Sugar Technology Reviews, 11(1984) 209-257

Elsevier Science Publishers B.V., Amsterdam - Printed in The Netherlands

VISCOSITY OF SUGAR SOLUTIONS

M . MATHLOUTHI and P . KASPRZYK

I n s t i t u t U n i v e r s i t a i r e de Technoloqie, D e ~ a r t e m e n t" B i o l o a i e Awnliqu@eU,
U n i v e r s i t P de DIJON, B.P. 510, 21014 DIJON CPdex ( F r a n c e ) .

Contents

I. I n t r o d u c t i o n , 210

11. Theory and B a s i c v i s c o s i t y r e l a t i o n s , 21 1

A. V i s c o s i t y - C o n c e n t r a t i o n r e 1 a t i o n s f o r Dure s o l u t i o n s , 21 1

1. E i n s t e i n ' s Equation, 211

2. O t h e r c l a s s i c a l r e l a t i o n s , 214
3 . Recent v i s c o m e t r i c equations, 216

B. Viscosity-Ternwerature r e l a t i o n s f o r n u r e s o l u t i o n s , 218

1. C l a s s i c a l t h e o r i e s and r e l a t i o n s , 218
2. E m o i r i c a l r e l a t i o n s , 220

C . V i s c o s i t y r e l a t i o n s f o r imnure s o l u t i o n s , 221

1. Homogeneous nhases : molasses, 221

2. Heterogeneous ohases : massecuites, 223
3 . S h e a r i n g c h a r a c t e r i s t i c s o f molasses and m a s s e c u i t e s , 225

111. Measurements o f v i s c o s i t y , 226

A. L a b o r a t o r y measurements, 227
B. I n d u s t r i a l measurements, 232
C . On l i n e c o n t r o l u s i n g v i s c o m e t e r s , 235

I V . R e s u l t s and D i s c u s s i o n , 236

A. V i s c o s i t y o f p u r e s o l u t i o n s , 236

1. D i l u t e s o l u t i o n s , 236
2. Concentrated s o l u t i o n s , 237
3. I n t e r p r e t a t i o n . 239

a - Hydration , 239
b - M o l e c u l a r a s s o c i a t i o n , 240

0081-9204/84/$14.70 O 1984 Elsevier Science Publishers B.V.

 8 . V i s c o s i t y of impure s o l u t i o n s , 240

1. V i s c o s i t y o f molasses, 240
2. V i s c o s i t y o f nlassecuites, 245
3. I n t e r p r e t a t i o n , 246
a - e f f e c t o f a d d i t i v e s , 247
b - f l o w o f non-Newtonian f l u i d s , 247

V. E f f e c t o f v i s c o s i t y on sugar manufacturing,248

A. E f f e c t on c r y s t a l l i z a t i o n , 248
8 . E f f e c t on molasses f o r m a t i o n and e x h a u s t i o n , 249
C . E f f e c t on t h e f l o w i n p i p e s , 250

V I . Conclusion, 251

Summary, 251 ( i n Spanish, 257)

Acknowledgements, 252

References , 252

V i s c o s i t y i s a p h y s i c a l n r o p e r t y o f sucrose s o l u t i o n s which p l a y s a
d e t e r m i n a n t r o l e i n t h e sugar t e c h n o l o q y . T h i s f a c t o r m a i n l y concerns t h e
crystallization station i n a sugar f a c t o r y . A f t e r t h e b o i l i n g Drocess, when
a saturated syrup i s obtained, a l l the f o l l o w i n q onerations, i . e . , flow,
c r y s t a l l i z a t i o n , c e n t r i f u g a t i o n , c o o l i n g , m i x i n g and molasses e x h a u s t i o n denend,
t o some e x t e n t on v i s c o s i t y . Thus v i s c o s i t y has been regarded f r e q u e n t l y
as a n h y s i c a l p r o o e r t y of aqueous sucrose s o l u t i o n s 1 o r a t e c h n i c a l
c o n d i t i o n i n manufacturinq ooerations each t i m e t h a t c r y ~ t a l l i z a t i o n ~ - ~
o r molasses was s t u d i e d . But, as f a r as we a r e aware, no s p e c i a l
r e v i e w was devoted, these l a s t t e n y e a r s , t o t h e v i s c o s i t y i t s e l f . The recom-
mendations o f t h e 3 l a s t meetings o f I C U M S A ~ - ~( s~ u b j e c t 23) were focused on
t h e methods o f d e t e r m i n i n q t h e v i s c o s i t y o f molasses and massecuites and t o
t h e f a c t o r s i n f l u e n c i n g t h e r h e o l o q i c a l p r o p e r t i e s o f t h e s e ~ r o d u c t s .One must
go back t o t h e 6 0 ' s i n o r d e r t o f i n d 11, on a m o l e c u l a r l e v e l
treatments
of t h e v i s c o s i t y o f aqueous sucrose s o l u t i o n s . Although t h e measurement o f
v i s c o s i t y i s a r e l a t i v e l y easy technique, t h e i n t e r n r e t a t i o n o f r e s u l t s and
t h e t h e o r i e s on which t h i s concent i s based a r e r a t h e r c o m p l i c a t e d . The r e a d e r s
o f t h i s j o u r n a l a r e u s u a l l y i n t e r e s t e d i n n r a c t i c a l f a c t o r y nroblems. However,
i t has been nroved t h a t t h e o r y i s t h e most e f f i c i e n t and e a s i e s t way t o s o l v e
p r a c t i c a l problems. T h a t i s why we s t a r t t h i s r e v i e w b y r e c a l l i n q t h e r e l a t i o n s
between v i s c o s i t y and c o n c e n t r a t i o n , v i s c o s i t y and temperature and t h e t h e o r i e s
t h a t p e r m i t t e d e s t a b l i s h i n g these r e l a t i o n s . Very o f t e n , t h e o r i e s a r e based on
s i m p l e models such as s u c r o s e i n w a t e r i s c o n s i d e r e d as a h a r d s ~ h - e r ef l o w i n g i n a
continuous is o t r o p e , incompressible medium. These c o n d i t i o n s a r e o b v i o u s l y
v e r y f a r f r o m t h e a c t u a l p h y s i c a l and t e c h n i c a l ones i n a sugar f a c t o r y .
Nevertheless, empirical r e l a t i o n s are derived from the t h e o r e t i c a l equations
and t h e i n t e r p r e t a t i o n o f e x p e r i m e n t a l r e s u l t s on a m o l e c u l a r l e v e l n e c e s s i t a t e s
t h e a d o p t i o n o f s i m p l i f i e d systems.
I n o r d e r t o o b t a i n comparable r e s u l t s of measurements, i t i s d e s i r a b l e t o be
i n f o r m e d on t h e v a r i o u s methods a p p l i e d t o sugar m a t e r i a l s . A l t h o u g h t h e
r o t a t i n g - c y l i n d e r method seems t o be s u i t a b l e f o r molasses, and t h e n i p e - f l o w
method f o r d e t e r m i n i n g r h e o l o g i c a l p r o p e r t i e s o f molasses and massecuites, t h e
d e s c r i p t i o n of l a b o r a t o r y methods as w e l l as t h e techniques used i n t h e
a u t o m a t i c c o n t r o l a r e reviewed. I n t e r p r e t a t i o n o f t h e e x p e r i m e n t a l r e s u l t s by
means of m o l e c u l a r s t r u c t u r e and i n t e r a c t i o n s h e l p s i n d e t e r m i n i n g t h e r 6 1 e of
v i s c o s i t y i n t h e f a c t o r y processes. C r y s t a l l i z a t i o n , molasses f o r m a t i o n and
s t r u c t u r e and t h e f l o w o f sugar s o l u t i o n s a r e i n f l u e n c e d by v i s c o s i t y . A r e v i e w
of t h e l i t e r a t u r e may be a c o m p i l a t i o n o f i n f o r m a t i o n s o r t h e o r i e n t e d s y n t h e s i s
of t h e s e i n f o r m a t i o n s . The way we have chosen t o p r e s e n t t h i s work i s t h e second
and o u r o r i e n t a t i o n i s an a t t e m p t o f c o o o e r a t i o n between t h e o r y and p r a c t i c e .

