i n g , a volume of naphtha c o r r e s p o n d i n g t o t h a t collected

i n the c o l d t r a p , was added t o the g r a d u a t e d c y l i n d e r . The

l i g h t f r a c t i o n , as much as 40 ml., was not i t s e l f added t o the

d i s t i l l a t e i n t h e graduate because of i t s h i g h volatility,

but was discarded. Subsequent r e a d i n g s , t a k e n a t approximate

volume i n t e r v a l s o f 100 ml. d i d not need f u r t h e r correction.

A f a l l i n g - o f f of the d i s t i l l a t i o n r a t e due to insuf-

f i c i e n t heat i n p u t t o the s t i l l - p o t was o b s e r v e d by counting

the number o f drops f a l l i n g i n t o the d i s t i l l a t e receiver

during a receiving period. The g l a s - c o l heater input was

a c c o r d i n g l y a d j u s t e d . When the r e f l u x t e m p e r a t u r e r e a c h e d
o
about 250 F., the column and s t i l l - h e a d r i b b o n h e a t e r s were
 22.

t u r n e d on. The temperature o f t h e r i b b o n h e a t e r a t t h e

s t i l l - h e a d was m a i n t a i n e d a t about 30°F. below t h e v a p o r

temperature as i n d i c a t e d by a thermometer placed inside

the heater. An i d e n t i c a l e l e c t r i c a l i n p u t was s u p p l i e d

t o t h e column r i b b o n h e a t e r ; t h e e x t e r n a l temperature o f

the column, a l t h o u g h undetermined, would be somewhat h i g h e r

because o f t h e e x t r a i n s u l a t i o n c o v e r i n g t h e h e a t e r . There

was l i t t l e danger o f d i s r u p t i n g t h e column o p e r a t i o n by

s u p p l y i n g t o o much heat by means o f t h e r i b b o n h e a t e r s s i n c e

b o t h t h e s t i l l - h e a d and column were vacuum-jacketed; moreover,

at h i g h temperature o p e r a t i o n , t h e h e a t e r s and i n s u l a t i o n

were e s s e n t i a l i n r e d u c i n g heat l o s s e s s u f f i c i e n t l y f o r

normal d i s t i l l a t i o n .

A f t e r t h e system was e v a c u a t e d t o 10 mm., and t h e

manostat a d j u s t e d , d i s t i l l a t i o n a t t h e reduced p r e s s u r e was

performed i n t h e same way as a t a t m o s p h e r i c pressure.. To

measure d i s t i l l a t e volumes, however, was a problem. When

a c o n v e n i e h t t volume, a g a i n about 100 m l . , was c o l l e c t e d

i n t h e r e c e i v e r , t h e vapor and s t i l l - p o t t e m p e r a t u r e s were

r e a d and t h e r e c e i v e r i n l e t and e v a c u a t i n g l i n e s t o p c o c k s

were c l o s e d . The r e c e i v e r was t h u s i s o l a t e d f r o m t h e r e s t

of t h e u n i t ; a i r c o u l d be v e n t e d i n t o i t , t h e d i s t i l l a t e

d r a i n e d , and volume measured w i t h o u t d i s r u p t i n g t h e column

operation. To a g a i n evacuate t h e c l o s e d and t h e r e c e i v e r

e v a c u a t e d , a l s o w i t h o u t d i s r u p t i n g t h e column operation.

T h i s method r e q u i r e d t h e r e a d j u s t m e n t o f t h e manostat each

time t h e d i s t i l l a t e volume was measured. A n o t h e r method w h i c h

e l i m i n a t e d t h e r e a d j u s t m e n t o f t h e manostat was t o evacuate

COX CHART FOR TBP EXTRAPOLATION
 24.

the r e c e i v e r w i t h an a u x i l i a r y vacuum pump.

To o b t a i n t h e complete TBP c u r v e a t a t m o s p h e r i c

p r e s s u r e , t h e t e m p e r a t u r e s o f t h e 10 mm. d i s t i l l a t i o n were

e x t r a p o l a t e d by means o f an e n l a r g e d Cox c h a r t (5) as shown

i n reduced s i z e i n F i g u r e 4« T h i s c h a r t was c o n s t r u c t e d i n

- t h e u s u a l way and the f o c a l p o i n t d e t e r m i n e d u s i n g v a p o r

p r e s s u r e v a l u e s from t h e l i t e r a t u r e f o r s e v e r a l normal

hydrocarbons ( 1 8 ) . E x t r a p o l a t i o n gave temperature v a l u e s

c o n s i s t e n t w i t h the a t m o s p h e r i c d a t a when p l o t t e d on a

g r a p h o f temperature v e r s u s volume p e r c e n t . F o r example,

t e m p e r a t u r e s o f 350oF. and 400°F. a t 10 mm. gave c o r r e s -

ponding e x t r a p o l a t e d v a l u e s o f 6l5°F. and 670°F. a t 760 mm.

pressure; (the p r e c i s i o n o f the e x t r a p o l a t e d temperatures

d e c r e a s e d t o about £5°F. a t h i g h t e m p e r a t u r e s due t o t h e

condensed t e m p e r a t u r e s c a l e o f t h e Cox c h a r t . ) I n t h i s way,

d a t a f o r TBP c u r v e s , complete t o a t e m p e r a t u r e o f about 300°F.,

were computed.

