THE VISCOSITY OF LIQUIDS

(a) Normal O c t a n o l a t Atmospheric P r e s s u r e

(b) An Equipment f o r H i g h P r e s s u r e s

by

GEORGES FRANCOIS DE VERTEUIL

B. A., Cambridge U n i v e r s i t y , 1956

A THESIS SUBMITTED I N PARTIAL FULFILMENT OF.

THE REQUIREMENTS FOR THE DEGREE OF

MASTER OF APPLIED SCIENCE

i n t h e Department

of

CHEMICAL ENGINEERING

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 t h e r e q u i r e d standard

THE UNIVERSITY OF BRITISH COLUMBIA

December 1958
 ii

ABSTRACT

T h e o r i e s of L i q u i d V i s c o s i t y l e a d t o e q u a t i o n s

g i v i n g the v a r i a t i o n of the v i s c o s i t y w i t h temperature and

p r e s s u r e , but g i v e poor agreement w i t h e x p e r i m e n t a l v a l u e s ,

p a r t i c u l a r l y f o r a s s o c i a t e d compounds such as normal a l c o h o l s .

The l a c k of a c c u r a t e measurements under p r e s s u r e f o r t h e s e

compounds i s b e i n g p a r t i c u l a r l y f e l t i n the development o f

such t h e o r i e s .

Apparatus has been assembled and c a l i b r a t e d f o r

c a r r y i n g out measurements on the normal a l c o h o l s over a range

of p r e s s u r e s t o 10,000 p s i and temperatures t o 100°C. Parallel

w i t h the development o f t h i s p r e s s u r e v i s c o m e t e r , the v i s c o s i t y

of n - o c t a n o l a t atmospheric p r e s s u r e has been determined in

s t a n d a r d c a p i l l a r y v i s c o m e t e r s f o r a range of 15° t o 90°C.

The d a t a have been examined and c o r r e l a t e d on the

b a s i s of s t a n d a r d v i s c o s i t y - t e m p e r a t u r e e q u a t i o n s w i t h

emphasis on t h e i r r e l e v a n c e i n an i m p o r t a n t homologous s e r i e s .

The r e s u l t s have l a i d the groundwork f o r measurement under

pressure.
 In p r e s e n t i n g t h i s t h e s i s i n p a r t i a l f u l f i l m e n t of

the r e q u i r e m e n t s f o r an advanced degree at the University

o f B r i t i s h Columbia, I agree t h a t the L i b r a r y s h a l l make

i t f r e e l y a v a i l a b l e f o r r e f e r e n c e and study. I further

agree t h a t p e r m i s s i o n f o r e x t e n s i v e copying of t h i s t h e s i s

f o r s c h o l a r l y purposes may be g r a n t e d by the Head o f my

Department o r by h i s r e p r e s e n t a t i v e . I t i s understood

that copying or p u b l i c a t i o n of t h i s t h e s i s f o r f i n a n c i a l

g a i n s h a l l not be a l l o w e d w i t h o u t my w r i t t e n permission.

George F. de V e r t e u i l

Department o f Chemical Engineering

The U n i v e r s i t y of B r i t i s h Columbia,
Vancouver S, Canada.

Date 19th December, 1958.

 iii

TABLE OP CONTENTS

ABSTRACT i i

TABLE OP CONTENTS i i i

LIST OP TABLES v

LIST OP FIGURES vi

LIST OP APPENDICES v i i

NOMENCLATURE viii

ACKNOWLEDGMENT xi

I INTRODUCTION 1

I I THEORY AND CORRELATION OP LIQUID VISCOSITIES

(a) G e n e r a l Theory 16

(b) Theory o f C o r r e s p o n d i n g S t a t e s 26

(c) E f f e c t o f Temperature on t h e V i s c o s i t y
of L i q u i d s 30
(d) E f f e c t o f P r e s s u r e on t h e V i s c o s i t y o f
Liquids 35
(e) Theory i n R e l a t i o n t o t h e Normal A l c o h o l s 42

I I I APPARATUS AND PROCEDURE

(a) C a p i l l a r y V i s c o m e t e r s • 47

(b) The P r e s s u r e V i s c o m e t e r 66

(c) D e n s i t y D e t e r m i n a t i o n s 85

(d) P r e s s u r e Equipment 87

(e) T r a n s f e r Apparatus 91

( f ) Procedure f o r I n t r o d u c t i o n o f Sample,
and P r e s s u r i z i n g 92
 iv

IV NORMAL OCTANOL PURIFICATION AND CHARACTERIZATION 95

V RESULTS
(a) V i s c o s i t i e s a t Atmospheric Pressure 98

(b) D e n s i t y D e t e r m i n a t i o n s 102

(c) C a l i b r a t i o n o f R o l l i n g - B a l l V i s c o m e t e r 102

VI DISCUSSION
(a) The P r e s s u r e Apparatus 112

(b) . V i s c o s i t y Measurements a t Atmospheric

Pressure 115
(c) The P u r i t y of n - o c t a n o l 117

(d) The V i s c o s i t y o f n - o c t a n o l 118

LITERATURE CITED 121

APPENDICES 130

i
 V

LIST OP TABLES

Table Page
1 Approximate V a l u e s of S u r f a c e T e n s i o n - D e n s i t y
R a t i o f o r Common Organic L i q u i d s 60

2 Physical Properties of n - O c t a n o l f r o m the

Literature 97a
3 C a l i b r a t i o n o f C a p i l l a r y V i s c o m e t e r s by
Comparison 104
4 C a l i b r a t i o n of- C a p i l a r y V i s c o m e t e r s w i t h
D i s t i l l e d Water a t 20°C 105

5 V i s c o s i t i e s and D e n s i t i e s of O i l s D,E and P 106

6 V i s c o s i t y and D e n s i t y o f n - O c t a n o l 107

7 C o r r e l a t i o n o f V i s c o s i t y - T e m p e r a t u r e Data f o r
n-Octanol 108

8 C a l i b r a t i o n of Pyknometers 109

9 C a l i b r a t i o n of P r e s s u r e V i s c o m e t e r 110

10 C o r r e l a t i o n f o r Pressure Viscometer 111

 vi

LIST OP FIGURES

To F o l l o w
Figure Page

1 Cannon-Fenske V i s c o m e t e r 47

2 D r y i n g System f o r C a p i l l a r y V i s c o m e t e r 48

3 R o l l i n g - B a l l Viscometer 68

4 T i m i n g System f o r P r e s s u r e V i s c o m e t e r 71
5 C r i t i c a l Reynold's No. f o r R o l l i n g - B a l l
Viscometer 77
6 Correlation Factor f o r R o l l i n g - B a l l
Viscometer 77
7 Assembly of P r e s s u r e System 87

8 T r a n s f e r Bomb 89

9 T r a n s f e r Apparatus 91

10 V i s c o s i t y of n - O c t a n o l 100

11 C a l i b r a t i o n of Pressure Viscometer 103

12 C a l i b r a t i o n of Thermometers 136

13 P u l s e Generator 143

/
 vii

APPENDICES

Page
I. Bibliography on P r e s s u r e V i s c o m e t r y . 130

II. Calibration Certificate for Capillary

V i s c o m e t e r , B78. 133
III. C a l i b r a t i o n o f Thermometers 135

IV. Operating I n s t r u c t i o n s f o r Pressure

Viscometer. 137

V. Electronic Timer 142

VI. D e s i g n o f P r e s s u r e Bombs 144

 viii

NOMENCLATURE

A = atomic w e i g h t , p r e - e x p o n e n t i a l f a c t o r

B = E/R i n v i s c o s i t y — t e m p e r a t u r e e q u a t i o n

C = c a l i b r a t i o n constant f o r viscometer

D = diffusivity, tube d i a m e t e r ( r o l l i n g - b a l l )

E = energy o f a c t i v a t i o n

E^ = i s o c h o r i c energy o f a c t i v a t i o n
P = shearing force, effective force on b a l l due t o
gravity

^P* = f r e e energy o f a c t i v a t i o n ( E y r i n g Theory)

H =
X-^ — X2

= d r i v i n g head i n c a p i l l a r y v i s c o m e t e r

AH* = enthalpy of a c t i v a t i o n (Eyring Theory)

I = Souders' c o n s t i t u t i v e factor

K = adiabatic compressibility, correlation factor for

r o l l i n g - b a l l viscometer

L = l e n g t h of c a p i l l a r y , l e n g t h o f v i s c o m e t e r tube

M = m o l e c u l a r weight

P = pressure

Q, = volume f l o w t h r o u g h c a p i l l a r y

R = r a d i u s o f c a p i l l a r y , gas c o n s t a n t , f l u i d resistance

AS^ = entropy of v a p o r i z a t i o n

AS* = entropy of a c t i v a t i o n (Eyring Theory)

 ix

T = absolute temperature
V = atomic vaolume, e f f e c t i v e volume o f c a p i l l a r y
viscometer, b a l l v e l o c i t y

W = constant i n B a c h i n s k i i equation, c o r r e c t i o n to
Stokes Law f o r w a l l - e f f e c t
A,B,C,D,G, and K are used as c o n s t a n t s

a = l a t t i c e parameter ( E y r i n g Theory)
d = diameter, b a l l diameter

d^ = d i a m e t e r o f lower r e s e r v o i r o f c a p i l l a r y v i s c o m e t e r

g = g r a v i t a t i o n a l constant

h = mean h y d r a u l i c d i a m e t e r , P l a n k ' s c o n s t a n t

k = Botlzmann c o n s t a n t , t h e r m a l c o n d u c t i v i t y

k^ = a b s o l u t e r e a c t i o n r a t e ( E y r i n g Theory)
m = mass o f a m o l e c u l e , k i n e t i c energy f a c t o r , mass o f
ball
n = number o f m o l e c u l e s / u n i t volume

n^- = p r e s s u r e c o r r e l a t i o n f a c t o r f o r E y r i n g Theory

p = pressure

q 0 = constant i n Lederer equation

r = l e n g t h parameter, r a d i u s of a m o l e c u l e

r-|_ = r a d i u s of e f f l u x bulb

= r a d i u s of lower r e s e r v o i r

t = time, e f f l u x time, r o l l time

u = mean f l u i d velocity

v = p o i n t v e l o c i t y , s p e c i f i c volume
x
a,b,c,and n are used as c o n s t a n t s
 X

c o n s t a n t i n Andrade e q u a t i o n c o e f f i c i e n t of t h e r m a l
?

expansion
= v a r i a b l e defined i n equation (72)

S = surface tension

S = l a t t i c e parameter ( E y r i n g Theory)

6 = bond energy, c o n s t a n t i n m o l e c u l a r p o t e n t i a l f u n c t i o n

*l = absolute v i s c o s i t y

^M = absolute v i s c o s i t y at m.p.
v i s c o s i t y a t law p r e s s u r e s

=
reduced v i s c o s i t y ( r e l a t i v e t o c r i t i c a l p o i n t )
+•
Tj= reduced v i s c o s i t y (Comings and E l g y )

reduced v i s c o s i t y (De Boer)

d = angle of r o l l

v = kinematic v i s c o s i t y , v i b r a t i o n frequency

<? =
density, density of l i q u i d

<?. = d e n s i t y of b a l l

<r = average d i s t a n c e between m o l e c u l e s , c o n s t a n t i n

molecular p o t e n t i a l f u n c t i o n

t = shearing stress
f l u i d i t y , f u n c t i o n o f (~) f o r r o l l i n g - b a l l
viscometer, equation (81)

a n d ^ were used as c o n s t a n t s
 xi

ACKNOWLEDGMENT

The author wishes t o express h i s thanks t o

D r . L.W. S h e m i l t , and o t h e r members o f t h e s t a f f a t t h e

Department o f Chemical E n g i n e e r i n g , U n i v e r s i t y o f

B r i t i s h Columbia, f o r a d v i c e and h e l p d u r i n g t h e course

of t h i s work, and t o t h e N a t i o n a l R e s e a r c h Council f o r

financial assistance.
 1

I, INTRODUCTION

(a) Viscosity

The e x i s t e n c e o f f r i c t i o n i n t h e f l o w o f f l u i d s was

f i r s t recognized b y N e w t o n ( 1 ) a t t h e end o f t h e 1 7 t h

century, when h e p o s t u l a t e d t h a t the f r i c t i o n a l f o r c e between

two l i q u i d s u r f a c e s was p r o p o r t i o n a l t o t h e a r e a and t o t h e

relative velocity of the f l u i d surfaces. Later, Newton's

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

defines the coefficient of v i s c o s i t y as follows.

where,, = c o e f f i c i e n t of v i s c o s i t y ,
= shearing stress
^Z' = v e l o c i t y g r a d i e n t e x i s t i n g a t same
dr " '
p o i n t , r,. a l e n g t h p a r a m e t e r
defined In a direction perpendicular
to the flow direction.

I n c.g.s. u n i t s , the u n i t of v i s c o s i t y i s the poise

= gm. cm."''' s e c . ^. The c e n t i p o i s e i s t h e common p r a c t i c a l

unit of viscosity. The r a t i o o f t h e v i s c o s i t y to the density

is called the kinematic viscosity and i s a f u n d a m e n t a l vari-

able i n hydrodynamics. The c . g . s . u n i t of kinematic viscosity

is the stoke = cm. sec.

(b) Newtonian and Non-Newton!an V i s c o s i t y

F o r many f l u i d s , i n equation (1) i s a t r u e

c o n s t a n t a t any p a r t i c u l a r v a l u e o f , s a y , t e m p e r a t u r e and

p r e s s u r e i . e . i t i s a t r u e f u n c t i o n s t a t e and independent of
A

the magnitude and n a t u r e o f the imposed s h e a r i n g s t r e s s ,

Those f l u i d s f o r w h i c h ^ i s a t r u e constant of s t a t e are

r e f e r r e d t o as Newtonian f l u i d s and T[ i s c a l l e d the

Newtonian V i s c o s i t y . Most pure l i q u i d s , homogeneous l i q u i d

m i x t u r e s , and gases show Newtonian b e h a v i o r .

On t h e a p p l i c a t i o n o f an e x t e r n a l s t r e s s many

substances do not obey the s i m p l e Newton law, but show anoma

l o u s e f f e c t s w h i c h a r e i n c l u d e d i n the g e n e r a l term of non-

Newtonian b e h a v i o r . I n f a c t a g e n e r a l r e l a t i o n s h i p between
dv
the imposed s h e a r i n g s t r e s s , , and the r a t e of s h e a r , —,

can be w r i t t e n i n the f o r m

= K#J (2)

f o r any m a t e r i a l , f l u i d or s o l i d , and Newton's law, equation

( 1 ) , i s m e r e l y a p a r t i c u l a r example of t h i s g e n e r a l r e l a t i o n

s h i p w h i c h i s found t o a p p l y f o r most pure gases and liquids

A g e n e r a l d i s c u s s i o n o f the r e l a t i o n , e q u a t i o n (2) is
? given

by Burgers (2) and Oldroyd (3).

(c) Importance of V i s c o s i t y

The concept of v i s c o s i t y i s now of g r e a t importance

i n pure s c i e n c e and e n g i n e e r i n g . I n a n a l y t i c a l and p h y s i c a l

chemistry i t i s a p r o p e r t y which i s u s e f u l i n c h a r a c t e r -

izing materials. F o r t h i s purpose, the i-Theochor, u

-,

.of F r i e n d and Hargraves (4) and l a t e r m o d i f i c a t i o n s by

C h a c r a v a r t i (5) and Jones and Bowden (6) i s p a r t i c u l a r l y

useful. I t i s found t o be l a r g e l y independent o f temperature

and, s i m i l a r t o t h e p a r a c h o r o f Sugden (7)^ i s an additive

p r o p e r t y o f o r g a n i c compounds. During recent years, interest

i n t h i s f i e l d o f c h e m i s t r y seems t o have been c o n s i d e r a b l y

reduced. However, i n t h e more r e c e n t v f i e l d o f h i g h polymer

chemistry the use of v i s c o s i t y i n e s t i m a t i n g molecular weight

and s t r u c t u r e has a t t a i n e d a new prominence as i s shown by t h e

v a s t l i t e r a t u r e on the v i s c o s i t y o f polymer m e l t s and s o l u t i o n s

I t i s i n r e l a t i o n t o t h i s f i e l d t h a t non-Newtonian Viscosity

is particularly developing.

In the f i e l d of engineering, the v i s c o s i t y of f l u i d s

i s a l s o v e r y i m p o r t a n t and an a c c u r a t e knowledge o f t h e

viscosity i s essential to the s o l u t i o n o f many d e s i g n problems

p a r t i c u l a r l y those a s s o c i a t e d w i t h f l u i d m o t i o n . It is

p a r t i c u l a r l y i m p o r t a n t i n Chemical E n g i n e e r i n g S c i e n c e f o r t h e

correlation o f d a t a i n t h e f i e l d o f heat, mass,and momentum

transfer. I n these c o r r e l a t i o n s t h e use o f d i m e n s i o n l e s s

groups i s s t a n d a r d p r a c t i c e , and t h e v i s c o s i t y i s r e p r e s e n t e d

i n many o f these groups, f o r example,

Reynolds No. Re = - Heat, Mass, Momentum

Prandtl No. P r = Y[C^ - Heat T r a n s f e r

I t i s a l s o i m p o r t a n t i n o t h e r e n g i n e e r i n g f i e l d s , such as

aerodynamics and h y d r a u l i c s and i n o t h e r f i e l d s where t h e

flow of f l u i d s i s of importance

(d) V i s c o s i t y a3 a T r a n s p o r t P r o p e r t y o f F l u i d s

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

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

i s t h e most e a s i l y and a c c u r a t e l y measurable o f the t r a n s -

p o r t p r o p e r t i e s o f f l u i d s and f o r t h i s r e a s o n , more r e l i a b l e

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

other t r a n s p o r t p r o p e r t i e s . At the present time, a l o t of

t h e o r e t i c a l work I s b e i n g done on the t h e o r y o f t h e gaseous

and l i q u i d s t a t e s , a n d when (these t h e o r i e s a r e a p p l i e d t o t h e

t r a n s p o r t p r o p e r t i e s of f l u i d s t h e y a r e almost invariably

t e s t e d w i t h v i s c o s i t y d a t a , ( f o r example, B i r d , H i r c h f e l d e r

and C u r t i s s ( 8 ) ). Thus v i s c o s i t y a f f o r d s a means o f pene-

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

matter.

(e) T h e o r i e s o f V i s c o s i t y

Many t h e o r i e s and m a t h e m a t i c a l r e l a t i o n s have been

proposed t o e x p l a i n the v i s c o s i t y o f l i q u i d s and i n p a r t i c u -

l a r t h e e f f e c t o f temperature and p r e s s u r e . Until recently,

t h e s e r e l a t i o n s have been m a i n l y e m p i r i c a l , o r s e m i t h e o r e t i -
LTV

c a l and have been l i m i t e d a p p l i c a b i l i t y , i . e . s u i t a b l e t o

A

c e r t a i n types o f compounds and n o t o t h e r s . D u r i n g the l a s t

 5
.20 y e a r s t h e r e have been attempts to relate viscosity to

a more g e n e r a l t h e o r y o f t r a n s p o r t p r o p e r t i e s , and more

fundamentally t o g e n e r a l t h e o r i e s o f t h e gaseous and l i g u i d

states. As i n o t h e r f i e l d s , t h e r e has been g r e a t e r success

w i t h gases than w i t h l i q u i d s , and i n f a c t w i t h t h e s i m p l i e r

gases agreement o f t h e o r y and e x p e r i m e n t i s w i t h i n the

experimental error. U n f o r t u n a t e l y , t h e agreement o f e x p e r i -

ment and t h e o r y w i t h l i q u i d s isstill i n the realm of "orders

of magnitude." However, t h e r e do e x i s t many e m p i r i c a l cor-

relations relating the v i s c o s i t y of l i q u i d s w i t h the funda-

mental i n t r i n s i c properties of pressure and t e m p e r a t u r e , which

show good a g r e e m e n t w i t h e x p e r i m e n t and a r e v e r y u s e f u l f o r

engineering applications.

The v i s c o s i t y of f l u i d s i s a very strong function

of temperature, gases showing a decrease i n v i s c o s i t y and

liquids an i n c r e a s e w i t h decrease of temperature. For

liquids, t h e e f f e c t i s p a r t i c u l a r l y m a r k e d , many l i q u i d s

s h o w i n g a 1 0 0 $ c h a n g e w i t h 2 0 - 30°C c h a n g e i n t e m p e r a t u r e .

All g a s e s and l i q u i d s so f a r . i n v e s t i g a t e d , w i t h t h e

e x c e p t i o n of water, h a v e shown a n i n c r e a s e i n v i s c o s i t y with

pressure (at constant temperature). W a t e r shows a minimum

i n the v i s c o s i t y pressure curve a t c e r t a i n temperatures, i.e.,

the v i s c o s i t y decreases with pressure at f i r s t and a f t e r a

c e r t a i n pressure begins to increase. The p r e s s u r e effect oia.

v i s c o s i t y i s quit-e s m a l l u p t o one h u n d r e d a t m o s p h e r e s !••

 6

but shows v e r y marked i n c r e a s e a t h i g h and extreme p r e s s u r e s ,

(f) Viscometry

The methods f o r m e a s u r i n g the v i s c o s i t i e s of gases

and l i q u i d s a r e e s s e n t i a l l y the same, d i f f e r e n c e s e x i s t i n g

o n l y i n the d e t a i l s of the a n c i l l a r y equipment. The methods

a r e b e s t summarized under the f o l l o w i n g h e a d i n g s , suggested

b y Bingham (9), page 6.

1) Flow methods,
2) Methods based on r e s i s t a n c e o f f e r e d t o s o l i d
bodies,
3) Other methods.
Many of these are r e a d i l y and e x a c t l y a n a l y s e d mathemati-

c a l l y and a r e t h e r e f o r e a b s o l u t e methods. However, i n many

c a s e s , the a p p l i c a t i o n o f the a p p r o p r i a t e e q u a t i o n s i n v o l v e s

f u r t h e r l a b o r i o u s work and the use of a d d i t i o n a l experimental

data which are u n c e r t a i n . As a r e s u l t , the m a j o r i t y of

p r a c t i c a l v i s c o m e t r y i s done on a r e l a t i v e s c a l e . For

example, the c a p i l l a r y ^ t u b e v i s c o m e t e r i s an a b s o l u t e instru-

ment, i n t h a t the e f f l u x time can be r e l a t e d e x a c t l y w i t h the

dimensions and the v i s c o s i t y by a p p l i c a t i o n of the P o i s e u i i l l e

Law (10),

(3)

where, volume f l o w
p r e s s u r e drop:
r a d i u s of tube
time of f l o w
U l e n g t h of c a p i l l a r y
 7

However, t h e a p p l i c a t i o n o f t h i s e q u a t i o n t o determine Y|_

would r e q u i r e , f o r example, a v e r y a c c u r a t e v a l u e f o r t h e

r a d i u s o f t h e tube, R, w h i c h i s d i f f i c u l t t o o b t a i n w i t h

s u f f i c i e n t accuracy. Other methods f o r measuring t h e

v i s c o s i t y cannot be a n a l y s e d e x a c t l y and a r e t h e r e f o r e

n e c e s s a r i l y r e l a t i v e methods.

W i t h most v i s c o m e t e r s , c a r e i s t a k e n t o ensure t h a t
o p e r a t i o n i s w i t h i n t h e v i s c o u s regime o f f l o w and i n g e n e r a l

that i n e r t i a l e f f e c t s are n e g l i g i b l e . W i t h some v i s c o m e t e r s ,

however, i n e r t i a l e f f e c t s a r e c o n s i d e r a b l e , b u t t h e method i s

d e s i g n e d t o t a k e these i n t o account and t o ensure determi-

n a t i o n o f t h e c o r r e c t v i s c o s i t y as d e f i n e d by Newton's Law

for viscous flow.

B r i e f l y , t h e f o l l o w i n g a r e some examples o f t h e

v i s c o m e t e r s i n common u s e :

1. Flow Methods

(a) E f f l u x t h r o u g h h o r i z o n a l c a p i l l a r i e s e.g.

Thorpe and Rodger (11) and Bingham and White ( 1 2 ) .

(b) E f f l u x t h r o u g h v e r t i c a l c a p i l l a r i e s . The

most i m p o r t a n t a r e t h e Ostwald v i s c o m e t e r ; (13) f o r l i q u i d s

w i t h I t s m o d i f i c a t i o n s b y Cannon and Fenske (14) Ubbelhode

( 1 5 ) , and t h e Rankine v i s c o m e t e r (16) f o r gases.

2. Methods based on R e s i s t a n c e t o s o l i d bodies

(a) R o t a t i n g b o d i e s i n t h e f l u i d . Discs,

c y l i n d e r s and spheres have been used commonly, because t h e s e

 ,8
are r e a d i l y analysed mathematically.

(b) O s c i l l a t i n g b o d i e s — also discs, cylinders

and spheres.

(c) Free f a l l o f a sphere t h r o u g h a l i q u i d —

Stoked'; l a w .

(d) F a l l o f b o d i e s i n c o n f i n e d s p a c e s . These

i n c l u d e t h e f a l l i n g c y l i n d e r i n s t r u m e n t of Bridgman-(17)

(and o t h e r s ) , the f a l l i n g sphere o f Hoppler (18) and t h e

r o l l i n g b a l l of Flowers (19) and Hersey and Shore (20)

3. Other Methods, i n c l u d e

(a) Decay o f o s c i l l a t i o n s o f l i q u i d i n a U-tube

(b) Measurement o f t h e v e l o c i t y o f sound i n a

liquid.

F o r a c c u r a t e work a t atmospheric pressure, c a p i l -

l a r y f l o w methods a r e most f r e q u e n t l y used f o r l i q u i d s , b u t

r o t a t o r y and o s c i l l a t o r y methods a r e common.

F o r h i g h p r e s s u r e s t u d i e s , t h e c a p i l l a r y method o f

Rankine i s i m o s t common f o r g a s e s . F o r l i q u i d s , some form o f

f a l l i n g body method I s u s u a l , s i n c e t h i s i s p a r t i c u l a r l y

s u i t e d t o h i g h p r e s s u r e d e s i g n , a l t h o u g h t h e c a p i l l a r y method

has been used ( 2 1 ) .

(g) V i s c o s i t y Standards and V i s c o m e t e r Calibration

i
A l t h o u g h t h e use o f r e l a t i v e v i s c o m e t e r s i s p r e f e r -

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

l e s s , a b s o l u t e v i s c o m e t x r y i s e s s e n t i a l i n o r d e r t o determine
 9

the c o r r e c t a b s o l u t e b a s i s t o w h i c h t o r e f e r t h e r e l a t i v e

measurements. Furthermore, i t i s p r e f e r a b l e t o use v i s c o -

meters w h i c h can be m a t h e m a t i c a l l y a n a l y s e d e x a c t l y , because

the a n a l y s i s i s o f t e n u s e f u l , and sometimes e s s e n t i a l , i n

c a l c u l a t i n g t h e c o r r e c t i o n s and e r r o r s due t o v a r i o u s e f f e c t s .

S i n c e most commonly used methods f o r v i s c o s i t y

measurement a r e r e l a t i v e , t h e v i s c o m e t e r s must be c a l i b r a t e d .

Great care s h o u l d be t a k e n w i t h t h e c a l i b r a t i o n i n o r d e r t o

ensure c o r r e c t v i s c o s i t y measurements as an a b s o l u t e b a s i s .

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

accepted as the v i s c o s i t y o f w a t e r a t 20°C. As a r e s u l t o f

the r e c e n t work o f S w i n d e l l s and co-workers (22) a t t h e N.B.S.

t h e v i s c o s i t y of w a t e r a t t h i s temperature I s now known v e r y

accurately. The v a l u e i s g i v e n as 0.010019 - 0.000003 c.g.s.

u n i t s o r 1.0019 c p . a t 20.00°C. S i n c e most v i s c o m e t e r s will

not g i v e v a l u e s t o b e t t e r t h a n 0.1%, i t has been recommended

(22) t h a t t h i s v a l u e be c o r r e c t e d t o 1.002 c p . f o r use as a

standard f o r r e l a t i v e determinations. I t i s surprising that

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

d i f f e r e n t by as much as 0.6$, w h i c h c o n t r i b u t e s t o some e x t e n t

to the l a c k o f c o n s i s t e n c y i n t h e v i s c o s i t y d e t e r m i n a t i o n s o f

various experimenters.

It i s usually preferable to calibrate viscometers

w i t h watery I n o r d e r t o m i n i m i z e e r r o r s i n t h e c a l i b r a t i o n b y

r e d u c i n g t h e number of e x p e r i m e n t a l d e t e r m i n a t i o n s between t h e
 10

a b s o l u t e s t a n d a r d and the f i n a l c a l i b r a t i o n . However, Cannon

(23) has d e s c r i b e d a proceedure based on t h e use o f s p e c i a l l y

designed c a p i l l a r y v i s c o m e t e r s as a b s o l u t e s t a n d a r d s f o r

v i s c o s i t y measurements. These "Master v i s c o m e t e r s " a r e

calibrated w i t h d i s t i l l e d water and used t o determine the

v i s c o s i t y o f o t h e r l i q u i d s w h i c h a r e used f o r r o u t i n e c a l i -

brations. T h i s proceedure has r e c e i v e d t h e s a n c t i o n o f the

N a t i o n a l Bureau o f Standards (24) and the A m e r i c a n S o c i e t y

f o r T e s t i n g M a t e r i a l s ( 2 5 ) , and i s now w i d e l y accepted.

(h) The Importance o f D e n s i t y Measurements

I n much work on v i s c o s i t y , the a v a i l a b i l i t y o f

accurate density i s e s s e n t i a l t o c a l c u l a t e the absolute

v i s c o s i t y f r o m the o t h e r e x p e r i m e n t a l measurements. For

example, i n the c a p i l l a r y v i s c o m e t e r , the p r o d u c t o f the e f f l u x

time and t h e c a l i b r a t i o n c o n s t a n t g i v e s t h e k i n e m a t i c viscosity

V = ~ , and i n the v a r i o u s f a l l i n g body i n s t r u m e n t s , t h e

d e n s i t y d i f f e r e n c e ( <P
S f ) between the f a l l i n g body and t h e

f l u i d must be known b e f o r e *^ c a n be e v a l u a t e d f r o m the

experimental r e s u l t s . I n o r d e r t h a t the e x p e r i m e n t a l e r r o r

in <f w i l l not be a l i m i t i n g f a c t o r i n t h e o v e r a l l e r r o r i n

the a b s o l u t e v i s c o s i t y , y\ , i t i s u s u a l l y s u f f i c i e n t t o keep

the e r r o r I n ^ l e s s t h a n 0.1$. This u s u a l l y r e q u i r e s accuracy

o f o n l y t h r e e s i g n i f i c a n t f i g u r e s i n the d e n s i t y measurements^

w h i c h i s e a s i l y a t t a i n a b l e w i t h s t a n d a r d equipment.
 11

( i ) The A v a i l a b i l i t y o f V i s c o s i t y D a t a

There e x i s t s a v a s t l i t e r a t u r e on t h e v i s c o s i t y o f

fluids. A p a r t i c u l a r l y l a r g e amount o f r e s u l t s i s a v a i l a -

ble f o r pure l i q u i d s and l i q u i d m i x t u r e s , a l t h o u g h t h e r e have

a l s o been a l a r g e number o f measurements on gases and vapours.

Most of the s i g n i f i c a n t d a t a up t o 1938 ctjie p r e s e n t e d i n the

I n t e r n a t i o n a l C r i t i c a l Tables (26) and i n the 5 t h

E d i t i o n of

L a n d o l t - B o r n s t e i n ( 2 7 ) . U n f o r t u n a t e l y , t h e r e has been no

complete c o m p i l a t i o n of d a t a s i n c e 1938. The 6 Edition

(1955)of L a n d o l t - B o r n s t e i n (28) l i s t s the v i s c o s i t y of about

150 pure l i q u i d s and gases over q u i t e wide temperature ranges,

but compared t o t h e volume of p u b l i s h e d d a t a , t h i s i s s m a l l .

A c e r t a i n amount o f d a t a a t a few temperatures i s available

i n some of t h e s t a n d a r d works on the p h y s i c a l p r o p e r t i e s of

pure o r g a n i c compounds (29, 3 0 ) , but the scope i s l i m i t e d .

The d a t a on hydrocarbons has been b r o u g h t up t o d a t e by the

American P e t r o l e u m I n s t i t u t e ' s P r o j e c t 44 " S e l e c t e d Values

of Thermodynamic P r o p e r t i e s o f Hydrocarbons and R e l a t e d

Compounds"(31). I t I s t o be hoped t h a t c o m p i l a t i o n s o f d a t a

on many o t h e r compounds w i l l be a v a i l a b l e t h r o u g h t h i s p r o j e c t .

Vogelpbhl ( 2 8 ) , i n an i n t r o d u c t i o n t o t h e d a t a

presented i n Landolt - Bornstein,estimates that absolute pre-

c i s i o n o f the v i s c o s i t y d a t a I s seldom g r e a t e r t h a n 1%.

Measurements by d i f f e r e n t workers a r e o f t e n I n much g r e a t e r

disagreement t h a n 1 $ , s i n c e t h e v i s c o s i t y i s s t r o n g l y a f f e c t e d

by i m p u r i t i e s . He notes t h a t i t i s u s u a l l y v e r y d i f f i c u l t t o
 12

a s s e s s v i s c o s i t y d a t a , because t h e r e i s seldom w e l l - d e f i n e d

d a t a on the degree of p u r i t y .

E x t e n s i v e temperature ranges have been c o v e r e d a t

atmospheric p r e s s u r e s . F o r l i q u i d s , the m a j o r i t y o f d a t a

c o v e r s the temperature range f r o m room temperature t o the

b o i l i n g p o i n t , but the c l a s s i c a l l o w t e m p e r a t u r e work of

Tonomura and M i t s u k u r i (32) has s e r v e d t o extend the range of

a v a i l a b l e d a t a on many l i q u i d s t o near the f r e e z i n g p o i n t s .