11. THEORY AND BASIC VISCOSITY RELATIONS

' V i s c o s i t y o f sugar s o l u t i o n s i s n o t easy t o p u t i n t o equations i f we t a k e
i n t o account t h e f a c t t h a t t h e sucrose m o l e c u l e i s canable o f h y d r a t i o n , sugar-
sugar a s s o c i a t i o n o r t h e p r o m o t i o n o f " w a t e r - s t r u c t u r e " . The d e f i n i t i o n o f
v i s c o s i t y when we c o n s i d e r an i s o t r o p e , i n c o m p r e s s i b l e , Newtonian 1 i q u i d and
n e g l e c t t h e volume f o r c e s i s d e r i v e d f r o m t h e r e l a t i o n 12. .

where f i s t h e q u a n t i t y o f energy t r a n s f o r m e d i n t o h e a t p e r u n i t t i m e , the

v i s c o s i t y c o e f f i c i e n t , d v t h e c o n s i d e r e d volume and 1 t h e d i s t a n c e between
the flowing layers.
The p i o n e e r i n a p p l y i n g v i s c o s i t y c a l c u l a t i o n t o sucrose s o l u t i o n s was
in stein'^^ who v e r i f i e d h i s t h e o r y o f t h e p e r t u r b a t i o n o f t h e f l o w o f a l i q u i d
by r i g i d spheres w i t h a 10 % c o n c e n t r a t e d sucrose s o l u t i o n .

A. VISCOSITY-CONCENTRATION RELATIONS FOR PURE SOLUTIONS

1. E i n s t e i n ' s E q u a t i o n .
A f t e r a l o n g c a l c u l a t i o n based on t h e N a v i e r e q u a t i o n s f o r t h e flow i n
c o n t i n u o u s media, E i n s t e i n , supposing spheres with a diameter l a r g e r than
those of t h e l i q u i d molecules, o b t a i n e d a r e l a t i o n which, i n t h e f i r s t o r d e r , i s :
where 7 and qo a r e r e s p e c t i v e l y t h e a b s o l u t e v i s c o s i t i e s o f t h e s o l u t i o n and
t h e s o l v e n t and 0 t h e volume f r a c t i o n o c c u p i e d by t h e s o l u t e .
The 1 i m i t and r e s t r i c t i v e c o n d i t i o n s f o r t h e a p p l i c a t i o n o f ( 2 )
a r e i n c l u d e d i n t h e terms i n which E i n s t e i n expressed h i s r e l a t i o n :
" I f v e r y small r i g i d spheres a r e i n suspension i n a l i q u i d , t h e c o e f f i c i e n t of
i n t e r n a l f r i c t i o n i n c r e a s e s by a f r a c t i o n equal t o t w i c e and h a l f t h e t o t a l
volume o f t h e spheres i n suspension i n t h e u n i t y o f volume n r o v i d e d , t h a t t h i s
volume i s v e r y s m a l l ".
L e t P t h e hydrodynamic r a d i u s o f t h e molecule, p t h e s p e c i f i c w e i g h t of
t h e s o l u t i o n , M t h e m o l e c u l a r w e i g h t o f t h e s o l u t e , n t h e number o f molecules
p e r volume u n i t and N t h e Avogadro number.Thenmay be deduced f r o m r e l a t i o n ( 2 ) :

which ,compared t o t h e r e l a t i o n between t h e d i f f u s i o n c o e f f i c i e n t D and t h e

hydrodynamic r a d i u s :

p e r m i t t e d E i n s t e i n t o g i v e numerical values o f e q u a t i o n s ( 2 ) and ( 3 ) i n t h e

case of an aqueous sucrose s o l u t i o n . The values o b t a i n e d f o r a 10 % sucrose
s o l u t i o n t a k i n g i n t o account t h e v i s c o s i t y o f w a t e r a t 9.5' C (0.0135 P) and t h e
2
d i f f u s i o n c o e f f i c i e n t a t 20' C (0.384 cm l d a y ) a r e :

These values were c o r r e c t e d i n a second p ~ b l i c a t i o n ' o~ f~ January 1906 where

t h e p y s i c a l c o n s t a n t s o f L a n d 8 l t and ~ 6 r n s t e i n 'were
~ adopted :

P = 0.49 tnm
N = 6.56 loz3 molecules/mole

The Avogadro number i s g i v e n w i t h a r e l a t i v e l y low e r r o r ( 5 %) w h i l e t h e

hydrodynamic r a d i u s o f t h e sucrose m o l e c u l e i s 20 % h i g h e r t h a n t h e v a l u e
0
o b t a i n e d from t h e c r y s t a l l o g r a p h i c d a t a (PC = 4.04 A). S i n c e 1906, E i n s t e i n
a d m i t t e d t h e p o s s i b i l i t y o f a n a s s o c i a t i o n of s e v e r a l w a t e r molecules w i t h t h e
sucrose molecule l e a d i n g t o an i n c r e a s e o f t h e hydrodynamic r a d i u s . The
0
c a l c u l a t i o n o f t h e number o f h y d r a t i o n f r o m P = 4.9 A and PC = 4.04 A g i v e s a
v a l u e of 5.3 Hz0 p e r molecule of sucrose w h i c h i s i n good agreement w i t h r e c e n t
d e t e r m i n a t i o n s 15'16. The sucrose m o l e c u l e has almost a s p h e r i c a l shape i n t h e
 c r y s t a l , b u t t h i s i s n o t t h e case i n aqueous s o l u t i o n . T h i s i s another f a c t o r
which c o n t r i b u t e s t o t h e d i f f e r e n c e between c a l c u l a t e d and e x p e r i m e n t a l v a l u e s .
I n o r d e r t o t a k e i n t o account t h e shape o f molecules, ~ e f f r e y ' s~u b t i t u t e d , i n
h i s c a l c u l a t i o n s , an e l l i p s o i d f o r t h e sphere. The t h e o r y was 4 r e a t l y
improved by Simha18 who i n t r o d u c e d a f a c t o r v f o r t h e d e f o r m a t i o n s o f t h e sphere
which have two l i m i t s : t h e d i s c and t h e r o d . Ifa/b i s t h e e x c e n t r i c i t y r a t i o
o f the e l l i p s o i d , the value o f v i s g i v e n by t h e f o l l o w i n g r e l a t i o n s

I
2 (a/b12 14
Rods : v = (ah) t + - (6)
i
!
15 ( L o g 2 ( a / b ) - 312) 5 (Log 2 ( a / b ) - l5

C o n s i d e r i n g t h e d e f o r m a t i o n o f t h e s o l v e n t by t h e s o l u t e , Simhalg c a r r i e d
I E i n s t e i n ' s c a l c u l a t i o n t o t h e second order,and o b t a i n e d f r o m r e l a t i o n ( 2 ) :

r'lo- 1 = 2,5 a2 t i 2 , 6 g 22

which g i v e s , when !a2 i s r e p l a c e d by v2c2/m2 ( v 2 = t h e volume o f t h e s o l u t e ,

m2 i t s mass and c 2 c o n c e n t r a t i o n i n g p e r u n i t volume) :

where t h e member o f t h e e q u a t i o n s on t h e l e f t s i d e i s t h e reduced v i s c o s i t y

20
and -'l-'lo , t h e s p e c i f i c v i s c o s i t y 'lsp
'lo
.
By comparing ( 8 ) t o t h e Huggins
relation :

1 where [ r ] ] = 1:b0m o, i s
'loC2
t h e i n t r i n s i c v i s c o s i t y . I f c 2 i s expressed i n

1 g.1100 ml, t h e u n i t o f [r]]is 100 m l / g and ( 8 ) may be w r i t t e n :

where V 2 and M2 a r e t h e m o l a r volume and m o l a r mass o f t h e s o l u t e . I t may be

deduced :
which g i v e s when we replace[n]by 2,5 V2/100 M2, k 1 = 1 ~ . 6 / ( 2 , 5 ) ~= 2.01.
T h i s value of Huggins c o e f f i c i e n t k t , o f about 2, i s c o n s i d e r e d as
t h e i d e a l v a l u e o f t h e E i n s t e i n - S i m h a model, and compared t o e x p e r i m e n t a l r e s u l t s .