(b) EFV S t i l l

The procedure f o l l o w e d f o r t h e EFV d e t e r m i n a t i o n s

was e s s e n t i a l l y as p r e s c r i b e d by Othmer e t , a l . ( 1 5 ) •

Both atmospheric and reduced p r e s s u r e d i s t i l l a t i o n s were

c a r r i e d out by t h e same method. Preliminary preparations

c o n s i s t e d o f p l a c i n g d r y - i c e i n t o t h e c o l d t r a p and s t a r t i n g

the c o o l i n g - w a t e r through t h e condensers. The s t i l l was

charged t h r o u g h t h e thermometer w e l l , a f t e r w h i c h t h e system

was evacuated t o t h e d e s i r e d o p e r a t i n g p r e s s u r e . Heat was

 25.

s u p p l i e d t o t h e s t i l l - p o t and vapor-arm, the vapor-arm b e i n g

kept a t a t e m p e r a t u r e about 30OF. h i g h e r than the expected

i n i t i a l boiling point. The temperature o f t h e initial

b o i l i n g p o i n t corresponded t o the f i f t h drop o f d i s t i l l a t e

f a l l i n g i n t o the d i s t i l l a t e (as suggested by Othmer e t , a l . ) ;

the c o r r e s p o n d i n g volume measurement wan not t a k e n as zero,

but as t h e volume o f t h e l i g h t f r a c t i o n s c o l l e c t e d i n t h e

cold trap.

To h e l p i n making t h e r e c y c l e c o n t r o l e f f e c t i v e a p o i n t e r

was a t t a c h e d t o the end of t h e s t o p c o c k so t h a t t h e p r o p e r

p o s i t i o n c o u l d be r e a d i l y a t t a i n e d as shown by a c i r c u l a r

scale. F u r t h e r m o r e , t h e r e c y c l e stream was partially

vaporized by means o f t h e r e c y c l e h e a t e r so t h a t i n t e r m i t t e n t

bubble's p a s s e d t h r o u g h the s t o p c o c k . The b u b b l e s a i d e d i n

e s t i m a t i n g t h e r a t e o f r e c y c l e as w e l l as p r e v e n t e d s u p e r -

h e a t i n g o f t h e charge i n t h e s t i l l - p o t .

The volume i n the r e s e r v o i r was i n c r e a s e d by

i n c r e a s i n g the s t i l l - p o t h e a t e r . E q u i l i b r i u m was established

when t h e d i s t i l l a t e was o f t h e same c o m p o s i t i o n as t h e vapor

i n e q u i l i b r i u m w i t h the l i q u i d charge. To a c c o m p l i s h t h i s

the l i q u i d temperature was kept c o n s t a n t r a t h e r than t h e

d i s t i l l a t e volume as suggested by Othmer e t a l . I n t h i s way

s m a l l temperature changes c o u l d be n o t i c e d and heat supplied

a c c o r d i n g l y , whereas s m a l l volume changes c o u l d n o t be

n o t i c e d soon enough t o p e r m i t easy c o r r e c t i v e a d j u s t m e n t .

A f t e r normal d i s t i l l a t i o n and r e c y c l e r a t e s o f about 120 drops

 26.

p e r hour were e s t a b l i s h e d , t h e o n l y c o n t r o l n e c e s s a r y was

the heat i n p u t t o t h e s t i l l ; t h e r e c y c l e s t o p c o c k was kept

i n t h e same p o s i t i o n t h r o u g h o u t t h e d i s t i l l a t i o n . For

o b t a i n i n g i n c r e a s e d volumes o f d i s t i l l a t e , t h e s t i l l temperature

was s l o w l y i n c r e a s e d i n i n c r e m e n t s o f about 50°F., w i t h a

c o r r e s p o n d i n g i n c r e a s e i n vapor-arm t e m p e r a t u r e . As t h e

temperature i n c r e a s e d t h e d i s t i l l a t i o n r a t e would increase

w i t h r e s u l t i n g h i g h e r volumes o f d i s t i l l a t e . Equilibrium

was assumed when no volume change was observed o v e r a

p e r i o d o f about i hour a t a c o n s t a n t s t i l l temperature, the

complete t i m e f o r a s i n g l e measurement t a k i n g up t o 4 h o u r s .

S i n c e t h e whole d e t e r m i n a t i o n c o u l d n o t be made i n

one e i g h t hour day, t h e d i s t i l l a t i o n had t o be d i s c o n t i n u e d

b e f o r e i t was completed. To p e r m i t easy s t a r t - u p n e x t day,

the r e c y c l e s t o p c o c k was c l o s e d t r a p p i n g t h e d i s t i l l a t e i n

t h e r e s e r v o i r . The vacuum l i n e a l s o was c l o s e d w i t h a p i n c h -

cock ( d u r i n g reduced p r e s s u r e d i s t i l l a t i o n ) . The f o l l o w i n g

day t h e d i s t i l l a t i o n c o u l d be c o n v e n i e n t l y c o n t i n u e d a t a

temperature a n o t h e r i n c r e m e n t above t h e one used p r e v i o u s l y .