Whereas the temperature e f f e c t of the v i s c o s i t y of

l i q u i d s has been e x t e n s i v e l y i n v e s t i g a t e d , t h e e f f e c t o f

p r e s s u r e has r e c e i v e d c o m p a r a t i v e l y l i t t l e attention. This i s

almost c e r t a i n l y due t o the r e l a t i v e l y s m a l l e f f e c t of

p r e s s u r e , u p t o moderate p r e s s u r e s . S i n c e most i n d u s t r i a l

o p e r a t i o n s a r e c a r r i e d on a t r e l a t i v e l y low p r e s s u r e s (below

100 Atm.) where the e f f e c t i s s m a l l , t h e r e has been little

i n c e n t i v e f o r e x p e r i m e n t a t i o n . I n the p e t r o l e u m i n d u s t r y a

knowledge o f the p r e s s u r e e f f e c t o f v i s c o s i t y i s u s e f u l f o r

s o l v i n g problems a s s o c i a t e d w i t h the p r o d u c t i o n of crude o i l

and w i t h l u b r i c a t i o n , and a c e r t a i n amount of d a t a i s a v a i l a -

ble i n this f i e l d . A p a r t from the e x p e r i m e n t s on p e t r o l e u m

p r o d u c t s the work of Bridgman (17,33,34,35) a t H a r v a r d stands

supreme, the number of l i q u i d s s t u d i e d i n h i s e x p e r i m e n t s

exceeding that of a l l other experimenters. I n t h i s work, the

p r e s s u r e range c o v e r e d was f r o m 0 t o 30,000 Atms. but

t e m p e r a t u r e s a r e l i m i t e d t o 30° and 75°C.

 13

There has a l s o been l i t t l e work i n the range of

temperatures above the b o i l i n g p o i n t s of l i q u i d s a n d ?

measurements near the c r i t i c a l p o i n t are v e r y s c a r c e . Indeed,

t h e r e remains a g r e a t d e a l to be done b e f o r e i t w i l l be

p o s s i b l e t o c o n s t r u c t a complete v i s c o s i t y - temperature -

p r e s s u r e s u r f a c e f o r o t h e r than a v e r y few s u b s t a n c e s . The

l a c k o f such d a t a i s b e i n g p a r t i c u l a r l y f e l t i n the d e v e l o p -

ment of t h e o r e t i c a l work i n the f i e l d of v i s c o s i t y and i s

c e r t a i n l y c o n t r i b u t i n g t o the slow development of the t h e o r y

of the l i q u i d state.

( j ) Purpose and Scope of t h i s Work

The l a c k of e x t e n s i v e and r e l i a b l e d a t a on -the e f f e c t

t
of p r e s s u r e on v i s c o s i t y of l i q u i d s , means t h a t the assembly

of an apparatus f o r o b t a i n i n g such d a t a would be o f g r e a t u s e .

A l i t e r a t u r e s u r v e y of the a v a i l a b l e d a t a and equipment used

f o r such d e t e r m i n a t i o n s was made, and i s p r e s e n t e d i n Appendix

I. I t became o b v i o u s t h a t the R o l l i n g - b a l l V i s c o m e t e r first

developed by F l o w e r s ( 1 9 ) and l a t e r used by Hersey and Shore

(20) and by Sage and a s s o c i a t e s (36-39) would be a c o n v e n i e n t

f o r m of apparatus t o use f o r t h i s r e s e a r c h , and s i n c e s u c h an

apparatus had been donated t o t h i s l a b o r a t o r y by I m p e r i a l O i l

Ltd. i t was d e c i d e d t o adopt I t . M o d i f i c a t i o n s were made t o

o b t a i n more a c c u r a t e measurements t h a n were p o s s i b l e i n i t s

o r i g i n a l form.
 14

I n l i n e w i t h p a s t and c u r r e n t work i n these l a b o r a -

t o r i e s on the p h y s i c a l and thermodynamic p r o p e r t i e s of the

n - a l c o h o l s ( 4 0 - 4 6 ) , i t was d e c i d e d t h a t the equipment

s h o u l d be d e s i g n e d w i t h a view t o making measurements on

these s u b s t a n c e s . Bridgman (33,34) has a l r e a d y made measure-

ments on t h e n - a l c o h o l s from to inclusive and

observed an i n c r e a s i n g e f f e c t o f p r e s s u r e on t h e v i s c o s i t y as

the l e n g t h o f the c a r b o n c h a i n i n c r e a s e s . A d d i t i o n a l data

on t h i s e f f e c t would prove v e r y u s e f u l , so i t was decided to

try t o extend the range of B r i d g m a n s measurements t o h i g h e r

1

members of the s e r i e s .

P a r a l l e l w i t h the development of the p r e s s u r e v i s c o -

meter, apparatus was r e q u i r e d f o r making a c c u r a t e measurements

at atmospheric p r e s s u r e on any a l c o h o l s s e l e c t e d f o r i n v e s t i -

g a t i o n , and on m a t e r i a l s s e l e c t e d f o r c a l i b r a t i o n o f the

pressure viscometer. F o r t h i s purpose, s t a n d a r d Cannon-

Fenske c a p i l l a r y v i s c o m e t e r s were c a l i b r a t e d a c c o r d i n g t o

accepted proceedures.

Normal o c t y l a l c o h o l , Gg H-^ OH, was s e l e c t e d as a

s u i t a b l e member of the n o r m a l a l c o h o l s e r i e s on w h i c h t o s t a r t

making measurements. I t i s a v a i l a b l e i n a f a i r l y pure

commercial grade and can be p u r i f i e d t o a h i g h degree by

f r a c t i o n a l d i s t i l l a t i o n , w h i c h i s not p o s s i b l e w i t h n - h e x a n o l

or n - h e p t a n o l , and b e i n g somewhat removed f r o m the C, t o C

x
5
members, i t would p r o v i d e p o s s i b l e i n t e r p o l a t i o n s f o r the
 15
homologous s e r i e s . A l i t e r a t u r e s u r v e y on c e r t a i n of t h e

physical properties of n -octanol including the v i s c o s i t y

a t a t m o s p h e r i c p r e s s u r e was r e q u i r e d . Also, atmospheric

p r e s s u r e measurements on i t s d e n s i t y and v i s c o s i t y , as w e l l

as s u f f i c i e n t measurements t o p r o v i d e an e s t i m a t e o f the

p u r i t y were n e c e s s a r y .

The b a s i s f o r i n v e s t i g a t i o n o f the p r e s s u r e

dependence of the v i s c o s i t y o f n - o c t a n o l c o u l d thus be

p r o v i d e d , a n d i t was a l s o p o s s i b l e t o e s t a b l i s h d a t a of

i n t e r e s t i n i n v e s t i g a t i n g the v i s c o s i t y of the homologous

s e r i e s of normal a l c o h o l s a t atmospheric p r e s s u r e .
 16

II THEORY Al© CORRELATION OP LIQUID VISCOSITIES

(a) G e n e r a l Theory

The theory of l i q u i d v i s c o s i t i e s i s c o n s i d e r a b l y

more i n v o l v e d t h a n t h a t o f gases and t h e l a r g e amount o f work

w h i c h has been p u b l i s h e d on t h e s u b j e c t i n d i c a t e s t h a t

agreement w i t h experiment has been g e n e r a l l y p o o r . A number

of good r e v i e w a r t i c l e s on t h e s u b j e c t have been p u b l i s h e d ,

w h i c h makes i t somewhat e a s i e r t o d i s c u s s t h e p r o b l e m . The

r e v i e w s b y Gemant (47) H i r s c h f e l d e r , C u r t i s s and B i r d ( 8 ) ,

Andrade (48) and V o l a r o v i c h (49) cover t h e f i e l d q u i t e ade-

q u a t e l y up t o r e c e n t y e a r s . L a t e s t developments a r e

c o n s i d e r e d b y Bond! ( 5 0 ) . These a u t h o r s agree t h a t the

g e n e r a l l y poor s t a t e o f development o f t h e t h e o r y i s

u n d o u b t e d l y a s s o c i a t e d w i t h an i m p e r f e c t knowledge o f t h e

l i q u i d state,compared w i t h t h a t o f e i t h e r t h e gaseous o r

solid states.

A good w o r k i n g p i c t u r e on w h i c h t o base a t h e o r y o f

l i q u i d v i s c o s i t i e s i s g i v e n by Gemant ( 4 7 ) :

I n t h e case o f gases, t h e v i s c o u s f o r c e
i s e q u i v a l e n t t o a t r a n s f e r o f momentum and
thus t h e t h e o r y i s based on t h e k i n e t i c
theory . . . .
W i t h l i q u i d s , the s i t u a t i o n i s d i f f e r e n t ,
m o l e c u l e s here a r e under s t r o n g mutual f o r c e s ,
and thus t h e p o s s i b i l i t y a r i s e s t h a t i t i s
these f o r c e s t h a t a r e d i r e c t l y connected w i t h
the v i s c o u s f o r c e . To o b t a i n a rough p i c t u r e ,
 .17
one c a n imagine t h a t m o l e c u l e s , i n o r d e r
to be d i s p l a c e d r e l a t i v e t o each o t h e r ,
have t o overcome t h e i r m u t u a l a t t r a c t i o n .
The s t r o n g e r the l a t t e r , t h e s m a l l e r t h e
flow f o r a given shearing s t r e s s . With
i n c r e a s i n g t e m p e r a t u r e , the randon k i n e t i c
energy o f t h e m o l e c u l e s h e l p s t o overcome
m o l e c u l a r f o r c e s , hence v i s c o s i t y must
d e c r e a s e ( c o n t r a r y t o t h e b e h a v i o r of g a s e s ) ,
a g e n e r a l l y observed f a c t . W i t h i n c r e a s i n g
p r e s s u r e , m o l e c u l e s come n e a r e r and t h e
mutual a t t r a c t i o n becomes s t r o n g e r , hence
v i s c o s i t y i n c r e a s e s , and t h i s , t o o , i s
confirmed by experiment.

Two t h e o r i e s of t h e v i s c o s i t y o f l i q u i d s w i l l be

mentioned here i n some d e t a i l . These a r e t h e t h e o r i e s o f

Andrade (51,52) and E y r i n g ( 5 3 , 5 4 , 5 5 ) , w h i c h approach t h e

problem from q u i t e d i f f e r e n t a s p e c t s , y e t a r r i v e a t t h e same

f o r m o f e q u a t i o n f o r the v a r i a t i o n o f v i s c o s i t y w i t h temper-

ature. B o t h t h e o r i e s a l s o l e a d t o a r e l a t i o n between t h e

v i s c o s i t y and the a p p l i e d p r e s s u r e . Other r e c e n t t h e o r i e s

w i l l be mentioned b r i e f l y f o r the sake o f c o m p l e t e n e s s .

Andrade's Theory

The m o l e c u l e s o f t h e l i q u i d a r e r e g a r d e d as v i b r a t i n g

w i t h a mean f r e q u e n c y ,y , about some e q u i l i b r i u m p o s i t i o n .

On t h i s p i c t u r e , t h e v i s c o s i t y a t t h e m e l t i n g p o i n t , y\ , i s

c a l c u l a t e d on t h e assumption t h a t a t the m e l t i n g p o i n t

momentum t r a n s f e r t a k e s p l a c e a t the extremes o f an o s c i l l a t i o n ,

which leads to the r e l a t i o n ,

(4)
 18

.where = fundamental vibration frequency,

"W\ = mass of a m o l e c u l e ,
0' i
= av volume of l i q u i d per molecule,
and C i s a c o n s t a n t near u n i t y r\j 1.33

I n o r d e r t o o b t a i n an e x p r e s s i o n f o r -V f o r

monatomic l i q u i d s , i t i s assumed f u r t h e r t h a t , s i n c e the

volume change on m e l t i n g i s s m a l l and t h e r e f o r e the m o l e c u l a r

f o r c e s i n the s o l i d and l i q u i d s t a t e s a t the m.p. cannot be

a p p r e c i a b l y d i f f e r e n t , the f r e q u e n c y o f v i b r a t i o n i n the

l i q u i d s t a t e a t the m.p. i s approximately equal to that i n

the s o l i d s t a t e . Hence the f o r m u l a o f L.Indemann (56) for

the f r e q u e n c y of v i b r a t i o n o f the s o l i d can be used f o r V

i n equation (4),

V = K / (5)

where K = 3.1 X 10 ,
1 2

A = atomic weight,

V = atomic volume.

S u b s t i t u t e d i n t o e q u a t i o n (4), t h i s r e l a t i o n gives

S - T ^ o ' ^ A T ^ V ' ^ (6)

By c o n s i d e r i n g the e x p e r i m e n t a l v a l u e s f o r 16 l i q u i d metals

and argon, Andrade c o n c l u d e s t h a t the t h e o r y i s i n s a t i s f a c t o r y

agreement i n a b s o l u t e magnitude, except f o r c e r t a i n m e t a l s

w h i c h have an anomalous c r y s t a l l i n e structure.

 19
I t i s f u r t h e r shown t h a t the v i s c o s i t y a t t h e

m e l t i n g p o i n t i s p r o p o r t i o n a l t o t h e ^ / 3 ^ ' power o f t h e
rc

d e n s i t y at the m e l t i n g p o i n t , , and t h i s r e l a t i o n i s

assumed t o h o l d f o r a l l l i q u i d s .

The v a r i a t i o n o f w i t h t e m p e r a t u r e i s d e r i v e d on

the b a s i s t h a t t h e t r a n s f e r o f momentum f o r v i s c o u s f l o w i s
a s s o c i a t e d w i t h an energy o f a c t i v a t i o n , £ , and a c c o r d i n g

t o t h e Boltzmann theory,

where, = v i s c o s i t y a t t e m p e r a t u r e T,
E. = a c t i v a t i o n e n e r g y ,
& = Boltzmann's constant,
assuming f o r t h e moment t h a t t h e energy o f a c t i v a t i o n i s

Independent o f t e m p e r a t u r e . F i n a l l y , the e f f e c t of the

v a r i a t i o n of t w i t h temperature i s a s s o c i a t e d w i t h the

volume change and i t i s assumed t h a t E i s inversely

p r o p o r t i o n a l t o t h e volume , <\j , b y comparison w i t h t h e

v a r i a t i o n o f t h e p o t e n t i a l energy o f a m o l e c u l e as g i v e n by

the v a n d e r Waal's e q u a t i o n . C o m b i n a t i o n o f e q u a t i o n s (4)

and (8) w i t h t h i s assumption l e a d s t o t h e e q u a t i o n ,

*1 T = C\r"' A
£ ^ (9)

where C and <X a r e c o n s t a n t s , w h i c h i s Andrade's b a s i c

equation f o r the v a r i a t i o n of v i s c o s i t y w i t h temperature.
 20
Equation (9) has been found t o g i v e e x c e l l e n t

c o r r e l a t i o n of the v a r i a t i o n of v i s c o s i t y w i t h temperature,

and Andrade, u s i n g the d a t a of Thorpe and Rodger (11), has

found t h a t i t g i v e s b e t t e r agreement over w i d e r temperature

ranges t h a n the more commonly used A r r h e n i u s f o r m o f the

equation,

^ T = A e B / T
do)
where A and B a r e c o n s t a n t s , independent of temperature.

To t a k e account of the v a r i a t i o n o f v i s c o s i t y o f

l i q u i d s w i t h p r e s s u r e , Andrade d e r i v e s the v i b r a t i o n

f r e q u e n c y a t h i g h p r e s s u r e s t o be g i v e n by,

-V = <W , / i
i<- , / a
- (li)

where \/ = atomic volume

K = adiabatic compressibility

and <o i s a constant.

Hence, the v a r i a t i o n o f v i s c o s i t y w i t h p r e s s u r e i s g i v e n by

the r e l a t i o n ,

\ - f^lV'VS ^i-4.) as)

x where the s u b s c r i p t 1 r e f e r s t o atmospheric pressure and

to h i g h p r e s s u r e .

S i n c e no d a t a on a d i a b a t i c c o m p r e s s i b i l i t y were
a v a i l a b l e , Andrade used the i s o t h e r m a l c o m p r e s s i b i l i t y and the
e x p e r i m e n t a l d a t a of Bridgman (17) t o t e s t e q u a t i o n (12).
 21
For l i q u i d Hg, he found t h a t t h e e q u a t i o n gave a v a l u e o f

1,32 for a t 12,000 Atras. w h i c h was e x a c t l y t h e f i g u r e

o b t a i n e d e x p e r i m e n t a l l y by Bridgman. F o r o t h e r l i q u i d s he

found t h a t t h e t h e o r y agreed m o d e r a t e l y well with experiment

up t o a p r e s s u r e o f 2,000 Atm. b u t above t h i s v a l u e gave

values of w h i c h were t o o l o w .

The t h e o r y o f Andrade i s , however, n o t an a b s o l u t e

theory. I t s t i l l l e a v e s two e m p i r i c a l c o n s t a n t s C and to

be a d j u s t e d t o f i t the e x p e r i m e n t a l d a t a f o r temperature

dependence, and no attempt has been made t o c o r r e l a t e these

w i t h o t h e r known p h y s i c a l p r o p e r t i e s o f l i q u i d s , except i n t h e

unique case o f monatomic m o l e c u l e s at t h e i r melting point.

The t h e o r y i s r e a l l y t o o s k e t c h y and vague t o be o f much

s i g n i f i c a n c e from a fundamental p o i n t of view.

Many o t h e r s e m i t h e o r e t i c a l developments ha.veappeared

f r o m time t o time w i t h a view t o o b t a i n i n g t h e A r r h e n i u s f o r m

of e q u a t i o n f o r t h e v a r i a t i o n o f v i s c o s i t y w i t h temperature.

Some w h i c h s h o u l d be mentioned a r e those o f v a n d e r Waals J r .

(57,58), F r e n k e l (59,60), and MacLeod (61,62), b u t none o f

these have a t t a i n e d t h e prominence o f t h e E r y i n g t h e o r y ,

summarized below.

E y r i n g * s Theory

U n l i k e p r e v i o u s t h e o r i e s which had been used t o

e x p l a i n t h e v i s c o s i t y o f l i q u i d s , t h e E y r i n g t h e o r y i s based
 22

on a c o n c r e t e p h y s i c o - c h e m i c a l p i c t u r e and a l l the c o n s t a n t s

can be r e l a t e d t o o t h e r p r o p e r t i e s o f the l i q u i d , i . e . , t h e r e

are no a r b i t r a r y c o n s t a n t s .

The t h e o r y i s based on an e x t e n s i o n o f the t h e o r y o f

a b s o l u t e r e a c t i o n r a t e s (63) i n w h i c h t h e v i s c o u s f l o w process

i s t r e a t e d as a f i r s t - o r d e r c h e m i c a l r e a c t i o n . I n order to
a
P P l y t h i s t h e o r y , t h e l i q u i d s t r u c t u r e i s d e s c r i b e d as a

mixture of molecules and v a c a n t l a t t i c e s i t e s o:r " h o l e s . "

I n o r d e r t o pass i n t o a v a c a n t l a t t i c e s i t e , a m o l e c u l e must

pass t h r o u g h a p o t e n t i a l b a r r i e r w h i c h e x i s t s because o f the

s t r o n g m o l e c u l a r f o r c e s between t h e m o l e c u l e s . I n t h e absence

o f any impressed f o r c e , t h i s p o t e n t i a l b a r r i e r i s symmetrical,

but on the a p p l i c a t i o n o f an e x t e r n a l f o r c e the b a r r i e r i s

d i s t o r t e d i n the d i r e c t i o n of the f o r c e . T h i s makes i t e a s i e r

f o r molecules t o be d i s p l a c e d i n the d i r e c t i o n o f t h e impressed

f o r c e than i n the r e v e r s e d i r e c t i o n and makes f o r a n e t

t r a n s f e r of molecules.

A p p l y i n g the theory of absolute r e a c t i o n r a t e s t o

the f o r w a r d and r e v e r s e p r o c e s s e s o u t l i n e d above, E r y i n g and

his a s s o c i a t e s have o b t a i n e d t h e f o l l o w i n g e q u a t i o n f o r t h e

v i s c o s i t y of a l i q u i d ,
 23

r] = EJ> (13)

where, |p = impressed shearing f o r c e ,

fc = 0 a b s o l u t e r e a c t i o n r a t e i n t h e absence of
an e x t e r n a l f o r c e ,
"VI = no. of m o l e c u l e s / u n i t volume,
k = soltzmann's constant,
T = absolute temperature,
and a, S a r e dimensions r e l a t e d t o the l a t t i c e s t r u c t u r e o f

o f the l i q u i d .

L 1
WT ~^H*/RT
w e e (u)
where, in. = Plank's constant,

AS = entropy of a c t i v a t i o n ,
ilH = enthalpy of a c t i v a t i o n .
=fc =fc *
4H — TAS = AF" ' i s t h e f r e e energy o f a c t i v a t i o n .
y
f

Thus, s u b s t i t u t i n g i n t o ( 1 3 ) , the e q u a t i o n f o r the

viscosity i s ,

v\ = ES ( U A
^RT ( 1 5 )

I n t h i s e q u a t i o n , t h e v i s c o s i t y i s g i v e n .as a

f u n c t i o n o f t h e s h e a r i n g f o r c e , p , and t h e t h e o r y t h e r e f o r e

t a k e s non-Newtonian b e h a v i o r i n t o a c c o u n t . However, when

a
^ / 2 S n k t i s s m a l l compared t o u n i t y , the s i n h can be r e p l a c e d

by the f i r s t term o f i t s T a y l o r e x p a n s i o n , and one o b t a i n s ,

(16)
 24

T h i s i s Eyring»s b a s i c e q u a t i o n w h i c h g i v e s the v i s c o s i t y ,

, f o r o r d i n a r y Newtonian liquids.

Although {§£)rik and A F * a r e i n no sense a r b i t r a r y

constants, y e t no means i s a v a i l a b l e t o e v a l u a t e them e x a c t l y

i n terms of known p r o p e r t i e s o f a l i q u i d . For a rough

estimate, i t i s assumed t h a t the dimensions S and a w h i c h

d e s c r i b e the l a t t i c e s t r u c t u r e are a p p r o x i m a t e l y equalise

that (JVcc*) " 2

!• Attempts have been made t o c o r r e l a t e

AF w i t h the thermodynamic p r o p e r t i e s of the l i q u i d , b u t no

r e a l l y good c o r r e l a t i o n has been o b t a i n e d . Empirically,

E y r i n g found that AP^ i s most c l o s e l y c o r r e l a t e d w i t h t h e

energy of v a p o r i z a t i o n , AE o.|3 V , per mole , and t h a t f o r many

liquids,

most s i g n i f i c a n t d e v i a t i o n s were o b t a i n e d for liquids, such

as t h e a l c o h o l s , w h i c h a r e a s s o c i a t e d by hydrogen-bonding.

On t h e s e two a s s u m p t i o n s , the approximate equation

f o r the v i s c o s i t y o f a l i q u i d i s g i v e n as

\ = A (A£v4/ .ASRT")
2 (18)

which i s a u s e f u l equation f o r rough estimates.

In developing an e q u a t i o n f o r the e f f e c t of pressure,

Eyring considers the energy term A F * and n o t e s t h a t i t t a k e s

account o n l y o f the energy s p e n t i n c r o s s i n g t h e e n e r g y b a r r i e r

 25

caused by the a t t r a c t i v e f o r c e s of n e i g h b o u r i n g molecules.

S i n c e t h i s p r o c e s s i s accompanied by the f o r m a t i o n of a
temporary h o l e , work i s done a g a i n s t the e x t e r n a l p r e s s u r e ,
\p , and a d d i t i o n a l energy must be s u p p l i e d f o r t h i s purpose.
He d e r i v e s t h a t t h i s energy i s g i v e n by the term W /y^ ,
where ^/v\' i s the volume o f h o l e per modecule. This term
m o d i f i e s the e q u a t i o n f o r the v i s c o s i t y t o ,

1 = nW exV^VRT (19)

U n f o r t u n a t e l y the v a l u e o f n 1
cannot be deduced on
t h e o r e t i c a l grounds. Values of 10 f o r pentane and 8 f o r e t h e r
were o b t a i n e d from the e x p e r i m e n t a l d a t a , w h i c h gave f a i r
agreement w i t h the t h e o r y .

Other T h e o r i e s

Panchenkov (64,65) has developed a t h e o r y based on

the t r a n s f e r of momentum, but t a k i n g i n t o account the bond
energy o f the m o l e c u l e i n the l i q u i d . His f i n a l expression
takes the form.

^ = o.^K /^ 5 4 / 5
T
, / 2
^ e / R T
0-- ( 2 0 )

where, <X = 3 j ^ ( ^ Q %
N 1
' 3
(21)
T" = r a d i u s of a m o l e c u l e ?

M = mol. wt.,
9 = density,
& = bond energy of m o l e c u l e i n the liquid,
R. = gas c o n s t a n t ,
N = Avogadros' No.
 26

B"y t a k i n g i n t o account t h e v a r i a t i o n o f and with

p r e s s u r e , s a t i s f a c t o r y agreement w i t h experiments on t h e
e f f e c t o f p r e s s u r e has been r e p o r t e d .

More r e c e n t l y , t h e t h e o r y of t r a n s p o r t phenomena i n
dense gases and l i q u i d s has been developed by means o f a non-
e q u i l i b r i u m s t a t i s t i c a l mechanics. The work i n t h i s f i e l d has"
been p u b l i s h e d p a r t i c u l a r l y by Kirkwood (66,67) and b y B o r n
and Green ( 6 8 ) . B i r d e t a l . (8) have p o i n t e d out t h e
p o t e n t i a l importance o f t h i s approach,and i m p l y t h a t i t i s
l i k e l y t o g i v e r e s u l t s w h i c h w i l l agree w e l l w i t h e x p e r i m e n t .
However, o n l y some approximate c a l c u l a t i o n s have been
r e p o r t e d so f a r , and much c o m p u t a t i o n work remains t o be done.

(b) The Theory o f C o r r e s p o n d i n g States

The g r e a t success o f t h e use o f t h e t h e o r y o f

corresponding s t a t e s i n i n t e r p r e t i n g t h e d a t a on c o m p r e s s i b i -
lity and v a r i o u s thermodynamic p r o p e r t i e s o f gases and
l i q u i d S j h a s lead t o a c o n s i d e r a t i o n of the a p p l i c a t i o n of
s i m i l a r concepts t o c o r r e l a t e t h e d a t a on t r a n s p o r t p r o p e r i t e s
of f l u i d s . The t h e o r y f i r s t developed b y v a n d e r Waals, i s
based on t h e c o n s i d e r a t i o n t h a t the c r i t i c a l p o i n t i s a " p o i n t
of c o r r e s p o n d i n g s t a t e s " and t h a t t h e r e f o r e , t h e r e l a t i o n
between a p a r t i c u l a r f l u i d p r o p e r t y , , s h o u l d be r e p r e s e n -
ted b y a unique f u n c t i o n o f t h a t p r o p e r t y a t t h e c r i t i c a l
p o i n t , <j> , f o r a l l s u b s t a n c e s . Further, this function i s
g i v e n i n terms o f t h e reduced temperature and p r e s s u r e ,
 27

r > as f o l l o w s ,

(22)
or
(23)

.g r e d u c e d p r o p e r t y .

This i s the b a s i s f o r the g e n e r a l i z e d c h a r t s o f

Hougen and Watson (69) f o r c o m p r e s s i b i l i t y , s p e c i f i c heat,

etc., w h i c h are v e r y u s e f u l i n e n g i n e e r i n g calculations.

U n f o r t u n a t e l y , the t h e o r y i s c e r t a i n l y not of completely

g e n e r a l a p p l i c a t i o n , some substances showing c o n s i d e r a b l e

d e v i a t i o n f r o m the g e n e r a l i z e d c o r r e l a t i o n .

T h i s problem has l o n g been r e c o g n i z e d and i n r e c e n t

y e a r s the a d d i t i o n o f a t h i r d parameter has been I n v e s t i g a t e d ,

(24)

The most comprehensive work has been done by P i t z e r and co-

workers ( 7 0 ) , who i n t r o d u c e d X as the reduced vapor pressure

measured a t T r = 0.7; R i e d e l (Ti') who i n t r o d u c e d X as the

temperature d e r i v a t i v e of the vapor p r e s s u r e a t the critical

p o i n t ; and L y d e r s e n , Greenkorn and Hougen (72) who used the

c r i t i c a l c o m p r e s s i b i l i t y , Z- , and d i d e x t e n s i v e c o m p i l a t i o n
c

of g e n e r a l i z e d thermodynamic p r o p e r t i e s based thereon.

F o r v i s c o s i t y , the c o r r e l a t i o n used has been o f the

form,

(25)
 28
Hougen and Watson (69) have a l s o p r e p a r e d a g e n e r a l i z e d

v i s c o s i t y c h a r t based on t h i s r e l a t i o n w h i c h i s s a i d t o be

a p p l i c a b l e t o b o t h gases and l i q u i d s over wide t e m p e r a t u r e

and p r e s s u r e r a n g e s . Although t h i s c o r r e l a t i o n i s undoubt-

e d l y v a l u a b l e f o r rough e s t i m a t e s a t h i g h p r e s s u r e s and temper-

a t u r e s i n t h e absence o f r e l i a b l e d a t a , i t g i v e s poor

a c c u r a c y o v e r much of the range o f v a r i a b l e s .

Grunberg and N i s s a n (72a) have p r e p a r e d a nomograph

f o r t h e reduced v i s c o s i t y as a f u n c t i o n o f reduced t e m p e r a t u r e

and reduced d e n s i t y . They c l a i m an a c c u r a c y o f — 10$ f o r

ranges of~N- f r o m 0.3 t o 15 and <?^_ f r o m 0.3 t o 18.

A p p a r e n t l y , the use o f some f o r m o f t h i r s parameter,

X, mentioned above, t o such t r a n s p o r t p r o p e r t i e s as v i s c o s i t y

has n o t y e t been attempted, a l t h o u g h g e n e r a l c o r r e l a t i o n t o

w i t h i n 2 t o 3$ s h o u l d r e s u l t .

They a p p l i e d t h i s r e l a t i o n t o gases and found e x c e l l e n t

agreement o f t h e v a l u e s f r o m t h e i r g e n e r a l i z e d c h a r t s w i t h

experiments. C a r r , P a r e n t and Peck (73) have extended t h e

c h a r t s o f Comings and E l g y t o h i g h e r p r e s s u r e s , b u t i t seems

t h a t t h e r e l a t i o n , e q u a t i o n ( 2 6 ) h a s not been t r i e d f o r
?

liquids.
 29

More r e c e n t l y , de Boer (74 ) has developed a

"quantum m e c h a n i c a l t h e o r y of c o r r e s p o n d i n g s t a t e s " i n

w h i c h the v a r i a b l e s , T and \r are reduced i n terms of

quantum m e c h a n i c a l parameters as follows;

- Wcr* , T ** = ^w-- (27)

where \r and £- are c o n s t a n t s i n the m o l e c u l a r p o t e n t i a l

function

*Cr) = £ -f(£) (28)

A g a i n , t h i s approach has not been c o n s i d e r e d f o r l i q u i d s .

Much c l o s e r c o r r e l a t i o n of v i s c o s i t y d a t a has been

o b t a i n e d by c o n s i d e r i n g a t h e o r y of c o r r e s p o n d i n g states

f o r a s m a l l group of r e l a t e d compounds, f o r example the

members of a s i n g l e homologous s e r i e s . I n p a r t i c u l a r , Smith

and Brown (75) o b t a i n e d good c o r r e l a t i o n w i t h i n a s i n g l e

homologous s e r i e s by p l o t t i n g ^ / T ' ^ I y-where I i s the

Souders c o n s t i t u t i v e f a c t o r (76). They o b t a i n e d single

curves f o r n - P a r a f f i n s , Ethers, acids, n - alcohols and i s o -

alcohols.

A good r e v i e w of reduced v i s c o s i t y e q u a t i o n i s

g i v e n by H e l l e r (77) i n a recent a r t i c l e .
 30

(c) The E f f e c t o f Temperature on t h e V i s c o s i t y o f L i q u i d s

The l a r g e d e c r e a s e i n the v i s c o s i t y o f l i q u i d s with

r i s e i n temperature has been t h e s u b j e c t o f e x t e n s i v e

r e s e a r c h f r o m t h e time o f P o i s e u i l l e up t o t h e p r e s e n t day.

As y e t , no s i n g l e r e l a t i o n s h i p between t h e v i s c o s i t y and t h e

temperature which i s a p p l i c a b l e to a l l l i q u i d s , w i t h i n

e x p e r i m e n t a l e r r o r , has been o b t a i n e d , and t h e s u b j e c t i s

s t i l l am "open" f i e l d of research. However, t h e r e do e x i s t

r e l a t i v e l y s i m p l e r e l a t i o n s i n v o l v i n g o n l y a few e m p i r i c a l

constants which are of q u i t e general a p p l i c a b i l i t y over

l i m i t e d t e m p e r a t u r e range, and o t h e r s wftich f i t d a t a f o r some

compounds v e r y c l o s e l y over extended t e m p e r a t u r e ranges.

In a f i e l d o f r e s e a r c h i n w h i c h t h e r e i s such a v a s t

l i t e r a t u r e , i t i s f o r t u n a t e t h a t many r e v i e w a r t i c l e s exist.

P a r t i c u l a r l y complete r e v i e w s are given by P a r t i n g t o n (78),

Bowden and Morgan ( 7 9 ) , S h r i n i v a s a n and P r a s a d ( 8 0 ) and

Landolt-Bornstein (28).

Partington l i s t s approximately 50 f o r m u l a e which

have been p u b l i s h e d between 1842 and 1947 and t h e l i s t i s

c e r t a i n l y not exhaustive. Many a r t i c l e s have a l s o appeared

s i n c e 1947 (81-93).

Among a l l t h e e q u a t i o n s w h i c h have been proposed,

t h e s i m p l e e x p o n e n t i a l f o r m u l a mentioned p r e v i o u s l y ,

e q u a t i o n (10), has been most w i d e l y used and f i t s t h e

m a j o r i t y o f d a t a f o r most l i q u i d s b e t t e r t h a n any o t h e r single

 31

formula. T h i s i s o f t e n r e f e r r e d t o as Andrade's f o r m u l a ,

but i t seems t o have been o r i g i n a l l y proposed b y Reynolds'-;

(see Bingham (9) page 1 3 0 ) . The f o r m u l a i s p a r t i c u l a r l y

a t t r a c t i v e because I t i s i n g e n e r a l agreement w i t h t h e b e s t

a c c e p t e d t h e o r i e s o f v i s c o s i t y ( f o r example, t h o s e mentioned

previously).