2. Other c l a s s i c a l r e l a t i o n s .
21
One o f t h e e a r l i e s t r e l a t i o n s i s t h a t o f Vand

where vr = V/vO i s r e l a t i v e v i s c o s i t y , k l i s a shape f a c t o r f o r s i n q l e spheres,

k 2 a shape f a c t o r o f c o l l i s i o n d o u b l e t s , r 2 a c o l l i s i o n t i m e c o n s t a n t , Q a
hydrodynamic i n t e r a c t i o n c o n s t a n t and c t h e c o n c e n t r a t i o n . C o n s i d e r i n g the two first
terms o f t h e developed formula ( 1 3 ) , m u l t i p l y i n g t h e 2 members o f t h e e q u a t i o n
by ( 1 - Q c ) and n e g l e c t i n g q2c2, we may w r i t e ( 1 3 ) i n t h e f o r m :

T h i s f o r m o f Vand's e q u a t i o n i s comparable t o ~ r a e m e r ' sr e~ l ~a t i o n used f o r

polymers :

I d e n t i f i c a t i o n o f (14)with(15) leads t o k l =[V]

Taking t h e sucrose molecule as a model h a v i n g an e l l i p s o i d a l f o r m w i t h

a/b = 1.84, vand2' o b t a i n e d t h e values o f k1 = 2.75, k z = 3.175, Q = 0.6 and
r 2 r a n g i n g f r o m 2.089 a t 0" C t o 1.489 a t 100° C. He a l s o o b t a i n e d a h y d r a t i o n
number o f 10.54 a t 0' C and 2.45 a t 100' C.
The model of Vand was a p p l i e d by Robinson and t o the study o f d i l u t e
solutions o f small molecules. Their r e l a t i o n :

where A3 and Q a r e c o n s t a n t s , compared t o ( 1 3 ) p e r m i t s i . d e n t i f i c a t i o n o f A3 w i t h

kl. This leads t o t h e same v a l u e f o r t h e h y d r a t i o n number o f sucrose a t
20" C, i .e. 7.7 H20 p e r sucrose. R e l a t i o n (16) i s c l o s e t o an e a r l y f o r m u l a
u t i l i z e d f o r polymers and due t o ~ r r h e n i u s - R o e t h e r Z 4 :

As n o t e d above,A3 i s i d e n t i f i e d t o k , w h i c h i s i d e n t i c a l t o [V] Thus

KAR = kl = Q ; which means t h a t Q c o n t a i n s i m p l i c i t l y [V] .
 I n o r d e r t o d e s c r i b e t h e v i s c o m e t r i c b e h a v i o r o f t h e b i n a r y m i x t u r e s water-
25
e t h y l e n e g l y c o l , w a t e r - q l u c o s e , water-sucrose and w a t e r - g l y c e r i n e , Furuse
oronosed t h e r e l a t i o n :

where @ has t h e same meaning as i n t h e r e l a t i o n ( 2 ) o f E i n s t e i n .

When P) i s r e p l a c e d by i t s v a l u e , and s n e c i f i c v i s c o s i t y T s n ( Vs-, = 9, - 1 )
i s adopted i n s t e a d o f 7 , (18) may be w r i t t e n :

where V z and ?42 a r e r e s p e c t i v e l y t h e volume and t h e m o l e c u l a r w e i g h t of t h e

solute.
( 1 8 b ) i s comparable t o t h e e q u a t i o n ( 1 9 ) proposed by F i c k e n t c h e r and
Narkz6 9 i n 1 9 3 0 , i n o r d e r t o d e s c r i b e t h e v i s c o s i t y o f polymers i n d i l u t e
solutions :

I f t h e F i c k e n t c h e r and M a r k ' s c o n s t a n t KFM i s i d e n t i f i e d w i t h 2/500 (V2/M2),

i t must be a d m i t t e d t h a t t h e e x t r a p o l a t i o n o f T s p towards c = o does n o t g i v e
d i r e c t l y t h e i n t r i n s i c v i s c o s i t y [ ~ ] , b u t a v a l u e of['?] altered by a
c o e f f i c i e n t r e l a t e d t o a c h a r a c t e r i s t i c of t h e substance, as i s t h e case o f t h e
h y d r a t e d molecules l i k e sucrose.
Most o f t h e v i s c o m e t r i c r e l a t i o n s used i n t h e t r e a t m e n t o f d i l u t e aqueous
s o l u t i o n s of sucrose a r e s i m i l a r t o t h o s e used f o r d i l u t e s o l u t i o n s o f polymers.
Indeed, t h e formula used by I n h a t e t a l . 27 t o determine t h e h y d r a t i o n
numbers o f sugar from v i s c o s i t y measurements,is t h e r e l a t i o n ( 9 ) o f Huggins 20
which i s v e r y p o p u l a r i n t h e polymer f i e l d .
The o t h e r r e l a t i o n s a p p l i e d i n t h e c a l c u l a t i o n o f t h e v i s c o s i t y o f sucrose
s o l u t i o n s as f u n c t i o n s of c o n c e n t r a t i o n a r e g e n e r a l l y comparable t o formulas
used f o r d i l u t e polymer s o l u t i o n s . T h i s i s t h e case of t h e r e l a t i o n o f Kaganov 28

Ln lr
= a1 + b l N (20)
where N i s t h e m o l e c u l a r c o n c e n t r a t i o n ( 2 0 ) may be w r i t t e n as f o l l o w s :
(a1 + by N)
Tr = (20 b )
which i s comparable t o one o f t h e s i m p l e s t and t h e e a r l i e s t r e l a t i o n s p r o ~ o s e d
~

t o g e n e r a l i z e t h e formulas of ~ a k e r " , t h a t i s , the r e l a t i o n o f

 30
Arrhenius :
kc (21)
?lr = e
staudinqer3' s p e c i f i e d t h a t k i n the Arrhenius formula (21) i s not d i f f e r e n t
from [q] the i n t r i n s i c v i s c o s i t y .
The f o r m u l a o f ~ a ~ a n o vi s' ~ a t t h e b a s i s o f t h e work o f ~ e n o t e l l e ~i ' n w h i c h
a r e l a t i o n i s proposed t o c a l c u l a t e v i s c o s i t y w i t h a good accuracy
f o r t h e range 0-85" B r i x and 10-80" C . T h i s r e l a t i o n i s a l s o s u i t a b l e
f o r rnol asses and i n t e r m e d i a t e syrups a f t e r a c a l i b r a t i o n t a k i n g i n t o account t h e
o u r i t y and t h e e f f e c t o f non-sucrose on t h e B r i x ( a p p a r e n t ) and on t h e s p e c i f i c
viscosity.
A formula i s given i n the and book^^
o f Chemistry and P h y s i c s f o r t h e whole
range o f sucrose c o n c e n t r a t i o n s . T h i s f o r m u l a i s c l o s e t o t h e r e l a t i o n (13) o f
vand2', and comparable t o Equation ( 1 5 ) o f ~ r a e m e r " i n i t s developed form. The
Handbook's r e l a t i o n i s :

where x i s t h e m a s s - t r a c t i o n s o l u t e / s o l u t i o n .
~ o u l i dk e~r i v~e d from E i n s t e i n ' s e q u a t i o n ( 2 ) a r e l a t i o n w h i c h i s v a l i d f o r
c o n c e n t r a t e d s o l u t i o n . Vand's e q u a t i o n was r e c e n t l y 3 5 a o p l i e d t o t h e a n a l y s i s
o f t h e v i s c o s i t i e s o f number o f polyhydroxy-compoundsamonqwhich i s sucrose.
The a u t h o r s 3 5 d e r i v e an e q u a t i o n which t a k e s i n t o account t h e shape of t h e
molecule as w e l l as t h e w a t e r of h y d r a t i o n , a n d d e c l a r e i t t o be a u n i v e r s a l
e q u a t i o n , v a l i d f o r c o n c e n t r a t e d s o l u t i o n s o f e l e c t r o l y t e s and n o n e l e c t r o l y t e s .
~ u r i a n e kproposed
~~ an e q u a t i o n a p p l i a b l e t o sugar i n d u s t r y syrups which
i s a l s o comparable t o ~ r a e m e r ' s ~ r' e l a t i o n .
V i s c o s i t y - C o n c e n t r a t i on r e l a t i o n s f o r p u r e sucrose s o l u t i o n s appear t o be
c l o s e t o t h e formulas proposed f o r polymers i n d i l u t e s o l u t i o n s . Most o f t h e
r e c e n t e q u a t i o n s a r e d e r i v e d from E i n s t e i n , Huggins o r Kraemer's r e l a t i o n s .
T h e m o d i f i c a t i o n s of t h e c l a s s i c a l r e l a t i o n s t e n d t o t a k e i n t o account t h e
problems posed by t h e h y d r a t i o n and t h e d e v i a t i o n from t h e s p h e r i c a l shape
of t h e s o l u t e molecules. R e s u l t s of c a l c u l a t i o n s u s i n g t h e m o d i f i e d e q u a t i o n s
w i 11 be d i s c u s s e d l a t e r . They do n o t seem t o g i v e a d e f i n i t e answer t o t h e
h y d r a t i o n problem.