The volume i n t h e c o l d t r a p was checked f o r l o s s due t o

evaporation.

The f l a s h c u r v e s a t e i t h e r a t m o s p h e r i c o r 10 mm.
pressure c o u l d be drawn d i r e c t l y from the d a t a f o r t h e l i q u i d
t e m p e r a t u r e and t h e c o r r e c t e d volume o f d i s t i l l a t e .
 27.

( c ) C a l i b r a t i o n o f Column

The t h e o r e t i c a l p l a t e e f f i c i e n c y o f t h e TBP column

was checked by r e f l u x i n g a t t o t a l r e f l u x a m i x t u r e of the

p u r i f i e d benzene and c a r b o n t e t r a c h l o r i d e . A charge o f about

2 1. o f 20 mole p e r c e n t carbon t e t r a c h l o r i d e was refluxed

f o r two h o u r s , t h e n s m a l l samples o f t h e overhead and still-

pot m i x t u r d s were t a k e n . These were a n a l y z e d by refractive

i n d e x a f t e r which r e f l u x i n g was continued f o r another three

hours t o ensure t h a t e q u i l i b r i u m had been a t t a i n e d . Second

samples drawn gave t h e same r e f r a c t i v e i n d e x v a l u e s as t h e

first. The r e f r a c t i v e i n d e x v a l u e s a t 2 5 ° C f o r t h e still-

pot c o m p o s i t i o n and overhead were 1.4916 and 1.4783, r e s -

pectively.

The r e f r a c t i v e i n d e x - c o m p o s i t i o n r e l a t i o n s h i p was

t h a t recommended by t h e U.S. Bureau o f Mines (20) and the

benzene-carbon t e t r a c h l o r i d e vapor-liquid equilibrium data

were o b t a i n e d from t h e I n t e r n a t i o n a l C r i t i c a l Tables ( 7 ) .

The p l a t e e f f i c i e n c y o f t h e column was determined by the

u s u a l McCabe and T h i e l e method (10) u s i n g an e n l a r g e d vapor-

l i q u i d equilibrium diagram. The v a l u e o b t a i n e d by t h i s

method was 11.4 equivalent theoretical plates f o r a column

of 22 i n c h e s of p a c k i n g i n c l u d i n g t h e s t i l l i - p o t * and still-

head as i l l u s t r a t e d i n F i g u r e $.
 29.

VI. RESULTS

F o r each o f t h e crude o i l s t e s t e d , t h r e e c h a r a c -

t e r i s t i c c u r v e s were d e t e r m i n e d : t h e a t m o s p h e r i c TBP,

^ . a t m o s p h e r i c EFV, and t h e 10 mm. EFV c u r v e s . The c u r v e s

are a l l p l o t t e d w i t h t h e volume p e r c e n t as a b s c i s s a and

temperature as o r d i n a t e . F i g u r e s 8 a - 8h show t h e

a t m o s p h e r i c TBP and EFV c u r v e s ; t h e n u m e r i c a l d a t a appear

i n liable I . The EFV c u r v e s a t 10 mm. and a t m o s p h e r i c

p r e s s u r e appear i n F i g u r e s l O a - l O h .

The r e l a t i o n s h i p between t h e a t m o s p h e r i c TBP and

EFV 50 p e r c e n t b o i l i n g p o i n t s can be approximated by a

straight l i n e . The d a t a p o i n t s a r e g i v e n i n SEable I I and

shown g r a p h i c a l l y i n F i g u r e 6 w i t h t h e b e s t s t r a i g h t line

f i t t e d by t h e method o f l e a s t s q u a r e s . The d o t t e d l i n e

c o r r e s p o n d s t o t h e c a l c u l a t e d r e s u l t s of Okamoto and Van

W i n k l e (14) f o r m i x t u r e s o f pure hydrocarbons assuming

i d e a l behaviour.

I f t h e EFV curve i s assumed t o be n e a r l y a s t r a i g h t

l i n e , t h e n a s l o p e and t h e 50 p e r c e n t p o i n t would c h a r a c t e r -

ize i t . An i n s p e c t i o n o f t h e TBP and EFV s l o p e s i n d i c a t e s

t h a t an a p p r o x i m a t e l y c o n s t a n t s l o p e d i f f e r e n c e between

the two c u r v e s e x i s t s . The average s l o p e d i f f e r e n c e i s

c a l c u l a t e d t o be 3.511 -0.271 degrees p e r volume p e r c e n t

where 0.271 i s t h e p r e c i s i o n . The v a l u e 3.511 i s s u b t r a c t e d

f r o m t h e TBP s l o p e g i v i n g t h e s l o p e o f t h e p r e d i c t e d EFV

curve. The c o n s t a n t s l o p e d i f f e r e n c e i s r e p r e s e n t e d by a
 30.

CORRELATION OF T B P a EFV 5 0 % BOILING POINTS

450 500 550 600 650

X =. EFV 50 PERCENT BOILING POINT ° F.
FIG. 6
COMPARISON OF SLOPE CORRELATIONS FIG. 7
 32.
LEDUC-WOODB'END CRUDE
 JOSEPH LAKE CRUDE

0 I 1 1 1 1 1 1 1 1 J
0 20 40 60 80 100
VOLUME PERCENT

FIG. 8 b
 34.