Prom the t h e o r e t i c a l development, w h i c h i n d i c a t e s

that R i s some f o r m o f energy o f a c t i v a t i o n , i t i s n o t t o be

expected t h a t 6 w i l l be a t r u e c o n s t a n t , independent o f

temperature. I t i s a g e n e r a l l y a c c e p t e d f a c t t h a t such energy

f u n c t i o n s change w i t h t e m p e r a t u r e , and one would expect t h e

energy o f a c t i v a t i o n f o r v i s c o u s f l o w t o change as w e l l , and

t h i s i s borne: out by e x p e r i m e n t . I f one w r i t e s t h e energy,

AP^, as a l i n e a r f u n c t i o n o f t e m p e r a t u r e ,

A F * = £ =-v- o ( T (29)

and s u b s t i t u t e s i n t o t h e R e y n o l d s ' f o r m u l a one o b t a i n s ,

v] - A e ^ = A e * / R
e £ / R T

, e
/«r

Hence, Y| = r\ e (30)

w h i c h i s of t h e same form as e q u a t i o n ( 1 0 ) . This i m p l i e s

t h a t a f i r s t - o r d e r v a r i a t i o n o f t h e energy term i s i m p l i c i t l y

i n c l u d e d i n t h e b o n s t a n t A, w h i c h may g i v e some i n d i c a t i o n

why t h e f o r m u l a works so w e l l f o r c o n s i d e r a b l e t e m p e r a t u r e

ranges.
 32

Many a t t e m p t s have been made t o adopt t h e s i m p l e

e x p o n e n t i a l f o r m u l a t o w i d e r temperature ranges by i n c l u d i n g

a temperature v a r i a t i o n of e i t h e r E o r A, or b o t h . Some o f

t h e s e w i l l be l i s t e d t o show t h e form of t h e a d a p t a t i o n s .

i ) Andrade's f o r m u l a , e q u a t i o n ( 9 ) w h i c h has been

?

d i s c u s s e d p r e v i o u s l y i s perhaps the b e s t attempt t o f i t t h e

d a t a more c l o s e l y , because i t i n t r o d u c e s no new c o n s t a n t s ,

a l t h o u g h i t r e q u i r e s d e n s i t y d a t a over t h e same temperature

range.

i i ) Hovorka, Lankelma, S t a n f o r d (94) proposed,

i v \ 4j- ~ •+ B i v f -l- C (31)

which i s e q u i v a l e n t t o the form

*1 = A T <3 (32)

suggested by Innes ( 9 3 ) much more r e c e n t l y , a n d found t o g i v e

good agreement f o r w a t e r , Hg, C^H^g a n <

3 Me OH. over wide

temperature ranges up t o near the b o i l i n g p o i n t .

i i i ) Gutmann and Simmons (84) suggested

J U v| = A + B»/CT>0 (33)

r| = A e J
(34)

and o b t a i n e d b e t t e r agreement f o r a l l l i q u i d s examined

i n c l u d i n g a s s o c i a t e d l i q u i d s , l i q u i d m e t a l s and e l e c t r o l y t e s ,
 33
Iv) G i r i f a l c o (92) considers the variation of the

activation energy by i n t r o d u c i n g a term which i s quadratic

in Vx i n addition t o the linear term of the b a s i c equation:

fi*vv^ = — - +
•% ^ ^ (35)

An a n a l y s i s of the data i n the l i t e r a t u r e showed t h a t t h e

equation correctly r e p r e s e n t s t h e d a t a f o r a l a r g e number

of a s s o c i a t e d l i q u i d s , whereas f o r n o n - a s s o c i a t e d liquids

o( = 0 and t h e b a s i c e q u a t i o n suffices;.

v) Lederer (95) by analogy w i t h Nernst's vapor

pressure equation derived the formula

£ o
3» A = s I R T - " * k
2 T
3 „ T + E T + c ( 3 6 )

but, Jaeger (58) indicates t h a t t h e f o r m u l a i s no b e t t e r

than t h a t o f Andrade, e q u a t i o n (6). This f o r m u l a has a l s o

b e e n r e c e n t l y c o n s i d e r e d b y Baum (87).

Other formulae which a r e based on t h e e x p o n e n t i a l

formula are,

v i ) C o r n e l i s s o n and Waterman (91)

U ± = A (37)
vii) Litovitz (83)
a "for*
A e ( 3 8 )

for associated liquids, excluding alcohols.

 34
viii) B a n e r j i (81)

1 = A - B T (39)

i x ) Douglas (95)

\ = -rCAe B / T
^ce V r
) (40)
and x ) Thomas (96)

V - 4
A e ^ ^ c e ^ ( 4 1 )

The l a s t two e q u a t i o n s g a v e e x c e l l e n t a g r e e m e n t f o r

associated liquids.

I n summary, t h e b a s i c e x p o n e n t i a l f o r m a l a e o f

Reynolds and A n d r a d e g i v e g e n e r a l l y good a g r e e m e n t with

e x p e r i m e n t f o r many l i q u i d s o v e r m o d e r a t e t e m p e r a t u r e ranges,

For a s s o c i a t e d l i q u i d ' s , where t h e degree of association

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

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

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

t e m p e r a t u r e must be i n t r o d u c e d t o t a k e a c c o u n t o f t h i s

variation adequately.

Bingham ( 9 ) p a g e 132, a p p r o a c h e s
? the problem from a

different point of view. He c o n s i d e r s t h e v a r i a t i o n of the

fluidity, <§> ~ 4^, t o b e t h e f u n d a m e n t a l v a r i a b l e , and h a s

found v a r i o u s equations i n the form,

~T~ = -K40 ( 42)

in particular,
X = A -v- B>^> c/4> (43)

and ~T = A •+- & 4 > -4- C/t4> + £ ) ( 4 4 )

 35

Bingham has applied extensive data f i t t i n g to these equations

and h a s found that equation (43) g i v e s agreement c l o s e t o the

e x p e r i m e n t a l e r r o r f o r most l i q u i d s , but d e v i a t i o n s are

c o n s i d e r a b l e f o r the n - a l c o h o l s f o r which equation (44) is

preferable. Tables a r e g i v e n f o r t h e v a l u e s o f A,B,C and D

for 87 l i q u i d s determined b y T h o r p e and R o d g e r (11).

Unfortunately, this approach has never a t t a i n e d the promi-

nence of the e x p o n e n t i a l t y p e of f o r m u l a , because i t i s not

related t o any corresponding theory. Although the f i t t i n g of

the d a t a i s good, e q u a t i o n s (43) and (44) are particularly

difficult t o use, because of t h e i r form, i n which T i s the

explicit variable, r e q u i r i n g a l a b i o r o u s c a l c u l a t i o n f o r <^>

at any p a r t i c u l a r temperature.

(d) E f f e c t o f P r e s s u r e on t h e V i s c o s i t y o f L i q u i d s

The l a c k o f p r e s s u r e d a t a on v i s c o s i t y makes i t

difficult to obtain r e l i a b l e equations to c o r r e l a t e viscosity

w i t h p r e s s u r e , and c o m p a r a t i v e l y few c o r r e l a t i o n s have been

attempted, w i t h r e l a t i v e l y poor success. As mentioned

p r e v i o u s l y , t h e b a s i c t h e o r i e s o f A n d r a d e and E y r i n g have l e d

to r e l a t i o n s h i p s from which the e f f e c t of p r e s s u r e can be

determined. However, t h e a g r e e m e n t h a s b e e n o n l y fair,

p a r t i c u l a r l y at v e r y h i g h p r e s s u r e s .

Good R e v i e w a r t i c l e s on t h e e f f e c t o f p r e s s u r e on

the v i s c o s i t y of l i q u i d s have been r e c e n t l y p u b l i s h e d by

Blok (97) and Dow (98).

 36
M o s t l i q u i d s show an i n c r e a s e o f v i s c o s i t y with

p r e s s u r e , the r a t e o f change w i t h p r e s s u r e i n c r e a s i n g , the

h i g h e r the p r e s s u r e . Some e x c e p t i o n s to t h i s general

b e h a v i o r have been r e p o r t e d . W a t e r seems t o be particularly

anomalous. Cohen (99) n o t i c e d t h a t a t 25°C t h e viscosity

decreased w i t h p r e s s u r e , but the r a t e of decrease was smaller

a t h i g h e r p r e s s u r e s , up t o 900 atm. Hauser (100) measured the

v i s c o s i t y of water at temperatures b e t w e e n 30° and 57°C a t

p r e s s u r e s up t o 400 atm. and observed t h a t a t a b o u t 32°C t h e

e f f e c t o f p r e s s u r e was not measurable. Below t h i s temperature

the v i s c o s i t y decreased with pressure and above t h i s tempera-

ture i t increased. B r i d g m a n (35) observed t h a t water behaved

n o r m a l l y a t 30° and 75°C, b u t a t 0° and 10.3°C, t h e viscosity

pressure c u r v e has a minimum a t a p r e s s u r e of approximately

1,000 atm. Suge (101) r e p o r t e d a., d e c r e a s e i n the viscosity

for vegetable o i l s with increased pressure. No confirmation

o f t h e ancraalous b e h a v i o r f o r vegetable o i l s has been r e p o r t e d .

I t has a l s o been q u i t e g e n e r a l l y observed, that the

e f f e c t of p r e s s u r e i s most p r o n o u n c e d a t l o w e r temperatures,

the p r e s s u r e coefficient of v i s c o s i t y d e c r e a s i n g w i t h r i s e

In temperature.

Finally, the e f f e c t of p r e s s u r e i s more p r o n o u n c e d

f o r l i q u i d s of h i g h m o l e c u l a r weight than f o r those of low

molecular w e i g h t s u c h as t h e common o r g a n i c l i q u i d s . For

e x a m p l e , B r i d g m a n (35) found t h a t f r o m 1 t o 12,000 a t m o s p h e r e s

 37
t h e v i s c o s i t y o f MeOH i n c r e a s e s l o t i m e s , n -Amyl a l c o h o l
7

700 t i m e s and e u g e n o l 10 t i m e s , a l l v a l u e s g i v e n a t a.

temperature o f 30°C.

A literature s u r v e y was made o f t h e a v a i l a b l e data

on t h e e f f e c t o f p r e s s u r e on t h e v i s c o s i t y o f l i q u i d s , from

the Chemical A b s t r a c t s o f 1926 t o 1957 a n d t h e r e f e r e n c e s

to t h i s work a r e g i v e n i n A p p e n d i x I . Most o f t h e a v a i l a b l e

d a t a p r i o r t o 1926 i s made r e f e r e n c e t o b y l a t e r authors

(9,35,78,97).

The e f f e c t o f p r e s s u r e on t h e v i s c o s i t y has been

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

correlations. The s i m p l e s t and h i s t o r i c a l l y t h e f i r s t o f

such c o r r e l a t i o n s i s t h e renowned e q u a t i o n o f B a c h i n s k i i

(102)

\ = (45)
1
V — W
w h e r e 1/ i s t h e s p e c i f i c v o l u m e and W a n d C a r e c o n s t a n t s .

W i s c o n s i d e r e d t o be t h e a c t u a l v o l u m e o f m o l e c u l e s , so

that (iT - W) r e p r e s e n t s t h e f r e e v o l u m e . Or, a s o r i g i n a l l y

stated, the f l u i d i t y i s d i r e c t l y proportional to the free

volume.

That t h e volume change i s c e r t a i n l y i m p o r t a n t , i s

supported b o t h b y t h e o r y and e x p e r i m e n t . I n both the theories

o f A n d r a d e and E y r i n g , t h e v a r i a t i o n o f t h e v o l u m e i s

c o n s i d e r e d t o b e m o s t i m p o r t a n t , and i n t h e P a n c h e n k o v f o r m u l a ,

e q u a t i o n 0.6), the v a r i a t i o n i s p a r t i a l l y attributed t othe

 38

density. On t h e e x p e r i m e n t a l s i d e , i t has been g e n e r a l l y

observed t h a t l i q u i d s w i t h h i g h c o m p r e s s i b i l i t i e s have l a r g e

viscosity-pressure coefficients and t h e r e v e r s e f o r t h o s e

w i t h low c o m p r e s s i b i l i t i e s . Mercury, f o r example, has t h e

lowest observed viscosity-pressure coefficient, increasing

o n l y 33$ f o r a p r e s s u r e r i s e o f 12,000 a t m . a t 30°C.

B r i d g m a n (35) h o w e v e r , h a s p o i n t e d o u t t h e i n a d e q u a c i e s o f

any t h e o r y which i s b a s e d e n t i r e l y on a c o n s i d e r a t i o n o f t h e

volume effect.

In spite of these limitations, some r e a s o n a b l y good

e m p i r i c a l and s e m i - t h e o r e t i c a l e q u a t i o n s h a v e b e e n proposed

on t h e b a s i s o f volume effects.

B i n g h a m , Adams and M c C o u s l i n (103) f o u n d that the

f l u i d i t y - v o l u m e c u r v e s f o r t h e n - a l c o h o l s were g i v e n b y a

p a r a b o l i c equation, s i m i l a r t o t h a t f o r temperature ,

equation (44),

V = A 4 > - &/(ct>+-^) C (46)

w h e t h e r t h e c h a n g e i n v o l u m e was due t o t e m p e r a t u r e or

pressure. They used Bridgman's h i g h p r e s s u r e d a t a t o c h e c k

this equation f o r pressure correlation.

MacLeod (104) d e r i v e d t h e g e n e r a l relationship,

V - ^[^/(vu-u.)] e E/RT U 7 )
where V w / (Vu-W) i s t h e r a t i o o f t h e t o t a l volume t o

f r e e s p a c e and \f| ^ a n d are the v i s c o s i t i e s of the l i q u i d

and vapor respectively.

De C a r v a l h o (105) o n s e m i t h e o r e t i c a l g r o u n d s ,

derived the formula

^ T ^ ' Vo ; (48)
where V| o i s the v i s c o s i t y a t atmospheric pressure and ^ a

and ^ a r e the d e n s i t i e s a t atmospheric and u n d e r h i g h pressure

respectively. He f o u n d t h a t h a n d b o o k d a t a f o r CS2 a n d MeOH

agree w i t h t h i s formula.

The f o l l o w i n g a r e some o t h e r c o r r e l a t i o n s w h i c h h a v e

been used f o r p r e s s u r e - v i s c o s i t y d a t a .

i ) W a r b u r g and S a c h s (106) p r o p o s e d a s i m p l e linear

relationship,

> = y\ (\
e + OLV) (49)

and found good a g r e e m e n t f o r w a t e r , CO z , e t h e r and b e n z e n e u p

to 150 atm.
iiO B r i d g m a n (17) h a s a p p l i e d a s i m p l e exponential

formula,

^ = Ae P
(50)
to h i s e x t e n s i v e data on o r g a n i c l i q u i d s , b u t o b t a i n e d

a p p r o x i m a t e c o r r e l a t i o n o n l y up t o m o d e r a t e p r e s s u r e s . Kuss

(107) a l s o used t h e f o r m u l a , i n the form

^ = y\ e*
0
k
5 ^ - c t -V-VD (5i)
 40

and has l i s t e d values o f at , C and b f o rseveral liquids

a t 25°C,up t o a p r e s s u r e o f 2000 atm.

iii) Irany (108) had d e s c r i p e d an e m p i r i c a l c o r r e l a

t i o n which would r e l a t e a l l v i s c o s i t y - p r e s s u r e f u n c t i o n s of

l i q u i d s by a general law c a l l e d t h e 'Tf - f u n c t i o n . Dow (98)

has pointed out that the c o r r e l a t i o n i s of l i m i t e d a p p l i c a -

bility because a l l e x p e r i m e n t a l evidence i s contrary to a

unique, e x p l i c i t , viscosity-pressure function. This

observation applies e q u a l l y t o the exponential formulae above.

The e f f e c t of pressure on t h e v i s c o s i t y o f o i l s , and

in p a r t i c u l a r l u b r i c a n t s , h a s b e e n t h e s u b j e c t o f much

research since the f i r s t m e a s u r e m e n t s i n 1916 b y H e r s e y and

Shore (20) w i t h t h e r o l l i n g - b a l l v i s c o m e t e r . A considerable

d e g r e e o f a g r e e m e n t b e t w e e n e x p e r i m e n t and e m p i r i c a l

c o r r e l a t i o n has been a c h i e v e d . The s u b j e c t h a s b e e n w e l l

r e c e i v e d b y H e r s e y and H o p k i n s ( 1 0 9 ) and b y Dow ( 9 8 ) .

The a p p l i c a b i l i t y o f t h e ASTM viscosity-temperature

c h a r t D341-39 f o r i n t e r p o l a t i n g h i g h p r e s s u r e data has been

shown b y Dow ( 9 8 ) . S a n d e r s o n (110) and l a t e r C l a r k (111) h a v e

e x t e n d e d t h e u s e o f t h e ASTM c h a r t b y n o t i n g t h a t temperature

and pressure have an e q u i v a l e n t e f f e c t on t h e v i s c o s i t y , which

is expressed by the e m p i r i c a l r e l a t i o n ,

(52)
 .41
o
where P i s i n p s i . and T in R .

C l a r k p o i n t e d o u t t h a t t h e c o r r e l a t i o n i s good u p t o

m o d e r a t e p r e s s u r e s , b u t d e v i a t i o n s up t o 100$ w e r e n o t e d f o r

some o i l s at high pressures.

I t i s concluded that the search f o r c o r r e l a t i o n of

-

v i s c o s i t y - p r e s s u r e data w i t h other p h y s i c a l p r o p e r t i e s has

n o t b e e n s u c c e s s f u l and much e x p e r i m e n t a l and t h e o r e t i c a l

w o r k r e m a i n s t o be d o n e .
 42
(e) T h e o r y i n R e l a t i o n t o t h e n-alcohols

The above c o n s i d e r a t i o n s on t h e theory of the

v i s c o s i t y of l i q u i d s w i t h p a r t i c u l a r reference t o the effect

o f t e m p e r a t u r e and pressure have i n d i c a t e d t h a t a s s o c i a t e d

liquids i n g e n e r a l a r e more d i f f i c u l t to f i t to accepted

t h e o r i e s and c o r r e l a t i o n s than non-associated liquids.

In particular, the n - a l c o h o l s show considerable

d e v i a t i o n s from the normal b e h a v i o r of the l a r g e m a j o r i t y of

unassociated compounds. This p a r a l l e l s the non-ideal

behavior of the n - a l c o h o l s f o r o t h e r p h y s i c a l p r o p e r t i e s of

liquids. I n essence, we are d e a l i n g w i t h a b i n a r y mixture

o f a s s o c i a t e d and unassociated s p e c i e s and o v e r much o f the

range, the degree of a s s o c i a t i o n i s changing r a p i d l y . It is

not s u r p r i s i n g t h e n t h a t anomalous b e h a v i o r i s observed in

p r o p e r t i e s of the l i q u i d state, s u c h as v i s c o s i t y , where the

s i z e of the molecules and the magnitude of the molecular

f o r c e s are of such obvious importance.

The behavior of the n - a l c o h o l s in relation to

t h e o r i e s of the l i q u i d s t a t e and of v i s c o s i t y i n p a r t i c u l a r ,

has a t t r a c t e d a c e r t a i n amount o f p r a c t i c a l and theoretical

research. The r e l a t i o n of the v i s c o s i t y v a r i a t i o n of the

members w i t h i n t h e s e r i e s t o m o l e c u l a r structure i s also

of great interest. F o r t u n a t e l y , the e f f e c t of temperature

and pressure h a v e b e e n s t u d i e d f o r t h e f i r s t f i v e members,

n o t a b l y by T h o r p e and Rodger (11) and by Bridgman (17,33-35)

 43
.(pressure). The p u r p o s e of the p r e s e n t work has been t o

attempt to extend the range t o h i g h e r members o f t h e series

and t h i s has been a c h i e v e d f o r the e f f e c t o f t e m p e r a t u r e on .

the v i s c o s i t y of n -octanol.

T h o r p e and R o d g e r (11) and D u n s t a n , , B e n s o n and

Thole (112) tried t o o b t a i n a c o r r e l a t i o n by p l o t t i n g the

l o g v i s c o s i t y of the n - a l c o h o l s at p a r t i c u l a r temperatures

a g a i n s t t h e number o f c a r b o n atoms i n t h e m o l e c u l e and

found a s t r a i g h t - l i n e r e l a t i o n s h i p f o r the C and h i g h e r

members a t e a c h t e m p e r a t u r e . Methanol and e t h a n o l were

anomalous i n t h i s r e s p e c t . T h o r p e and R o d g e r s u g g e s t e d that

c o m p a r i s o n s h o u l d be made a t t e m p e r a t u r e s f o r w h i c h the

temperature c o e f f i c i e n t , 5— , was t h e same, i m p l y i n g that

d

s u c h t e m p e r a t u r e s w e r e some f o r m o f " c o r r e s p o n d i n g

t e m p e r a t u r e s , " b u t no i m p r o v e m e n t i n t h e c o r r e l a t i o n was

obtained.

S m i t h and B r o w n (75) found that a s p e c i f i c theory

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

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

temperatures by plotting vs.TV, where I i s t h e

Senders c o n s t i t u t i v e f a c t o r mentioned previously (76)• They

a l s o o b t a i n e d good c o r r e l a t i o n f o r t h e s a t u r a t e d l i q u i d s and

vapors by plotting

critical p r e s s u r e o f EtOH
it •it
 44
a g a i n s t the reduced temperature , T . Again a single

c u r v e was obtained. The m e t h o d i s l i m i t e d in applicability

because of the l a c k of c r i t i c a l t e m p e r a t u r e and p r e s s u r e

data.

G o l i k , R a v i k o v i c h and Orishchenko (113) h a v e made

a detailed s t u d y o f t h e v i s c o s i t y o f n - a l c o h o l s and m i x t u r e s

i n r e l a t i o n to molecular structure. They a n a l y s e d their

measurements by t h e s i m p l e e x p o n e n t i a l f o r m u l a , e q u a t i o n (10),

and f o u n d t h a t t h e a c t i v a t i o n e n e r g y i n c r e a s e s and the pre-

e x p o n e n t i a l f a c t o r decreases w i t h i n c r e a s e of the critical

temperature of the a l c o h o l , i . e . , with increasing molecular

weight, which, they note, i s i n complete agreement w i t h t h e

shape of t h e p o t e n t i a l e n e r g y c u r v e s f o r t h e s e s u b s t a n c e s .

Andrade (51) has c a l c u l a t e d the v a l u e s of C and

i n h i s r e l a t i o n f o r t h e e f f e c t o f t e m p e r a t u r e on viscosity,

equation ( 9 ) , f o r t h e a l c o h o l s f r o m C]_ t o C^. The increase

of o< and d e c r e a s e o f C w i t h i n c r e a s e of m o l e c u l a r wt. is in

concordance w i t h t h e o b s e r v a t i o n s o f G o l i k , R a v i k o v i c h and

Orishchenko, mentioned above.

Jaeger (58) h a s n o t e d t h a t t h e p l o t o f l o g Y| v s . J/-f

for EtOH and n — P r l O H tends to a s t r a i g h t l i n e a t h i g h temper-

a t u r e s , b u t shows o b v i o u s c u r v a t u r e a t l o w temperatures.

He assumes t h a t t h e d e g r e e of a s s o c i a t i o n g r a d u a l l y decreases

w i t h i n c r e a s i n g temperature and that at high temperature

attains a f i x e d v a l u e i n d i c a t e d by a c o n s t a n t v a l u e of the
 45

energy of a c t i v a t i o n (or the slope of the logvj \/^- plot.

J o b l i n g and L a w r e n c e (114) h a v e r e c e n t l y e x a m i n e d

t h e e x i s t i n g v i s c o s i t y - p r e s s u r e and v o l u m e - p r e s s u r e data of

the normal a l c o h o l s to and i s o b u t a n o l and h a v e obtained

good c o r r e l a t i o n o f t h e d a t a . T h e y show t h a t a t constant

temperature, t h e v i s c o s i t y - v o l u m e d a t a l i e on a smooth curve.

Further, a p l o t of l o g against gave s t . l i n e s , at

constant volume. From t h i s p l o t , they obtained the i s o c h o r i c

energy a c t i v a t i o n , E^, as a f u n c t i o n o f t h e v o l u m e f r o m atmo-

spheric pressure to very high pressures. Unfortunately, the

temperature data i s l i m i t e d to only three or four temperatures

and f o r some i s o c h o r e s o n l y two t e m p e r a t u r e s . A graph showing

the r e l a t i o n s h i p between E and V f o r t h e f o u r a l c o h o l s i s

v

g i v e n and i n d i c a t e s t h a t t h e e n e r g y o f a c t i v a t i o n increases

c o n t i n u o u s l y as t h e v o l u m e d e c r e a s e s (with increase of press-

ure). E t h y l a l c o h o l shows a n a p p a r e n t l y a n o m a l o u s behaviour,

i n h a v i n g a minimum a c t i v a t i o n e n e r g y a t a r e l a t i v e v o l u m e o f

about 0.95. The a u t h o r s note t h a t t h i s may be p a r t l y due t o

experimental e r r o r I n the data, but t h a t the depth of the

minimum seems t o o l a r g e t o be a c c o u n t e d for entirely by

experimental error. The b e h a v i o r i s particularly anomalous

s i n c e MeOH shows no s u c h b e h a v i o r . (The f i r s t two members o f

a h o m o l o g o u s s e r i e s o f t e n show a n o m a l i e s i n physical

properties).

T h i s a p p r o a c h has p r o v i d e d a very significant

advance i n t h e c o r r e l a t i o n o f p r e s s u r e d a t a f o r a l c o h o l s .
 46

I t w o u l d u n d o u b t e d l y be m o s t r e w a r d i n g to extend pressure

measurements t o o t h e r t e m p e r a t u r e s , and to higher members

of the s e r i e s w i t h a view to confirming this correlation

and p o s s i b l y p r e d i c t i n g the g e n e r a l viscosity-temperature-

pressure behavior of the n-alcohols.

Bondi (50) concludes that, i n a quantitative way,

the v i s c o s i t y r e f l e c t s the s t r e n g t h of the h y d r o g e n bonds

i n l i q u i d s w i t h continuous a s s o c i a t i o n and substantiates

t h i s by showing the h i g h degree of c o r r e l a t i o n between the

I s o c h o r i c e n e r g y o f a c t i v a t i o n f o r t h e v i s c o s i t y and the

excess energy of v a p o r i z a t i o n TdS , where, A S v V i s the entr

v
of v a p o r i z a t i o n .
 47

APPARATUS AND PROCEDURE

(a) C a p i l l a r y Viscometers

I) D e s c r i p t i o n and O p e r a t i o n . Five c a p i l l a r y

v i s c o m e t e r s were used i n t h i s r e s e a r c h ; t h e s e were r o u t i n e

Cannon-Fenske v i s c o m e t e r s o f t h e t y p e recommended b y t h e

ASTM f o r t e s t i n g p e t r o l e u m p r o d u c t s , w h i c h i s d e s c r i b e d b y

Cannon and Fenske (14) and i n t h e ASTM p u b l i c a t i o n s ( 2 5 ) .

Two o f these (Nos. A54 and A91) were s i z e 50, two (Nos, B78

and B82) were s i z e 100 and one (N0.C8) was s i z e 200. A

diagram o f one o f these v i s c o m e t e r s , i s g i v e n i n f i g u r e I .

The s p e c i f i c a t i o n s f o r t h e t h r e e s i z e s used a r e as f o l l o w s :

Size I.D. o f tube C,m.m. I.D. o f tube F,m.m. Rang;;e, CS.

50 2 . 6 - 3.4 0.42 - 0.02 0.8 - 3.2

100 2.8 - 3 . 6 0 . 6 3 - 0.02 3 - 12

200 2.8 - 3 . 6 1.02 - 0.02 20 - 80

Other i m p o r t a n t d i m e n s i o n s , which are standard f o r a l l s i z e s ,

a r e shown i n f i g u r e I .

V i s c o m e t e r no. B78 was o b t a i n e d w i t h a c a l i b r a t i o n

c e r t i f i c a t e from the Cannon I n s t r u m e n t Co., S t a t e C o l l e g e , P a .

A copy o f t h e c a l i b r a t i o n c e r t i f i c a t e i s reproduced i n

Appendix I I .
 3?o f o l l o w page

F i g u r e 1. C a n n o n - F e n s k e Viscometer
 48
The O p e r a t i o n o f t h e s e v i s c o m e t e r s was essentially

t h e same as t h a t recommended b y t h e ASTM ( 2 5 ) . The visco-

m e t e r was f i r s t filled by i n v e r t i n g , p l a c i n g the opening of

limb C under the l i q u i d being tested, and a p p l y i n g s u c t i o n

at arm A t o draw l i q u i d up i n t o b u l b s D and E . This filling

p r o c e e d u r e was done a t r o o m t e m p e r a t u r e . The l i q u i d was

d r a w n up as f a r as t h e e t c h e d m a r k ,H, on t h e c a p i l l a r y tube,

F. The v i s c o m e t e r was t h e n q u i c k l y w i t h d r a w n from the l i q u i d

and inverted. Any l i q u i d c l i n g i n g t o the o u t s i d e of tube C

was t h e n w i p e d off with f i l t e r paper, and t h e v i s c o m e t e r

placed i n a constant temperature bath, maintained a t the

appropriate test temperature. By t h i s f i l l i n g proceedure, a

c o n s t a n t v o l u m e was I n t r o d u c e d i n t o t h e v i s c o m e t e r a t e a c h

filling, thus e n s u r i n g a c o n s t a n t f l u i d d r i v i n g head f o r e a c h

determination. A n o t e was made o f t h e room t e m p e r a t u r e at

the time o f f i l l i n g , i n c a s e i t was n e c e s s a r y t o c o r r e c t f o r

t h e same f i l l i n g temperature f o r each r u n . However, i t w i l l

be shown t h a t t h i s c o r r e c t i o n i s n e g l i g i b l e f o r c h a n g e s o f

u p t o 5°C i n r o o m t e m p e r a t u r e . F o r a l l the determinations

on t h e a l c o h o l s , p r e c a u t i o n s were t a k e n t o e n s u r e that

m o i s t u r e d i d n o t come i n t o c o n t a c t w i t h t h e l i q u i d f o r more

t h a n a few m i n u t e s . T h i s was n e c e s s a r y b e c a u s e t h e n - a l c o h o l s

are somewhat h y g r o s c o p i c and a b s o r b a c o n s i d e r a b l e amount o f

m o i s t u r e i f exposed f o r long periods t o moist a i r . The drying

system illustrated i n f i g u r e 2 was a t t a c h e d t o t h e v i s c o m e t e r s

as s o o n as t h e y were p l a c e d i n t h e c o n s t a n t t e m p e r a t u r e bath.
 To f o l l o w p a g e 48

TO
ATMOSPHERE

TO SUCTION

SILICA-GEL
DRYING
TUBE

n>4- HX1-
C D

t
TO LOWER TO EFFLUX
RESERVOIR BULB

F i g u r e 2. D r y i n g S y s t e m f o r C a p i l l a r y Viscometer
 49

In order to a p p l y s u c t i o n to the e f f l u x b u l b valve

B was c l o s e d , v a l v e A o p e n e d and suction applied. When t h e

l i q u i d s passed e t c h e d mark, G, f i g u r e 1, v a l v e A was closed,

v a l v e B opened and t h e e f f l u x t i m e t a k e n as d e s c r i b e d

previously. One or other viscometer c o u l d be s e l e c t e d by

c l o s i n g t h e a p p r o p r i a t e v a l v e C o r D o r t h e y c o u l d be filled

s i m u l t a n e o u s l y by l e a v i n g b o t h v a l v e s open. Between r u n s ,

v a l v e A was a l w a y s k e p t c l o s e d so t h a t t h e s y s t e m was only

open t o t h e atmosphere t h r o u g h the d r y i n g tube. Suction for

the f i l l i n g and o p e r a t i o n was supplied by a standard rubber

suction bulb.

The constant temperature b a t h used f o r these determi-

n a t i o n s was a g l a s s c y l i n d r i c a l b a t h 12" d i a . b y 12" high.

It was s u p p l i e d w i t h two h e a t e r s o f 250 watts each, One of

the h e a t e r s b e i n g c o n t r o l l e d by a t h e r m o r e g u l a t o r an elect-

r o n i c r e l a y f o r o n - o f f c o n t r o l and the o t h e r b e i n g permanent-

ly on. B o t h t h e h e a t i n p u t s c o u l d be v a r i e d c o n t i n u o u s l y

from zero t o f u l l load through Variac auto-transformers. The

t h e r m o r e g u l a t o r was a Hg-ln-glasstype (Precision Scientific,

Micro set d i f f e r e n t i a l range) w i t h v a r i a b l e contact a l l o w i n g

for c o n t r o l a t any temperature w i t h i n a 45°C r a n g e without

changing t h e amount o f Hg i n the b u l b . The electronic relay

was s u p p l i e d by P r e c i s i o n S c i e n t i f i c Co., ( C a t . No. 6535,

Serial No. C-10). The b a t h was i n s u l a t e d w i t h a few layers

of asbestos paper, uncovered portions being l e f t i n the front

and the back of the bath, i n order to view the p o s i t i o n of

 5,0

the l i q u i d i n t h e v i s c o m e t e r s . A s m a l l (5 - w a t t ) light

b u l b was shone t h r o u g h the back o f the b a t h t o h e l p i n

viewing the viscometers c l e a r l y . Pour v e r t i c a l l i n e s about

2" a p a r t were marked on t h e o u t s i d e of t h e b a t h t o h e l p i n

adjusting the viscometers to a v e r t i c a l p o s i t i o n before

each r u n . I n o r d e r t o make t h i s adjustment the c e n t r e l i n e

t h r o u g h C,D,E and B was made t o c o i n c i d e w i t h a t l e a s t two

of these v e r t i c a l l i n e s . The b a t h was equipped w i t h a

c o o l i n g c o i l which c o u l d be s u p p l i e d w i t h c o l d t a p w a t e r .

The b a t h medium used was t a p w a t e r . The o p e r a t i o n o f t h i s

c o n s t a n t - t e m p e r a t u r e b a t h was found t o be v e r y s a t i s f a c t o r y ,

any temperature between 15° and 90°C, b e i n g m a i n t a i n e d

c o n v e n i e n t l y a t - i 0.02°C. The temperature was. r e a d f r o m Hg-

thermometers graduated i n ^ - ° C , and equipped w i t h thermo-

meter l e n s , enabled r e a d i n g s t o t h e n e a r e s t 0.01°C.