3. Recent v i scornetri c Equations .

Two models o f p a r a m e t r i c t r a n s c e n d e n t a l e q u a t i o n s have been
proposed i n o r d e r t o g e n e r a l i z e t h e r e l a t i o n s h i p s between t h e
v i s c o s i t y o f t h e polymers and t h e i r c o n c e n t r a t i o n s . The t r a n s c e n d e n t a l f o r m
o f t h e e q u a t i o n s takes c a r e o f o v e r a l l i n t e r a c t i o n s o f t h e molecules when t h e
c o n c e n t r a t i o n o f t h e polymer s o l u t i o n i n c r e a s e s . Both transcendental
e q u a t i o n s were t h e n combined i n t o one t r a n s c e n d e n t a l e q u a t i o n 4 ' w h i c h was
found u s e f u l i n p r e d i c t i n g a c c u r a t e l y t h e i n t r i n s i c v i s c o s i t y and Huggins
c o n s t a n t k ' f o r t h e o l i gomers and model molecules i n c l u d i n g sucrose. The
mathemati c a l e x p r e s s i ons o f t h e t r e n s c e n d e n t a l e q u a t i o n s proposed by
~ e f f r o ~ - ~ i ~ aer et ~: ~ - ~ '

where Y = q S p , Y + 1 =qr, X = c[T], p ( x ) a polynomial i n x w i t h o u t a constant

term, r ( x ) i s a p o l y n o m i a l i n x o f degree two and t h e c o e f f i c i e n t s b and f
a r e temperature and c o n c e n t r a t i o n dependent parameters.
v i s c o s i t y and may a l s o be w r i t t e n i n t h e form

70
I n t r o d u c t i o n o f such a new f u n c t i o n p e r m i t s i n c r e a s e i n t h e accuracy of t h e
s p e c i f i c v i s c o s i t y w h i c h i s h e n c e f o r t h o b t a i n e d by t h e t r i p l e e x t r a p o l a t i o n
towards c = o o f t h e reduced v i s c o s i t y , 7 s p / c , the inherent v i s c o s i t y ~ n T r / c ,
and t h e reduced d i f f e r e n t i a l v i s c o s i t y . The e x p r e s s i o n s o f these t h r e e
f u n c t i o n s show t h a t t h e a n g u l a r c o e f f i c i e n t s o f [ ? ] c a r e comparable :

I t was a l s o d e m o n ~ t r a t e dt ~h ~
a t i n h e r e n t v i s c o s i t y i s equal t o h a l f t h e
sum o f reduced and d i f f e r e n t i a l reduced v i s c o s i t i e s ( L n ' l r l c = T s n / c + ' 7 d i f f ./c)
2
Although t h i s r e c e n t t r e a t m e n t o f t h e v i s c o s i t y o f polymer s o l u t i o n s has
o n l y been v e r i f i e d f o r low c o n c e n t r a t i o n s , i t i s p o s s i b l e t o e x t e n d i t s v a l i d i t y
t o c o n c e n t r a t e d s o l u t i o n s .A s i m i 1 arapproach t o g e n e r a l i z a t i o n o f c o n c e n t r a t i o n
dependence o f z e r o - s h e a r v i s c o s i t y i n polymer s o l u t i o n s was adopted by Dreval
e t a1 .43. These a u t h o r s found t h a t t h e p r o p e r t i e s o f an i n d i v i d u a l macromolecule
and i t s i n t e r a c t i o n s i n d i l u t e s o l u t i o n s r e t a i n t h e i r s i g n i f i c a n c e o v e r t h e
whole range o f c o n c e n t r a t i o n s . The c o n c e n t r a t i o n - v i s c o s i t y r e l a t i o n s t h e y g i v e 43
a r e independent of m o l e c u l a r w e i g h t and o f t h e n a t u r e o f t h e s o l v e n t .
Our o p i n i o n i s t h a t t h e use of modern computers and a d a p t a t i o n o f r e c e n t
e q u a t i o n s l i k e those of M e f f r o y - B i g e t s h o u l d l e a d t o a c c u r a t e r e s u l t s even f o r
c o n c e n t r a t e d impure s o l u t i o n s . Such p r e d i c t i v e c a l c u l a t i o n s c o u l d be h e l p f u l
i n determining f l o w c o n d i t i o n s i n p i ~ e sand i n i n t e r p r e t i n g the
s t r u c t u r e o f t h e aqueous s o l u t i o n s .

B. VISCOSITY-TEMPERATURE RELATIONS FOR PURE SOLUTIONS

I
The r e v i e w o f t h e o r e t i c a l , e m p i r i c a l and s e m i - e m p i r i c a l e q u a t i o n s r e l a t i n g
v i s c o s i t y w i t h c o n c e n t r a t i o n showed t h e s i m i l a r i t y between polymer and sugar
s o l u t i o n s a t l o w c o n c e n t r a t i o n s . I t i s , however, more u s u a l i n t h e sugar
technology l i t e r a t u r e t o f i n d r e l a t i o n s between v i s c o s i t y and t e m p e r a t u r e . Such
r e l a t i o n s a r e g e n e r a l l y based on t h e r a t e process t h e o r y o f E y r i n g o r on t h e
" f r e e volume" dependence on temperature.

1. C l a s s i c a l t h e o r i e s and r e l a t i o n s .
Beside t h e hydrodynamic approach t o t h e s t u d y of t h e r h e o l o g i c a l o r o p e r t i e s
13
o f suspensions and s o l u t i o n s , m a i n l y developed by ~ i r c h h o f f l ' and E i n s t e i n ,
t h e r e i s t h e m o l e c u l a r k i n e t i c t h e o r y due t o E y r i n g e t a1 .44. I n t h i s t h e o r y ,
t h e v i s c o s i t y o f a l i q u i d i s c o n s i d e r e d as a r a t e process because i t takes p l a c e
w i t h a d e f i n i t e v e l o c i t y under g i v e n c o n d i t i o n s . T h i s s t a t e m e n t f o l l o w s from
t h e d e f i n i t i o n o f v i s c o s i t y i t s e l f . Indeed, i f we c o n s i d e r t w o l a y e r s o f
molecules i n a l i q u i d a t a d i s t a n c e 1 a p a r t and i f one l a y e r s l i d e s p a s t t h e
o t h e r under an a p p l i e d f o r c e p e r u n i t s u r f a c e , f , t h e n by d e f i n i t i o n :

w h e r e 2 i s t h e c o e f f i c i e n t o f v i s c o s i t y and A v t h e d i f f e r e n c e i n t h e v e l o c i t y
o f t h e two l a y e r s . I n o r d e r t o assure t h e movement o f one l a y e r w i t h r e s p e c t
I
t o t h e o t h e r , i t i s supposed t h a t molecules pass from one e q u i l i b r i u m p o s i t i o n
t o a n o t h e r . F o r such a passage t o o c c u r , i t i s necessary t h a t a " h o l e " r e q u i r e s
t h e e x p e n d i t u r e of energy s i n c e work must be done i n pushing back o t h e r
molecules44. The jump o f t h e moving molecule f r o m one e q u i l i b r i u m p o s i t i o n t o
t h e n e x t was regarded14 as a passage o f t h e system o v e r a p o t e n t i a l - e n e r g y
b a r r i e r . I t was demonstrated14 by r e f e r e n c e t o thermodynamics and t a k i n g A s
as c o n s t a n t and c o n s i d e r i n g t h a t t h e m o l a r volume does n o t v a r y w i t h temperature,
t h a t v i s c o s i t y may be expressed as f o l l o w s :

where B i s a c o n s t a n t , E v i s t h e energy r e q u i r e d f o r t h e v i s c o u s f l o w ( o r f o r
t h e jump o f m o l e c u l e s ) , R t h e gas c o n s t a n t and T t h e a b s o l u t e temperature i n
OK. E q u a t i o n (30) d e r i v e d f r o m t h e r a t e process t h e o r y i s comparable t o t h e
r e l a t i o n s suggested e m p i r i c a l l y b y ~ r r h e n i u s ~ and
' by ~ u z m a n ~An~ .e q u a t i o n o f
t h e same k i n d was g i v e n by ~ n d r a d e il n~ o r d e r t o d e s c r i b e v i s c o s i t y - t e m p e r a t u r e
relations :
 w h e r e T i s t h e v i s c o s i t y , T t h e temperature i n OK and A and b a r e c o n s t a n t s . T h i s
e q u a t i o n was found47 s u c c e s s f u l f o r s i m p l e 1 i q u i d s b u t s e r i o u s d e v i a t i o n s were
observed w i t h a s s o c i a t e d l i q u i d s . I n t h e case of many l i q u i d s t h e v i s c o s i t y
i s expressed by ~ n d r a d ei n~ t~h e f o r m 72 = a v1l3 e b j T where a and b a r e
c o n s t a n t s and V t h e m o l a r volume, which means t h a t i n t h e " h o l e " t h e o r y of
E y r i n g as w e l l as i n t h e e a r l i e r t h e o r i e s , t h e m o l a r volume must be t a k e n
i n t o account. I t may be s t a t e d f r o m t h e s e t h e o r i e s t h a t t h e f l u i d i t y of a l i q u i d
i s p r o p o r t i o n a l t o t h e nomber o f h o l e s . I t may a l s o be considered44 t h a t t h e
e s s e n t i a l d i f f e r e n c e between a s o l i d and a l i q u i d i s t h e presence o f h o l e s i n
t h e l i q u i d ; so t h a t i f V i s t h e molar volume o f t h e l i q u i d , Vs t h e m o l a r
volume of t h e unexpanded s o l i d , t h e d i f f e r e n c e V - Vs i s p r o p o r t i o n a l t o t h e
number of h o l e s and hence t o t h e f l u i d i t y (I/? ) o f t h e l i q u i d . I t f o l l o w s t h a t :