TEXAS PIPELINE CRUDE

0 20 40 60 80 100
VOLUME PERCENT

FIG.8C
 35

PEMBINA CRUDE

o» i 1 1 1 1 1 1 1— J 1

0 20 40 60 80 100
V O L U M E P E R C E N T

FIG.8d
WIZARD LAKE CRUDE
 37.

REDWATER CRUDE

1
A. j
F o r atmosj>heric p r e s s u r e
f

800

1
\

1
/ /
600 i
1
1

r ^ ^ ^ ^

O 1
1
1

//
• 400

ut
or

< • 1
CC
Ul
Q.
/ / i

UJ

1
200

• — — •

. 1 i
20 40 60 80 100
VOLUME PERCENT

FIG. 8f
STETTLER CRUDE
GOLDEN SPIKE CRUDE
 40.

45 degree l i n e on a p l o t o f EFV s l o p e as o r d i n a t e and TBP

s l o p e as a b s c i s s a . T h i s p l o t i s g i v e n by Okamoto and

Van W i n k l e as c a l c u l a t e d f o r t h e hydrocarbon mixtures. It

i s reproduced i n F i g u r e 7 showing t h e d a t a p o i n t s , a l s o

l i s t e d i n Table I I , f o r the crudes. I n c l u d e d on t h i s

p l o t i s a c o r r e l a t i o n o f the TBP and EFV s l o p e s p r o p o s e d

by N e l s o n and Harvey determined from d a t a on p e t r o l e u m

fractions (12).

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

i n d i c a t e d i n F i g u r e s 8a - 8h. The a t m o s p h e r i c TBP and EFV

e x p e r i m e n t a l c u r v e s as w e l l as t h e p r e d i c t e d c u r v e s , t h e

d o t t e d l i n e s , a r e shown f o r each c r u d e . The p r e d i c t e d

curves show t h e b e s t a c c u r a c y i n t h e r e g i o n 10-60 volume

percent.

Phase d i a g r a m s , c o n s t r u c t e d f r o m t h e EFV d a t a a t

atmospheric and 10 mm. p r e s s u r e s , a r e shown i n F i g u r e 9.

The 20 and 60 p e r c e n t v a p o r i z e d v a l u e s were chosen as b e i n g

most a c c u r a t e and c o n v e n i e n t f o r d e t e r m i n i n g t h e f o c a l

p o i n t s of t h e v a r i o u s c r u d e s . No f u n c t i o n o f e i t h e r t h e

TBP o r EFV c u r v e s was found t o c o r r e s p o n d t o t h e r e l a t i o n

between t h e f o c a l p o i n t s and, as a r e s u l t , no c o r r e l a t i o n

i s g i v e n f o r l o c a t i n g them. I t i s e v i d e n t t h a t i f some means

were a v a i l a b l e f o r l o c a t i n g t h e f o c a l p o i n t s t h e n an EFV

curve a t one p r e s s u r e would determine i t f o r any o t h e r

pressure. F o r comparison, the f o c a l point f o r a petroleum

s t o c k , s t o c k I , i s g i v e n as determined by Okamoto and Van

 PHASE DIAGRAM FIG. 9

10

A GOLDEN SPIKE

0 TEXACO PIPELINE

V JOSEPH LAKE
10'
<D STETTLER

• WIZARD LAKE

"f PEMBINA

io ED REDWATER
UJ
_J
< O W00DBEND-LEDUC
o
CO
CD ® STOCK I
O

- 5
>-IO
or
O
cr
UJ

UJ

CO - m m - ®
UJ
or

10
• i r i—|—i I I i j i i i i j I i i i | i 111 j 1 ]—p
1500
200 0 400 600 1000
TEMPERATURE F , RECIPROCAL SCALE
 42

Winkle (13). This f o c a l p o i n t i s only s l i g h t l y s h i f t e d

f o r a s e r i e s of stocks of d i f f e r e n t weights.

An attempt was made t o u t i l i z e t h e U.O.P. c h a r a c -

t e r i z a t i o n f a c t o r , K, fbr c o r r e l a t i n g purposes. Maxwell's

method (22) was used i n d e t e r m i n i n g K from t h e 2 0 , 5 0 , and

80 p e r c e n t TBP t e m p e r a t u r e s , t h e TBP s l o p e , and t h e API

g r a v i t y f o r each c r u d e . The K v a l u e s determined'ranged

from 1 1 . 6 0 t o 31.90 w i t h no a p p a r e n t r e l a t i o n t o t h e o t h e r

variables correlated.
JOSEPH LAKE EFV
PEMB INA EFV
 47.

WIZARD LAKE EFV

 48.

REDWATER EFV r

800

20 40 60 80 100
PERCENT VAPORIZED
FIG. lOf
STETTLER EFV
 50.