Thermometers No.821 (0 - 60°C) and No.3502 (50- 110°C) were

used, b o t h h a v i n g been c a l i b r a t e d a g a i n s t a P l a t i n u m

R e s i s t a n c e thermometer w i t h an N.B.S. c e r t i f i c a t e . The

d e t a i l s o f t h e c a l i b r a t i o n o f t h e s e thermometers a r e g i v e n

i n Appendix III. I t i s f e l t t h a t these c a l i b r a t i o n s were

a c c u r a t e t o t h e n e a r e s t 0.02°C and t h a t t h e r e f o r e t h e temper-

a t u r e o f t h e v i s c o s i t y d e t e r m i n a t i o n s were known t o t h e

n e a r e s t 0.04°C. Care was t a k e n t o ensure t h a t the same

Immersion used i n t h e c a l i b r a t i o n was m a i n t a i n e d d u r i n g a l l

the d e t e r m i n a t i o n s so t h a t no c o r r e c t i o n f o r the emergent

stem was n e c e s s a r y (assuming c o n s t a n t room t e m p e r a t u r e ) .

 51

I n order to determine the e f f l u x time, s u c t i o n was

a p p l i e d a t C, a f t e r sufficient time had elapsed to ensure

t h a t the l i q u i d i n t h e v i s c o m e t e r had attained the tempera-

t u r e o f t h e b a t h , and l i q u i d was drawn f r o m b u l b B into

b u l b E and a b o u t 1 cm. p a s t t h e e t c h e d m a r k G. The time was

taken f o r the l i q u i d s u r f a c e t o move f r o m e t c h e d m a r k G t o

etched mark H.

F o r most o f t h i s work a s t o p - w a t c h g r a d u a t e d i n

t e n t h s o f a s e c o n d was used f o r t i m i n g the j s f f l u x of the

liquid. For the c a l i b r a t i o n runs i n which the time of

e f f l u x o f t h e same l i q u i d i n v i s c o m e t e r B78 and o t h e r s w e r e

c o m p a r e d , i t was u n n e c e s s a r y t o have the s t o p - w a t c h calibrated.

However, f o r t h e c a l i b r a t i o n r u n s w i t h d i s t i l l e d water, and

o t h e r a b s o l u t e d e t e r m i n a t i o n s , i t was n e c e s s a r y t o know t h e

exact times a b s o l u t e l y . T h i s s t o p - w a t c h was therefore

c a l i b r a t e d , by c o m p a r i s o n w i t h an e l e c t r i c laboratory timer

w h i c h was r u n by a synchronous m o t o r , and g r a d u a t e d i n s e e s .

According to the B r i t i s h Columbia E l e c t r i c Co. L t d . (115),

t h e f r e q u e n c y o f e l e c t r i c power i n Vancouver was maintained

c o n s t a n t t o w i t h i n 0.05 c y c l e a t a l l times e x c e p t "peak"

p e r i o d s d u r i n g which the v a r i a t i o n would not exceed 0.1

cycle. A e h a r t f o r v a r i a t i o n of the f r e q u e n c y over an

average day i n d i c a t e d the t i m e s o f t h e "peak" p e r i o d s , and

showed t h a t t h e v a r i a t i o n s w e r e r o u g h l y o s c i l l a t o r y , and

t h a t over a p e r i o d o f one h o u r , the average v a r i a t i o n would

 5 2

be much s m a l l e r t h a n 0.05 c y c l e . This corresponds t o t h e

synchrons t i m i n g d e v i c e h a v i n g an a c c u r a c y considerably greater

t h a n 0.1$ f o r p e r i o d s o f about one h o u r .

The f o l l o w i n g comparison was o b t a i n e d ,

Synchronous Stopwatch, % Diff.

Timer,mins. Seconds slow

45 4.3 0.159
60 6.0 0.167
45 4.2 0.156

Mean d e v i a t i o n = 0.16$ slow.

At t h e end o f a l l c a l i b r a t i o n r u n s , t h e watch was r e a d j u s t e d

u n t i l no a p p r e c i a b l e d i f f e r e n c e was o b t a i n e d between i t s

time and those o f t h e synchronous t i m e r . A f t e r the l a s t

a d j u s t m e n t , t h e f o l l o w i n g comparison was o b t a i n e d ,

Synchronous Stopwatch $ Diff.

Timer

45 m i n s . +0.2 sec. +0.008

45 m i n s . - 0.5 s e c . -0.018

45 mins. 0.0 s e c . 0.0

Mean d e v i a t i o n = 0.01$ slow.

Finally, t h e s t o p - w a t c h was compared w i t h t h e t i m e r

used i n c o n j u n c t i o n w i t h t h e p r e s s u r e v i s c o m e t e r (see below),

T h i s m a g n e t i a l l y operated t i m e r was guaranteed b y t h e

 53
manufacturers t o have an a b s o l u t e p r e c i s i o n o f i - j ^ second

i n f o u r minutes, o r about — 0.04% Oomparison o f t h e s t o p -

watch w i t h t h e t i m e r over s e v e r a l p e r i o d s o f about thirty

minutes, show no s i g n i f i c a n t d e v i a t i o n I n t h e t i m e s r e a d b y

both instruments. D u r i n g t h e l a t t e r p a r t o f t h i s w o r k , and

i n p a r t i c u l a r t h e d e t e r m i n a t i o n s o n n - a l c o h o l , b o t h t h e stop-.,

w a t c h and t h e m a g n e t i c a l l y o p e r a t e d t i m e r were used t o

determine the e f f l u x times i n t h e c a p i l l a r y v i s c o m e t e r s .

During a l l the c a l i b r a t i o n runs i n which viscometer

B 7 8 was c o m p a r e d w i t h o t h e r ' v i s c o m e t e r ^ t h e two w e r e . f i l l e d

within, minutes, p l a c e d i n t h e b a t h t o g e t h e r , and t h e e f f l u x

times t a k e n i m m e d i a t e l y f o l l o w i n g one a n o t h e r . This

proceedure ensured t h a t d u r i n g c a l i b r a t i o n r u n s no c o r r e c t i o n

was necessary f o r v a r i a t i o n i n either f i l l i n g temperature or

bath temperature. T h e r e was a l s o no e r r o r due t o i n a c c u r a c y

i n t h e t i m i n g d e v i c e , i f i t I s assumed t h a t t h e s t o p - w a t c h

operated c o n s i s t e n t l y d u r i n g the comparative calibrations.

The e f f l u x t i m e s f o r each r u n were r e p e a t e d a t

l e a s t three times,and t h e mean o f t h e t h r e e v a l u e s was taken

as t h e c o r r e c t t i m e t o b e u s e d t o determine the kinematic

viscosity. R e p r o d u c i b i l i t y o f e f f l u x t i m e s was u s u a l l y

w i t h i n 0.1% a n d i n e v e n e x t r e m e c a s e s , n e v e r exceeded 0.2$.

All t h e a b s o l u t e d e t e r m i n a t i o n s w e r e made i n

d u p l i c a t e w i t h two d i f f e r e n t v i s c o m e t e r s k e p t i n t h e b a t h a t

t h e same t i m e , a n d t h e a v e r a g e o f t h e two v i s c o s i t i e s
 54

^ o b t a i n e d i s r e p o r t e d as t h e v i s c o s i t y o f t h e l i q u i d . These

do n o t s e r v e a s two i n d e p e n d e n t determinations, since the

two v i s c o m e t e r s h a v e b e e n c a l i b r a t e d a g a i n s t t h e same

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

be p r e s e n t i n t h e c o n s t a n t s o f t h e o t h e r s . However, this

proceedure does h e l p t o r e d u c e e r r o r s due t o a l i g n m e n t o u t

of t h e v e r t i c a l and d i f f e r e n c e s i n t h e volume o f sample

taken filling.
A I t also serves t o b r i n g out i r r e g u l a r

b e h a v i o r w h i c h may a r i s e o u t o f d u s t e n t e r i n g t h e v i s c o m e t e r

and grease c l i n g i n g t o the c a p i l l a r y .

When a d e t e r m i n a t i o n was c o m p l e t e , the viscometers

w e r e washed w i t h s o l v e n t . F o r d e t e r m i n a t i o n s on o i l s , they

w e r e washed t w i c e w i t h b e n z e n e , and t w i c e w i t h a c e t o n e , and

for other d e t r m i n a t i o n s , three washings w i t h acetone were

used. F i n a l l y t h e v i s c o m e t e r s were d r i e d b y p a s s i n g a i r

through them. The a i r was c o n t i n u o u s l y p u r i f i e d and d r i e d i n

a t r a i n c o n s i s t i n g o f c o n e . NaOH s o l r i , d i s t i l l e d w a t e r and

s i l i c a g e l supported b e t w e e n two l a y e r s o f c o t t o n - w o o l . This

ensured t h a t no d u s t e n t e r e d the viscometers during drying.

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

an i n v e r t e d p o s i t i o n , t h e o p e n ends r e s t i n g o n a f l a t glass

plate.

From t i m e t o t i m e , i t was n o t i c e d t h a t one o r o t h e r

of the v i s c o m e t e r s began t o g i v e i r r e g u l a r t i m e s a n d when

t h i s o c c u r r e d t h e v i s c o m e t e r was c l e a n e d i n h o t c h r o m i c acid,
 55

washed s u c c e s s i v e l y i n r u n n i n g t a p w a t e r and w i t h distilled

w a t e r , and d r i e d . This would i n v a r i a b l y cure the e r a t i c

behavior w h i c h was p r o b a b l y due t o g r e a s e o r d u s t i n the

capillary,

ii) T h e o r y o f and C o r r e c t i o n s f o r C a n n o n - F e n s k e

Viscometers. A n e x c e l l e n t summary o f t h e t h e o r y o f c a p i l l a r y

viscometers, with p a r t i c u l a r reference t o t h e Cannon-Fenske

modified Ostwald v i s c o m e t e r , i s g i v e n b y Cannon (116), It

makes r e f e r e n c e to important w o r k on t h e m a g n i t u d e o f t h e

k i n e t i c e n e r g y c o r r e c t i o n w h i c h was n o t a v a i l a b l e i n a n

e a r l i e r a r t i c l e b y C a n n o n and F e n s k e ( 1 4 ) .

The basic equation governing the viscous flow of a

fluid i n a c a p i l l a r y of f i n i t e l e n g t h i s g i v e n i n terms o f

t h e d r i v i n g head as f o l l o w s : "

(53)

The first term r e p r e s e n t s the f r a c t i o n of the d r i v i n g head

w h i c h goes t o o v e r c o m e t h e v i s c o u s f o r c e i n t h e l e n g t h L

of c a p i l l a r y , as g i v e n b y P o i s e u i l l e s l a w .
1
The s e c o n d term

I s t h e f r a c t i o n o f t h e d r i v i n g head w h i c h i s used t o overcome

the i n e r t i a l e f f e c t s a t the entrance and e x i t o f t h e c a p i l l a r y .

Solving f o r the kinematic viscosity, — , one

obtains the basic v i s c o s i t y equation as,

The m e a n i n g o f a l l symb.ols u s e d h e r e and e l s e w h e r e i n

t h i s r e p o r t a r e c o n t a i n e d under "Nomenclature" i n t h e
p r e l i m i n a r y pages o f t h e r e p o r t . .
 56

V - i = - ^ ^ ( K . - V X ) - ( 4)
5

? 8UV V
8 ITU-T

V = Ct -Jfc/t " (55)

where,
\/
(56)
6UV 1

In these equations, i f c.g.s. u n i t s are used throughout,

"Y|_ i s i n p o i s e s and V in stokes.

Kinetic Energy C o r r e c t i o n

The t e r m B/ t i s the k i n e t i c energy c o r r e c t i o n .

Unfortunately, B i s not a constant because m i s a f u n c t i o n

o f t h e Reynolds:;; Ho, and will t h e r e f o r e vary w i t h the efflux

time. Barr (4) has indicated that values of m from 0 t o

1.12 have been r e p o r t e d ^ a n d C a n n o n (116) quotes experimental

v a l u e s w h i c h show t h a t e v e n f o r t h e same v a l u e o f Re, m

v a r i e s f r o m one instrument t o a n o t h e r , d e p e n d i n g on the shape

of the e n t r a n c e and exit of the c a p i l l a r y . The general

conclusions drawn are t h a t m approaches zero at very low

values o f Re and i n c r e a s e s w i t h i n c r e a s i n g Re up to a value

of about u n i t y ; a l s o , square-ended c a p i l l a r i e s show a l a r g e r

value o f m t h a n do those w i t h g r a d u a l l y tapered or trumpet-

shaped ends. Prom t h e f i g u r e s g i v e n b y Cannon, i t c a n be

concluded that m w i l l not e x c e e d 0.4 i n an i n s t r u m e n t with

g r a d u a l l y tapered entrance and exit (as i n t h e Cannon-Penske

viscometer), p r o v i d i n g t h e R e y n o l d s No. does not exceed 100

 57
r On s u b s t i t u t i n g f o r m, V and L i n the e x p r e s s i o n

f o r B/j., i t i s found t h a t the c o r r e c t i o n w i l l be l e s s t h a n ,

0.4 x 3.15 1 = 5.3 x 1 0 " 3

3 t o k e

8 Tf x 9.5 t t
As a percentage of the approximate v i s c o s i t y C t , the

c o r r e c t i o n i s l e s s than,

53- ^ centistoke ,
% where C i s i n /sec.
On t h i s b a s i s , the minimum v a l u e o f t f o r a maximum
a l l o w a b l e k i n e t i c energy c o r r e c t i o n has been c a l c u l a t e d f o r
the t h r e e s i z e s of v i s c o m e t e r , as f o l l o w s : -

Size Approx Value o f Minimum Value o f t f o r max. error

constant C. 0.1$ 0.2$ 0.3$

50 0.0025 460 325 265

100 0.012 210 150 120

200 0.10 70 50 40

The c o r r e s p o n d i n g v a l u e s of the Reynolds No. are

a p p r o x i m a t e l y as follows •

C o r r e s p o n d i n g Re a t max. e r r o r of

Size 0.1$ 0.2$ • 0.3$

50 18 29 55 . '
100 12 23 37
200 8 15 22

S i n c e t h e s e v a l u e s of Re are w e l l below 100, the

r e l e v a n t v a l u e of m i s l i k e l y t o be l e s s t h a n 0.4 and hence

 58

the minimum times g i v e n are c o n s e r v a t i v e estimates.

Surface Tension

On the assumption t h a t , f o r the purposes of

s u r f a c e t e n s i o n c o r r e c t i o n , the v i s c o m e t e r behaves as a u-

tube w i t h the arms h a v i n g d i f f e r e n t , c o n s t a n t , r a d i i T; and

N~ a t the exposed s u r f a c e , the e f f e c t i v e d i f f e r e n c e i n

2

d r i v i n g head, A H S T , f o r two l i q u i d s of d i f f e r e n t surface

tension,is given by,

I n f a c t , t h e r a d i u s of the e f f l u x bulb,'C, and the lower

r e s e v o i r ^ b o t h change a t the f r e e s u r f a c e of the l i q u i d , so

that equation (57) i s not exact.

An a c c u r a t e method of c a l c u l a t i o n w h i c h i n c l u d e s the

c h a n g i n g d i a m e t e r a t the f r e e s u r f a c e has been developed by

B a r r ( 1 1 7 ) and Sugden (118). Gannon, however, has shown t h a t

the e f f e c t i s s m a l l and t h a t the use of e q u a t i o n (57) will

g i v e s u f f i c i e n t l y a c c u r a t e r e s u l t s f o r the c o r r e c t i o n .

I t i s i n t e r e s t i n g t o c o n s i d e r the magnitude of t h i s

effect f o r various l i q u i d s . S u b s t i t u t i n g the appropriate

v a l u e s f o r t , , -C x and H i n t o e q u a t i o n (5T) g i v e s ,

or ArU-r r v.
Or- /o - - ' ' 0 1

H = 0 0 1 0 6
(.T. - T,) ( 5 8 )
 5-9

The value o f V, , w h i c h has been s u b s t i t u t e d i s 0.8 ( TJ )

max., where ( ) max = 1.5 cm.

Hence, i n o r d e r t o keep the c o r r e c t i o n l e s s than

0.1$, t h e c h a n g e i n (^~) m u s t be l e s s t h a n a b o u t 11 units.

Values of (-^ ) were c a l c u l a t e d f r o m t h e d a t a i n Timmermans

(29) and are reproduced i n t a b l e 1 f o r a v a r i e t y of liquids.

Prom t h e t a b l e , i t c a n be s e e n t h a t a t 20°C, t h e v a l u e of

for aromatics, p a r a f f i n s and a l c o h o l s v a r i e s f r o m 28 to 35

and f o r " o t h e r s " f r o m 26 t o 43. F u r t h e r m o r e , a 60° rise in

temperature causes a reduction^about 7 units. This shows

t h a t the s u r f a c e t e n s i o n c o r r e c t i o n f o r measurements on

organic l i q u i d s i s q u i t e s m a l l , i f t h e c a l i b r a t i o n has been

done w i t h o r g a n i c l i q u i d s or i s r e f e r r e d to a value of (^)

o f a b o u t 33 units.

The c o r r e c t i o n f o r w a t e r compared w i t h organic

liquids i s quite important. Perry (119) gives the surface

t e n s i o n o f w a t e r as 7 2 . 8 d y n e s p e r cm^ a t 20°C w h i c h gives

a value of (—) c l o s e t o 73 u n i t e s whence A ( - ^ ) r^j 40 units

and the c o r r e c t i o n i s about 0.4$ a t 20°C. This c o r r e c t i o n

m u s t be a p p l i e d when c a l i b r a t i o n s a r e b e i n g done w i t h w a t e r .

Variation i n Filling T e m p e r a t u r e and Test Temperature.

T h i s causes a change i n the t o t a l volume o f l i q u i d in

the viscometer and consequently changes the d r i v i n g head, H.

For o i l s , C a n n o n and Fenske (1) recommend u s i n g a linear

i n t e r p o l a t i o n based on 0.5$ d i f f e r e n c e f o r 60°C c h a n g e i n

 TABLE I 60
APPROXIMATE VALUES OF (|r) FOR COMMON ORGANIC LIQUIDS

Temperature, C v dynes/cm*
Liquid
^ * gma/cirr
Aromatics

.Benzene 20
60
33
27.5
Toluene 20 33
30 32
E t h y l Benzene 20 33.5
O-xylene 20 34.5
Decalin 20 35
Paraffins

n-C 20 31"
8

85 24.5
3-MeHeptane 20 30
50
20
27
n-C„
85 32
n-C 20
14 24"
34.5
Alcohols

20 28.5
°i 30 28.

°2 20 28.5
30 27.5
n-C~ 20 29.5
i-c| 30 27.5
20 30.0
°4
30 30.5
C
8
"Others"
20 26.5
EtOAc 30 25.5
20 38
Acetophenone 30 38
Phenol 50 34
Aniline 20 42.5
80
38
 61

temperature. However, t h i s i s not v e r y a c c u r a t e and f o r

an e x a c t c a l c u l a t i o n the f o l l o w i n g f o r m u l a was developed,

C r ^ C x L , V-- '
V
(59)

where and C-^ are t h e c a l i b r a t i o n c o n s t a n t s and and

V-^ the volume of l i q u i d a t the two t e m p e r a t u r e s , r e s p e c t i v e -

ly.
S u b s t i t u t i n g f o r H and d one o b t a i n s

% p = 1.46 ( V- z V, )

= 1.46 V, (<?•/?,- \ )

and s i n c e V^ = 7 ccs.

AC
% ~c = 10.5 I) (60)

T h i s c a l i b r a t i o n can be used f o r c a l c u l a t i n g the

temperature correction quite accurately. The c o r r e c t i o n I s

u s u a l l y l e s s t h a n 0.1$ f o r a 10°C change, and I n g e n e r a l

the magnitude o f t h e c o r r e c t i o n depends on the l i q u i d being

tested.

V a r i a t i o n i n Bath Temperature.

The e r r o r s due t o v a r i a t i o n I n b a t h temperature

d u r i n g a r u n and i n a c c u r a c y i n the r e p o r t e d t e s t temperature,

are c l e a r l y not a f u n c t i o n of the v i s c o m e t e r . These e r r o r s

can be e s t i m a t e d from a knowledge of the approximate r^ — T

data f o r the l i q u i d being t e s t e d . Assuming a l i n e a r

 62

v a r i a t i o n of l o g against ]/y , one c a n w r i t e

\ - ^
or l o g Y| = l o g A + -=^.

Differentiating this relation

P r o m a k n o w l e d g e o f t h e v a l u e o f oL y t h e e r r o r c a n be

calculated. F o r n-PrOH a t 30°C, a c h a n g e i n t e m p e r a t u r e o f

0.05°C l e a d s t o a v a l u e o f =£j r^j 0.05$. At low

temperatures, t h e e f f e c t i s - o b v i o u s l y more i m p o r t a n t t h a n a t

higher temperatures.

"Overshooting" the f i l l i n g mark.

This c o r r e c t i o n i s s i m i l a r t o that f o rv a r i a t i o n i n

filling temperature. The c o r r e c t i o n i s g i v e n i n t e r m s o f t h e

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

It c a n b e r e a d i l y shown t h a t f o r t h e s e r i e s 200 v i s c o m e t e r s a

l o a d i n g e r r o r o f 0.1$ w i l l o n l y a r i s e i f t h e f i l l i n g mark i s

o v e r s h o t b y a b o u t 10 cms. The c o r r e c t i o n w i l l c l e a r l y be l e s s

for t h e s e r i e s 100 and 50, s o i t i s u n i m p o r t a n t .

Alignment Error

The C a n n o n - P e n s k e V i s c o m e t e r s a r e d e s i g n e d w i t h t h e

e f f l u x b u l b d i r e c t l y a b o v e t h e l o w e r r e s e r v o i r , and w i t h t h i s

d e s i g n t h e minimum d e v i a t i o n i s o b t a i n e d f o r •."alignment errors.

 63

An e r r o r o f 0.1$ w i l l o n l y a r i s e i f the alignment i s out by

as much as 2 ^° which i s very easily avoided.

ill) C a l i b r a t i o n of C a p i l l a r y V i s c o m e t e r s . The

proceedure f o r the c a l i b r a t i o n of c a p i l l a r y viscometers i s

g i v e n i n d e t a i l i n t h e ASTM " T e s t f o r K i n e m a t i c Viscosity"

(D445-53T) (25). The m e t h o d i s b a s e d on t h e u s e of "Master

V i s c o m e t e r s " as p r i m a r y s t a n d a r d s . These v i s c o m e t e r s have

b e e n d e s c r i b e d b y C a n n o n (23) and a n a l y s e d as a b s o l u t e

i n s t r u m e n t s b y S w i n d e l l s , H a r d y and C o t t i n g t o n (24) at the

N a t i o n a l B u r e a u o f S t a n d a r d s , who found that calibrated

with freshly d i s t i l l e d water, are A very accurate primary

standards•

In the "Master V i s c o m e t e r s , " the d r i v i n g head, H,

i s a b o u t 47 cms. which i s about 5 times the d r i v i n g head f o r

the r o u t i n e viscometers. Since the other dimensions are

a p p r o x i m a t e l y t h e same as i n t h e r o u t i n e i n s t r u m e n t s , this

means t h a t t h e c o r r e c t i o n s a r e a p p r o x i m a t e l y 1/5 of those

for the r o u t i n e viscometers. S w i n d e l l s , H a r d y and C o t t i n g t o n

(74) found t h a t t h e t o t a l o f a l l t h e c o r r e c t i o n s amounted t o

o n l y 0.13$ i n e x t r e m e c a s e s and t h a t the c o r r e c t i o n s c o u l d be

applied very accurately.

The ASTM recommends u s i n g M a s t e r v i s c o m e t e r s which

have been c a l i b r a t e d w i t h w a t e r , to determine the viscosity

of a s e r i e s of hydrocarbon l i q u i d s and describe a "step-up"

proceedure by which t h i s c a n be done f o r a w i d e r a n g e o f

 64
v i s c o s i t i e s w i t h a minimum e r r o r . E i t h e r o f two proceedures

a r e recommended f o r c a l i b r a t i n g r o u t i n e v i s c o m e t e r s o f t h e

t y p e used i n t h i s work; (1) c a l i b r a t i c h d i r e c t l y w i t h oils

w h i c h have been determined i n "Master V i s c o m e t e r s " or (2)

b y means o f I n s t r u m e n t S t a n d a r d s , i . e . d i r e c t c o m p a r i s o n o f

u n c a l i b r a t e d r o u t i n e viscometers w i t h those c a l i b r a t e d by

method (1), above. In t h i s work, v i s c o m e t e r B78 w h i c h was

c a l i b r a t e d b y t h e Cannon I n s t r u m e n t Co. i s s u c h ana Instru-

ment S t a n d a r d . I n b o t h m e t h o d s (1) and (2), above,the ASTM

recommends c a l i b r a t i o n o f e a c h v i s c o m e t e r w i t h a t l e a s t two

liquids of d i f f e r e n t viscosity.

The c a l i b r a t i o n p r o c e e d u r e o u t l i n e d above e n s u r e s

that the c a l i b r a t i o n ! of a r o u t i n e viscometer i s a c c u r a t e l y

done r e l a t i v e t o w a t e r . I n o r d e r t o measure viscoities

a c c u r a t e l y on a n a b s o l u t e b a s i s , i t i s n e c e s s a r y t o know t h e

v a l u e o f t h e v i s c o s i t y o f w a t e r on a n a b s o l u t e b a s i s . Until

quite recently, t h e v i s c o s i t y o f w a t e r was not accurately

known* I n 1952, S w i n d e l l s , Coe and G o d f r e y (22) p u b l i s h e d

r e s u l t s based on v e r y a c c u r a t e e x p e r i m e n t s f r o m w h i c h they

d e t e r m i n e d t h e v i s c o s i t y o f w a t e r a t 20°C as 1.0019 - 0.0003

centipoise. T h e y recommend t h a t a v a l u e o f 1.002 cp. be

u s e d as t h e s t a n d a r d f o r V i s c o s i t y m e a s u r e m e n t s . Swindells,

H a r d y and C o t t i n g t o n (24) h a v e r e p o r t e d t h a t t h e leading

p h y s i c a l l a b o r a t o r i e s i n Europe have agreed t o c o n c u r i n t h i s

recommendation w i t h t h e i r American c o u n t e r p a r t s . Previous

t o 1952, the v a l u e accepted by the N a t i o n a l Bureau of Standards

 65
and t h e ASTM was 1.005 c p . However, o t h e r r e p u t a b l e sources
have g i v e n v a l u e s which do n o t agree w e l l w i t h t h i s f i g u r e .
The I n t e r n a t i o n a l C r i t i c a l Table (26) f o r example g i v e s t h e
f i g u r e of 1.0087. L a n d o l t - B o r n s t e i n , 5 TH
E d i t i o n (27) l i s t s
the v a l u e s o b t a i n e d by w e l l known e x p e r i m e n t e r s , and these
range from 0.9978 t o 1.007 c p . This u n c e r t a i n t y i n the
v a l u e o f v i s c o s i t y o f water a t some s t a n d a r d temperature makes
i t v e r y d i f f i c u l t t o compare v i s c o i t y measurements b e f o r e
1952 from d i f f e r e n t s o u r c e s . I t would be a r e l a t i v e l y s i m p l e
m a t t e r t o c o r r e c t p r e v i o u s measurements i n accordance with
the v a l u e o f 1.002 c p . a t 20°C i f the s t a n d a r d b e i n g used
was quoted, b u t , u n f o r t u n a t e l y , t h i s i n f o r m a t i o n i s seldom
given.

I n t h i s work, the c a l i b r a t i o n c o n s t a n t s f o r v i s c o -
meters A54, A91 and B82 were o b t a i n e d by d i r e c t comparison o f
the e f f l u x times of t h r e e l i q u i d s i n these v i s c o m e t e r s and
v i s c o m e t e r B78. The k i n e m a t i c v i s c o s i t i e s o f these liquids
v a r i e d from about 2 t o 8 c e n t i s t o k e s . A f o u r t h comparison
was made between B78 and B82 w i t h an o i l w i t h k i n e m a t i c
v i s c o s i t y o f about 10 c e n t i s t o k e s . The c a l i b r a t i o n c o n s t a n t
of v i s c o m e t e r C8 was determined a p p r o x i m a t e l y by a s i n g l e
comparison w i t h B78>using an o i l w i t h k i n e m a t i c v i s c o s i t y o f
about 35 c e n t i s t o k e s . No f u r t h e r measurements were made w i t h
C8 d u r i n g t h e course o f t h i s work. As a f i n a l check, runs
w i t h f r e s h l y d i s t i l l e d water were c a r r i e d out w i t h t h e s e r i e s
50 v i s c o m e t e r s (A54 and A91) and t h e v a l u e s o f t h e c a l i b r a t i o n
 66

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

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

decalin, n - p r o p a n o l and 3 p e t r o l e u m o i l s , designated o i l s A,

B and C, w h i c h w e r e p r e p a r e d b y m i x i n g v a r i o u s p r o p o r t i o n s o f

SAE 10 and k e r o s e n e ; o i l C was u n d i l u t e d SAE 10. The samples

o f d e c a l i n and n - p r o p a n o l w e r e C P . grades used w i t h o u t

f u r t h e r p u r i f i c a t i o n , because of the comparative nature of the

determinations. A l l t h e l i q u i d s u s e d were f i l t e r e d into clean,

dry f l a s k s w h i c h were p r o v i d e d w i t h g r o u n d - g l a s s s t o p p e r s .

The d i s t i l l e d w a t e r u s e d f o r ..the c h e c k calibrations

was f r e s h l y d i s t i l l e d i n a standard laboratory s t i l l . The

w o r k o f S w i n d e l l s , Coe and G o d f r e y ( 2 2 ) h a s shown t h a t results

obtained w i t h water produced by a s i m p l e d i s t i l l a t i o n , s u c h as

is accomplished by a commercial l a b o r a t o r y still,produces

water of a s u f f i c i e n t l y u n i f o r m composition. Hence, no o t h e r

f o r m of p u r i f i c a t i o n , n o r a second d i s t i l l a t i o n was required.

(b) The P r e s s u r e V i s c o m e t e r

i) Historical The r o l l i n g ball viscometer consists

e s s e n t i a l l y o f a n i n c l i n e d t u b e o f u n i f o r m d i a m e t e r down

which a b a l l of smaller diameter r o l l s under the i n f l u e n c e of

gravity. The a n g l e o f r o l l i s u s u a l l y between 4 5 ° t o 5 ° from

the horizontal. The m o t i o n o f t h e b a l l i s resisted by the

fluid, and h e n c e t h e t i m e o f r o l l f o r a fixed distance i s a

f u n c t i o n of the v i s c o s i t y of the f l u i d . T h e r e i s no

\
 6?

fundamental d i f f e r e n c e between t h i s i n s t r u m e n t and t h e

f a l l i n g - b a l l viscometer a t t r i b u t e d t o Hoppler (18) i n

w h i c h the a n g l e o f the i n c l i n e d tube i s kept c l o s e t o t h e

vertical.

The i n s t r u m e n t was f i r s t developed i n 1914 by

Flowers ( 1 9 ) , who used i t f o r atmospheric p r e s s u r e measure-

ments. He d i s c u s s e d i n g r e a t d e t a i l t h e t h e o r y o f t h e

i n s t r u m e n t and t h e c o r r e c t i o n s which must be a p p l i e d .

Flowers a l s o l i s t e d the many advantages o f t h e i n s t r u m e n t

and suggested i t s a d a p t a t i o n t o h i g h p r e s s u r e work, where i t

would have many advantages over the c a p i l l a r y v i s c o m e t e r .

Hersey and Shore (120) i n 1916 p u b l i s h e d t h e f i r s t

results o b t a i n e d w i t h t h i s i n s t r u m e n t under p r e s s u r e up t o

7,000 p s i . L a t e r developments (121,122,20) l e d t o t h e

d e s i g n o f a p r e s s u r e i n s t r u m e n t which c o u l d be used f o r

measurements up t o 60,000 p s i . and temperatures up t o 14-0°C,

i n t h e v i s c o s i t y range from 0.004 t o 300 p o i s e s .

The i n s t r u m e n t has s i n c e been used e x t e n s i v e l y f o r

h i g h p r e s s u r e measurements o f t h e v i s c o s i t y o f l i q u i d s over

wide ranges o f p r e s s u r e and t e m p e r a t u r e . H o c o t t and B u c k l e y

(123) have developed t h e i n s t r u m e n t f o r r o u t i n e t e s t s on

s u b s u r f a c e o i l s a m p l e s a n d m o d i f i c a t i o n s a r e now a v a i l a b l e
1

commercially. Sage and a s s o c i a t e s (36,38,39) have made

e x t e n s i v e measurements on b o t h gases and l i q u i d s and have

 68

discussed the theory of the instrument. More recently,

measurements w i t h the r o l l i n g - b a l l v i s c o m e t e r have been

r e p o r t e d b y E x l i n e and En D e a n (124) M a s o n , W i l c o x and Sage

(37) M a k i t a (125,126) and Lundberg (107).

The t h e o r y o f t h e i n s t r u m e n t was i m p e r f e c t l y known

until 1943,when H u b b a r d and B r o w n (128) published a theory

b a s e d on d i m e n s i o n a l a n a l y s i s o f t h e r e l e v a n t v a r i a b l e s and

checked b y l i t e r a t u r e d a t a and many m e a s u r e m e n t s o f their

own. T h i s t h e o r y e n a b l e s m e a s u r e m e n t s t o be p u t on a s o u n d

basis and makes f o r a much more c e r t a i n e v a l u a t i o n o f the

v a r i o u s e r r o r s and corrections. Lewis (129) has recently

analysed the instrument i n terms of the hydrodynamics of

viscous f l u i d s and f o u n d good a g r e e m e n t w i t h H u b b a r d and

Brown.

i i ) D e s c r i p t i o n and Operation. The form of Rolling-

b a l l v i s c o m e t e r u s e d i n t h i s r e s e a r c h was essentially that

d e s c r i b e d b y Hoc.ott and Buckley (123) f o r measuring the

v i s c o s i t y of sub-surface samples of o i l . The description

and o p e r a t i n g i n s t r u c t i o n s f o r the o r i g i n a l d e s i g n are

reproduced i n A p p e n d i x I V fr-om t h e o r i g i n a l manufacturers

sheets. A detailed sectioned drawing of the v i s c o m e t e r has

a l s o been reproduced and i s shown i n f i g u r e 3« Modifications

h a v e b e e n made, p a r t i c u l a r l y i n t h e t i m i n g s y s t e m , with a

view t o improving the a c c u r a c y of the instrument.