where c i s a c o n s t a n t . T h i s r e l a t i o n i s i d e n t i c a l i n f o r m w i t h t h e e q u a t i o n of
at chin ski^^ found t o h o l d f o r a l a r g e number o f nonassociated l i q u i d s . I n t h e
equation o f Batschinski 11 = c / ( v - w ) , where q and c have t h e same d e f i n i t i o n
as i n ( 3 2 ) , v
i s t h e s p e c i f i c volume o f t h e l i q u i d and w i s a c o n s t a n t s i m i l a r
49
t o t h e van d e r W a l l s b . B a t s c h i n s k i ' s r e l a t i o n was m o d i f i e d by H i l d e b r a n d
i n a way t h a t y i e l d e d an e q u a t i o n a l m o s t i d e n t i c a l t o (32) : V = c / ( V - Vo)
where V i s t h e m o l a l volume of t h e l i q u i d and Vo t h e m o l a l volume a t which
f l u i d i t y i s zero. H i l d e b r a n d exDressed t h e f l u i d i t y as a l i n e a r f u n c t i o n o f

I
t h e r e l a t i v e expansion (V - Vo/Vo) :

The parameters B =Vo/C and Vo a r e o b t a i n e d f r o m t h e p l o t s o f fl a g a i n s t V, which

a r e 1inear o v e r l o n g ranges o f temperature. However, H i l d e b r a n d ' s e q u a t i o n i s
based on a c e r t a i n t h e o r y o f l i q u i d 5 0 9 5 1 s t r u c t u r e i m p l y i n g a m o l e c u l a r chaos
w i t h no " s o l i d - l i k e " c l u s t e r s ; so t h a t such an e q u a t i o n i s n o t a ~ p l i c a b l et o
sugar s o l u t i o n s which a r e s t r o n g l y a s s o c i a t e d l i q u i d s . N e v e r t h e l e s s a r e c e n t
work by Soesanto and ~ i l l i a m used s ~ ~ Hi l d e b r a n d ' s concept o f f r e e volume i n
o r d e r t o i n t e r p r e t v i s c o s i t y r e s u l t s f o r d i l u t e as w e l l as c o n c e n t r a t e d sugar
s o l u t i o n s . I n f a c t t h e f r e e volume t r e a t m e n t o f v i s c o s i t y was found t o be
f i t t i n g when i t s v a l u e i s v e r y low; i.e. n e a r t h e g l a s s t r a n s i t i o n r e g i o n and
t h e r e l a t i o n used52 t o c o r r e l a t e V t o T was i n s p i r e d f r o m t h e polymer
l i t e r a t u r e 53 ..
log ( r ] / v g ) = - 17.44 ( T - Tg) C51.6 + (T - T ~ ) ]
(34)
where q i s t h e v i s c o s i t y of t h e s o l u t i o n a t t h e temperature T, and q g t h e
v i s c o s i t y a t t h e g l a s s t r a n s i t i o n temperature Tg. P l o t t i n g l o g q a g a i n s t 1/T
by analoqy w i t h A r r h e n i u s e q u a t i o n was c r i t i c i z e d by ~i
ldebrandi4. The
i n t e r o r e t a t i o n of l o g 17 as an " a c t i v a t i o n energy" i m p l i e s t h e presence of
b a r r i e r s opposed t o t h e flow c o n s i s t i n g of a q u a s i - l a t t i c e s t r u c t u r e . T h i s i s a
54
m a j o r d i f f e r e n c e between E y r i n g and H i l d e b r a n d ' s t h e o r i e s . I t i s even found
i n Hi l d e b r a n d ' s c r i t i c i s m o f t h e a c t i v a t i o n energy concept f o r v i s c o u s flow 9

t h a t " i t makes no p h y s i c a l sense t o e x t e n d t o l i q u i d s a t h e o r y of d i f f u s i o n i n

s o l i d s t h a t p o s t u l a t e s t h e presence o f h o l e s o f m o l e c u l a r s i z e " . However, i t i s
a d m i t t e d by H i l d e b r a n d t h a t h i s r e l a t i o n ( 3 3 ) i s o n l y c o n v e n i e n t f o r s i m p l e n o n '
a s s o c i a t e d l i q u i d s . On t h e o t h e r hand most o f t h e e m p i r i c a l e x p r e s s i o n s o f 7
as a f u n c t i o n o f T a r e o f t h e A r r h e n i u s type,and have proved t o be u s e f u l
i n sugar f a c t o r i e s .

2. E m p i r i c a l R e l a t i o n s .

I t i s p a r t i c u l a r l y i n t e r e s t i n g i n a sugar f a c t o r y where c o n c e n t r a t i o n s
and temperatures a r e changing d u r i n g t h e process t o h a v e f o r c o n t r o l o n l y t h e
refractometric B r i x and t o r e f e r t o c a l c u l a t e d t a b l e s o f v i s c o s i t y as a
f u n c t i o n o f temperature. Many r e l a t i o n s o f t h i s t y p e , a1 though based on p r e v i o u s
t h e o r i e s , have been adapted i n o r d e r t o f i t t h e t e c h n i c a l c o n d i t i o n o f sugar
s o l u t i o n s . One o f t h e e a r l i e s t works i s t h a t o f ~ a g a n o v " i n which t h e r e l a t i o n -
~N/T
s h i p between v i s c o s i t y and temperature i s an A r r h e n i u s r e l a t i o n = Ae ,
where A and b a r e c o n s t a n t s , N t h e c o n c e n t r a t i o n and T t h e t e m p e r a t u r e . The
e q u a t i o n g i v e n by ~ i d o u xi n~ o~r d e r t o e x p r e s s 7 as a f u n c t i o n o f T a t a g i v e n
concentration i s :

where a and b a r e c o n s t a n t s , T i s t h e temperature i n OK and To = 273.15 OK. T h i s

r e l a t i o n was found by t h e a u t h o r s a t i s f a c t o r y i n t h e t e m n e r a t u r e ranqe, 0 to
100 "C. The e q u a t i o n used b y ~ a r b e gave
r ~ ~him r e s u l t s w i t h a
d e v i a t i o n o f l e s s t h a n 1 % f r o m t h e t a b u l a t e d NBS d a t a :

log 72 mTI = A +--B-

T t C

where 72 Tim i s t h e v i s c o s i t y o f a sucrose s o l u t i o n a t a g i v e n c o m p o s i t i o n and