WOODBEND-LEDKC EFV

800

0 20' 40 60 80 100

PERCENT VAPORIZED
FIG. lOh
 51.
TABLE i :
WIZARD LAKE

TBP EFV (ATM) EFV 10 (MM)

Temp. OF Vol. % Temp. °F V o l . Temp. OF Vol. %

93 1.7 152 1.0 179 16.2

124 3.8 248 6.0 203 20.2
165 6.1 288 12.0 280 33.2
190 9.6 325 17.0 343 45.2
203 11.3 363 24.0 405 53.2
237 15.1 392 28.0 457 62.2
279 20.1 457 39.0 588 76.2
336 . 26.0 522 49.0
397 32.2 583 58.0
457 38.6 653 67.0
487 41.7 680 70.0
£
586 51.7
650 28.2
719 65.2
760 68.3
± extrapolated

TEXAS PIPELINE

TBP EFV (ATM) EFH 10 (MM)

Temp. °F Vol. % Temp. °F Vol. f Temp. °F Vol. %

104 4.5 133 1.0 172 15.0

122 6.0 -216 6.0 183 18.0
157 8.4 244 7.0 . 205 22.0
187 12.0 261 11.0 215 24.0
213 17.5 279 15.0 270 34.0
257 21.9 313 21.0 327 45.0
295 26.1 .372 32.0 387 55.0
338 32.1 426 41.0 442 63.0
372 33.5 442 44.0 447 67.0
A 491 < '53.0
427 41.6 531 59.0
472 48.1 563 64.O
544 54.6 615 72.0
601 61.1
670 68.5
726 73.4
760 77.0

ft e x t r a p o l a t e d
 52.

JOSEPH LAKE
TBP EFV (ATM) EFV 10 (MM)
Temp. °F Vol. % •femp.oF' V o l . $ Temp. OF Vol. %
108 1.2 208 0.2 158 10.8
124 1.9 286 4.0 226 24.8
183 4.7 293 5.6 306 38.8
200 6.7 302 6.6 345 45.8
225 9.6 322 10.6 394 55.8
261 14.6 340 14.6 417 59.8
318 20.9 385 22.6 484 70.8
358 26.6 437 31.6
ft 498 42.6
429 32.7 558 53.6
471 37.7 615 63.6
544 44.5 673 72.6
587 50.6
644 57.0
704 64.I
778 70.8
4 extrapolated

PEMBINA
TBP EFV (ATM) EFV (10 MM)
Temp. °F Vol. % Temp. °F V o l . $>. Temp. °F Vol. %

93 1.6 158 0.6 189 15.4

122 2.8 262 6.0 214 18.4
.145 4.0 270 8.0 286 30.4
196 8.4 284 10.0 349 40.4
252 14.8 290 12.0 405 48.4
297 20.0 333 18.0 484 60.4
354 25.7 379 25.0. 540 67.0
414 30.6 455 36.0 591 73.0
468 36.0 520 46.O
507 40.9 581 56.0
ft 646 64.O
566 45.4 682 69.0
628 51.9
691 58.3
772 66.0

ft e x t r a p o l a t e d
 53.

REDWATER

TBP EFV (ATM)- EFV (10 MM)

Temp, °F Vol. $ Temp. °F Vol. $ Temp. °F Vol. %

81 2.3 151 0.6 215 22.0
133 4.7 261 7.0 243 27.0
160 6.1 273 8.0 293 36.0
189 8.2 298 12.0 334 43.0
214 11.5 343 19.0 359 47.0
280 19.8 388 26.0 381 52.0
338 25.0 457 37.0 429 60.0
385 29.5 529 48.0 477 65.0
424 32.8 579 56.0 489 66.0
ft • r' 631 63.0 554 72.0
466 35.3 669 69.0
523 42.3
618 50.6
662 55.4
714 60.3
752 66.0 o

ft e x t r a p o l a t e d

LEDUC-WOODBEND

TBP EFV (ATM) EFV (10 MM)

Temp. °F Vol. $ Temp. °F Vol. % Temp. °F Vol. %

97 ^ 153 0.6 185 11.6

HI 2.3 230 4.0 216 19.6
142 3.9 246 6.2 250 26.6
\l\
198 io.O
& ...
279
300
12.2
17.2
325
392
42.6
53.6
3 2 ?
23.2 482 66.0
263 2011 370 31.2 572 77.0
307 24.8 423 40.2
487 52.4
401 35.g 554 61.6
603 68.6
484 45.0 669 77.6

Ilk
5?6
51.0
56.5
711
711
6
' 4

70.1
5

ft e x t r a p o l a t e d
 54.