 69
Placing the v i s c o m e t e r tube i n the l a t h e indicated

that i t was n o t p e r f e c t l y s t r a i g h t along i t s length. This

meant t h a t , since no p r o v i s i o n was made f o r o r i e n t i n g t h e

b a r r e l i n a constant p o s i t i o n r e l a t i v e to the viscometer

b o d y , t h e p a t h f o l l o w e d b y t h e b a l l was n o t t h e same f o r

each d e t e r m i n a t i o n . The f i r s t two s e t s of c a l i b r a t i o n runs

(see below) g a v e - i n c o n s i s t e n t r e s u l t s , i n d i c a t i n g t h a t this

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

t u b e , I n t h e same r e l a t i v e p o s i t i o n f o r e a c h r u n . In this

way, a l t h o u g h t h e b a l l d i dnot t r a v e l along a f i x e d slope

f o r t h e whole l e n g t h o f t h e tube, i r r e g u l a r i t i e s i n t h e tube

would n o t a f f e c t t h e c o n s i s t e n c y o f t h e i n s t r u m e n t . I n order

to maintain the b a r r e l i n a fixed position, t h e r o l l - t u b e was

keyed t o t h e l o c k - n u t w h i c h i s u s e d t o keep t h e b a r r e l i n

place. S i n c e t h e l o c k - n u t was s c r e w e d t i g h t l y i n t o the b a r r e l

and was t h e r e f o r e i n a f i x e d p o s i t i o n , t h e t u b e was a l s o main-

tained i n a fixed position r e l a t i v e to the b a r r e l . Aftker

t h i s was done, f u r t h e r c a l i b r a t i o n runs indicated that the

instrument operated consistently.

The d i a m e t e r o f t h e b a r r e l was d e t e r m i n e d w i t h a

t r a v e l l i n g microscope. S e v e r a l t r a v e r s e s w e r e made a c r o s s

d i f f e r e n t d i a m e t e r s and t h e mean o f a l l t h e v a l u e s t a k e n a s

the true diameter. A s i n g l e b a l l was u s e d t h r o u g h o u t this

work. I t was a s t a i n l e s s s t e e l b a l l f r o m a l o t o f 12 w h i c h

was o b t a i n e d f r o m a b a l l - b e a r i n g m a n u f a c t u r e r , and h a d a

rated d i a m e t e r o f 0.2500 ± 0.0005 i n . E a c h o f t h e 12 b a l l s

 70
were weighed and found t o have w e i g h t s v a r y i n g f r o m 1.0261

t o 1.0315 gflis., w i t h a mean w e i g h t o f 1.0285 grm. I t was

assumed t h a t the v a r i a t i o n i n w e i g h t was due t o v a r i a t i o n

i n t h e d i a m e t e r and n o t the d e n s i t y o f the m a t e r i a l , ' and

the d e n s i t y was c a l c u l a t e d from the mean w e i g h t and t h e

rated diameter. The f o l l o w i n g i s a summary o f these measure-

ments,

Tube d i a . (measured) = 0.2583 - 0.0008 i n s .

B a l l d i a . (manufacturer) = 0.2500 i 0.0005 I n s .

B a l l wt. (measured) = 1.0261 gms.

B a l l density (calculated) = 7.671^ gms/cm 3

on the b a s i s o f mean wt. o f 12 b a l l s .

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

w h i c h i n d i c a t e s the i n s t a n t a t w h i c h t h e b a l l r e a c h e s t h e

end o f i t s r o l l was a l s o m o d i f i e d slightly. A short copper

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

r e p l a c e d by a nichrome c o n t a c t about 2 cms. l o n g . This

means t h a t the e f f e c t i v e l e n g t h o f the v i s c o m e t e r tube was

reduced from about 20 t o 18 cms.

l"
A f l a t s p i r a l s p r i n g was made from t h e g stainless

s t e e l t u b i n g w h i c h was used i n t h e p r e s s u r e system,and

connected t o the body c o n n e c t o r w i t h t h e s p r i n g i n a v e r t i c a l

p l a n e , and i n such a way t h a t the t e n s i o n of t h e s p r i n g kept

the v i s c o m e t e r body f i r m l y down on t h e f i x e d s t o p . Another

m o d i f i c a t i o n w h i c h was made t o the i n s t r u m e n t was t o

 71
i n c o r p o r a t e a back s t o p , s i m i l a r t o the f i x e d s t o p mentioned

i n the o p e r a t i n g i n s t r u c t i o n s .

Most e x t e n s i v e m o d i f i c a t i o n s were made t o the

o r i g i n a l , m a n u a l l y o p e r a t e d , system used f o r t i m i n g the

t r a v e r s e of the b a l l . A new t i m i n g system was d e s i g n e d t o

r e g i s t e r a u t o m a t i c a l l y the time of r o l l , as shown i n f i g u r e

4.

A prime c o n s i d e r a t i o n i n t h i s d e s i g n was to m a i n t a i n

as s m a l l a c u r r e n t as p o s s i b l e t h r o u g h the b a l l and the

i n s u l a t e d c o n t a c t a t the bottom of the v i s c o m e t e r t u b e . In

order to a t t a i n this,, a s e n s i t i v e e l e c t r o n i c r e l a y (Cenco

E l e c t r o n i c R e l a y , C a t . No. F3961, S e r i a l No. 113) was used.

Designed f o r o n - o f f c o n t r o l of h e a t i n g systems,110V a.c. was

p r o v i d e d a t the t e r m i n a l s , J , but f o r the p r e s e n t purpose i t

was m o d i f i e d by i s o l a t i n g the power r e l a y c o n t a c t s , D. A

c u r r e n t of about 10 microA. i s s u f f i c i e n t t o o p e r a t e t h i s

relay.

The t i m e r used f o r most of t h i s work was a J a c q u e t

l a b o r a t o r y stop-watch, c a t . No. 308d (130) w h i c h i s graduated

in s e c . and i s p r o v i d e d w i t h an " i n p u l s e " e l e c t r o m a g n e t f o r

s t a r t i n g and s t o p p i n g . I n t h i s d e s i g n , the watch i s s t a r t e d

o r stopped by c l o s i n g the magnet c i r c u t , and opening the c i r c u i t

m e r e l y d e - e n e r g i z e s the magnet and r e l e a s e s the s t a r t - s t o p

p l u n g e r , making the watch r e a d y f o r a n o t h e r c y c l e of o p e r a t i o n .

 To f o l l o w page 71

VISCO-
METER

MERCURY
SWITCH

TIMER

110 V ru

F i g u r e 4. T i m i n g S y s t e m f o r P r e s s u r e V i s c o m e t e r
 7 2

A n o t h e r t i m e r was d e v e l o p e d d u r i n g t h e c o u r s e of this work,

but i t was n o t u s e d f o r a n y m e a s u r e m e n t s r e p o r t e d here,

although i t was f o u n d t o o p e r a t e satisfactorily. I t i s described

i n A p p e n d i x V.

A glass enclosed m e r c u r y s w i t c h , A, was c l a m p e d t o

the outside of the viscometer b o d y and p a r a l l e l to i t , i n

s u c h a way t h a t t h e s w i t c h was o p e n when t h e b o d y was i n t h e

p o s i t i o n w i t h t h e i n s u l a t e d c o n t a c t u p , a n d c l o s e d when t h e

b o d y was i n i t s n o r m a l p o s i t i o n a g a i n s t t h e f i x e d - s t o p . The

m e r c u r y s w i t c h t e r m i n a l s were c o n n e c t e d i n p a r a l l e l w i t h t h e

I n s u l a t e d c o n t a c t , C, and a t t a c h e d t o t h e "T" t e r m i n a l s o f

the electronic relay. A manually operated s w i t c h B was

c o n n e c t e d i n s e r i e s w i t h t h e m e r c u r y s w i t c h , a s shown. The

r e l a y c o n t a c t s , D, w e r e c o n n e c t e d d i r e c t l y to the on-off

t e r m i n a l s , F ^ o f t h e magnet o f t h e t i m e r . F i n a l l y power was

supplied t o t h e e l e c t r o n i c r e l a y and t h e t i m e r a t E and G,

respectively. The b o d y o f t h e v i s c o m e t e r was " g r o u n d e d " t o

the frame which supported the constant temperature bath i n

which the viscometer was i m m e r s e d d u r i n g determinations.

The constant t e m p e r a t u r e b a t h was 27" x 14" s e c t i o n and 19"

h i g h , made f r o m 1/4" s h e e t a l u m i n i u m and a l u m i n i u m w e l d e d ;

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

b a t h was s u p p o r t e d on a s o l i d D e x i o n frame w i t h t h e b o t t o m

horizontal according to a spirit level.

 73
I t was I n s u l a t e d w i t h 2" o f l o o s e r o c k w o o l and the

b o t t o m was s u p p o r t e d on 2" i n s u l a t i n g b r i c k s , the spaces

between the b r i c k s b e i n g filled i n w i t h rock wool. The top

was c o v e r e d w i t h 1/2" p l y w o o d on w h i c h t h e h e a t e r s and thermo-

r e g u l a t o r were mounted, as w e l l as t e r m i n a l s f o r t h e electrical

connections t o the v i s c o m e t e r . The b a t h medium was Chevron No.

9 W h i t e O i l w i t h a v i s c o s i t y o f 190 saybolt sees, a t 100°P and

a f l a s h p o i n t o f 350°F.

The b a t h was s t i r r e d b y a ! / l 6 H.P. Eastern Electric

v a r i a b l e speed (rheostat controlled) s t i r r e r . Two 500 watt

Calrod heaters w i t h s t a i n l e s s s t e e l s h e a t h s were u s e d , one

being c o n n e c t e d d i r e c t l y t o t h e m a i n s w i t h a s w i t c h and 5&mp.

f u s e i n s e r i e s , and the o t h e r t o an e l e c t r o n i c r e l a y f o r 5n-

off control. The r e l a y was a Cenco R e l a y Control Unit, Cat,

No. 60940,.which was, v e r y similar to the one used f o r the

t i m i n g system. The thermoregulator was a mercury-in-glass

t y p e w i t h b o t h l a r g e s u r f a c e and l a r g e volume. The on-off

heater was h o o k e d up i n s u c h a way that normally p a r t of the

l o a d was p e r m a n e n t l y on and p a r t was on o n - o f f c o n t r o l , and a

s w i t c h was provided w h i c h c o u l d b r i n g a l l of the load to on-

off control. The power s u p p l i e d was c o n t r o l l e d by rheostats,

and ammeters w e r e p r o v i d e d to i n d i c a t e the heat input.

Switches, reheostats, ammeters and pilot l i g h t s w e r e mounted

on a p a n e l f o r convenience.
 74
The t e m p e r a t u r e was m e a s u r e d b y a Centrigrade

M e r c u r y t h e r m o m e t e r No. 6343 w i t h 0.1°C g r a d u a t i o n s and

range 0 — 110°C w h i c h h a d b e e n p r e v i o u s l y c a l i b r a t e d against

a p l a t i n u m r e s i s t a n c e t h e r m o m e t e r c e r t i f i e d b y t h e N.B.S.

(see A p p e n d i x I I I f o r c a l i b r a t i o n ) . C a r e was t a k e n t o

maintain t h e i m m e r s i o n t h e same a s t h a t u s e d i n t h e c a l i b r a -

t i o n s o t h a t no c o r r e c t i o n f o r t h e e m e r g e n t s t e m was r e q u i r e d .

After the determination on e a c h o i l , t h e v i s c o m e t e r

was e m p t i e d and d i s m a n t l e d , and a l l t h e p a r t s were thoroughly

cleaned. The c l e a n i n g p r o c e e d u r e i n v o l v e d two o r t h r e e

w a s h i n g s w i t h b e n z e n e , and a s i m i l a r number w i t h a c e t o n e and

f i n a l l y d r y i n g w i t h a i r f o r one h o u r . The viscometer.tube

was t h e n r e p l a c e d i n t h e b o d y a n d - a new c a l i b r a t i n g liquid

was p o u r e d i n w i t h t h e b o d y s u p p o r t e d i na vertical position.

L i q u i d was i n t r o d u c e d u p t o a f e w m.m. above t h e s h o u l d e r

which supports t h e b o d y c l o s u r e , and t h e n t h e b a l l w a s , ; i n t r d -

duped. I n f a l l i n g down t h e t u b e , the b a l l d i s p l a c e d any a i r

b u b b l e s w h i c h may h a v e b e e n t r a p p e d i n t h e t u b e and f o r c e d '

these through the s l o t s on t h e o u t s i d e o f t h e tube. The

c l o s u r e was t h e n r e p l a c e d , w i t h t h e p l u n g e r completely with-

d r a w n , and t i g h t e n e d down f i r m l y . Initally, l i q u i d was

d i s p l a c e d b e t w e e n t h e b o d y and t h e c l o s u r e a n d t h r o u g h t h e

tubing attached t o t h e body connector, ensuring t h a t no a i r

was t r a p p e d i n the viscometer. F i n a l l y , the viscometer was

placed i n the constant temperature bath and t h e a p p r o p r i a t e

e l e c t r i c a l and t u b i n g c o n n e c t i o n s w e r e made.
 75
S e v e r a l hours were a l l o w e d f o r t h e v i s c o m e t e r t o

reach temperature equilibrium. A f t e r about 2-3 hrs;, the

v i s c o m e t e r was r o t a t e d t o t h e r e v e r s e p o s i t i o n and t h e b a l l

allowed t o r o l l out i n t o t h e upper chamber. Then t h e v i s c o -

m e t e r was r o t a t e d b a c k t o t h e v e r t i c a l p o s i t i o n a n d t h e b a l l

entered t h e tube a g a i n , d i s p l a c i n g t h e l i q u i d i n t h e tube

i n t o t h e upper chamber v i a t h e s l o t s . This mixing proceedure

was repeated s e v e r a l times t o ensure u n i f o r m temperature

e q u i l i b r i u m b e t w e e n t h e v i s c o m e t e r and i t s c o n t e n t s , and t h e

bath o i l . F i n a l l y t h e f r o n t and b a c k f i x e d s t o p s were p u t i n

p l a c e , and t h e p l u n g e r s c r e w e d down t i g h t l y f i x i n g t h e tube

f i r m l y a g a i n s t t h e b a r r e l g a s k e t and c l o s i n g o f f t h e u p p e r end

of the tube.

I n order t o determine the time o f r o l l , the visco-

m e t e r b o d y was r o t a t e d a g a i n s t t h e t e n s i o n o f t h e s p r i n g , and

kept i n t h e r e v e r s e p o s i t i o n / w i t h the i n s u l a t e d c o n t a c t up,

until s u f f i c i e n t time had e l a p s e d t o ensure t h a t t h e b a l l had

r e t u r n e d t o t h e t o p o f t h e t u b e and r e s t e d o n t h e end o f t h e

plunger. When s u f f i c i e n t t i m e h a d e l a p s e d , t h e b o d y was h e l d

a g a i n s t t h e b a c k - s t o p and t h e n s u d d e n l y r e l e a s e d w i t h s w i t c h

B i n the closed position. As t h e b o d y r o t a t e d b y t h e a c t i o n

of t h e s p r i n g , the mercury s w i t c h was a u t o m a t i c a l l y c l o s e d a n d

the e l e c t r o n i c r e l a y a c t i v a t e d . This closed the r e l a y contacts

D, w h i c h e n e r g i z e d t h e e l e c t r o - m a g n e t and s t a r t e d the timer.

The e l e c t r o - m a g n e t was d e - e n e r g i z e d a n d made r e a d y f o r t h e

s t o p p i n g o p e r a t i o n b y o p e n i n g t h e manual s w i t c h , B , A t t h e end
 •76
of t h e r o l l , when t h e b a l l touched the i n s u l a t e d contact,
C, the e l e c t r o n i c r e l a y was a g a i n a c t i v a t e d and stopped the
timer. I n t h i s way the time o f r o l l was o b t a i n e d automatic-
a l l y and was read t o the n e a r e s t sec. A t the end o f
one d e t e r m i n a t i o n , t h e body was a g a i n r o t a t e d t o t h e r e v e r s e
p o s i t i o n and the b a l l a l l o w e d t o r o l l back t o the i n i t i a l
position. As the b a l l l e f t the i n s u l a t e d c o n t a c t , the r e l a y
c i r c u i t was b r o k e n and the e l e c t r o m a g n e t again de-energized.

Between 5 and 20 s u c c e s s i v e d e t e r m i n a t i o n s were made

on each l i q u i d a t each temperature and t h e mean o f these was
t a k e n as t h e c o r r e c t time o f r o l l .

Hi) Theory and E r r o r s . The b a s i c e q u a t i o n d e s c r i b -

ing the r e l a t i o n s h i p between the v a r i a b l e s i n the r o l l i n g -

b a l l v i s c o m e t e r , as d e r i v e d by Hubbard and Brown (128), i s ,

ri = H aCt>4-d) (62)

where, K i s t h e c o r r e l a t i o n f a c t o r and i s a f u n c t i o n o f t h e
diameter r a t i o ( /D) o n l y . A c c o r d i n g t o t h i s e q u a t i o n , when
a s i n g l e b a l l and tube a r e b e i n g c o n s i d e r e d , so t h a t d and D
a r e c o n s t a n t , and when the a n g l e from the h o r i z o n t a l , 0 , i s
c o n s t a n t , the v i s c o s i t y i s g i v e n by t h e r e l a t i o n ,

^ = C ' J L ^ L s C ' F E _ ? ) T ( 6 3 )

or ri = C (ft-?)-t (64)
Prom t h i s e q u a t i o n , G i s t h e c a l i b r a t i o n c o n s t a n t , and i f i t
i s known, t h e v i s c o s i t y o f any l i q u i d can be determined from
 77

the t i m e o f r o l l , -fc; , and t h e d e n s i t y difference

Prom t h e H u b b a r d and B r o w n e q u a t i o n , t h e calibration

c o n s t a n t i s g i v e n by,

c =
W a(t>+<9 (65

Equation (65) i s the b a s i s from which the v a r i a t i o n of the

c a l i b r a t i o n w i t h v a r i o u s e f f e c t s c a n be determined.

The correlation factor , K, i s d e f i n e d by a friction

factor Reynold^:.: No. e q u a t i o n ,

& = _L 1 (66)

where R i s t h e r e s i s t a n c e of the f l u i d to motion of the ball.

E q u a t i o n . (Gt>) o n l y h o l d s f r o m l o w v a l u e s o f Re up t o t h e

critical value Re , c i . e . , i n the v i s c o u s regime of f l o w .

A b o v e t h e c r i t i c a l R e y n o l d ^ ; No., the f r i c t i o n f a c t o r i s not

linear i n R e . H u b b a r d and Brown, f r o m a n a n a l y s i s of the

l i t e r a t u r e d a t a and f r o m s u p p l e m e n t a r y e x p e r i m e n t s o f their

own, have o b t a i n e d c o r r e l a t i o n s f o r R e c and K as a function

of t h e d i a m e t e r r a t i o d/D. These c o r r e l a t i o n s a r e g i v e n i n

figures 5 and 6. The f o r m e r i s v e r y u s e f u l i n d e t e r m i n i n g

the minimum t i m e s o f r o l l w h i c h must be u s e d i n o r d e r t o

r e m a i n below t h e c r i t i c a l Reynold^;.; No. , the l a t t e r f o r

o b t a i n i n g a n e s t i m a t e o f t h e c a l i b r a t i o n c o n s t a n t , C, from

equation (&;5),' and i n c a l c u l a t i n g t h e m a g n i t u d e o f certain

errors.
 45

40

35

O
UJ
cr 30

cc
o

0 I 1 1 1 1
0.84 0.88 0.92 0.96 1.00

DIAMETER RATIO — <*/D

F i g u r e 5 . - C r i t i c a l R e y n o l d s - : No. for Rolling-Ball Viscometer
 ?8

Unfortunately, t h e s e c o r r e l a t i o n s a r e n o t known

a c c u r a t e l y enough t o c a l c u l a t e t h e c a l i b r a t i o n c o n s t a n t t o

c l o s e r t h a n a b o u t i 10%. Hence, t h e i n s t r u m e n t ' m u s t be

calibrated using fluids o f known v i s c o s i t y and d e n s i t y , and

from the times of r o l l obtaining the best straight line

c o r r e l a t i o n between and (^-?)t#

Equation (3) i s t h e same a s t h e e q u a t i o n p r o p o s e d

o r i g i n a l l y by Flowers (19) t o c o r r e l a t e t h e v i s c o s i t y w i t h

the time of r o l l , and i t h a s b e e n u s e d consistently ever

s i n c e t o c o r r e l a t e t h e m e a s u r e m e n t s o f r o l l i n g - b a l l and

f a l l i n g - b a l l viscometers. Flowers d i d n o t d e r i v e an

expression f o r the absolute value of C s i m i l a r to equation

(65). He b a s e d h i s a n a l y s i s o n t h e S t o k e s e q u a t i o n f o r f r e e

fall of a sphere,

-t = (67)
4 3 (<?*-?>
Z<

and assumed f o r t h e r o l l i n g - b a l l viscometer, an equation

c o u l d be w r i t t e n i n t h e f o r m ,

-t = W ^4 (68)

w h e r e W i s a c o r r e c t i o n f a c t o r f o r t h e " w a l l - e f f e c t , and

hence, '

C = - d j _ (69)
18W

This type of approach, i n which the Stokes law e q u a t i o n i s

modified t o accomodate w a l l - e f f e c t s , has s i n c e been used by

 IS
Francis (131) and Bacon (132) but no c o n s i s t a n t c o r r e l a t i o n

has been o b t a i n e d , except f o r v a l u e s o f d/D w h i c h a r e much

smaller than u n i t y . The approach o f Hubbard and Brown (128)

and o f Lewis (129) Is'- more fundamental and seems t o be much

c l o s e r t o the t r u e p i c t u r e . However, t h e r e s t i l l seems t o be

some doubt about the v a l i d i t y of e q u a t i o n (&,5) w h i c h g i v e s t h e

a b s o l u t e v a l u e of t h e c o n s t a n t ,C, I n p a r t i c u l a r , i t seems

t h a t the s i n e f u n c t i o n does not a p p l y except a t r e a s o n a b l y

s m a l l angles from t h e h o r i z o n t a l and t h i s has been s u b s t a n t i -

ated by the work of B l o c k (133) and Young ( 1 3 4 ) . The l a t t e r

a t t r i b u t e s the d e v i a t i o n f r o m the s i n e f u n c t i o n a t h i g h e r

a n g l e s o f s l o p e t o a c o m b i n a t i o n o f r o l l i n g and s l i d i n g .

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

between G and the d i a m e t e r r a t i o , ^/E>, i s much more import-

ant, and i t seems t h a t the Hubbard and Brown e q u a t i o n gives

t h i s c l o s e l y enough t o enable one t o c a l c u l a t e the c o r r e c t -

i o n s t o be a p p l i e d f o r temperature and p r e s s u r e v a r i a t i o n s .

E r r o r s and Corrections

In general, t h e r e a r e many c o r r e c t i o n s t o be a p p l i e d

t o the time of r o l l , t , and t h e c a l i b r a t i o n c o n s t a n t ,C,

before the v i s c o s i t y can be e v a l u a t e d a c c u r a t e l y from equation

(64). Under many c o n d i t i o n s , however, the c o r r e c t i o n s a r e

zero or s m a l l so t h a t they do n o t a p p l y .
 80

1) Timing c o r r e c t i o n s . There may be a time l a g i n

the measuring system, i n o t h e r words, the t r u e time o f r o l l

may d i f f e r from the observed time by a c o n s t a n t f a c t o r due

to f i n i t e time l a g s i n the r e l a y s o p e r a t i n g t h e t i m i n g

circuit. T h i s may show up i n the c a l i b r a t i o n o f the i n s t r u -

ment by g i v i n g a f i n i t e i n t e r c e p t on the curve o f t V . ^ ^— s

v

T h i s time l a g c a n be determined from the c a l i b r a t i o n and

a p p l i e d t o subsequent measurements, s i n c e i t i s independent

of the v i s c o s i t y b e i n g d e t e r m i n e d ,

2) A c c e l e r a t i o n e f f e c t . The b a l l s t a r t s i t s r o l l

f r o m r e s t , and t h i s means t h a t i t t a k e s a f i n i t e time t o

a t t a i n i t s t e r m i n a l v e l o c i t y ; t h i s s h o u l d a l s o be a p p l i e d as

a c o r r e c t i o n t o the observed t i m e . An e s t i m a t e o f the e f f e c t

can be o b t a i n e d by s o l v i n g the d i f f e r e n t i a l e q u a t i o n r e l a t i n g

to the m o t i o n o f the b a l l f r o m r e s t up t o t h e time i t a t t a i n s

its terminal v e l o c i t y ,

— k g | = P _ p V (70)

where P=S'g S i n 6 IL^l (ft-?) (71)

and P = 17 (-^—) ( 7 2 )

The g e n e r a l s o l u t i o n o f e q u a t i o n (70) i s r e a d i l y o b t a i n e d a s ,

V = Ae ^ + JL (73)

and from t h e i n i t i a l c o n d i t i o n , t = 0, V = 0,one o b t a i n s

 81

(74)

or, t h e time t a k e n t o a t t a i n a v e l o c i t y V i s g i v e n by,

t = f JU(l- v£) (75)

This equation g i v e s the time t o a t t a i n the t e r m i n a l velocity,

w h i c h i s P/^ , as i n f i n i t e . However, a v e r y c l o s e e s t i m a t e

of the c o r r e c t i o n necessary f o r the a c c e l e r a t i o n e f f e c t i s

o b t a i n e d b y d e t e r m i n i n g t h e t i m e t o r e a c h , s a y , 99% of the

terminal velocity. The a p p r o p r i a t e v a l u e s o f F and p can

be c a l c u l a t e d f r o m t h e d i m e n s i o n s of the apparatus and the

H u b b a r d and B r o w n c o r r e l a t i o n f o r K.

3) E f f e c t of pressure. I f the l i q u i d i s under h i g h

p r e s s u r e , t h e t u b e may i n c r e a s e i n diameter, thus changing

t h e v a l u e o f ^/B from that at atmospheric pressure,and the

e f f e c t i v e v a l u e of the c a l i b r a t i o n c o n s t a n t . Some i n s t r u m e n t s ,

like t h e one u s e d i n t h i s w o r k , a r e d e s i g n e d s o t h a t t h e fluid

being tested i s u n d e r t h e same p r e s s u r e i n s i d e and outside

the r o l l - t u b e . I n s u c h a c a s e , no p r e s s u r e c o r r e c t i o n i s

necessary. The m a g n i t u d e o f t h e c o r r e c t i o n c a n be determined

by c a l c u l a t i n g t h e i n c r e a s e i n d i a m e t e r and a p p l y i n g the

formula

Sc. ofd/ \
e = J(V y D ">6

The f o r m o f -~r- w i l l be d e v e l o p e d i n the following-section

4C /D) a

on t h e e f f e c t o f t e m p e r a t u r e .
 82

4) E f f e c t of Temperature. T h i s i s somewhat more

complicated t h a n the e f f e c t of p r e s s u r e , because temperature

may have an i m p o r t a n t e f f e c t on tube d i a m e t e r , tube l e n g t h ,

b a l l d i a m e t e r and b a l l d e n s i t y . Rewriting equation (65)

one obtains,

or o = g <3S-e < K i ) ^ - r <vs)

Considering the s m a l l change g> C f o r s m a l l changes i n * V d ,

d an L , by t a k i n g l o g s and d i f f e r e n t i a t i n g , one obtains,

| = ii _SU (79)

° 4> di t_
The f i r s t termvcan be put e x p l i c i t y i n terms of a change of
d
/D, i n the form,

Prom a knowledge of the c o e f f i c i e n t of e x p a n s i o n of the ball

and the t u b e the v a l u e of £ (^/P), £d

? and £L can be obtained

and s u b s t i t u t e d i n t o equation (79) and (80) i n o r d e r to

o b t a i n the r e q u i r e d c o r r e c t i o n . I n p a r t i c u l a r , to evaluate

• &$> » o n e
must w r i t e ,

4> = k(4 0 + (81)

(82)
 83
The v a l u e s o f K a n d •—— c a n be o b t a i n e d f r o m t h e
d(d/o)
correlation o f H u b b a r d and B r o w n .

I f t h e t u b e and t h e b a l l a r e b o t h made f r o m t h e same

m a t e r i a l so t h a t t h e c o e f f i c i e n t of thermal expansion i sthe

same f o r b o t h , (^/D) i s z e r o and e q u a t i o n C79) r e d u c e s t o ,

£ = 2 ^ _ ? t (83)

P o r a change i n t e m p e r a t u r e , and ^£ a r e e q u a l and a r e

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

coefficient of linear expansion, , i n the temperature range,

and the temperature d i f f e r e n c e , A t ?

% = oCXt (84)
Finally, a c o r r e c t i o n s h o u l d be a p p l i e d to the

density of the b a l l . I t c a n be e a s i l y shown t h a t this

correction i s given c l o s e l y by,

ijr = - 3°tAt ( 8 5 )

which i s three times the c o r r e c t i o n t o the c a l i b r a t i o n

constant i n the s p e c i a l c a s e when S(^/D) i s z e r o . In this

case the t o t a l c o r r e c t i o n t o t h e v i s c o s i t y c a l c u l a t e d from

the c a l i b r a t i o n c o n s t a n t and b a l l d e n s i t y a t t h e c a l i b r a t i o n

temperature i s g i v e n approximately by A t , w h e r e o< i s t h e

coefficient of thermal expansion of the b a l l (and t h e tube)

and A t i s the d i f f e r e n c e i n temperature.

 4
I — E X — H H—tXt" K

B
t>

1/8
1
1/8" 1/4"
-CXr - X H
la lb

0
 84
iv) Calibration. The p r e s s u r e v i s c o m e t e r was

c a l i b r a t e d at atmospheric pressure u s i n g three petroleum

oils ( O i l s D, E and P) a t t e m p e r a t u r e s o f 30°, 4 5 ° and 60°C.

A c a l c u l a t i o n based on e q u a t i o n s ( 2 3 ) a n d ( 3 4 ) showed t h a t t h e

c o r r e c t i o n f o r temperature i n t h i s range was v e r y s m a l l (see

below) and i t was t h e r e f o r e u n n e c e s s a r y t o c a l i b r a t e a t a

s i n g l e temperature. C a l i b r a t i o n s were made a t two s l o p e s ,

a p p r o x i m a t e l y 11° and 23° f r o m t h e h o r i z o n t a l , the three o i l s

b e i n g used a t 11° and two ( O i l s D and E) a t 23°, so t h a t n i n e

and s i x p o i n t s , r e s p e c t i v e l y , were o b t a i n e d f o r t h e two s l o p e s .

The range o f v i s c o s i t i e s covered was from about 1 . 5 t o 10

centipoises. The p e t r o l e u m o i l s were b l e n d e d from SAE 10 and

kerosene and were f i l t e r e d i n t o c l e a n glass stoppered f l a s k s .

The o i l s were i n t r o d u c e d i n t o t h e v i s c o m e t e r and t h e

v i s c o m e t e r brought up t o the t e s t temperature by t h e proceedure

outlined previously. The t i m e s o f r o l l a t any p a r t i c u l a r

temperature were determined f o r the two s l o p e s b e f o r e moving

on t o a new t e m p e r a t u r e . U s u a l l y , d e t e r m i n a t i o n s were made a t

30°C f i r s t , l a t e r 4 5 ° and 60°C, and i n some cases t h e temperture

was a g a i n lowered t o 30°C and a few runs made t o check t h e

c o n s i s t a n c y of o p e r a t i o n . I t was found t h a t good agreement

was o b t a i n e d between t h e two s e t s a t 30°C and t h i s check was

omitted i n l a t e r determinations.

The k i n e m a t i c v i s c o s i t y and d e n s i t y o f t h e o i l s were

determined by t h e methods o u t l i n e d above,and f r o m t h e s e t h e

a b s o l u t e v i s c o s i t y was c a l c u l a t e d . The v i s c o s i t y , d e n s i t y and

 ,85

time of r o l l f o r each o i l a t each temperature were correlated

i n o r d e r t o o b t a i n t h e c a l i b r a t i o n c o n s t a n t f o r t h e two

slopes.

A t t h e end o f t h e d e t e r m i n a t i o n s o n e a c h o i l , t h e

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

bath^and the o u t s i d e near t h e c l o s u r e was c l e a n e d and d r i e d .

The c l o s u r e was t h e n opened and a s a m p l e o f t h e o i l

p i p e t t e d o u t f o r a c h e c k d e t e r m i n a t i o n on t h e k i n e m a t i c

viscosity. I n t h i s way, a n y c o n t a m i n a t i o n o f t h e c a l i b r a t i n g

l i q u i d b y b a t h o i l o r b y o t h e r means c o u l d b e r e a d i l y checked

and attended t o .

(c) D e n s i t y Determinations

D e n s i t y d e t e r m i n a t i o n s were c a r r i e d out i nd u p l i c a t e

i n two s p e c i f i c g r a v i t y b o t t l e s o f a p p r o x i m a t e l y 25 m l .

volume. The p y k n o m e t e r s w e r e s t a n d a r d V i c t o r M e y e r t y p e and

were p r o v i d e d w i t h g r o u n d - g l a s s caps t o p r e v e n t evaporation

from the l i q u i d surface. The p r o c e e d u r e u s e d f o r f i l l i n g and

weighing t h e p y k n o m e t e r s was e x a c t l y a s o u t l i n e d b y B a u e r

(135). The p y k n o m e t e r s w e r e f i r s t washed two o r t h r e e times

w i t h acetone, dried i n a n o v e n a t 250°P f o r a f e w h o u r s ,

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

chamois c l o t h , were p l a c e d I n t h e b a l a n c e case.