temperature, T t h e temperature i n "C, and A, B and C a r e c o n s t a n t s t h a t depend
on composition a l o n e . The f o r m of t h e e q u a t i o n p e r m i t s t r e a t m e n t o f t h e
v i s c o s i t y o f sucrose s o l u t i o n s by ~ o o l i t t l ef r ~e e~ volume approach. I n t h i s
approach v i s c o s i t y i s expressed as a f u n c t i o n o f f r e e volume : ? = Aexp (Bvo/vf),
A and B a r e c o n s t a n t s , vf = v-vo and v f t h e f r e e volume, v t h e s p e c i f i c volume and
vo i s t h e occupied volume o b t a i n e d by e x t r a p o l a t i o n a t 0 OK o f a v - T plot.
The e f f e c t s o f temperature on v i s c o u s flow of l i q u i d s was s t u d i e d by M i l l e r 58,59
I by means o f a m o d i f i e d A r r h e n i u s (M.A.) e q u a t i o n and t h e D o o l i t t l e S 7 r e l a t i o n .
The M.A. e q u a t i o n used 72
= A exp B/(T - To) t o determine thedenendence of t h e B
c o e f f i c i e n t on t e m p e r a t u r e and on f r e e volume. The B and o t h e r t e m ~ e r a t u r e
c o e f f i c i e n t s given i n the empirical relation^^^-^' were plotted against
concentrationi5 o r expressed as a f u n c t i o n o f c o n c e n t r a t i o n S 6 O r free
volume58. I t i s shown5' c l e a r l y t h a t even f o r an a s s o c i a t e d l i q u i d l i k e w a t e r ,
e q u a t i o n s d e r i v e d from t h e M.A. and D o o l i t t l e r e l a t i o n s may c o r r e l a t e t h e
1 v i s c o s i t y and t h e s t r u c t u r e o f t h e l i q u i d s . Such a c o r r e l a t i o n i s based on t h e
assumption t h a t unbonded w a t e r may be c o n s i d e r e d as a " f r e e volume". The E y r i n o
theory, c o n s i d e r i n g t h e v i s c o s i t y as an a c t i v a t e d f l o w process,was adopted by
~ h o m a s ~who
' proposed an e m p i r i c a l r e l a t i o n i n which t h e r a t i o , a,of t h e energy
o f a c t i v a t i o n o f v i s c o u s f l o w t o t h e energy o f v a p o r i z a t i o n a t t h e same
temperature i s found t o be dependent on t h e s i z e , shane and o o l a r i t y o f molecules.
I t i s argued t h a t v i s c o u s f l o w does n o t r u p t u r e t h e a s s o c i a t i o n by hydrogen
bonds i n a s s o c i a t e d l i q u i d s . The a b s o l u t e r e a c t i o n - r a t e t h e o r y o f E y r i n g was
a p p l i e d t o Newtonian as w e l l as non-Newtonian f l o w . I n p a r t i c u l a r t h e Ree-Eyring
e q u a t i o n was found t o agree w i t h E i n s t e i n ' s r e l a t i o n f o r Newtonian flow w i t h
l s p / C E 2.5 and a l s o f o r p s e u d o - p l a s t i c f l o w , T s p / C as i t approaches 2.5 which
means t h a t t h e f l o w i n g p a r t i c l e s i n t h e suspension a r e r i g i d o r s e m i - r i g i d
spheres. l h e r e t o r , i t may be concluded t h a t e m p i r i c a l e q u a t i o n s a r e i n t i m a t e l y
r e l a t e d t o t h e o r e t i c a l t r e a t m e n t . The same e x p e r i m e n t a l d a t a can each
time f i t w i t h one o r a n o t h e r r e l a t i o n .

C. VISCOSITY RELATIONS .FOR IMPURE SOLUTIONS

The c a l c u l a t i o n o f v i s c o s i t y and i t s e x p r e s s i o n by a mathematical r e l a t i o n

as a f u n c t i o n o f c o n c e n t r a t i o n o r temperature,was used t o s u o a o r t a
t h e o r y on l i q u i d s t r u c t u r e o r on hydrodynamic f l o w . I n t h a t case,the model has
t o be v e r y s i m p l e ( h a r d spheres f l o w i n g i n u n a s s o c i a t e d l i q u i d ) . However, i n a
sugar f a c t o r y t h e sucrose m o l e c u l e i s never a l o n e i n s o l u t i o n . I t i s mixed t o
o t h e r sugars, m i n e r a l s a l t s , p r o t e i n s , . ..
and o t h e r comnonents from the beet
o r cane. So t h a t an "a p r i o r i " mathematical t r e a t m e n t o f l i g h t syrups o r
molasses of d i f f e r e n t B r i x and p u r i t i e s i s u n c e r t a i n . Most o f t h e c a l c u l a t i o n s
of t h e v i s c o s i t y o f impure s o l u t i o n s a r e e m p i r i c a l a d a p t a t i o n s o f one o f t h e
models of e q u a t i o n s d e s c r i b e d above t o t h e impure sugar s o l u t i o n s

1. Homogeneous phases.
~ i d o u xadapted
~ ~ t h e r e l a t i o n ( 3 5 ) i n which 0= -
t o different
-7-
molasses e x t r a c t e d from b e e t s o r sugar cane. The e q u a t i o n proposed f o r impure
s o l u t i o n s o f sucrose i s s i m i l a r t o eq. 35 :

log = a' + blQ)

w i t h a ' and b ' constants r e l a t e d t o a and b o f ( 3 5 ) by a ' = a a and b ' = p b,
a and p b e i n g c o e f f i c i e n t s c h a r a c t e r i s t i c of t h e s t u d i e d molasses a t
a g i v e n c o n c e n t r a t i o n . ~ e n o t e l l e ~proposed
' a relation applicable t o a l l
i n d u s t r i a l sugar s o l u t i o n s :
1.25)
Log 7 = 22.46 N - 2.114 + Ot (1.1 + 43.1 A.N.
Bo Pa
where N = lgOO - 18 Bo w i t h Bo = Ba x ( k + (1 - k)m)

30 - to
and Ot = 91+tr ; A = 0.85 -t 0.15 Pa/100

Ba i s t h e apparent B r i x , Pa i s t h e p u r i t y and 7 the viscosity i n poises at a

temperature t o , and k a c o e f f i c i e n t o f c a l i b r a t i o n . Eq. 38 was found by t h e
a u t h o r t o f i t w i t h t h e NBS and S c h n e l d e r ' s d a t a f o r pure s o l u t i o n s , as w e l l as
28
f o r molasses and i n t e r m e d i a t e syrups : Simi l a r e q u a t i o n s based on Kaganov's
r e l a t i o n p e r m i t t e d S i l i n and ~ i l i n tao ~draw
~ nomograms g i v i n g t h e v i s c o s i t y of
sugar bee; molasses a t d i f f e r e n t temperatures and B r i x v a l u e s a n d t o d e f i n e a
"normal" molasses a t 40" C and 82" B r i x w i t h a v i s c o s i t y o f 44 p o i s e s .
D e s c r i p t i o n o f t h e b e h a v i o r o f molasses as a Newtonian o r a non-Newtonian
63
f l u i d w i l l be d i s c u s s e d l a t e r , b u t r e f e r e n c e must me made t o r e c e n t work
t r e a t i n g molasses as a non-Newtoni an f l u i d and t h e anal ic a t i on t o . d e t e r m i n e i t s
64
r h e o l o g i c a l c h a r a c t e r i s t i c s o f a Dower law model o f e q u a t i o n d e r i v e d f r o m R e i n e r :

- K d u n
Crx = - (-)
g dr
where Crx i s t h e shear s t r e s s a t a d i s t a n c e r i n t h e d i r e c t i o n of f l o w , K i s
t h e f l o w c o n s i s t e n c y i n d e x , d u t h e v e l o c i t y g r a d i e n t and, n , t h e f l o w b e h a v i o r
i n d e x . For l a m i n a r flow, t h e model of e q u a t i o n i s m o d i f i e d as f o l l o w s :

where Cw i s t h e w a l l shear s t r e s s , D t h e d i a m e t e r o f t h e tube, AP t h e pressure

d r o p a l o n g t h e tube, L t h e l e n g t h o f t h e t u b e , V t h e v e l o c i t y o f f l u i d , K' t h e
m o d i f i e d f l o w c o n s i s t e n c y and n ' t h e m o d i f i e d b e h a v i o r i n d e x , d i m e n s i o n l e s s .
The v a r i a t i o n o f t h e c o n s i s t e n c y i n d e x K' w i t h temperature i s g i v e n by :
K' = Kexp where E i s t h e energy o f a c t i v a t i o n of f l o w .
Constants K ' and n ' were c a l c u l a t e d f r o m t h e a p p l i c a t i o n o f eq. 40 t o
molasses, and these r e s u l t s were found u s e f u l i n t h e d e s i g n o f p i p e s t r a n s p o r t i n g
such a non-Newtonian f l u i d . I n f a c t , t h e m o l e c u l a r i n t e r a c t i o n s between t h e
d i f f e r e n t molecules and i o n s p r e s e n t i n t h e impure aqueous s o l u t i o n o f sugar
a r e f a r from b e i n g s i m p l e t o p r i t i n t o e q u a t i o n . These phenomena c o u l d be
d e s c r i b e d q u a l i t a t i v e l y i n o r d e r t o e x p l a i n t h e molasses f o r m a t i o n mechanism.
However, f o r t h e p r e d i c t i o n o f t h e v i s c o s i t y o f molasses o n l y e m p i r i c t r e a t m e n t s
 such as those o f ~ a ~ a n o v ' ~~ , i d o u xo r~ Genotelle3'
~ are possible

2. Heterogeneous phases.
The f l u i d s f l o w i n g i n t h e c r y s t a l l i z a t i o n s t a t i o n o f a sugar f a c t o r y a r e
heterogenous i n n a t u r e ( m i x t u r e of syrups and c r y s t a l s ) c a l l e d massecuites. The
r h e o l o g i c a l b e h a v i o r o f t h e massecui t e s i s d i f f e r e n t f r o m t h a t o f c o n c e n t r a t e d
homogenous s o l u t i o n s . The mathematical t r e a t m e n t o f such m i x t u r e s i s complex, and
most o f t h e r e l a t i o n s g i v e n i n o r d e r t o p r e d i c t t h e v i s c o s i t y ( o r c o n s i s t e n c y )
o f massecui t e s a r e e m p i r i c a l . They tend t o f i n d a c o r r e l a t i o n between t h e
v i s c o s i t y of molasses and t h a t o f t h e massecuites. ~i
l i n a 6 5 studied the v i s c o s i t y
of low-grade massecuites. She found t h a t t h i s parameter obeys P o i s e u i l l e ' s law
and i s p r o p o r t i o n a l t o t h e mother-molasses v i s c o s i t y . She a l s o f o u n d a r e l a t i o n -
s h i p between t h e percentage o f c r y s t a l s i n t h e massecuites and t h e r a t i o of t h e
v i s c o s i t i e s of massecuites and molasses. These r e s u l t s a r e summarized i n Table 1
I and F i g . 1.