SOLDEN SPIKE

TBP EFV (ATM) EFV (10 MM)

Temp. °F Vol. % Temp. ° F Vol. $ Temp. ° F Vol. %

102 2.2 153 2.0 172 ° 11.0

111 3.3 235 6.0 190 14.0
138 4.7 264 10.0 223 30.0
174 8.1 290 , 15.0 273 30.0
226 13.8 329 22.0 336 41.0
255 19.1 378 31.0 392 50.0
298 24.0 414 37.0 442 57.0
322 26.8 459 46.0 487 63.0
365 31.6 502 52.0
ft 541 58.0
441 39.9 574 64.O
492 44.9 617 70.0
520 48.3 646 . 73.0
576 54.6 680 76.0
651 63.1
696 68.3
744 73.3

ft extrapolated

STETTLER

TBP EFV (ATM! EFV (10 MM)

Temp. ° F Vol. % Vol. % Temp. ° F Vol. %

127 3.3 192 1.0 255 19.4

162 , 6.2
225
252
10.4
13.7
III
351
5.0
7.0
343
399
32.4
39.4
12.0 471 49.4
332 19.5 425 22.0 525 57.0
392 24.6 498 33.0 586 64.O
ft 563 42.0 649 70.0
487 31.7 629 51.0
538 36.1 680 57.0
570 39.5
598 43.2
658 48.1
712 53.5
752 58.6
800 62.7

ft extrapolated
 TABLE I I

SAMPLE TBP EFV P r e d i c t e d EFV

50% p o i n t ° F s l o p e T / V o l $ 50% point°F slope'F/vol.^ 5<$ point °F s l o p e °F/Vol. %
- f t ft

Texas P i p e l i n e 503 8.93 477 5.70 464 5.42

Golden S p i k e 534 9.10 490 5.83 491 5.59

Woodbend-Leduc 527 8.83 475 5.63 485 5.32

Joseph Lake 584 9.10 540 5.63 535 5.59

Pembina 610 .10.33 546 6.67 557 6.82

W i z a r d Lake 571 9.77 531 6.47 523 6.26

Redwater 604 10.80 541 6.47 552 7.29

Stettler 678 10.80 621 7.17 616 7.29

ft average d e v i a t i o n o f 50 p e r c e n t p o i n t = 8.1°F
 56.

VII.DISCUSSION OF RESULTS

E m p i r i c a l c o r r e l a t i o n s r e q u i r e a s u f f i c i e n t amount
o f d a t a t o a d e q u a t e l y r e p r e s e n t t h e complete range o f
variables. This i s d e f i n i t e l y a l i m i t a t i o n w i t h c o r r e l a t i o n s
f o r A l b e r t a crude o i l s ; a l t h o u g h TBP d a t a a r e more e a s i l y
a v a i l a b l e , both TBP and t h e c o r r e s p o n d i n g EFV d a t a i n
a d d i t i o n t o t h o s e g i v e n here a r e almost n o n - e x i s t e n t . The
c h a r t s r e s u l t i n g from t h e t e s t s on t h e e i g h t A l b e r t a crudes
a r e , t h e r e f o r e , somewhat l i m i t e d i n t h e i r v a l u e as
correlations. The c u r v e s o b t a i n e d f o r t h e i n d i v i d u a l samples,
however, c o u l d be u s e f u l i n d e s i g n c a l c u l a t i o n s .

The c o r r e l a t i o n o f t h e TBP and EFV 50 p e r c e n t boiling

p o i n t s g i v e n here adds weight t o t h a t o f Okamoto and Van
Winkle. I t s h o u l d be noted t h a t t h e i r 50 p e r c e n t p o i n t s
a r e n o t e x p e r i m e n t a l l y determined b u t a r e c a l c u l a t e d f o r
m i x t u r e s o f pure hydrocarbons s i m u l a t i n g petroleum fractions.
P r o p e r t i e s o f t h e components a r e a v a i l a b l e f o r t h e s e
c a l c u l a t i o n s , e s p e c i a l l y f o r t h e common hydrocarbons i n the
b o i l i n g range used by Okamoto and Van W i n k l e (150 t o 350°F).
When i t becomes e v i d e n t t h a t t h e TBP and EFV s l o p e p l o t i s
a l s o c o r r o b o r a t e d by a s i m i l a r p l o t f o r t h e c r u d e s , t h e
s i m i l a r i t y i s even more s i g n i f i c a n t . T h i s approach t o the
c h a r a c t e r i z a t i o n curves o f crude o i l s may prove t o be more
u s e f u l t h a n i the reference t o petroleum f r a c t i o n s , t h e
u s u a l method adopted.

The a c c u r a c y o f t h e EFV 50 p e r c e n t p o i n t determined

 57.

by t h e Okamoto and Van W i n k l e method i s good when compared

w i t h t h a t o b t a i n e d f o r t h e b e s t A.S.T.M. - EFV c o r r e l a t i o n .

The c o r r e l a t i o n o f E d r a i s t e r and P o l l o c k (4) g i v e s t h e

s m a l l e s t mean d e v i a t i o n o f ±12.5°F. i n t h e p r e d i c t e d flash

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

a v a i l a b l e c o r r e l a t i o n s , as shown by Ghu and S t a f f e l ( 2 ) .

The l o w e r v a l u e o f - 8.1°F. was o b t a i n e d f o r t h e c r u d e s .

A l t h o u g h t h e A.S.T.M. d i s t i l l a t i o n s a r e somewhat l e s s

r e p r o d u c i b l e t h a n t h e TBP d i s t i l l a t i o n s , t h e r e l a t i v e l y s m a l l

mean d e v i a t i o n i s v e r y f a v o u r a b l e .