A f t e r about one-half hour, t h e b o t t l e s were weighed

to t h e n e a r e s t ^rz m i l l i g r a m o n a M e t t l e r G r a m a t l c Analytical
 86
B a l a n c e , the w e i g h i n g s b e i n g r e p e a t e d u n t i l c o n s t a n t r e a d i n g

was o b t a i n e d .

The pyknometers were c a l i b r a t e d a t 30°, 4-5° a n

^
60°C w i t h f r e s h l y d i s t i l l e d water w h i c h had a measured
r e s i s t i v i t y o f 800,000 ohm cm. and w h i c h was b o i l e d just
p r i o r t o use t o remove d i s s o l v e d a i r . Thermostatting at
30°C was c a r r i e d out i n the same c o n s t a n t temperature b a t h
used f o r the v i s c o s i t y d e t e r m i n a t i o n s i n the c a p i l l a r y v i s c o -
meters, and about 20 mins. were a l l o w e d t o a t t a i n temperature
equilibrium. The pyknometers were n e x t removed f r o m t h e b a t h ,
wiped f r e e o f any c l i n g i n g water w i t h f i l t e r paper and
f i n a l l y w i t h a m o i s t chamois c l o t h , and p l a c e d i n the b a l a n c e
case. Weighings o f t h e f u l l pyknometerswere done as above.
T h i s proceedure was r e p e a t e d f o r 45°C and 60°G, and. t h e n t h e
pyknometers were washed, d r i e d and weighed a g a i n t o check t h e
empty w e i g h t .

The volumes o f t h e pyknometers were c a l c u l a t e d a t

each temperature by d i v i d i n g t h e w e i g h t o f water by t h e
d e n s i t y o f water a t t h e a p p r o p r i a t e temperature ( 1 3 6 ) . In
c a l c u l a t i n g t h e weight o f w a t e r , a c o r r e c t i o n f o r the w e i g h t
of a i r i n the empty b o t t l e was a p p l i e d .

The same proceedure f o r o b t a i n i n g the t r u e w e i g h t

of l i q u i d i n the pyknometer was used f o r the a b s o l u t e
measurements. The d e n s i t y was c a l c u l a t e d b y d i v i d i n g t h e
w e i g h t o f l i q u i d by the volume o f the pyknometer a t t h e
 87

p a r t i c u l a r temperature.

D u p l i c a t e d e n s i t y d e t e r m i n a t i o n s w e r e made a t 30°,

45° a n d 60°G o n t h e t h r e e o i l s u s e d i n c a l i b r a t i n g t h e

p r e s s u r e v i s c o m e t e r and o n n - o c t a n o l a t 25°, 30°, 45° a n d

60°C. The d e n s i t i e s a r e r e p o r t e d a s , d ^ , gma/ml.

(d) P r e s s u r e E q u i p m e n t

The p r e s s u r e s y s t e m was d e s i g n e d a n d a s s e m b l e d f o r

a maximum w o r k i n g p r e s s u r e o f 10,000 p s i . An assembly

d r a w i n g o f t h e s y s t e m i s g i v e n i n f i g u r e 7. A l l the

c o m p o n e n t s e x c e p t t h e t r a n s f e r bomb, B, a r e s t a n d a r d c a t a l o g

i t e m s a n d were" o b t a i n e d f r o m t h e m a n u f a c t u r e r s .

The system c o n s i s t s e s s e n t i a l l y of the viscometer,A,

w h i c h has been d e s c r i b e d above, c o n t a i n i n g the l i q u i d t o be

m e a s u r e d , t h e t r a n s f e r bomb,B, i n w h i c h a m e r c u r y l e v e l i s

m a i n t a i n e d , and t h e p r e s s u r e g e n e r a t o r , C , w h i c h i s k e p t full

o f m e r c u r y and i s u s e d f o r p r e s s u r i z i n g t h e s y s t e m b y

positive displacement. A p r e s s u r e gauge,D, i s c o n n e c t e d b y a

t e e a t K t o measure t h e p r e s s u r e i n t h e s y s t e m . A glass

mercury r e s e r v o i r , E , i s connected t o the p r e s s u r e system

through the Kovar g l a s s - m e t a l joint, H, a n d i s u s e d f o r d i s -

p l a c e m e n t when t h e s y s t e m i s n o t u n d e r p r e s s u r e . The m e r c u r y

reservoir, p r e s s u r e g e n e r a t o r and t r a n s f e r bomb a r e j o i n e d

a t t h e d o u b l e - s t e m two-way v a l v e , I . A n o t h e r v a l v e , 2, i s

provided i n the l i n e t o t h e t r a n s f e r bomb, s o t h a t a n y two

 88

or a l l o f these components c a n be i n t e r c o n n e c t e d . The

t r a n s f e r bomb i s connected near i t s c l o s u r e t o t h e g l a s s

t r a n s f e r apparatus, f i g u r e 9. (see below) v i a another Kovar

g l a s s - m e t a l j o i n t , J , V a l v e s , 3 and 4, a r e p r o v i d e d between

the t r a n s f e r bomb and t h e g l a s s t r a n s f e r a p p a r a t u s and t h e

p r e s s u r e gauge, r e s p e c t i v e l y . A b l e e d l i n e t o atmosphere

i s p r o v i d e d a t t h e p r e s s u r e gauge and c a n be c l o s e d by v a l v e

5. The main components and v a l v e s a r e i n t e r c o n n e c t e d by

s t a n d a r d p r e s s u r e t u b i n g and f i t t i n g s , as shown.

The v i s c o m e t e r , A, i s d e s c r i b e d i n d e t a i l above.

P r e c i s e i n f o r m a t i o n was n o t a v a i l a b l e on the p r e s s u r e and

temperature t o w h i c h t h i s i n s t r u m e n t had been t e s t e d .

I m p e r i a l O i l L t d . , have i n d i c a t e d (137) t h a t i t has been

used a t p r e s s u r e s up t o 7,500 p s i , and t h a t t h i s m a k e o f . *

viscometer i s u s u a l l y designed f o r a maximum w o r k i n g pressure

of 10,000 p s i , b u t c o u l d n o t p r o v i d e i n f o r m a t i o n on t h e e x a c t

t e m p e r a t u r e and p r e s s u r e t o w h i c h i t was t e s t e d . A calcula-

t i o n based on t h e minimum d i a m e t e r r a t i o i s g i v e n i n Appendix

VI,oh t h e recommendations of t h e A.S.M.S. (138) f o r t h e

design of pressure v e s s e l s . A t 10,000 p s i . , t h e r e i s a

s a f e t y f a c t o r o f about 5 o r 6 on t h e u l t i m a t e s t r e n g t h w h i c h

i s w i t h i n the recommendations o f the A.S.M.E. Catalog data

on p r e s s u r e bombs (139) shows t h a t a t e m p e r a t u r e i n c r e a s e

f r o m 70° t o 500°P corresponds t o approximately 10$ d e c r e a s e

i n maximum w o r k i n g p r e s s u r e , w h i c h s t i l l l e a v e s an a c c e p t a -

ble f a c t o r of safety. The v i s c o m e t e r was t e s t e d t o

 89

p r e s s u r e up t o 11,000 p s i a t room temperature, and was found

to be s a f e and p r e s s u r e t i g h t under these c o n d i t i o n s .

The t r a n s f e r bomb ,B, shown i n f i g u r e 8 was d e s i g n e d

and machined i n these l a b o r a t o r i e s from 3" b a r s t o c k 316

stainless steel. The o v e r a l l dimensions a r e 10" h i g h , 3"O.D.

and 1^/4" I.D., g i v i n g a d i a m e t e r r a t i o o f 1.72 and a w o r k i n g

volume o f 300 c c s . The p r e s s u r e d e s i g n on t h i s bomb i s g i v e n

i n Appendix V I a l o n g w i t h the v i s c o m e t e r . The e n c l o s u r e i s a

s e l f - s e a l i n g type d e s c r i b e d by Comings (140),and i s provided

w i t h a t a p e r e d t e f l o n gasket , Q, Initially pressure i s

a p p l i e d t o t h e gasket b y t i g h t e n i n g t h e screws ,P, a g a i n s t

the s t e e l washer ,0, and thus r a i s i n g t h e i n n e r core , L . A

12 gauge nichrome w i r e ,T, e n t e r s t h e bomb t h r o u g h the

e l e c t r i c a l c o n n e c t o r and i s i n s u l a t e d b y c e r a m i c s . Three

d e s i g n s o f e l e c t r i c a l c o n n e c t o r were t r i e d , b u t a l l f a i l e d

under p r e s s u r e o f about 10,000 p s i . The type shown was a

commercial d e s i g n (139) w h i c h c o n s i s t s o f a double-ended

soapstone cone ,S, t o w h i c h p r e s s u r e i s a p p l i e d b y t i g h t e n -

ing t h e n u t ,R, on t o t h e s t e e l f o l l o w e r ,TJ. I t i s thought

t h a t t h i s f a i l e d because t h e cone f i t t e d t o o l o o s e l y i n i t s

r e c e p t a c l e , and t h e r e f o r e i n s u f f i c i e n t p r e s s u r e was a p p l i e d

to the wire by t i g h t e n i n g the nut. A l e n g t h ,V, o f 0.003"

s t a i n l e s s s t e e l w i r e connects the nichrome w i r e , T, and a

1"
s m a l l s t a i n l e s s s t e e l p l a t e ,X, w h i c h i s s u p p o r t e d on two.g-

s t a i n l e s s s t e l l r o d s , W, t h e w i r e b e i n g kept t i g h t b y t h e

a c t i o n o f two s m a l l h e l i c a l s p r i n g s ,Y, made from 0.02"

 qo
nichrome w i r e .

I t i s n e c e s s a r y t o know t h e l e v e l o f mercury i n t h e

t r a n s f e r bomb t o g e t an I n d i c a t i o n o f t h e r e l a t i v e amount o f

l i q u i d i n the viscometer. T h i s i s done by m e a s u r i n g t h e

r e s i s t a n c e o f t h e exposed p o r t i o n o f r e s i s t a n c e w i r e , i . e . ,

the r e s i s t a n c e between t h e nichrome w i r e ,T, and t h e body o f

the bomb. T h i s bomb c a n be r e a d i l y adapted for liquid

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

i s used t o measure t h e r e s i s t a n c e o f exposed w i r e .

The P r e s s u r e G e n e r a t o r ,C, i s a High Pressure

Instrument Co., Model 50-3, d e s i g n e d f o r a w o r k i n g pressure

o f 15,000 p s i . P o s i t i v e displacement o f 10 c c s . i s p r o v i d e d ,

w i t h a s t o k e o f 3".

The P r e s s u r e Gauge i s a 16" d i a l , Heiss-Bourdon

t y p e r e a d i n g f r o m 0 t o 15,000 p s i i n 20 p s i i n t e r v a l s . A

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

the i n s t r u m e n t i s guaranteed t o read c o r r e c t l y t o the nearest

15 p s i . Other s p e c i a l f e a t u r e s o f t h e gauge i n c l u d e t h e

p r o v i s i o n o f an e x t e r n a l b l e e d e r , and a u t o m a t i c temperature

compensation f o r temperatures up t o 100°P.

A l l f i t t i n g s and p r e s s u r e t u b i n g a r e s t a n d a r d items

r a t e d f o r p r e s s u r e s up t o 15,000 p s i i n t h e m a n u f a c t u r e r s '
1"
catalogs (139,141). Most o f t h e l i n e s were ^ O.D. b y 0.043

I.D. t u b i n g b u t V 4 " O.D. b y / 3 2 " I.D. was used i n c e r t a i n

5
 91

l o c a t i o n s , i n d i c a t e d i n f i g u r e 7. V4-" t o - t u b i n g adaptors

were machined i n these l a b o r a t o r i e s a c c o r d i n g t o s t a n d a r d

design (141).

(e) T r a n s f e r Apparatus

The t r a n s f e r apparatus i s used t o i n t r o d u c e t h e

sample b e i n g t e s t e d , f r o m t h e f l a s k i n w h i c h i t i s c o l l e c t e d

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

viscometer. The d e s i g n of t h e g l a s s w a r e i s based on t h e work

of Kay and Donham ( 1 4 2 ) . A s k e t c h o f t h e equipment i s shown

i n f i g u r e 9« The system was assembled and vacuum t e s t e d and

found t o h o l d a vacuum o f 0.01 m.m. o f mercury f o r a p e r i o d

of about 24 h o u r s , w i t h o u t a p p r e c i a b l e change. Vacuum was

p r o v i d e d by a Cenco Megavac Pump w i t h 1/2 H.P. motor and was

measured by a s t a n d a r d McLeod gauge.

The system c o n s i s t s o f a 500 ml. f l a s k , a, i n w h i c h

the Sample i s s t o r e d a f t e r p u r i f i c a t i o n , and two c y l i n d r i c a l

v e s s e l s b and c, o f a p p r o x i m a t e l y 300 m l . c a p i c i t y . Standard

ground-glass j o i n t s and h i g h vacuum s t o p - c o c k s are provided

where i n d i c a t e d . The s t o p - c o c k 10 and ground j o i n t d have

mercury s e a l s w h i c h enable a h i g h vacuum t o be a t t a i n e d

without greasing. Stop-cocks 6 and 7 and t h e ground j o i n t o f

the c o l d - t r a p ,e, were greased w i t h h i g h vacuum rubber-base

grease and s t o p - c o c k s 8 and 9 w i t h h i g h vacuum s i l i c o n e

grease. Other j o i n t s and s t o p - c o c k s were n o t g r e a s e d .

 TO VACUUM
TO TRANSFER
BOMB
8
4 4
10 H± tin 9
1'

12 TO
MC LEOD e
GUAGE

o
l-b
•o
0

Figure 9. T r a n s f e r Apparatus
0
 92

(f) Proceedure f o r I n t r o d u c t i o n o f S a m p l e and Pressurizing-;:-

1. F i l l i n g w i t h M e r c u r y . The mercury r e s e r v o i r ,E,

is f i l l e d , and the two-way s t o p - c o c k ,6, closed. Valves lb

and 4 a r e t h e n c l o s e d and a l l other pressure valves left

open. Vacuum i s a p p l i e d t h r o u g h the glass equipment,

e v a c u a t i n g t h e t r a n s f e r bomb and the pressure generator,

a l o n g w i t h a l l the c o n n e c t i n g lines. A f t e r a b o u t an hour,

v a l v e l b i s opened s l i g h t l y so t h a t m e r c u r y e n t e r s the

pressure e q u i p m e n t and rises i n t h e bomb ,B, up to about

half-way. Next the r e s e r v o i r ,E, i s evacuated, drawing

mercury back. This proceedure i s repeated, i n much t h e same

way as e v a c u a t i n g a McLeod g a u g e , u n t i l vacuum e x i s t s i n the

bomb ,B, and t h e r e s e r v o i r , E, The vacuum i s r e l e a s e d i n

t h e same way as a McLeod gauge b y s u c c e s s i v e l y c r a c k i n g v a l v e

3 and stop-cock 6 to atmosphere.

2. I n t r o d u c t i o n o f S a m p l e t o T r a n s f e r Bomb. The

s a m p l e i s i n t r o d u c e d b y vacuum d i s t i l l a t i o n . First the

e n t i r e system i s evacuated, care being taken to m a i n t a i n the

c o r r e c t l e v e l s o f m e r c u r y i n B and E d u r i n g the o p e r a t i o n .

S t o p - r c o c k 7, w h i c h i s a t t a c h e d t o low p r e s s u r e n i t r o g e n , i s

t h e n opened s l o w l y , l e t t i n g n i t r o g e n i n t o t h e s y s t e m and care

is a g a i n taken to ensure m a i n t a i n i n g the c o r r e c t mercury

l e v e l s by s i m u l t a n e o u s l y l e t t i n g a i r i n t o the mercury r e s e r v o i r

E.

See f i g u r e s 7 and 9.
 93
When the e n t i r e system i s under an atmosphere of

n i t r o g e n , v e s s e l a c o n t a i n i n g the sample, a l s o under an

atmosphere of n i t r o g e n , i s a t t a c h e d t o the system and about

300 c c s . of sample a r e n i t r o g e n d i s p l a c e d i n t o v e s s e l b by

opening s t o p - c o c k 11 and applying n i t r o g e n pressure at 12.

V a l v e 11 i s t h e n c l o s e d , the sample f o r z e n i n b and the

e n t i r e system evacuated as b e f o r e . Next v a l v e 3 i s c l o s e d

and the sample i s vacuum d i s t i l l e d i n t o the v e s s e l c, the

f i r s t 50 c c s . b e i n g c o l l e c t e d i n the c o l d - t r a p ,e, and the

f i n a l 50 c c s . r e m a i n i n g i n b. When a p p r o x i m a t e l y 200 ccs.

have been c o l l e d t e d i n c , s t o p - c o c k 10 i s c l o s e d , v a l v e 3

opened and the e n t i r e system a g a i n e v a c u a t e d , w h i l e the pure

sample i s kept f r o z e n i n v e s s e l c. The l i n e s are then

purged by thawing s l i g h t l y and a l l o w i n g a l i t t l e vapor t o

e n t e r the p r e s s u r e system. T h i s may be r e p e a t e d a few times,

as i t s e r v e s t o remove f i n a l t r a c e s of a i r i n the pressure

system. F i n a l l y , the whole 200 c c s . of sample are vacuum

d i s t i l l e d f r o m c i n t o the t r a n s f e r bomb ,B, and v a l v e 3 i s

closed.

3. I n t r o d u c t i o n of Sample t o V i s c o m e t e r . The
sample i s a l l o w e d t o thaw and attain vapor-liquid equilibrium
i n the t r a n s f e r bomb, the v i s c o m e t e r and the c o n n e c t i n g lines.
Air i s then allowed t o e n t e r v e s s e l , E , p u s h i n g mercury i n t o
the t r a n s f e r bomb,and when a t m o s p h e r i c p r e s s u r e i s attained,
valve l a i s closed.
 Q4
4.Pressurizing. The system i s p r e s s u r i z e d by

p r o v i d i n g p o s i t i v e displacement at the p r e s s u r e generator

a f t e r t h e s a m p l e has r e a c h e d temperature e q u i l i b r i u m i n the

viscometer.

It i s recommended t h a t m e a s u r e m e n t s be made a t

constant temperature over the whole p r e s s u r e range from 0

t o 1 0 , 0 0 0 p s i b e f o r e m o v i n g o n t o a new temperature.
 95

NORMAL OCTANOL ~ P U R I F I C A T I O N AND CHARACTERIZATION

A Fisher Certified Reagent grade o f n - O c t a n o l was

purified f o r use i n t h i s r e s e a r c h .

Lot p r o p e r t i e s were g i v e n a s ,

B o i l i n g range 1 9 4 . 3 ° - 195.3°C

Non-volatile matter 0.008 %

Free acid 0.005 %

D e t e r m i n a t i o n s w e r e made o n t h e d e n s i t y and v i s c o s i t y a t

30°C and t h e tfefractive i n d e x a t 20°C f o r s a m p l e s taken from

the bottle, and t h e f o l l o w i n g r e s u l t s w e r e o b t a i n e d .

Density a t 30°C, d ^ ° , 0.8187

Viscosity a t 30°C 6.390 c . p .

R e f r a c t i v e I n d e x a t 20°C 1.4294^

The l i q u i d was p u r i f i e d b y a s i n g l e fractionation

in a Todd P r e c i s e F r a c t i o n a t i o n A s s e m b l y , w i t h a 25 m.m.

column packed w i t h 4 m.m. glass helices,giving approximately

60 t h e o r e t i c a l p l a t e s . Seven hundred and f i f t y m i s . were

charged to the s t i l l - p o t and d i s t i l l e d a t a r e f l u x r a t i o o f 50:

1, t h e f i r s t and l a s t 200 m i s . b e i n g r e j e c t e d . The m i d d l e c u t

of 3 5 0 m i s . was c o l l e c t e d a t an overhead temperature o f 194.4°C

(751 m.m.) which remained constant to w i t h i n ^Q°C throughtout

the c o l l e c t i o n of the middle c u t . The p u r i f i e d o c t a n o l was

collected and s t o r e d i n a w e l l stopped 500 m l . g r o u n d - g l a s s

flask.
 96

The corresponding properties obtained after

p u r i f i c a t i o n were,

D e n s i t y , 30°C, d ° 3
O.8I84
V i s c o s i t y a t 30°C 6.396 c p .

R e f r a c t i v e Index, 20°C 1.4294 2

The data from the l i t e r a t u r e of the physical

p r o p e r t i e s o f n - o c t a n o l shows l a r g e i n c o n s i s t e n c i e s . Table 2

gives the r e s u l t s of the l i t e r a t u r e search i n chronological

order from 1884 o n , i n c l u d i n g t h e r e s u l t s o f t h i s w o r k . The

only points of reasonable agreement i n t h e d a t a a r e t h e

d e n s i t y a t 25°C, and t h e r e f r a c t i v e i n d e x a t 20°C. Many

authors r e p o r t values of the former c l o s e t o 0.8221 a n d o f

t h e l a t t e r b e t w e e n 1.4291 and 1.4296 and t h e v a l u e s obtained

i n t h i s work c o r r e s p o n d c l o s e l y with these. The d e n s i t y d a t a

o f Smythe and S t o o p s (143) f r o m 0 t o 60°C c o m p a r e v e r y closely

w i t h t h e v a l u e s o b t a i n e d i n t h i s work, and these d a t a were

interpolated and e x t r a p o l a t e d u p t o 90°C a n d t h e v a l u e s u s e d

to c a l c u l a t e the absolute v i s c o s i t y from the kinematic visco-

s i t y obtained i nthe c a p i l l a r y viscometers (see b e l o w ) . Errors

g r e a t e r t h a n 0.05$ w e r e c e r t a i n l y n o t i n t r o d u c e d b y t h i s - .

proceedure.

There i s g r e a t e r disagreement i nthe data f o r the

v i s c o s i t y a t various temperatures. In particular, the reported

v a l u e s f o r 20°C d i f f e r b y a s much a s 8$. I n some c a s e s t h e

reported densities d i f f e r g r e a t l y from those mentioned above,

and t h e r e f o r e t h e p u r i t y o f the m a t e r i a l i s i n doubt, and i n

 97

o t h e r c a s e s no d e n s i t y m e a s u r e m e n t s n o r a n y c r i t e r i a of

p u r i t y a r e r e p o r t e d and i t i s t h e r e f o r e i m p o s s i b l e t o a s s e s s

the degree of p u r i t y . Close agreement on v i s c o s i t y v a l u e s

have been o b t a i n e d i n t h i s w o r k w i t h t h e d a t a o f B i n g h a m and

Darall (144) and Mumford and P h i l l i p s (145).

 TABLE 2 97a

PHYSICAL PROPERTIES OP N-OCTANOL PROM THE LITERATURE

t Visco-
Author Date b.p.°C. Temp. n d slty
4 cp.
Perkin (146) I884 195-6 15 0.82935,
25 0.82249 ]

Zander (147) I884 — 0.8359

Garten-
meister (148) 1890 20 0.8264 8.925
Dunstan 25 7.22
et a l (149) 1914 50 3.22
90 1.21

Lowry (150) 1914 — 20 0.8270

Behal (151) 1919 194-6 20 0.8342
20.5 1.43035
Verkade
34.6 0.8146
and Coops (152) 1927
0 0.8391
Smythe 10 0.8322
and S t o o p s ( 1 4 3 ) 1929 20 0.8253
30 0.8186
40 0.8115
50 0.8042
60 0.7970
Bingham 1930 0 20.82'
and D a r a l l ( 1 4 4 ) 10 13.45
20 9.066
30,. 6.357
40 4.589
60 2.600
80 1.608
100 1.069
Deffet (153) 1931 0 0.84216
15 0.83202 IO.64
30 0.82192 6.125
Ellis 0 0.83848
and R e i d (154) 1932 25 1.4274 0.82137
Butler 1933 194.5 20 1.42937
et a l (155) 25 0.82238
N e v j i and
Jatkar (156) 1934 30 1.4256 0.8256
 97b
T a b l e 2. continued

P h y s i c a l P r o p e r t i e s of n-octanol f r o m the L i t e r a t u r e .

Visco-
Author Date b.p.C Temp. a sity
cp.

Butler ;:(.I57) 1935:; 194.5 20 1.42957

et a l 25 0.82322

Oliver (158) 1937 195.1-4 20 0.8249

(764.6m.m.)

Komarews ky(15 9) 1941 194-5 25 1.4296

and C o l e y

Dorough (160) 1941 195.0 0 0.8394

et a l . 25 1.4275 0.8224
Muller (161) 1942 — 20 8.420

Jones e t a l ( l 6 2 ) 1948 — 25 0.8221 7.33

D r e i s b a c h (163) 20 1.42913 0.82555
and M a r t i n 1949 195.28 25 1.42749 0.82209
Mumford & (145) 20 1.4287 0.8265 9.13
Phillips 1950 194.6 25 0.82332 7.55

Van 20 1.4292 0.8254

1952 —
Erichsen (I64)
15 11.05
T h i s work 20 1.4294 9.123
25 0.8219 7.626
30 0.8184 6.396
45 0.8079 3.965
50 3.420
60 0.7972 2.600
75 1.796
90 1.296

I . C a l c u l a t e d f r o m d.

2. C a l c u l a t e d from f l u i d i t y .
 §8
RESULTS

(a) V i s c o s i t i e s a t Atmospheric Pressure

i) Calibration of Capillary Viscometers. The results

o f t h e c a l i b r a t i o n o f the c a p i l l a r y v i s c o m e t e r s are given i n

table 3. The t e s t temperature g i v e n i s the temperature after

c o r r e c t i o n s were a p p l i e d according theA c a l i b r a t i o n of the

thermometer. The k i n e m a t i c v i s c o s i t y l i s t e d was calculated

f r o m t h e e f f l u x t i m e i n BY8 a n d t h e c a l i b r a t i o n c o n s t a n t a t

37.78°C (100.00°F). For the runs a t 20.00°C, t h e r e i s a

s l i g h t temperature c o r r e c t i o n t o be a p p l i e d t o t h e s e valueSj

b u t t h i s was n o t a p p l i e d . The v a l u e o f t h i s correction,

a c c o r d i n g t o Cannon's a p p r o x i m a t i o n m e n t i o n e d a b o v e , was a b o u t

+ 0.1$. N o r was t h e c o r r e c t i o n f o r t h e c a l i b r a t i o n o f t h e

stop-watch applied t o these values. The f i g u r e s a r e g i v e n a s

an i n d i c a t i o n of the range of kinematic v i s c o s i t y covered i n

the c a l i b r a t i o n s . The c a l i b r a t i o n c o n s t a n t was calculated

from the formula,

C = 0.01245 l i - (86)

where t . was t h e e f f l u x t i m e i n B78 and t„ t h a t i n t h e

i 2
uncalibrated viscometer. This equation gives the c a l i b r a t i o n

constant a t 3 7 . 7 8 ° C s i n c e t h e v a l u e o f t h e constant,-:- 0 . 0 1 2 4 5 ,

f o r B78 was d e t e r m i n e d a t t h i s temperature. Assuming t h a t t h e

temperature c o r r e c t i o n i s t h e same f o r a l l t h e v i s c o m e t e r s , and

 99
the t h e o r y above i n d i c a t e s t h a t t h i s i s c l o s e l y so, t h e n ,

t h e r e i s no e r r o r i n t r o d u c e d by c a l i b r a t i o n a t a d i f f e r e n t

temperature and c a l c u l a t i n g t h e c o n s t a n t a t 37.78°C.

At t h e bottom o f t a b l e 3 a r e g i v e n t h e mean v a l u e s

of the c a l i b r a t i o n c o n s t a n t f o r each v i s c o m e t e r calculated

from the v a l u e s o f t h e l a s t column.

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

are g i v e n i n t a b l e 4» The approximate calibration constant

i s c a l c u l a t e d from the f o r m u l a ,

C = 1.0038 ( 8 ? )

where, 1.0038 i s t h e v a l u e o f t h e k i n e m a t i c v i s c o s i t y o f water

i n CS. a t 20°C c a l c u l a t e d from an a b s o l u t e v i s c o s i t y o f 1.002 c p .

and a d e n s i t y of 0.9982 gms/cm.3. The t i m i n g c o r r e c t i o n was

determined from t h e c a l i b r a t i o n o f t h e stop-watch mentioned

above. The k i n e t i c energy c o r r e c t i o n was c a l c u l a t e d as ^/0t^ f

u s i n g t h e approximate c a l i b r a t i o n c o n s t a n t and t h e e f f l u x time.

The s u r f a c e t e n s i o n c o r r e c t i o n was a p p l i e d u s i n g e q u a t i o n (58)

with a value of 33 f o r ( /f) and a value of 72.8 f o r (V?)

'V
(water).

The values o f C c a l c u l a t e d on t h i s b a s i s a r e a p p r o x i -

m a t e l y 0.15 and 0.20 % lower t h a n t h o s e o b t a i n e d i n t h e

comparative calibrations.
 100

il) Viscosities of Oils. These a r e g i v e n i n t a b l e 5

t o g e t h e r w i t h t h e d e n s i t y and t h e c o r r e c t i o n s f o r c h a n g e o f

c a l i b r a t i o n constant w i t h temperature. The mean k i n e m a t i c

v i s c o s i t y was c a l c u l a t e d f r o m d u p l i c a t e r u n s made i n two

viscometers placed i n the constant temperature bath a t the

same t i m e , f r o m 3 bo 6 d e t e r m i n a t i o n s o f t h e e f f l u x time

b e i n g made f o r e a c h v i s c o m e t e r . Reproducibility of efflux

t i m e s was u s u a l l y w i t h i n 0.1$, b u t i n extreme cases amounted

to about 0.2$. The o n l y c o r r e c t i o n w h i c h was a p p l i e d t o t h e

k i n e m a t i c v i s c o s i t y was t h a t due t o t h e c h a n g e i n v i s c o m e t e r

constant w i t h temperature. The a b s o l u t e v i s c o s i t y was

c a l c u l a t e d from the corrected kinematic v i s c o s i t y and t h e

density.

HI) V i s c o s i t y o f Normal O c t a n o l a t V a r i o u s Temperatures.

The v i s c o s i t y of n-octanol a t temperatures f r o m 1 5 ° t o 90°C i s

g i v e n i n t a b l e 6. The same comments a s a b o v e o n t h e a p p l i c a t i o n

of corrections apply to this data. F o r some o f t h e t e m p e r a t u r e s ,

t h e d e n s i t y d a t a o f Smythe and S t o o p s (143) w e r e u s e d ; t h e

a c c u r a c y o f t h e s e d a t a have been d i s c u s s e d above. The d a t a a r e

also presented g r a p h i c a l l y i n f i g u r e 10, along w i t h the values

f r o m t h e l i t e r a t u r e w h i c h were g i v e n i n t a b l e 2 above.

The v i s c o s i t y was c o r r e l a t e d w i t h t e m p e r a t u r e on t h e

b a s i s o f some o f t h e e q u a t i o n s suggested i n the l i t e r a t u r e

w h i c h have been d i s c u s s e d u n d e r t h e s e c t i o n on Theory. In a l l

 8 10 11

ABSOLUTE VISCOSITY, CENTI POISE

 101
cases, t h e b e s t f i t f o r t h e d a t a was o b t a i n e d b y t h e m e t h o d

of l e a s t squares. F o r the two-constant equations, the

c a l c u l a t i o n s were p e r f o r m e d on a manual m a c h i n e . For the

three-and four-constant equations theregression c o e f f i c i e n t s

were o b t a i n e d o n t h e TJ.B.C. e l e c t r o n i c d i g i t a l computer,

Alwac I I I E. The u s e o f R o u t i n e S-3 (165) for correlation

and r e g r e s s i o n made i t u n n e c e s s a r y t o do a n y s p e c i a l

programing. I n a l l cases, sufficient significant figures

were c a r r i e d through the calculations so that e r r o r s greater

than 0.05$ were n o t i n t r o d u c e d .

The f o l l o w i n g c o r r e l a t i o n s w e r e obtained:-

I n ^ = -8.0503 + 3.006 - | - (88)

I n n = -5.8205 + 2871.8 — (89)
• Tv
I n Y[ = -14.8932 + 4100,5 — + 0.010631 T (90)
I n *\ = -4.5553 + 761.50 + 3.5820 - i « (91)
I n Y> = - 56.6584 + 5357.0 — + 7.3227 I n T (92)
v
. - T
l n v | = -44.1010 + 5077.4 - | - +
0.0023920 T
+ 5.6847 I n T (93)

The v a l u e s o f C a l c u l a t e d from these equations

are g i v e n f o r each temperature i n t a b l e 7, along w i t h the

average % d e t e r m i n a t i o n from t h e experimental values.

 102

(b) D e n s i t y Determinations

The c a l i b r a t i o n o f t h e p y k n o m e t e r s w i t h d i s t i l l e d

w a t e r a t 30, 45 a n d 60°C i s g i v e n i n t a b l e 8 . The d e n s i t i e s

o f O i l s D, E and P a n d o f n - o c t a n o l a r e g i v e n i n t a b l e s 5 and

6 respectively, a l o n g w i t h t h e v i s c o s i t y measurements.

(c) C a l i b r a t i o n o f R o l l i n g B a l l Viscometer

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

b a l l viscometer are presented i n t a b l e 9. The a c t u a l t i m e s o f

r o l l w i t h t h e a v e r a g e d e v i a t i o n ; f r o m t h e mean i s g i v e n f o r

each s e r i e s a t each temperature and s l o p e . The d e n s i t y differ-

e n c e was c a l c u l a t e d f r o m t h e b a l l d e n s i t y , 7.672 g m s / c . c , a n d

the d e n s i t y o f each o i l . The d e n s i t i e s a n d v i s c o s i t i e s of the

o i l s were r e p r o d u c e d f r o m t a b l e 5. and t ( ) were

c o r r e l a t e d by a r e g r e s s i o n a n a l y s i s i n accordance w i t h an

equation o f t h e form,

y[ = a+ b C (^~f)] t
(94)
The b e s t v a l u e f o r a and b f o r t h e two s l o p e s w e r e f o u n d t o be,

11° s l o p e , *\ = 0.082 + 5.139 x 1 0 ~ 3

t (fc - ? )(95)

23° s l o p e , rj = 0.037 + 9.197 x l o " 3

t )(96)

For these c o r r e l a t i o n s , only the data of series 3,

4 and 5 were u s e d . The o m i s s i o n o f t h e d a t a f r o m s e r i e s 1

and 2 w i l l be d i s c u s s e d l a t e r . The e x p e r i m e n t a l and t h e

 103
calculated viscosities, t o g e t h e r w i t h the percentage

d e v i a t i o n s a r e g i v e n i n t a b l e 10. The c a l i b r a t i o n i s also

presented i n figure 11.