Table .1 : R a t i o o f massecuites t o molasses v i s c o s i t i e s - as a f u n c t i o n

'PMC
2 mol .
o f c r y s t a l content.

C r y s t a l s % k g , massecui t e s 30 35 40 42 44 46 48

72 M . C .
mol .
I t i s g e n e r a l l y a d m i t t e d t h a t low-grade massecui t e s s h o u l d n o t c o n t a i n more
t h a n 40-42 % c r y s t a l s . T h i s i s n o t t h e o p i n i o n o f ~ i l i n fao r~ whom
~ a percentage
of 46-48 % i s p o s s i b l e p r o v i d e d c e r t a i n t e c h n i c a l a d a p t a t i o n o f t h e c r y s t a l l i z e r s
The v i s c o s i t y o f massecuites i s known66 t o be t h e d o m i n a t i n g f a c t o r i n
c r y s t a l l i z e r t e c h n o l o g y . I t i s i m p o r t a n t t o c o n t r o l t h e c o m p o s i t i o n of non-
sucrose c o n s t i t u e n t s , s o l i d s c o n t e n t s and temperature i n o r d e r t o r e a c h o ~ t i m u m
o p e r a t i o n a l procedures which correspond t o an o p t i m a l v i s c o s i t y . The f a c t o r s
g o v e r n i n g t h e o u t f l o w o f massecuites t h r o u q h a c i r c u l a r o r a r e c t a n g u l a r
a p e r t u r e have been d e r i v e d f r o m v i s c o s i t y measurements by Gebler and ~i z67. The
r e 1 a t i onshi ps between t h e f l o w f a c t o r , and t h e geometry o f t h e ~ i p ewere g i v e n 67
by means o f a H a g e n - P o i s e u i l l e e q u a t i o n p r o v i d e d t h a t t h e f l o w i s l a m i n a r which
i s t h e case f o r massecuites.
The e f f e c t s o f t e m p e r a t u r e and c r y s t a l c o n t e n t on t h e r h e o l o g i c a l p r o p e r t i e s
of molasses and massecuites have a l s o been s t u d i e d by D i a z The
i n f l u e n c e o f t e m p e r a t u r e on t h e c o n s i t e n c y o f massecui t e s as w e l l as molasses
i s expressed by an e x p o n e n t i a l r e l a t i o n :
K = A e-"'T
(41)
 F i g . 1 : Dependence o f v i s c o s i t y r a t i o ( massecui t e / n ~ o l a s s e s )o n
the crystal content

F i g . 2 : U n i d i r e c t i o n a l shearing a
F i g . 3 : S h e a r i n g c h a r a c t e r i s t i c s zo f
s t r e s s i n a Newtonian f l u i d N e w t o n i a n and non-Newtoni a n
f l u i d s (N : N e w t o n i a n ;
D : d i l a t a n t ; P P : pseudo-
p l a s t i c ; RP : r e a l ~ l a s t i c;
B : Bingham p l a s t i c )
where K i s t h e c o n s i s t e n c y i n d e x , A and m c o n s t a n t s , and T t h e temperature i n
"C.
I f t h e c o n s i s t e n c y f a c t o r K i s known a t a c e r t a i n temperature; i . e . 40" C,
i t may be c a l c u l a t e d f o r any o t h e r temperature by means o f t h e e q u a t i o n :

The dependence o f t h e c o n s i s t e n c y o f massecuites i s f i r s t determined experimen-

t a l l y a t d i f f e r e n t c r y s t a l c o n t e n t s and 35" C, t h e n an e m p i r i c a l r e l a t i o n i s
d e r i v e d i n o r d e r t o express I(Mc35Oc i n f u n c t i o n o f Kmo1350C :

Conibi n i n g eqs. 42 and 43 g i v e s :

where KM,C.T, i s t h e c o n s i s t e n c y of massecuites a t T°C, Kmol : the consistency

o f molasses, and S t h e c o n t e n t o f c r y s t a l s i n %.
These e m p i r i c a l r e 1 a t i o n s p e r m i t t e d D i a z - C a r c i a68 t o e s t a b l i s h nomograms
p r e d i c t i n g t h e i n f l u e n c e o f temperature and c r y s t a l c o n t e n t s on t h e v i s c o s i t y
o f massecuites. The r e l a t i o n between v i s c o s i t y and c o n s i s t e n c y b e i n g :
K
(45)
0

where 7 i s t h e v i s c o s i t y o f non-Newtonian f l u i d i n p o i s e s , Y,the velocity

g r a d i e n t i n t h e f l u i d and, n, t h e f l o w f a c t o r .
The f l o w f a c t o r n v a r i e s l i n e a r l y as a f u n c t i o n o f t h e percentage o f c r y s t a l s
following the r e l a t i o n :

n = 14.65/S + 0.5364 (46 1

I t was a l s o observed68 t h a t t h e s i z e o f t h e c r y s t a l a f f e c t s t h e v a r i a t i o n
o f n which i n c r e a s e s w i t h t h e d i a m e t e r o f t h e c r y s t a l . However, t h e c o n s i s t e n c y
i s a l m o s t u n a f f e c t e d by t h e s i z e o f c r y s t a l s when t h e i r d i a m e t e r s range
between 0.25 and 1.50 mm.

3. S h e a r i n g c h a r a c t e r i s t i c s o f molasses and massecui t e s .

As seen above (eq. 4 5 ) , v i s c o s i t y i s o b t a i n e d from t h e r a t i o of t h e
c o n s i s t e n c y f a c t o r t o t h e v e l o c i t y g r a d i e n t i n a f l u i d . As a r u l e , i t may be
r e c a l l e d t h a t v i s c o s i t y accounts f o r t h e i n t e r n a l f r i c t i o n o f a f l u i d when i t
flows through a pipe.
I n t h e s i m p l i f i e d case of a u n i d i r e c t i o n a l (Ox) f l o w , shown i n F i a . 2 , i f
t h e upper s u r f a c e moves w i t h a v e l o c i t y vx, t h e l o w e r s u r f a c e r e m a i n i n g f i x e d ,
then t h e Newton r u l e i s a p p l i e d i n o r d e r t o express t h e f o r c e , F, r e q u i r e d f o r
such a displacement :

FX = A''- dvx
dz

where A i s t h e area of t h e d i s p l a c e d s u r f a c e , 77 t h e dynamic v i s c o s i t y and

-3
dv
the g r a d i e n t o f v e l o c i t y . Eq. 46 may be w r i t t e n as f o l l o w s :

7 i s t h e t a n g e n t i a l shear s t r e s s , % = D t h e shear r a t e ; Eq. 47 i s a l s o

w r i t t e n 7 = 17 D . If,a t a g i v e n temperature and p r e s s u r e , 11 i s c o n s t a n t and
independent o f t h e shear r a t e , t h e f l u i d i s s a i d t o be Newtonian (Curve N,
F i g . 3 ) . I t i s t h e case f o r pure sugar s o l u t i o n s as w e l l as i n b e e t - s u u a r molasses
The f l u i d s t h a t do n o t obey t h e Newton law, a r e c a l l e d non-Newtonian f l u i d s .
T h e i r b e h a v i o r may be r e p r e s e n t e d by c u r v e B ( F i g . 3 ) f o r Bingham p l a s t i c o r
i d e a l p l a s t i c which r e s i s t s t r e s s e s up t o a c r i t i c a l v a l u e 7, before f l o w
t a k e s p l a c e . Once t h i s v a l u e has been reached, t h e f l o w obeys a l i n e a r r e l a t i o n :