I n t h e i r s l o p e c o r r e l a t i o n Okamoto and Van W i n k l e

c a l c u l a t e d t h e 10-70 p e r c e n t s l o p e s f o r t h e h y d r o c a r b o n

mixtures. T h i s i s a s l o p e commonly used i n s l o p e c o r r e l a t i o n s ;

however, s i n c e b o t h t h e TBP and EFV curves f o r c r u d e s a r e

s t r a i g h t o n l y f o r t h e 25-55 p e r c e n t range, t h e s e s l o p e s

were used i n p r e f e r e n c e . Very l i t t l e change i n s l o p e would

be observed i f t h e 10-30 p e r c e n t s l o p e was used as

suggested by E d m i s t e r and P o l l o c k (4). s i n c e t h e v a r i a t i o n

i n t h i s r e g i o n was o n l y s l i g h t . A l t h o u g h t h e TBP s l o p e s

a r e a p p r o x i m a t e l y c o n s t a n t over the complete range o f

10-70 p e r c e n t , t h e EFV s l o p e s have a pronounced c u r v e

upward i n t h e 55-70 p e r c e n t range. The 25-55 p e r c e n t s l o p e s ,

t h e r e f o r e , a r e most c h a r a c t e r i s t i c .

The use o f a t m o s p h e r i c TBP and EFV d i s t i l l a t i o n s

i n s t e a d o f a t p r e c i s e l y 760 mm. p r e s s u r e may be q u e s t i o n e d .

V a r i a t i o n s i n a t m o s p h e r i c p r e s s u r e have been n o t e d from

 58.

757 "to 760 mm. f o r t h e i n d i v i d u a l d e t e r m i n a t i o n s . The

t e m p e r a t u r e adjustment c o r r e s p o n d i n g t o t h i s p r e s s u r e

v a r i a t i o n i s no more t h a n 2°F. a s e s t i m a t e d from t h e Cox

c h a r t and i s o f t h e o r d e r o f a c c u r a c y t h a t t h e Cox c h a r t

can be r e a d . The u s u a l method i s t o n e g l e c t t h i s small

temperature discrepancy. The C a l i f o r n i a R e s e a r c h C o r p o r a t i o n

p u b l i c a t i o n (1) on t h e comprehensive a n a l y s i s o f Redwater

urude showed t h e TBP curve as o b t a i n e d a t a t m o s p h e r i c

p r e s s u r e (358 mm.) w i t h o u t c o r r e c t i o n . S i m i l a r adjustment

o f t h e EFV d a t a w a s ' n e g l e c t e d f o r t h e same r e a s o n .

Chu and S t a f f e l ( 2 ) , i n t h e i r r e c e n t s u r v e y o f t h e

c o r r e l a t i o n s o f A.S.T.M. and EFV c u r v e s gave an i n t e r e s t i n g

discussion on t h e use o f the'U.O.P. c h a r a c t e r i z a t i o n factor,

K, as a c o r r e l a t i n g v a r i a b l e . The w r i t e r s agree t h a t the

K f a c t o r c o r r e c t i o n i s a p p l i e d t o t h e 50 p e r c e n t p o i n t o f

the p r e d i c t e d f l a s h curve w i t h some advantage i n such

c o r r e l a t i o n s as t h a t by E d m i s t e r and P o l l o c k ( 4 ) ; however,

t h e y doubt t h a t i t s use a c t u a l l y a c c o u n t s f o r t h e d i f f e r e n c e

i n aromaticity of the f r a c t i o n s :
" I t i s assumed that t h e c h a r a c t e r i z a t i o n
f a c t o r would have a s much e f f e c t on any
p o i n t on t h e f l a s h c u r v e as i t does on
the 50 p e r c e n t p o i n t . As i t does n o t
appear t o b e n e f i t t h e 10 and 70 p e r c e n t
p o i n t s some doubt i s c a s t on t h e v a l i d i t y
o f t h e c o r r e c t i o n by t h e c h a r a c t e r i z a t i o n
f a c t o r a t t h e 50 p e r c e n t p o i n t " ( 2 )

The a p p l i c a t i o n o f a K f a c t o r c o r r e c t i o n t o t h e TBP-EFV
c o r r e l a t i o n s would be l i k e w i s e c r i t i e i z e d .
 59.

Some a s p e c t s o f t h e i n i t i a l d e t e r m i n a t i o n s o f

t h e TBP and EFV curves s h o u l d be f u r t h e r c o n s i d e r e d . One

of t h e problems c o n c e r n i n g t h e TBP d i s t i l l a t i o n was t h e

method o f e x t e n d i n g the. second p o r t i o n o f t h e curve o b t a i n e d

at 10 mm. t o atmospheric p r e s s u r e . The s t a n d a r d method

has heen t o f o l l o w t h e l i n e f o r t h e n - p a r a f f i n o f e q u a l

b o i l i n g p o i n t on a Cox c h a r t t o determine the corresponding

atmospheric temperature. A p o s s i b i l i t y f o r t e s t i n g the

v a l i d i t y o f t h i s method o f e x t r a p o l a t i o n appeared t o be a

complete TBP d i s t i l l a t i o n a t 10 mm. p r e s s u r e and t h e compar-

i s o n w i t h one p a r t i a l l y completed a t atmospheric pressure.