 TABLE 3

CALIBRATION OP CAPILLARY VISCOMETERS BY COMPARISON

Calibration
Test L i q u i d Temp.°C Kinematic Viscometer Mean E f f l u x Time,Sees. Const, a t
Viscosity No. B78 Test Viscometer 37.78°C

n-PrOH 20.00 2.72 B82 218.6(5)** 222.7(4) 0.012221

A54 218.6(5) 1092.7(3) 0.0024907
A91 218.6(5) 1137.05(2) 0.0023936
Decalin 20.00 2.83 B82 226.8(2) 231.15(2) 0.012216
A54 226.8(2) 1134.0(2) 0.0024900
A91 226.8(2) 1179.65(2) 0.0023936
Oil A 20.00 7.05 B82 565.5(3) 57§.9(3) 0.012226
A54 565.5(3) 2828.8(3) 0.0024897
A91 565.5(3) 2942.6(3) 0.0023926
Oil B 37.78 8.24 B82 661.7(2) 674.05(2) 0.012222

(100°F)

Oil C 37.78 36.6 08 2941.3(5) 337.3(6) 0.10856

«• ( ) r e f e r s t o number o f nuns averaged.

MEAN VALUES OF CALIBRATION CONSTANT

V i s c o m e t e r No. B78 B82 A54 " . A91 C8

Mean V a l u e o f

C o n s t a n t a t 37.78°C 0.01245 0.01222 0.002490 0.002393 0.1086

(Cannon Instrument Co.)
 105
TABLE 4

CALIBRATION OP CAPILLARY VISCOMETERS

WITH DISTILLED WATER AT 20°C

Mean Observed Approximate

V i s c o m e t e r No. E f f l u x time,Sees. C a l i b r a t i o n constant

A54 405.4 (16)"* 0.0024761

A91 421.95(16) 0.0023790

C o r r e c t i o n s t o be a p p l i e d , %

Kinetic Surface
Timing Energy Tension

A54 -0.16 +0.13 +0.42

A91 -0.16 +0.12 +0.42

Corrected
ToJbal C o r r e c t i o n s , % C a l i b r a t i o n constant

A54 +0.39 0.002486

A91 +0.38 0.002388

Vt ( ) r e f e r s t o number o f runs averaged

 106

TABLE 5

V I S C O S I T I E S AND D E N S I T I E S OF OILS D,E AND P

T e m p e r a t u r e , °C OilD O i lE O i lF

Mean K i n e m a t i c 30 3.272 6.350 11.59

Viscosity 45 2.441 4.366 7.483

60 1.903 3.207 5.143

Density, 30 0.8264 0.8365 O.8464

45 0.8119 0.8263 0.8369

60 0.8014 0.8162 0.8271

Temperature 30 +0.003 +0.006 +0.007

Correction
to V i s c o s i t y 45 -0.002 -0.004 -0.004

60 -0.005 -0.008 -0.009

Corrected Kinematic 30 3.275 6.356 11.60

Viscosity, cs. 45 2.439 4.362 7.479

60 1.898 3.119 5.134

Absolute 30 2.706 5.307 9.869

Viscosity, cp. 45 1.980 3.615 6.259

60 1.521 2.624 4.246

 TABLE 6 107
VISCOSITY AND DENSITY OP N-OCTANOL

AT VARIOUS TEMPERATURES

A Mean Density Temp. c o r r . Corrected Absolute

Temp.°C Kinematic dt To V i s c o s i t y Kinematic Visco.
Viscosity 4 % Viscosity cp.

15 13.310 0.8288* +0.21 13.348 11.054

20 11.035 0.8253* +0.17 11.054 9.123

25 9.268 0.8219 +0.12 9.279 7.626

30 7.807 > 0.8184 +0.08 7.815 6.396

45 4.9H 0.8079 -0.07 4.908 3.965

50 4.258 0.8042*" -0.11 4.253 3.420

60 3.268 0.7972 -0.20 3.261 2.600

75 2.293 0.7862* -0.34 2.285 1.796

90 1.679 0.7754* -0.48 1.671 1.296

Smythe and Stoops (143)

 TABLE 7

CORRELATION OF VISCOSITY-TEMPERATURE DATA FOR N-OCTANOL

Temp.°C Expt. Eqn.(88) Eqn.(89) Eqn.(90) Eqn.(91) Eqn.(92) Eqn.(95)

15 11.05 10.80 10.775 11.03 11.04 10.99 10.98

20 9.123 9.052 9.024 9.121 9.128 9.146 9.139

25 7.626 7.613 7.600 7.592 7.596 7.600 7.597

30 6.396 6.451 6.459 6.396 6.387 6.400 6.399

45 3.965 4.042 4.058 3.965 3.963 3.963 3.963

50 3.420 3.490 3.480 3.425 3.425 3.422 3.422

60 2.600 2.641 2.652 2.603 2.606 2.602 2.602

75 1.796 1.791 1.793 1.796 1.798 1.796 1.796

90 1.296 1.254 1.254 1.295 1.294 1.295 1.295

Mean % I.46 1.56 0.11 0.16 0.17 0.16

Deviation
 TABLE 8

CALIBRATION OP PYKNOMETERS

Temperature, C 30 45 60

Density of 0.99567 0.99025 0.98324

w a t e r , d^
' 4

P y k n o m e t e r No. 147 124 . 147 124 147 124

Wt. o f Water 24.9536 24.7586 24.8223 24.6259 24.6502 24.4566

and A i r

A p p r o x . Volume 25.0621 24.8663 25.0667 24.8684 25.0704 24.8735

Buoyancy 0.0301 0.0298 0.0301 0.0298 0.0301 0.0298

Correction

Wt. o f W a t e r 24.9837 24.7884 24.8524 24.6557 24.6803 24.4864

H

Pyknometer 25.0924 24.8962 25.0971 24.8985 25.1010 24.9038

o
U5
Volume m l .
 110
TABLE 9

CALIBRATION OP PRESSURE VISCOMETER

Density Mean T i m e ,
Temp.°C Slope Difference Sees. Viscosity t(p -p s

Series 1 _ O i l D, V i s c o m e t e r tube not keyed.

30 11° 6.846 70.81 ± 0.04 2.706 484.8

45 11° 6.860 52.37 - 0.05 1.980 359.3
60 11° 6.871 40.41 ± 0.06 1.521 277.7

Series 2 — O i l E, V i s c o m e t e r tube not keyed.

30 11° 6.835 145.43 ± 0 . 1 4 5.307 994.0

45 11° 6.846 98.61 ± 0.14 3.615 675.1
60 11° 6.856 72.20 + 0.04 2.624 488.1

Series 3 — O i l E,V i s c o m e t e r t u b e n o t k e y e d ,b u t
in fixed position.

30 11° 6.835 147.07+ 0.16 5.307 1005.2

45 11° 6.846 99.52 + 0.06 3.615 681.3
60 11° 6.856 71.96 ± 0.06 2.624 493.4

Series 4 — O i l P - tube keyed

30 11° 6.826 279.62 i 0.44 9.869 1908.5

23° 157.00 ± 0.08 1071.7
45 11° 6.835 175.06 ± 0.16 6.259 1203.3
23° 98.85 ± 0.08 .675.6
60 11° 6.845 119.09 ± 0.14 4.246 • 815.2
23° 66.84 - 0.07 457.5

Series 5 _ O i l D, t u b e keyed

30 11° 6.846 73.84 - 0.06 2.706 505.5

23° 41.55 ± 0.03 284.2
45 11° 6.860 54.63 ± 0.04 1.980 374.8
23° 30.88 1 0.02 211.8
60 11° 6.871 41.94 ± 0.06 1.521 288.2
23° 23.94 ± 0.01 164.5
 Ill

TABLE 10

CORRELATION FOR PRESSURE VISCOMETERS

Slope (expt.) (calc.) $ Deviation

11° 5.307 5.250 +1.07

3.615 3.583 +0.89
2.624 2.618 +0.23
9.869 0.896 -0.21
6.259 6.266 -0.11
4.242 4.271 -0.68
2.706 2.679 +0.68
1.980 2.008 -1.41
1.521 1.563 -2.76

Mean d e v i a t i o n = 0.93$

23° 9.869 9.893 -O.24

6.259 6.250 +0.14
4.242 4.245 +0.07
2.706 2.653 +1.96
1.980 1.985 -0.25
1.521 1.550 -1.91

Mean d e v i a t i o n = 0.76$
 112
DISCUSSION

(2) The P r e s s u r e Apparatus

1) P r e s s u r e V i s c o m e t e r . I n the c a l i b r a t i o n of the
\
\

pressure viscometer at atmospheric pressure, the f i r s t two

s e r i e s o f r u n s were I n c o n s i s t e n t . Two straight lines could

be d r a w n t h r o u g h t h e p o i n t s f o r O i l D and O i l E, b u t t h e

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

5 p e r c e n t w h e r e a s t h e s c a t t e r o f p o i n t s on e a c h l i n e was less

than h a l f a per cent. T h i s was a t t r i b u t e d t o a bend i n t h e

v i s c o m e t e r t u b e , and r e p e a t r u n s w i t h O i l E ( s e r i e s 3) w i t h t h e

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

values a g a i n of the time of r o l l , i n d i c a t i n g that the e f f e c t

was important. L a t e r , t h e t u b e was k e y e d i n t h e same p o s i t i o n

as f o r S e r i e s 3 and new m e a s u r e m e n t s made w i t h O i l P and O i l D.

The r o l l t i m e s f o r O i l D were a l s o s i g n i f i c a n t l y d i f f e r e n t from

the p r e v i o u s runs (series 1.)

The f i n a l c o r r e l a t i o n d i s c u s s e d above i s based on t h e

l a s t three s e r i e s , w i t h the tube i n a constant p o s i t i o n . The

average d e v i a t i o n of the experimental v i s c o s i t i e s from those

c a l c u l a t e d from the c a l i b r a t i o n equation i s s t i l l larger than

the average d e v i a t i o n f o r a n y one s e r i e s , as i s shown b y t h e

trends of the d e v i a t i o n s ( t a b l e 10). Considering the c a l i b r a -

t i o n f o r a s l o p e o f 11°, much c l o s e r a g r e e m e n t i s o b t a i n e d b y

o m i t t i n g the runs of s e r i e s 5 w i t h O i l D
} ( t h e most f l u i d oil),

which suggests that i n e r t i a l e f f e c t s may h a v e b e e n i m p o r t a n t

 113

at low v i s c o s i t i e s . An a n a l y s i s b a s e d o n t h e t h e o r y o f t h e

Instrument can i n d i c a t e whether these e f f e c t s are r e l e v a n t .

The a p p r o x i m a t e value of the diameter r a t i o f o r the

b a l l and t u b e u s e d i n t h i s w o r k i s 0 . 9 6 9 , w h i c h gives a

c r i t i c a l R e n y o l d S r . No. o f a b o u t 18.5 and a c o r r e l a t i o n factor

of a b o u t 1.5 x 10~5(Figures 5 and 6 ) . The Reynold§J NO. i s

given by the expression,

Re = ^ hgL ( ^ \ (97)
\ n

or Re = J L . ^ (98)

In this case,

L = 18 cms. , d = 0.2500 cm, D = 0.2583 cm.

.-. Re = la|S' (99)

v t

H e n c e , t h e s m a l l e s t v a l u e s o f Re w e r e a p p r o x i m a t e l y 8.6 f o r

t h e 11° s l o p e , and 13.5 f o r t h e 23° s l o p e . These v a l u e s a r e

below the c r i t i c a l v a l u e (18.5), a c c o r d i n g t o t h e c o r r e l a t i o n

of H u b b a r d and Brown, and t h e r e f o r e a l l m e a s u r e m e n t s w e r e

made w e l l w i t h i n t h e l a m i n a r r e g i m e o f f l o w , ^ i n e r t i a l effects

c o u l d n o t have been i m p o r t a n t .

The i m p o r t a n c e of the a c c e l e r a t i o n e f f e c t a t the

s t a r t o f r o l l c a n be r e a d i l y d e t e r m i n e d from e q u a t i o n (T5).

For a t y p i c a l r u n w i t h a time o f 70 s e e s , and a v i s c o s i t y o f

2.6 c p . ( s e r i e s 3, 60°C), ^ = 540 g m . / s e c , F = 123 gm.cm./

p
sec. and m = 1.03 gm., whence,
 - 114

where, V = terminal velocity,

t
Hence, t h e t i m e r e q u i r e d t o a t t a i n 99$ o f t h e t e r m i n a l

v e l o c i t y i s about 0 . 0 0 9 s e c . and t o a t t a i n 9 9 . 9 $ I s a b o u t

0.013 s e c . T h i s e f f e c t was c l e a r l y n o t i m p o r t a n t f o r any o f

the runs i nthis work.

The e f f e c t o f temperature must a l s o be c o n s i d e r e d .

Since both theb a l l and t h e t u b e w e r e o f s t a i n l e s s steel,

equation (84) i s a p p l i c a b l e a n d t h e c o r r e c t i o n f o r C i s g i v e n

b y 2"OCAT. The v a l u e o f o< f o r s t a i n l e s s s t e e l i s a b o u t 1.4

x 10 °C7 which gives a c o r r e c t i o n of approximately 0.14$

f o r a temperature range o f 50°C. This i s quite small i n

comparison w i t h thed e v i a t i o n s obtained.

No c o m p l e t e e x p l a n a t i o n o f t h e l a r g e r d e v i a t i o n s a t

low v a l u e s o f v i s c o s i t y i s apparent, b u t i t may b e concluded

t h a t measurement o f v i s c o s i t i e s g r e a t e r t h a n 3 c p . c a n be

obtained with the present c a l i b r a t i o n t o b e t t e r than 1.0$,

w h i c h compares f a v o u r a b l y even w i t h t h e a c c u r a t e work o f

H u b b a r d and Brown (128).

B e f o r e making measurements under p r e s s u r e , i t w i l l

be necessary to estimate the density v a r i a t i o n with pressure,

since experimental data arenot available.Bridgman (35) has

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

temperature c a n be e s t i m a t e d f r o m the d e n s i t y a t atmospheric

p r e s s u r e and t h e c o m p r e s s i b i l i t y d a t a o f a c h e m i c a l l y s i m i l a r
 115

compound. I n t h e case o f n - o c t a n o l , a l o w e r member o f t h e

h o m o l o g o u s s e r i e s o f n - a l c o h o l s w o u l d be u s e d . Since the

v i s c o s i t y c a l c u l a t e d from the c a l i b r a t i o n equation i s not

s t r o n g l y dependent on t h e f l u i d density, sufficiently close

v a l u e s s h o u l d b e o b t a i n e d b y t h i s m e t h o d , and i f more

a c c u r a t e v a l u e s a r e r e q u i r e d , t h e t r a n s f e r bomb c a n b e

adapted f o r c o m p r e s s i b i l i t y measurements.

i i ) A u x i l i a r y Pressure Equipment. The p r e s s u r e system

proved convenient t o operate and s a t i s f a c t o r y u n d e r pressure,

with the exception of the e l e c t r i c a l connection i n the transfer

bomb, w h i c h f a i l e d under 10,000 p s i p r e s s u r e . The d o u b l e - e n d e d

s o a p s t o n e c o n e s e a l w h i c h was u s e d i s d e s c r i b e d b y t h e

manufacturers and Comings (140) as s a t i s f a c t o r y f o r p r e s s u r e s

up t o 2 0 , 0 0 0 p s i , and i t i s p r o b a b l e t h a t f a i l u r e was due t o

p o o r d e s i g n and m a c h i n i n g o f the r e c e p t a c l e f o r the cone.

Advice s h o u l d be s o u g h t f r o m t h e m a n u f a c t u r e r s on l i m i t s o f

t o l e r a n c e and m a c h i n i n g techniques.

Before the apparatus i s operated under p r e s s u r e , the

w h o l e s y s t e m s h o u l d b e r e t e s t e d a t one and a h a l f t i m e s t h e

maximum w o r k i n g pressure with the viscometer a t t h e maximum ;

test temperature.

(b) V i s c o s i t y M e a s u r e m e n t s a t A t m o s p h e r i c Pressure

E r r o r s i n t h e v i s c o s i t y m e a s u r e m e n t s i n t h e Cannon-

Fenske v i s c o m e t e r s h a v e a r i s e n f r o m two s o u r c e s , (1) e r r o r s i n

the c a l i b r a t i o n constant and ( 2 ) e x p e r i m e n t a l errors during

 116

calibration.

The e r r o r i n the c a l i b r a t i o n constant f o r the

instrument standard, viscometer B 7 8 , w h i c h was c a l i b r a t e d b y

t h e Cannon I n s t r u m e n t Co. i s n o t known; h o w e v e r i t i s

p r o b a b l y a b o u t 0.1 t o 0.2$. I t i sfelt that errors greater

t h a n 0.1$ w e r e n o t i n t r o d u c e d i n t h e c a l i b r a t i o n o f t h e o t h e r

viscometers b y c o m p a r i s o n w i t h B78, s i n c e t h e c o n s t a n t

obtained with several l i q u i d s i n a wide range o f v i s c o s i t i e s

all gave t h e same v a l u e s w i t h i n 0.1$. The e r r o r i n t h e

constant f o r the other viscometers was t h e r e f o r e a maximum o f

0.2 t o 0.3$.

The s l i g h t disagreement between the c a l i b r a t i o n

c o n s t a n t b y c o m p a r i s o n and w i t h d i s t i l l e d water i s not

surprising. Routine viscometers are not designed f o r calibra-

t i o n w i t h water, s i n c e t h e magnitude o f t h e c o r r e c t i o n s t o be

applied are quite large, and t h e method o f c a l c u l a t i n g them

is not exact. The s m a l l e r . v a l u e o f t h e c o n s t a n t may mean

l a r g e r c o r r e c t i o n s were n e c e s s a r y f o r the kinetic e n e r g y or-

the s u r f a c e t e n s i o n . However, t h e d i f f e r e n c e i s s m a l l , and

the runs w i t h d i s t i l l e d w a t e r have s e r v e d as a u s e f u l c h e c k .

The a b s o l u t e d e t e r m i n a t i o n s were n e c e s s a r i l y s u b j e c t

to greater errors. H e r e e r r o r due t o i n a c c u r a c y , i n t h e t e s t

temperature come i n t o p l a y . T h i s amounted t o a b o u t 0.1$,

because o f the p o s s i b i l i t y o f e r r o r i n the t e s t temperature of

about 0.04°C The d i f f e r e n c e b e t w e e n t h e c a l c u l a t e d kinematic

 117

v i s c o s i t y f o r t h e two v i s c o m e t e r s used f o r each determination

was u s u a l l y w i t h i n 0,1$, i n d i c a t i n g t h a t e r r o r s due t o

a l i g n m e n t and t i m i n g w e r e s m a l l . The t e m p e r a t u r e c o r r e c t i o n

to the c a l i b r a t i o n constant c o u l d b e a c c u r a t e l y c a l c u l a t e d and

no e r r o r s were i n t r o d u c e d i n applying this correction. The

surface t e n s i o n c o r r e c t i o n was n o t known, b u t , as m e n t i o n e d

a b o v e , was n e g l i g i b l e . Finally, the k i n e t i c energy c o r r e c t i o n

was k e p t b e l o w 0.1$ i n most c a s e s , by u s i n g s u f f i c i e n t l y long

e f f l u x times, but f o r the determination on n - o c t a n o l a t 90°C

it was a b o u t 0.2$. The maximum e r r o r i n t h e a b s o l u t e viscosity

determinations was t h e r e f o r e a b o u t 0.5 t o 0.6$.

( c ) The P u r i t y o f n - O c t a n o l

A good c h e c k on t h e c o n s i s t e n c y of the absolute

v i s c o s i t y measurements i s a c c o r d e d b y t h e c l o s e f i t o f t h e

data on n - o c t a n o l t o a smooth curve,and t h e s m a l l p e r cent

d e v i a t i o n s f o r t h e t h r e e and f o u r c o n s t a n t viscosity-temper-

ature equations. -This i n sharp c o n t r a s t t o the poor agree-

ment b e t w e e n t h e v a l u e s from d i f f e r e n t sources i n the

literature ( f i g u r e 1 0 ) , w h i c h i s due i n p a r t t o d i f f e r e n c e s i n

the absolute v i s c o s i t y standard used, but mainly to difference

i n degree of p u r i t y . A l t h o u g h no q u a n t i t a t i v e e s t i m a t e was

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

research, t h e c l o s e a g r e e m e n t o f t h e d e n s i t y a t 25°C and

the r e f r a c t i v e index a t 20°G w i t h v a l u e s assessed from the

literature, i n d i c a t e s t h a t t h e m a t e r i a l was o f a h i g h p u r i t y .
 118
Large disagreement on the v i s c o s i t y a t v a r i o u s temperatures

was o b t a i n e d between the p r e s e n t work and t h a t of p r e v i o u s

investigators. I n most c a s e s , i t was i m p o s s i b l e to assess

the r e l i a b i l i t y of the p r e v i o u s V i s c o s i t y d a t a because of no

i n d i c a t i o n of the degree of p u r i t y . I n other cases, the

d e n s i t y and /ov r e f r a c t i v e i n d e x g i v e c l e a r i n d i c a t i o n of

unacceptable p u r i t y . No weight can be put t o the agreement of

t h i s work w i t h the d a t a o f Bingham and D a r a l l (144) and

Mumford and P h i l l i p s (145), as no d e n s i t y d a t a are a v a i l a b l e

for the f o r a i e r ^ a n d the d e n s i t y d a t a of the l a t t e r d i f f e r i n

the t h i r d s i g n i f i c a n t f i g u r e from the v a l u e s recommended

above.

(d) V i s c o s i t y of n-Octanol

A t h r e e - c o n s t a n t e q u a t i o n i s r e q u i r e d t o f i t the

viscosity-temperature data f o r n-octanol. The simple

e x p o n e n t i a l f o r m u l a , e q u a t i o n ( 1 0 ) , and the Andrade t h e o r y ,

e q u a t i o n (9), g i v e almost i d e n t i c a l r e p r e s e n t a t i o n of the

d a t a w i t h a maximum spread of 5$ and an average d e v i a t i o n of

1.5$ (table 7). The v e r y c l o s e f i t of the d a t a t o a l l the

t h r e e and f o u r c o n s t a n t e q u a t i o n s (maximum spread 0.7$, average

d e v i a t i o n 0.15$) i n d i c a t e s t h a t over t h e range of temperatures

covered, the v a r i a t i o n i n the a c t i v a t i o n energy i s s u f f i c i e n t l y

s m a l l t o be r e p r e s e n t e d by any a d d i t i o n a l term. These forms

of e q u a t i o n must be t e s t e d over more extended ranges of

temperature t o show any s i g n i f i c a n t difference.

 119

Equation (88) c a n be c o n v e r t e d t o the e x p o n e n t i a l

f o r m t o o b t a i n t h e p r e - e x p o n e n t i a l f a c t o r and the energy o f

activation,
-4 5 970
= 3.19 x 10 exp( — ) , centipoise.
T h i s v a l u e o f t h e energy o f a c t i v a t i o n (5,970 c a l . / m o l e )

compares f a v o u r a b l y w i t h the v a l u e o f 6,290 c a l s . / m o l e obtained

f r o m E y r i n g s Theory.
1
I n order t o c a l c u l a t e t h i s l a t t e r value,
the l a t e n t heat o f v a p o r i s a t i o n was i n t e r p o l a t e d a t t h e mean

temperature o f t e s t (about 50°) from t h e v a l u e s o f 25°C and

the b o i l i n g p o i n t , g i v e n by W e i s s b u r g e r ( 3 0 ) j t o g i v e 16,680

cals./mole,

Hence, A E D n = 16,680-323 R = 15,980 c a l . / m o l e

and AF* = > = 6,290

15 9 8 0

2.45 mole

Comparing t h e e x p o n e n t i a l c o r r e l a t i o n o f t h e d a t a

f o r n - o c t a n o l w i t h t h a t o f lower members o f t h e homologous s e r -

i e s shows t h a t the t r e n d observed by G o l i k , R a v i k o v i c h and

Orishchenko (113) f o r C. t o C members (see above on Theory) i s

continued . The f o l l o w i n g i s a comparison of t h e a c t i v a t i o n

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

A. X 1 0 5
AF*/R
C-, 22 1042
C 9 '5 1752
2.3 2079
1.0 2442
4

6 0.32 3006
(poise x K T ) (°Kelvin)
 120

The apparent c o n s i s t e n c y of these two constants

s h o u l d mean t h a t a r e a s o n a b l e c o r r e l a t i o n m i g h t be developed

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

e q u a t i o n f o r t h e C,_, C^ and C n o r m a l a l c o h o l s , and extra-

s' 6 • 7 '
p o l a t i o n t o h i g h e r members. Although some m e a s u r e m e n t s on

o t h e r n o r m a l a l c o h o l s h a v e b e e n made (11,27, 112) the data

are s u f f i c i e n t l y i n c o n s i s t e n t to warrant re-examination and

e v e n t u a l l y c o r r e l a t i o n w i t h t h e o t h e r members. I n view of

t h e f a c t t h a t t h r e e and four constant equations fitted the

n - o c t a n o l d a t a so much b e t t e r , i t i s recommended t h a t a more

thorough examination o f a l l t h e d a t a o n n - a l c o h o l s be made,

and the p o s s i b i l i t y of c o r r e l a t i n g the c o n s t a n t s w i t h the

number o f c a r b o n atoms be examined.

E v e n t u a l measurement o f t h e e f f e c t o f p r e s s u r e on

t h e v i s c o s i t y o f n - o c t a n o l s h o u l d a l s o p r o v i d e means o f

establishing pressure-temperature-viscosity relations for the

homologous s e r i e s . The c o r r e l a t i o n o f J o b l i n g and Laurence

(114) m e n t i o n e d i n t h e t h e o r y seems t h e most l i k e l y t o g i v e

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

members o f t h e s e r i e s n o t p r e v i o u s l y m e a s u r e d .
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113. G o l i k , A . Z . . R a v i k o v i c h , S.D. and O r i s h c h e n k o , A.V.
U k r a i n . K h i m . Z h u r . 21, I 6 7 (1955)
114. J o b l i n g , A. and L a u r e n c e , A.S.C. J . Chem. P h y s . 20, 1296
(1952)
115. B r i t i s h C o l u m b i a E l e c t r i c Co. L t d . , P r i v a t e communication
F e b . 1958.
116. Cannon, M.R. " D e r i v a t i o n o f t h e V i s c o s i t y E q u a t i o n and
Sources o f E r r o r i n Viscometry" - P r i v a t e r e p o r t t o
ASTM c o m m i t t e e D-Z, 1950)
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117 B a r r , G. "A M o n o g r a p h o n V i s c o m e t e r " , O x f o r d (1933)

118 S u g d e n , S. J . Chem. S o c . ( L o n d o n ) 119, 1483 (1921)

119 P e r r y , J . H . " C h e m i c a l E n g i n e e r s Handbook", p.363

M c G r a w - H i l l (1950)
120 H e r s e y , M.D. and S h o r e , H. J . Wash. A c a d . S c i . , 6,

525 (1916)

121 Hersey, M.D. and S h o r e , H. M e c h . E n g . 41, 537 (1919)

122 Hersey, M.D. a n d S h o r e , H. I b i d . 45, 315 (1923)

123 H o c o t t , C R . and B u c k l e y , S.E. I n s t . M i n . M e t . E n g r s .

T e c h . P u b . No. 1220 X-5940)
124 E x l i n e , P.G. and E n d e a n , H . J . O i l Gas J . 45 (45) 82
(1947)

125 M a k i t a , T. R e v . P h y s . Chem. J a p a n , 24, 74 (1954)

126 M a k i t a , T, K y o t o T e c h U n i v . , S c i . and T e c h n o l . , No.4

19 (1955)

127 Lundberg, S. J . I n s t . P e t r o l e u m 40, 104 (1954)

128 H u b b a r d , R.M. and Brown, G.G. I n d . E n g . Chem. (Anal.

Ed.) 15, 212 (1943)

129 L e w i s , H.W. A n a l . Chem. 25, 507 (19530'

130 C a t a l o g 595, "Time R e g i s t e r i n g A p p a r a t u s , J a q u e t L t d . ,

Basle, Switzerland.
131 F r a n c i s , A.W. P h y s i c s , 4 , 403 (1933)
132 B a c o n , L.R. J . F r a n k l i n I n s t . , 221, 251 (1936)

133 B l o c k , R.F. J . A p p . P h y s . 11, 635 (1940)

134 Y o u n g , J.W. " D e v e l o p m e n t o f V i s c o m e t e r s f o r O i l

D i l u t i o n Measurement" I m p e r i a l O i l L t d . , C a l g a r y ,
A l b e r t a (1954)

135 B a u e r , N. C h . V I o f " T e c h n i q u e s o f O r g a n i c C h e m i s t r y "

V o l . 1 . P a r t I , E d . W e i s s b u r g e r , I n t e r s c i e n c e (1949)

136 Handbook o f P h y s i c s and C h e m i s t r y , p . 1971, Chemical

R u b b e r P u b l i s h i n g Co., 37 e d . (1955)
 128
137 Imperial O i l Ltd., Private Communication,August,1958
138 P e r r y , J.H. " C h e m i c a l E n g i n e e r i n g Handbook", p.1238
M c G r a w - H i l l (1950)
139 S u p e r p r e s s u r e C a t a l o g 407, A m e r i c a n I n s t r u m e n t ' C o . ,
Inc. S i l v e r S p r i n g , M a r y l a n d , Washirigton,D.C. (1957)
140 Comings, " H i g h P r e s s u r e Technology" M c G r a w - H i l l , (1956)
141 H i g h P r e s s u r e Equipment C a t a l o g , H i g h P r e s s u r e
Equipment Co., I n c . E r i e , P a .
142 Kay, W.B. and Donham, W.E. Chem. Eng. S c i . , 4, ( 1 ) 1
(1955)
143 Smythe, C P . and S t o o p s , W.N. " J . Am. Chem. Soc. 51,
3312 (1929)

144 Bingham, E . C and D a r a l l , L.B. J . Rheology, 1, 174 (1930)

145 Mumford,. S.A. and P h i l l i p s , J.W.C. J . Chem. Soc. (London)

1950, 75

146 D e r k i n , W.K. I b i d , 45, 421 (1884)

147 Zander, Ann. 224, 84 (1884)

1 4 8 G a r t e n m e i s t e r , R. Z, P h y s i k . Chem. 6, 524 (1890)

149 Dunstan, A.Ev T h o l e , P.B. and Benson, P. J . Chem. Soc.

London) 105, 782 (1914)
150 Lowry, T.M. I b i d , 105, 81 (1914)
151 B e h a l , A. B u l l . Soc. Chim (Prance) 25, 473 (1919)
152 Verkade, O.E. and Coops, J . Rec. T r a v . Chim, 46,903
(1927)
153 D e f f e t , L. B u l l . Soc. Chim. B e l g . 40, 385 (1931)
154 E l l i s , L.M. and R e i d , E.E. J . Am. Chem. Soc. 59, 1674
(1932)
155 B u t l e r , J.R.V. Thomson, D.W. and MacLennan, W.H. J .
Chem. Soc. (London) 1933, 674
156 N e v j i , G.V. and J a t k a r , S.K.K. I n d i a n J . P h y s i c s ,
397 (1934)
 129

157 Butler, J.A.V. R a c h a n d a n i , C.N. and Thomson, D.W.

J . Chem. S o c . ( L o n d o n ) 1935, 280

158 O l i v e r , P. R e c . T r a v . C h i m . 56, 247 (1937)

159 Komarewsky, V . I . and C o l e y , J.R. J . Am. Chem. S o c . 63,

3269 (1950)
160 D o r o u g h , G-.L. e t a l . I b i d . 63 3100 (1941)
161 Muller, A.,Pette u Seifen 49, 572 (194), Chem. A b s .
37, 6510^
162 J o n e s , W.J. Bowden, S.T. Y a r n o l d , W.W. and J o n e s , W.H.
J . P h y s . Chem. 52, 753 (1948)

163 D r e i s b a c h , R.R. a n d M a r t i n , R.A. I n d . E n g . Chem. 41,

2875 (1949)
164 M u m f o r d , S.A. a n d P h i l l i p s , J.W.G. J . Chem. S o c .
( L o n d o n ) 1950, 75

165 U.B.S. C o m p u t i n g C e n t r e , R o u t i n e S-3, " C o r r e l a t i o n and

R e g r e s s i o n " (1957)
 130
r

APPENDIX I

B i b l i o g r a p h y on P r e s s u r e Viscometry

1. B r i d g m a n , P.W. P r o c . N a t . A c a d . S c i . 11, 603 (1925)

2. B r i d g m a n , P.W. P r o c . Am. A c a d . A r t s S c i . 61, 57 (1926)

3. H e r s e y , M.D. and S h o r e , H. Mech. E n g . 50, 221 (1928)

4. S u g e , Y. B u l l . I n s t . P h y s . Chem. R e s e a r c h ( T o k y o ) 1 1 ,

977 (1932) .