When.: t h i s was attempted t h e q u a n t i t y o f condensate

removed by t h e d r y Q i c e t r a p was e x c e s s i v e making e v a c u a t i o n

t o 10 mm. i m p o s s i b l e . Careful!,, r e f e r e n c e t o t h e Cox c h a r t

i n d i c a t e d t h a t a l l t h e l i g h t e s t f r a c t i o n s , up t o about 20

p e r c e n t would be v a p o r i z e d a t 10 mm. and a t room temperature.

The reduced p r e s s u r e d i s t i l l a t i o n was u s u a l l y begun a t about

35 volume p e r c e n t . The o v e r l a p o f t h e two d i s t i l l a t i o n s

was c o n s i d e r e d t o o s m a l l t o be s i g n i f i c a n t ; as a r e s u l t ,

t h e complete 10 mm. d i s t i l l a t i o n was abandoned. No g r o s s

e r r o r i n the TBP curve i s p o s s i b l e , however, s i n c e t h e

e x t r a p o l a t e d p o r t i o n o f t h e curve f o l l o w s c o n s i s t e n t l y

from t h e i n i t i a l p a r t o f t h e c u r v e .

The a p p l i c a t i o n o f t h e Cox c h a r t f o r t h e e x t r a -
p o l a t i o n o f EFV curves has, q u i t e j u s t l y , r e c e i v e d more
criticism. S i n c e t h e o i l f r a c t i o n s i n a TBP d i s t i l l a t i o n
 60.

are r e l a t i v e l y narrow - f r a c t i o n s , i t i s l i k e l y t h a t t h e

assumption t h a t t h e y can be c h a r a c t e r i z e d by n - p a r a f f i n

hydrocarbons i s v a l i d . I n t h e EFV d e t e r m i n a t i o n s t h e con-

densate volume i n c l u d e s components o f a wide b o i l i n g range;

the o b v i o u s p o s s i b l e e r r o r i s t h a t t h i s o i l f r a c t i o n does

not have t h e same c h e m i c a l c h a r a c t e r i s t i c s as t h e n - p a r a f f i n

o f t h e same b o i l i n g p o i n t . The Cox c h a r t method f o r

e x t e n d i n g EFV d a t a t o h i g h p r e s s u r e s has been sh^mm t o be

i n e r r o r by E d m i s t e r and P o l l o c k (4) who a l s o p r e s e n t a

c o r r e l a t i o n s u i t a b l e f o r t h i s purpose. F o r subatmospheric

pressures, however, t h e Cox c h a r t i s g e n e r a l l y a c c e p t e d as

a c o n v e n i e n t and dependable means f o r e x t r a p o l a t i n g EFV

d a t a a v a i l a b l e a t two p r e s s u r e s . S l i g h t l y l e s s dependable

i s the p l o t o f t h e l o g a r i t h m of the pressure versus t h e

r e c i p r o c a l t e m p e r a t u r e ( F i g u r e 9)5 however, i t a l s o i s

q u i t e adequate i n t h e l o w p r e s s u r e r e g i o n . The f o c a l p o i n t s

f o r t h e c r u d e s , as shown on t h e l a t t e r p l o t , a r e l o c a t e d

a t p r e s s u r e s so f a r beyond t h e c r i t i c a l p r e s s u r e s o f

petroleum f r a c t i o n s that the question a r i s e s as t o t h e i r

significance. The l o c a t i o n o f a f o c a l p o i n t i s a f u n c t i o n

of t h e a b s o l u t e v a l u e o f t h e 50 p e r c e n t p o i n t a t a t m o s p h e r i c

p r e s s u r e and t h e temperature d i f f e r e n c e o f t h e two 50 p e r c e n t

points. F o c a l p o i n t s o f o t h e r c r u d e s would have t o be com-

p a r e d i n t h e l i g h t o f t h e s e two v a r i a b l e s b e f o r e any

conclusions c o u l d be drawn.
\ 61.

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Report on Redwater Crude a n a l y s i s , F e b . 9 (1953)•
2. Chu, J . C , and S t a f f e l , E . J . ,
J , I n s t , o f P e t . , Ul 3 7 5 , 9,2 ( 1 9 5 5 ) .
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3 . C o l l i n s , F.C., and Vernon, L., ''

I n d . E n g . Chem., 1 8 , 673 ( 1 9 4 6 ) .
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2, 2 8 7 , (1928).
9 . K a t z , O.L., and Brown, G.G.,
I n d . E n g . Chem., 2 £ , 1278 ( 1 9 3 3 ) .

1 0 . McCabe, W.L., and T h i e l e , E.W.,

I n d . Eng. Chem., 12, 605 ( 1 9 2 5 ) .
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O i l Gas J o u r n a l , 22, June 1 7 , (1948).
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14. Ibid.,
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15. Othmer, D.F., Ten E y c k , E.H., and T o l i n , S.,

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Handbook o f P h y s i c a l a n d C h e m i s t r y , 2016; ( 1 9 5 3 ) .
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U.S. B u r . Mines Tech. P a p e r s , 600 ( 1 9 3 9 ) .
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I n d . Eng. Chem., 2£, 880 (1933).
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Data Book on Hydrocarbons, v a n N o s t r a n d Co., N.Y.,(]9 50).