5. Sage, B.H. I n d . E n g . Chem. ( A n a l . E d . ) 5, 261 (1933)

6. H o p p l e r , P. Z. t e c h . P h y s i k , 14, 165 (1933)

7. H o p p l e r , P. P r o c . 2 n d
World P e t . Congr. London, 503 (1933)

8. F r a n c i s , A.W. P h y s i c s , 4, 403 (1933)

9. Knop, W. Z. V e r . d e n t . Z u c k e r i n d , 83, 932 (1933)

10. Suge, Y. B u l l . I n s t . Chem. P h y s . R e s e a r c h ( T o k y o ) 12,

643 (1933)

11. Knapp, R.T. I n d . E n g . Chem. ( A n a l . E d . ) 6, 80 (1934)

12. Dow, R.B. P h y s i c s , 6, 71 (1935)

13. Sage, B.H.- S h e r b o r n e , J . E . and L a c e y , W.N. Ind. Eng.

Chem. 27, 954 (1935)

14. Mason, C.C. P r o c . P h y s . S o c . ( L o n d o n ) 47, 519 (1935)

15. E b b e c k e , U. a n d H a n d b r i c h , R. A r c h . g e s . P h y s i o l .
( P f l u g e r s ) 238,. 429 (1936)
16. B l o k k e r , P.C. R e c . t r a v . c h i m . 55, 170 (1936)
1 7 . B a c o n , L.R. J . F r a n k l i n I n s t . 221, 251 (1936)

18. V e r s l u y s , J . M i c h e l s , A. and B e r b e r J . P h y s i c a 3, 1093

(1936)
 131
19. Thomas, B.W. Dow. R.B. and Ham, W.R. P h y s . Rev. 53,
926 (1938)

20. K h a l i l o v , K. J . Tech. Phys. (U.S.S.R.) 8, 1249 (1938)

2 D . Sage, B.H. and L a c e y , W.N. I n d . Eng. Chem. 30, 829 (1938)

22. Dow, R.B. P h i l . Mag. 28, 403 (1939)

23. K h a l i l o v , K. J . Exp. T h e o r e t . P h y s . (U.S.S.R.) 9, 335

(1939)
24. v a n Wyk, W.R. e t a l . , P h y s i c a 7 45, (1940)

25. Sage, B.H. and L a c e y , W.N. I n d . Eng. Chem. 32, 587 (1940)

26. H o c o t t , C R . and B u c k l e y , S.E. I n s t . M i n i n g Met. E n g r s .

Tech. Pub. No. 1220 (1940)
27. Hubbard, R.M. and Brown, C C End. Eng. Chem. (Anal.Ed.)
15, 212 ( 1 9 4 3 )

28. Pugh, H.L.D. J . S c i . I n s t r u m e n t s 21, 177 (1944)

29. E x l i n e , P.G. and En Dean, H.J. O i l Gas J . , 45, (45) 82

(1947c)

30. W a l t e r , P. and Weber, W. Angew Chem. B19, 123 (1947)

31. Bridgman, P.W. P r o c . Am. Acad. A r t s S c i . 77, 115 (1949)

32. Thompson, A.M. J . S c i . I n s t r u m e n t s 26, 75 (1949)

33. L a z a r r e , P. J . phys. r a d i u m 11, D51 (1950)

34. I w a s a k i , H. S c i . R e p t s . R e s . I n s t . Tohoku U n i v . 3A,

247 (1951)

35. Kuss, E. N a t u r w i s s e n s c h a f t e n , 38, 102 (1951)

36. J o b l i n g , A. and L a u r e n c e , A.S.C. P r o c . Roy. S c . (London)
0

206A, 257 (1951)

37. Mason, D.M. W i l c o x , 0.W, Sage, B.H. J . Chem. Phys. 5 6 ,
1008 (1952)
38. C a r m i c h a e l , L.T. and Sage, B.H. I n d . Eng. Chem. 44,2728
(1952)
 1.32

39. N a i k i , T., e t a l . B u l l . I n s t . Chem. R e s . , K y o t o U n i v .

31,(1) 56 (1953)

40. L e w i s , H.W. A n a l . Chem. 25, 507 (1953)

41. K u s s , E. E r d o l . u K o h l e 6, 266 (1953)

42. Y o u n g , J.W. " D e v e l o p m e n t o f a n I n s t r u m e n t f o r O i l
D i l u t i o n Measurement", I m p e r i a l O i l L t d . C a l g a r y ,
A l b e r t a , (1954)

43. L u n d b e r g , S . J . I n s t . P e t r o l e u m , 40, 105 (1954)

44. M a k i t a , T. R e v . P h y s . Chem. ( J a p a n ) 24, 74 (1954)

45. D e r a z h n e , R . I . P o p o v , V.D. and T r e n k e l , Y.B.

Z a v o d s k a y a L a b . 21, 731 (1955)
46. K u s s , E . Z. Angew P h y s . 7, 372 (1955)

47. M a k i t a , T. Mem.'Fac. I n d . A r t s . K y o t o U n i v . , S c i . a n d

T e c h n o l . No.4. 19 (1955)

48. K u s s , E. ChemTlng^-Tech. 28, 141 (1956)

49. H e i k s , J.R. and O r b a n , E. J . P h y s . Chem. 60, 1025 (1956)

 133
APPENDIX I I

C E R T I F I C A T E OF CALIBRATION

VISCOMETER NO. g°g

CANNON*FENSKE-OSTWALD TYPE

C o n s t a n t a t 1 0 0 ° F. 0.01245 Centistokes/Second

Constant a t 2 1 0 ° F. 0.01239 Centistokes/Second

To o b t a i n v i s c o s i t y i n c e n t i s t o k e s m u l t i p l y t i m e i n

seconds by the viscometer constant. The v i s c o m e t e r constant

at other temperatures may be o b t a i n e d b y i n t e r p o l a t i o n o r

extrapolation.

V i s c o s i t i e s o f t h e s t a n d a r d u s e d i n c a l i b r a t i n g were e s t a b l i -
shed i n M a s t e r V i s c o m e t e r s as d e s c r i b e d i n I n d . E n g . C h e m . A n a l .
E d . 16, 708 (1944) b y M.R. C a n n o n . T h i s method h a s b e e n f a v o r -
a b l y checked a t the U n i t e d S t a t e s Bureau o f Standards by
S w i n d e l l s , H a r d y and C o t t i n g t o n and t h e i r w o r k i s p u v l i s h e d - i n
the J o u r n a l o f Research of t h e N a t i o n a l Bureau of Standards,
V o l . 52, No.3 March, 1954, R e s e a r c h P a p e r 2479.

V i s c o s i t i e s a r e b a s e d on t h e new v a l u e f o r w a t e r a d o p t e d b y t h e
U n i t e d S t a t e s B u r e a u o f S t a n d a r d s and The A m e r i c a n S o c i e t y f o r
T e s t i n g M a t e r i a l s J u l y 1, 1953. The new v i s c o s i t y b a s i s i s
1.0038 c e n t i s t o k e s f o r w a t e r a t 68° F.

CALIBRATION DATA AT £00° F.

Viscosity Viscosity E f f l u x Time Constant

Standard Centistokes Seconds Centistokes/Seconds

20K 4.598 369.0 0.012461

3D2D 3.480 279.7 0.012442

A v e r a g e = 0.01245

Room Temp, ( a p p r o x . ) 78 F.

Charge (approx.) 7.1 ml.

D r i v i n g f l u i d head ( a p p r o x . ) 9 . 6 cm.
 .134

Working diameter o f lower r e s e r v o i d 3 cm.

C o n s t a n t a t 210° P. i s 0.5 % d i f f e r e n t t h a n a t 100° P.

C a l i b r a t e d b y RVS-I46PP u n d e r s u p e r v i s i o n o f R.E.Manning

R.E.Manning,Ph.D.,
Chemical Engineer-
M.R.Cannon, Ph.D.,
C o n s u l t i n g Chemical
Engineer
Registered Professi-
onal Engineer
S t a t e C o l l e g e , Penn.

D i r e c t i o n s f o r u s e a r e p u b l i s h e d i n A.S.T.M. S t a n d a r d s o n
P e t r o l e u m P r o d u c t s and L u b r i c a n t s and a l s o i n I n d . E n g . Chem.
A n a l . E d . V o l . 10, page 297, J u n e 1938

V i s c o m e t e r s f o r opaque l i q u i d s a r e a v a i l a b l e . For their

d e s c r i p t i o n and u s e s e e I n d . Chem. A n a l . E d . , V o l . 13
299 ( 1 9 4 D .
 1-35

APPENDIX I I I

CALIBRATION OP THERMOMETERS

The m e r c u r y thermometers used i n t h i s work were

calibrated a g a i n s t a Leed and N o r t h r o p p l a t i n u m r e s i s t a n c e

thermometer, No.679368 w h i c h had b e e n r e c e n t l y c a l i b r a t e d by

t h e N.B..S. The r e s i s t a n c e o f t h e t h e r m o m e t e r was measured

w i t h a Leeds and N o r t h r o p . t e m p e r a t u r e bridge.

B e f o r e a n y c a l i b r a t i o n was made, t h e r e s i s t a n c e of

t h e t h e r m o m e t e r a t t h e i c e p o i n t was d e t e r m i n e d w i t h t h e same

b r i d g e used f o r the c a l i b r a t i o n s . Crushed i c e prepared from

distilled w a t e r and t h r o u g h w h i c h a i r was c o n t i n u o u s l y bubbled

was used f o r t h i s d e t e r m i n a t i o n .

The r e s i s t a n c e was converted t o temperature by appli-

c a t i o n of the well-known equation,

R,-R +. .
t o , c /_JL 1 ^ t
o< Ro
0
^100 *' 100

where R = 25.5395 a b s . ohms ( d e t e r m i n e d i n t h i s work)

o - -
= 0.0039232 (N.B.S.)
c

" 75
= 1.49^ ( M B S .J )
34

The c a l i b r a t i o n of the t h r e e thermometers used i n

t h i s work a r e g i v e n i n f i g u r e 1 2 , where t h e c o r r e c t i o n i s

plotted a g a i n s t the true temperature. S i n c e the emersion

was kept constant d u r i n g the d e t e r m i n a t i o n s , the large

deviations at higher temperatures i s mainly accounted

for i n terms of a stem correction.

 137
APPENDIX I V

OPERATING INSTRUCTIONS FOR PRESSURE VISCOMETER

N o t e . F i g u r e 1. i s r e p r o d u c e d as f i g u r e 3, o f t h i s thesis.

Humble Type P r e s s u r e V i s c o s i m e t e r Type D

The Humble Type P r e s s u r e V i s c o s i m e t e r i s a n i n s t r u -

ment o f t h e r o l l i n g b a l l t y p e f o r m e a s u r i n g t h e v i s c o s i t y o f
s u b s u r f a c e samples o f o i l under v a r i o u s c o n d i t i o n s o f temper-
a t u r e and p r e s s u r e .

The a p p a r a t u s c o n s i s t s e s s e n t i a l l y o f a r e m o v a b l e ,
a c c u r a t e l y bored c y l i n d r i c a l b a r r e l of o n e - f o u r t h i n c h
nominal i n t e r n a l diameter, e i g h t inches long, i n which a
c l o s e l y f i t t i n g s t e e l b a l l r o l l s through the o i l w i t h the
barrel inclined at a d e f i n i t e angle. The b a l l makes c o n t a c t
a t one end o f t h e b a r r e l w i t h a n i n s u l a t e d e l e c t r o d e , c l o s i n g
an e l e c t r i c a l c i r c u i t w h i c h a c t u a t e s a b u z z e r . The m e a s u r e -
ments c o n s i s t e s s e n t i a l l y i n d e t e r m i n i n g t h e t i m e r e q u i r e d f o r
the b a l l t o t r a v e l t h e l e n g t h of the b a r r e l .

The d e t a i l s o f t h e c o n s t r u c t i o n a r e s h o w n b y d r a w i n g .
The b a r r e l i n w h i c h t h e b a l l r o l l s i s made f r o m s t a i n l e s s
s t e e l , e s p e c i a l l y b o r e d t o an e x a c t u n i f o r m d i a m e t e r and
polished. F o r extreme c o r r o s i v e c o n d i t i o n s a monel b a r r e l c a n
be f u r n i s h e d . The b a r r e l s l i d e s s n u g l y i n t o a h o l e b o r e d i n a
s o l i d s t a i n l e s s s t e e l c y l i n d e r , an u p p e r e x t e r n a l s h o u l d e r o f
t h e b a r r e l c o m p r e s s i n g a s m a l l s p r i n g , and i s h e l d i n p l a c e b y
a hollow nut. The s p r i n g p r e v e n t s t h e b a r r e l f r o m s e a t i n g
a g a i n s t t h e bottom of t h e bored hole i n t h e c y l i n d e r , w h i l e
narrow e x t e r n a l l o n g i t u d i n a l s l o t s i n t h e b a r r e l permit f l u i d
t o f l o w a r o u n d i t and t h r o u g h t h e b o t t o m .

The u p p e r p a r t o f t h e r e c e s s i n t h e s t e e l c y l i n d e r i s
e n l a r g e d t o f o r m a t a p e r e d chamber w h i c h a c t s as a r e s e r v o i r
f o r t h e o i l a f f o r d s space f o r a g i t a t i o n t o i n s u r e e q u i l i b r i u m
between t h e gas and o i l . The t a p e r p e r m i t s t h e b a l l t o r o l l
r e a d i l y i n t o t h e b a r r e l when t h e i n s t r u m e n t i s at.' a n a n g l e o f v

i n c l i n a t i o n o f 75 d e g r e e s . The u p p e r e n d o f t h e - c h a m b e r i s
s e a l e d b y a p o l i s h e d p i s t o n s e a t e d on a s h o u l d e r , t h e c l o s u r e
made w i t h a n e o p r e n e g a s k e t " o f a r e a s m a l l e r t h a n t h a t o f t h e
lower surface of the p i s t o n . The p r i m a r y g a s k e t c o m p r e s s i o n i s
e f f e c t e d b y means o f a h o l l o w n u t w h i c h s l i p s o v e r t h e p i s t o n .
 138
A r e t r a c t a b l e plunger w i t h a polished lower surface
i s screwed t h r o u g h t h e c y l i n d e r head i n s u c h a f a s h i o n t h a t
i t i s a c c e s s i b l e and may be t u r n e d w i t h a s m a l l w r e n c h w h i l e
t h e i n s t r u m e n t i s immersed i n a h i g h t e m p e r a t u r e b a t h . While
the v i s c o s i m e t e r i s b e i n g charged w i t h o i l o r t h e contents
b e i n g a g i t a t e d t o b r i n g about e q u i l i b r i u m , t h e p l u n g e r i s kept
p a r t l y o r f u l l y r e t r a c t e d . D u r i n g t h e c o u r s e o f a measurement,
however, t h e p l u n g e r i s screwed i n t o the c y l i n d e r , s e a l i n g t h e
u p p e r end o f t h e b a r r e l and s i m u l t a n e o u s l y s e a l i n g t h e l o w e r
end o f t h e b a r r e l b y p r e s s i n g i t a g a i n s t a g a s k e t i n t h e b o t t o m
of t h e b o r e d r e c e s s i n t h e c y l i n d e r . Since the pressure i s at
a l l t i m e s e q u a l i n s i d e and o u t s i d e o f t h e r o l l b a r r e l , t h e
i n s t r u m e n t h a s no p r e s s u r e c o e f f i c i e n t , and t h e d o u b l e s e a l i n g
of t h e b a r r e l a d e q u a t e l y p r e v e n t s l e a k a g e d u r i n g a measurement.

The s t e e l c y l i n d e r i s mounted o n t r u n n i o n s i n s u c h a
manner t h a t i t may b e r o t a t e d t h r o u g h a n a n g l e o f a p p r o x i m a t e l y
330 d e g r e e s . The t r u n n i o n b e a r i n g s a r e s e t i n a l u m i n u m p l a t e s
which a r e f a s t e n e d i n t u r n t o a t h i r d aluminum p l a t e equipped
w i t h f o u r l e v e l i n g screws. The s u p p o r t i n g p l a t e s w e r e s e t
c a r e f u l l y p e r p e n d i c u l a r t o t h e b a s e p l a t e and m a c h i n e d a c c r u a - -
t e l y i v i t h t h e t o p s p a r a l l e l t o ' t h e b a s e and o f t h e same h e i g h t ,
to p e r m i t use o f an o r d i n a r y b u b b l e type l e v e l i n a l i g n i n g t h e
i n s t r u m e n t f o r v i s c o s i t y measurement. Handles on t h e p l a t e s
make t h e i n s t r u m e n t r e a d i l y p o r t a b l e .

The t r u n n i o n p l a t e s a r e e q u i p p e d w i t h one f i x e d s t o p ,
c o n s i s t i n g o f a c y l i n d r i c a l b a r , w h i c h g i v e s t h e b a r r e l an
a n g l e o f i n c l i n a t i o n a p p r o x i m a t e l y 75 d e g r e e s f r o m t h e h o r i z o -
n t a l , and two r e m o v a b l e p o s i t i v e s t o p s a t a n g l e s o f i n c l i n a t i o n
o f a p p r o x i m a t e l y 23 d e g r e e s and 11 d e g r e e s , p e r m i t t i n g t h e r o l l
t i m e t o be v a r i e d i n t h e r a t i o s o f a p p r o x i m a t e l y 4:2:1 f o r a n y y

g i v e n v i s c o s i t y and s i z e o f b a r r e l and b a l l . Additional f l e x i -

b i l i t y i n t h e r o l l time i s o b t a i n e d t h r o u g h t h e u s e o f remova-
b l e r o l l b a r r e l s and b a l l s o f d i f f e r e n t d i a m e t e r s . The r o l l
t i m e u s u a l l y i s k e p t b e t w e e n 20 and 60 s e c o n d s . F o r t h e r§nge
o f v i s c o s i t y t h u s f a r e n c o u n t e r e d , 0.5 t o 10 c p . A b a r r e l o f
0.258 i n c h d i a m e t e r w i t h b a l l s o f .2495, .250, .2505 and .2510
i n c h diameter have s u f f i c e d . The b o t t o m o f t h e c y l i n d e r
e n c l o s i n g t h e b a r r e l i s c l o s e d b y means o f a n e l e c t r o d e a s s e m b l y .

The a u x i l i a r y a p p a r a t u s c o n s i s t s o f a v a c u u m t u b e r e l a y
and b u z z e r c i r c u i t f o r i n d i c a t i n g t h e i n s t a n t o f c o n t a c t o f t h e
b a l l with' t h e e l e c t r o d e , a c a l i b r a t e d s t e e l tube bourdon p r e s s -
u r e g a u g e , - a m a n i f o l d w i t h V a l v e s f o r a d m i t t i n g and w i t h d r a w i n g
t h e s a m p l e , and a w a t e r b a t h w i t h e l e c t r i c a l h e a t i n g c e l l s and
thermostat. A s m a l l f i l t e r , u s e d o n l y when a b s o l u t e l y n e c e s s a -
r y ; i s p l a c e d i n t h e l i n e b e t w e e n t h e m a n i f o l d and t h e v i s c o -
s i m e t e r i n s u c h p o s i t i o n t h a t t h e s a m p l e w i l l be f i l t e r e d a t
the r e s e r v o i r temperature.
 139
V i s c o s i t y d e t e r m i n a t i o n s c a n r e a d i l y be made on a s
l i t t l e as 2 0 - c c . o f l i q u i d . The e n t i r e s y s t e m , i n c l u d i n g t h e
v i s c o s i m e t e r , p r e s s u r e g a u g e , m a n i f o l d , and c o n n e c t i n g 1/8
i n c h s t e e l t u b i n g r e q u i r e s a c h a r g e o f a p p r o x i m a t e l y 80* c c . o f
s a t u r a t e d subsurface o i l , l e e s than 20$ o f the contents o f t h e
usual subsurface sampler.

Due t o t h e ' s m a l l c l e a r a n c e b e t w e e n t h e r o l l i n g b a l l
and t h e b a r r e l , a b s o l u t e c l e a n n e s s i s e s s e n t i a l t o s u c c e s s f u l
operation. A f t e r each s e r i e s o f measurements, t h e b a r r e l i s
r e m o v e d , washed w i t h e t h e r , and p o l i s h e d w i t h a s i l k r a g , and
t h e c y l i n d e r and c o n n e c t i n g l i n e s washed c a r e f u l l y w i t h e t h e r
and evacuated.

CALIBRATION

The i n s t r u m e n t s h o u l d be r e c a l i b r a t e d f r o m t i m e t o -
time w i t h a s e r i e s o f f l u i d s c o n s i s t i n g o f hexane, kerosene, a
l i g h t l u b r i c a t i n g o i l , and v a r i o u s b l e n d s o f t h e s e t h r e e m a t e r -
ials. The v i s c o s i t i e s o f t h e c a l i b r a t i n g f l u i d s w e r e d e t e r -
mined w i t h a Ubbelohde suspended l e v e l c a p i l l a r y i n s t r u m e n t
c a l i b r a t e d b y t h e U.S. B u r e a u o f S t a n d a r d s .

As i t i s p r a c t i c a l l y i m p o s s i b l e , now, t o p u r c h a s e ,
Ubbelohde suspended l e v e l c a p i l l a r y i n s t r u m e n t s t h r e e Ostwald-
Harris c a l i b r a t e d ' V i s c o s i m e t e r s covering c e n t i s t r o k e ranges
o f 0.8-2.0, 1.8-4.0 and 4.0-15 c a n be u s e d . The d e n s i t i e s o f
the c a l i b r a t i n g f l u i d s a r e determined w i t h a pycnometer.

C a l i b r a t i o n charts are prepared f o r a given s i z e bar-

r e l and b a l l b y p l o t - t i m e t h e a b s o l u t e v i s c o s i t y o f e a c h f l u i d
a g a i n s t t h e p r o d u c t o f t h e r o l l t i m e and t h e d i f f e r e n c e i n
d e n s i t y b e t w e e n t h e f l u i d and t h e b a l l , a c c o r d i n g t o t h e m e t h o d
s u g g e s t e d b y K e n n e d y and u s e d b y S a g e 5 .

EXPERIMENTAL PROCEDURE

M e a s u r e m e n t s a t r e s e r v o i r t e m p e r a t u r e a r e ,made w i t h
t h e i n s t r u m e n t immersed i n a w a t e r b a t h , t h e t e m p e r a t u r e o f
w h i c h i s c o n t r o l l e d t o i 0.5°P. O i l and g a s a r e e x p a n d e d i n t o
t h e v i s c o s i m e t e r t h r o u g h 1/8 i n c h o u t s i d e d i a m e t e r s t e e l t u b -
i n g d i r e c t from a subsurface sampler, t h e contents of which
have been s a t u r a t e d p r e v i o u s l y . D u r i n g c h a r g i n g , t h e r e t r a c t a -
b l e p l u n g e r i s t u r n e d t o a p o s i t i o n midway b e t w e e n t h e s e a t e d
and f u l l y r e t r a c t e d p o s i t i o n s , w i t h t h e b a l l i n t h e e n l a r g e d
p o r t i o n of the c y l i n d e r . The p a r t i a l l y r e t r a c t e d p l u n g e r p r e v -
ents the b a l l from e n t e r i n g the r o l l b a r r e l but permits f l u i d s
t o p a s s b a c k and f o r t h f r e e l y . The c h a r g i n g I s done w i t h t h e
v i s c o s i m e t e r t i l t e d t o t h e p o s i t i o n w i t h t h e e l e c t r o d e u p and
t h e e n l a r g e d p a r t o f t h e c y l i n d e r down, s o t h a t d u r i n g t h e
i n i t i a l stages of c h a r g i n g t h e oil:'.is r e t a i n e d i n t h e enlarged
p a r t o f t h e c y l i n d e r and o n l y g a s i s t r a p p e d i n t h e b a r r e l .
As t h e p r e s s u r e i n t h e i n s t r u m e n t b u i l d s u p w i t h t h e a d d i t i o n
 140
o f o i l and g a s , t h e o i l i s r e s a t u r a t e d by v i g o r o u s r o c k i n g o f
t h e c y l i n d e r , t h e b a l l a s s i s t i n g i n k e e p i n g t h e o i l homogeneous.
Charging i s c o n t i n u e d u n t i l the o i l i n the v i s c o s i m e t e r i s
c o m p l e t e l y r e s a t u r a t e d and t h e p r e s s u r e c o n s i d e r a b l y e x c e e d s
the s a t u r a t i o n pressure.

The p l u n g e r i s t h e n r e t r a c t e d t h e f u l l amount, t h e c y l -
i n d e r t i l t e d t o t h e 75 d e g r e e i n c l i n a t i o n , t h e e l e c t r i c a l s y s t e m
c o n n e c t e d , and t h e b a l l a l l o w e d t o e n t e r t h e b a r r e l . The f a l l -
i n g b a l l a c t s as a pump, d i s p l a c i n g t h e o i l i n t h e b a r r e l down
and o u t t h e b o t t o m and u p t h r o u g h t h e e x t e r n a l s l o t s i n t h e b a r -
r e l to the e n l a r g e d upper p a r t of the c y l i n d e r . When t h e b u z z e r
i n d i c a t e s c o m p l e t i o n of the f a l l , the c y l i n d e r i s r o t a t e d t o the
r e v e r s e p o s i t i o n and t h e b a l l a l l o w e d t o r o l l o u t o f t h e b a r r e l ,
f l u s h i n g t h e o i l downward i n t o t h e e n l a r g e d p a r t o f t h e c y l i n d e r ,
w i t h the b a r r e l r e p l e n i s h e d t h r o u g h the e x t e r n a l s l o t s . Oil is
t h u s pumped b a c k and f o r t h b e t w e e n t h e b a r r e l and t h e c y l i n d e r
a number o f t i m e s t o i n s u r e a b s o l u t e h o m o g e n e i t y .

The b a l l i s t h e n a l l o w e d t o e n t e r t h e b a r r e l and t h e
r e t r a c t a b l e p l u n g e r s e a t e d f i r m l y on t h e t o p o f t h e b a r r e l ,
c o m p r e s s i n g t h e s p r i n g , and s i m u l t a n e o u s l y s e a t i n g t h e b a r r e l
a g a i n s t the lower g a s k e t . The c y l i n d e r i s r o t a t e d ' t o a p p r o x i m a -
t e l y a v e r t i c a l p o s i t i o n w i t h t h e e l e c t r o d e and up, s u f f i c i e n t
t i m e a l l o w e d f o r t h e b a l l t o t r a v e l t h e l e n g t h o f t h e b a r r e l and
s t o p a g a i n s t t h e p l u n g e r , and t h e c y l i n d e r t h e n r o t a t e d t o a
p o s i t i o n j u s t s h o r t of h o r i z o n t a l . The r o l l t i m e i s t h e n d e t e r -
mined by r o t a t i n g the c y l i n d e r s u d d e n l y u n t i l i t s t r i k e s the
p o s i t i v e s t o p w i t h t h e e l e c t r o d e down, a t t h e t i m e m e a s u r e d w i t h
a s t o p w a t c h f o r t h e b a l l t o r e a c h t h e e l e c t r o d e and s o u n d t h e
buzzer. S e v e r a l d e t e r m i n a t i o n s a r e made, u s u a l l y a t two a n g l e s
of i n c l i n a t i o n . The r o l l t i m e s a r e r e a d i l y r e p r o d u c i b l e t o 0.2
second.

A f t e r d e t e r m i n a t i o n o f the r o l l time i n the supercomp-

r e s s e d s a t u r a t e d o i l , t h e p l u n g e r i s r e t r a c t e d s l i g h t l y and t h e
p r e s s u r e r e d u c e d by w i t h d r a w i n g a s l i g h t amount o f o i l t h r o u g h
t h e i n l e t c o n n e c t i o n , t h e p l u n g e r r e s e a t e d , and t h e r o l l t i m e
d e t e r m i n e d a t t h e new p r e s s u r e . A f t e r the s a t u r a t i o n p r e s s u r e
h a s b e e n r e a c h e d , gas o r gas and o i l a r e w i t h d r a w n i n i n c r e -
m e n t s w i t h t h e p l u n g e r f u l l y r e t r a c t e d - and t h e e n l a r g e d p a r t o f
t h e chamber u p . A f t e r each w i t h d r a w a l , the f l u i d s i n the cy-
l i n d e r a r e a g i t a t e d b y r o t a t i n g t h e c y l i n d e r b a c k and f o r t h f r o m
a h o r i z o n t a l p o s i t i o n u n t i l t h e p r e s s u r e becomes c o n s t a n t ,
i n d i c a t i n g e q u i l i b r i u m b e t w e e n t h e r e s i d u a l o i l and g a s . The
p l u n g e r i s t h e n r e s e a t e d and t h e r o l l t i m e m e a s u r e d as b e f o r e .
T h i s procedure i s r e p e a t e d u n t i l the p r e s s u r e i n the v i s c o s i -
m e t e r has b e e n r e d u c e d t o a t m o s p h e r i c . The d e t e r m i n a t i o n o f t h e
complete p r e s s u r e - r o l l time curve r e q u i r e s u s u a l l y three to f o u r
hours. O c c a s i o n a l l y some d i f f i c u l t y i s e x p e r i e n c e d i n a t t a i n i n g
e q u i l i b r i u m at atmospheric p r e s s u r e , i n w h i c h case the i n s t r u m e n t
i s u s u a l l y allowed to stand f o r s e v e r a l hours or over n i g h t
before t h i s point i s determined.
 141
A f t e r c o m p l e t i o n of the d e t e r m i n a t i o n a t atmos-
p h e r i c p r e s s u r e , the r e s i d u a l o i l i s d r a i n e d from the p r e s s u r e
v i s c o s i m e t e r and t h e v i s c o s i t y d e t e r m i n e d a t t h e Same t e m p e r -
a t u r e w i t h the Ubbelohde, or the O s t w a l d - H a r r i s - v i s c o s i m e t e r .
T h i s f u r n i s h e s a c h e c k on t h e o p e r a t i o n o f t h e p r e s s u r e v i s -
c o s i m e t e r f o r each s e r i e s of measurements.

The d e n s i t y o f t h e r e s i d u a l o i l d r a i n e d f r o m t h e
v i s c o s i m e t e r i s d e t e r m i n e d a t room t e m p e r a t u r e w i t h a pycno-
m e t e r and c o r r e c t e d t o t h e r e s e r v o i r t e m p e r a t u r e w i t h t h e
N a t i o n a l Standard Petroleum O i l Tables. The d e n s i t y o f t h e
s a t u r a t e d o i l charged to the v i s c o s i m e t e r i s determined
s e p a r a t e l y d u r i n g the course of the r e g u l a r s u b s u r f a c e sample
examination. The d e n s i t y a t t h e i n t e r m e d i a t e p r e s s u r e s i s
e s t i m a t e d by a l i n e a r i n t e r p o l a t i o n . Since the d e n s i t y of
the s t e e l b a l l i s 7.85 gm./cc/ and t h e d e n s i t y o f m o s t o f t h e
o i l s e x a m i n e d i s o f t h e o r d e r o f 0 . 7 t o 0.8 g m . / c c , e s t i -
m a t i o n o f t h e o i l d e n s i t y t o t h e n e a r e s t 0 . 0 7 gm./cc. s u f f i c e s
t o g i v e an a c c u r a c y o f 1% i n t h e d e n s i t y d i f f e r e n c e . The
v i s c o s i t y a t each p r e s s u r e i s d e t e r m i n e d by m u l t i p l y i n g the
r o l l t i m e b y t h e c o r r e s p o n d i n g d e n s i t y d i f f e r e n c e and r e a d i n g
the a p p r o p r i a t e v a l u e from the c a l i b r a t i o n curve.
 142

APPENDIX V

ELECTRONIC TIMER

The electronic t i m e r w h i c h was developed as an

alternative to the Jacquet m a g n e t i c a l l y - o p e r a t e d stop-watch,

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

o p e r a t e d f r o m 115 Volts a . c , and a main-synchronized pulse

generator. The p u l s e c o u n t e r was a "Type 37-7-C, s c a l e of

128", manufactured b y C.S.R.D.E. o f C a n a d a , u s e d by the N a t i o n a l

Research C o u n c i l of Canada. The d e v i c e r e g i s t e r e d up to 128

p u l s e by a seven p l a c e b i n a r y n u m b e r d i s p l a y e d
7 on a c a s c a d e of

"magic e y e s " , and u n i t s o f 128 w e r e r e l a y e d t o a s m a l l d e c i m a l

counter.

The p u l s e g e n e r a t o r was designed to operate from a

power s u p p l y o f 6.3 V o l t s a.c. and 400 V o l t s d . c , which was

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

t o t h e one m e n t i o n e d above. A circuit diagram f o r the pulse

g e n e r a t o r i s g i v e n i n f i g u r e 13. P u l s e s w i t h mains frequency

w e r e f e d f r o m t h e o u t p u t t e r m i n a l , B, to the counter, the

first stage of which counted a t the mains f r e q u e n c y . It was

t h e r e f o r e p o s s i b l e t o read the time t o the n e a r e s t l/60 sec.

The a c c u r a c y o f t h e d e v i c e i s n e c e s s a r i l y d e p e n d e n t on the

f r e q u e n c y of the domestic power s u p p l y , b u t as mentioned

 143

above, t h i s i s not a serious limitation. This timing

d e v i c e was tested against t h e J a c q u e t s t o p - w a t c h and found

to give consistent r e s u l t s t o w i t h i n 0.01$ over periods of

a b o u t one hour.
 + 400V.
•

• C

*3
O
H)
O
H
H
O

p
©
H

F i g u r e 13. Pulses-Generator
 144
APPENDIX V I

DESIGN OP PRESSURE BOMB

The d e s i g n i s b a s e d o n t h e A.S.M.E. Code f o r

Pressure Vessels which i s described by Perry.1 The maximum

stresses i n the walls o f a t h i c k w a l l e d p r e s s u r e v e s s e l due

to an i n t e r n a l pressure of P are g i v e n by the r e l a t i o n s ,

/ R +
1
( t ^max
S P
l (
~2 )

(a,.)
r 'max

s
RR2 - 1

where (S. ) maximum h o o p stress

t max
( -n )max
s maximum r a d i a l s t r e s s

longitudinal stress (constant)'

and diameter r a t i o O.D./ I.D.

F o r a maximum w o r k i n g p r e s s u r e o f 10,000 p s i . , t h e

maximum s t r e s s e s f o r t h e p r e s s u r e v i s c o m e t e r and t h e t r a n s f e r

bomb a r e as f o l l o w s ,

Viscometer, R =2.0

< t ) max =
S 1 6
>7° 0
P s i

( r) s
max = 1 0 , 0 0 0 p s i

1. P e r r y , J . H . - " C h e m i c a l Engineers Handbook", p . 1 2 3 8 ,

M c G r a w - H i l l (1950)
 145

S Q = 3,300 p s i

Maximum s t r e s s = 16,700

Safety factor = 5*4

T r a n s f e r bomb, R Q = 1.72

<Vmax = 20,200 p s i

< S
rW = 10,000 p s i

S e = 5,100 p s i

Maximum s t r e s s = 20,200

Safety factor = 4.5

The safety factors a r e b a s e d o n a v a l u e o f 90,000

psi f o rthe ultimate strength o f 304 o r 316 s t a i n l e s s steel,

The A.S.M.E. recommend a f a c t o r of s a f e t y o f 4- t o 5 on t h e

ultimate strength.