A d i l a t a n t f l u i d ( c u r v e D, F i g . 3 ) has a v i s c o s i t y which i n c r e a s e s w i t h
s h e a r i n g r a t e . A p s e u d o - p l a s t i c m a t e r i a l i s one whose v i s c o s i t y decreases w i t h
s h e a r i n g r a t e (Curve PP, F i g . 3 ) and a r e a l p l a s t i c (Curve RP, F i g . 3 ) i s
intermedi a r between B i ngham p l a s t i c and p s e u d o p l a s t i cs.
F o r p s e u d o p l a s t i c s and d i l a t a n t f l u i d s , i t may be w r i t t e n :

w i t h a and n c o n s t a n t s depending on t h e f l u i d . n >1 f o r d i l a n t a n t and <1 f o r

o s e u d o p l a s t i c substances. a i s a l s o c a l l e d t h e c o n s i s t e n c y c o e f f i c i e n t ( K i n Diaz-
Cargia paper) and n i s t h e f l o w parameter. I t was noted6' t h a t the f l u i d s
encountered i n a sugar f a c t o r y a r e Newtonian o r p s e u d o p l a s t i c s . Low-grade
massecuites were found7' t o have a p s e u d o - p l a s t i c b e h a v i o r . The r h e o l o g i c a l
c h a r a c t e r i s t i c s o f molasses depend on t h e i r c o m p o s i t i o n . Cane sugar molasses
was found7' t o e x h i b i t a non-Newtonian ( s l i g h t l y p s e u d o - p l a s t i c ) v i s c o -
e l a s t i c i t y . T h i s p s e u d o p l a s t i c i t y was caused by s o l u b l e c o l l o i d s (gums). The
v i s c o e l a s t i c p r o p e r t i e s of molasses have been ~ t u d i e d ' e~x p e r i m e n t a l l y .
D i s c u s s i o n s o f e x p e r i m e n t a l r e s u l t s w i l l be d e t a i l e d i n IIV.
I I I.MEASUREMENTS OF VISCOSITY
D i f f e r e n t viscometers have been used i n o r d e r t o d e t e r m i n e t h e r h e o l o g i c a l
P r o p e r t i e s o f sugar s o l u t i o n s . The most used viscometers can be c l a s s i f i e d by
reference t o t h e p r i n c i p l e s on which t h e y a r e based :

- f l o w t i m e i n a c a p i l l a r y tube
- r a t e of f a l l o f a c a l i b r a t e d sphere i n t h e v i s c o u s medium
- t o r q u e r e q u i r e d t o r o t a t e a s o l i d body a t a d e f i n i t e a n g u l a r v e l o c i t y
i n t h e v i s c o u s sample
- damping e f f e c t o f a medium on a t h i n p l a t e v i b r a t i n g i n t h e medium
- r a t e o f f l o w under p r e s s u r e t h r o u g h o r i f i c e s and p i p e l i n e s

To these methods o f d e t e r m i n a t i o n o f v i s c o s i t y , we s h o u l d add i n d i r e c t

methods l i k e s p i n - l a b e l probes techniques used i n E.S.R. (electron spin
resonance) s p e c t r o s c o p y o r u l t r a s o n i c i n t e r f e r o m e t r y measurements. The d i f f e r e n t
v i s c o m e t r i c methods w i 11 be grouped f o l l o w i n g t h e i r major use
s t r u c t u r e , mi c r o v i s c o s i t y and c o n t r o l i n t h e 1a b o r a t o r y , f a c t o r y measurement of
v i s c o s i t y and r h e o l o g i c a l p r o p e r t i e s o f molasses and massecui t e s , and apparatus
used i n t h e m o n i t o r i n g of b o i 1 i n g and c r y s t a l 1 iz i n g processes.

A. LABORATORY MEASUREMENTS
a. Capi 1 l a r y v i s c o m e t e r ~ ' ~: these viscometers measure t h e t i m e necessary
t o a g i v e n volume i n o r d e r t o flow t h r o u g h a c a p i l l a r y . I f 1 i s t h e l e n g t h o f
t h e c a p i l l a r y , R i t s r a d i u s and P t h e p r e s s u r e d i f f e r e n c e under w h i c h t h e
l i q u i d f l o w s , and i f t h e l i q u i d i s Newtonian, t h e f r i c t i o n f o r c e Der u n i t
s u r f a c e i s equal t o t h e p r o d u c t o f v i s c o s i t y , 17 , by t h e g r a d i e n t o f v e l o c i t y
dv
I f the f l o w i s laminar, i t i s then possible t o w r i t e :
?Fa

I n t e g r a t i o n o f eq. 5 1 y i e l d s a p a r a b o l i c e x p r e s s i o n o f t h e v e l o c i t y :

The volume Q which f l o w s d u r i n g t h e t i m e t, i s :

which gives :

T h i s v a l u e o f v i s c o s i t y i s o n l y v a l i d f o r l a m i n a r f l o w , f o r w h i c h i t has
been shown by Reynolds t h a t t h e mean v e l o c i t y = Q must be l e s s t h a n a
c r i t i c a l v e l o c i t y vc. F o r usual c a p i l l a r y viscometers, v c ~ ~ ! $ ~ , w h e r de i s t h e
d e n s i t y o f t h e l i q u i d . T h i s c o n d i t i o n i m p l i e s t h a t t h e dimensions o f t h e
c a p i l l a r y obey t h e e q u a t i o n
P R ~ 5600
< ?z2 .
The dynamic o r a b s o l u t e v i s c o s i t y i s , g e n e r a l l y o b t a i n e d f r o m eq. 54 r e l a t i n 5
1t o t, t h e d u r a t i o n o f f l o w of a volume Q i n a v e r t i c a l c a p i l l a r y . This
e q u a t i o n i s known as t h e P o i s e u i l l e r e l a t i o n :

The l i q u i d f l o w s under t h e s o l e e f f e c t o f i t s w e i g h t and P may be o b t a i n e d

from :

where 6 i s t h e mean h e i g h t o f l i q u i d i n t h e c a p i l l a r y , P i t s s p e c i f i c mass

and g, t h e g r a v i t y a c c e l e r a t i o n . So t h a t , f o r a g i v e n v i s c o m e t e r :

where K i s t h e c o n s t a n t o f t h e v i s c o m e t e r . C o r r e c t i o n s must be made i n o r d e r

t o t a k e i n t o account t h e convergence and d i v e r g e n c e o f s t r e a m l i n e s r e s n e c t i v e l y
a t t h e i n l e t and o u t l e t o f t h e c a p i l l a r y ( C o u e t t e c o r r e c t i o n ) and
c o n s i d e r i n g t h e f a c t t h a t a p a r t o f t h e p r e s s u r e P i s used t o communicate
k i n e t i c energy t o t h e l i q u i d i n s t e a d o f v a n q u i s h i n 4 the f r i c t i o n forces.
C o r r e c t i o n s were discussed i n d e t a i 1 7 3 - 7 5 i n t h e case o f c a p i l l a r y v i s c o m e t e r s
used f o r polymer s o l u t i o n s . The most used c a p i l l a r y v i s c o m e t e r s a r e those o f
Ostwald, Cannon and Fenske, Ubbelohde, and t h e S c h u r t z and Immergut v i s c o m e t e r
with varyinq rates o f speed. They a r e shown on F i g . 4. The dimensions73 o f
t h e Ostwald (Fig, 4a) v i s c o m e t e r s a r e g e n e r a l l y as f o l l o w s ( f o r v i s c o s i t i e s
equal t o few c e n t i p o i s e s ) :

volume o f t h e b u l b B 2 - 5ml
volume o f t h e r e s e r v o i r A 10 ml
length o f the c a p i l l a r y 12 cm
diameter o f the c a p i l l a r y 0.3 t o 0.6'mm
d i s t a n c e between g u i d e marks a and b 10 cm

The measurements depend on t h e v e r t i c a l p o s i t i o n o f t h e c a p i l l a r y t u b e s . A

d e v i a t i o n o f l o r e s u l t s i n an e r r o r o f 0.2 %. I n o r d e r t o r e d u c e t h i s d i s a d -
vantage, Cannon and Fenske propose an apparatus i n w h i c h t h e b u l b a n d t h e r e s e r v o i r
a r e on t h e same v e r t i c a l a x i s ( F i g . 4 b ) . The Ubbelohde v i s c o m e t e r ( F i g . 4c)
g i v e s t h e advantage of measurements independent o f t h e volume o f t h e l i q u i d . I n
t h e S c h u r t z and Immergut v i s c o m e t e r ( F i g . 4 d ) , t h e g r a d i e n t o f v e l o c i t y o f
t h e l i q u i d a r e deduced from d i f f e r e n t h e i g h t s o f l i q u i d i n t h e c a p i l l a r y .
F i g . 4 : C a p i l l a r y v i s c o m e t e r s : a ) O s t w a l d U v i s c o m e t e r ; b ) Cannon and Fenske
v i s c o m e t e r ; c ) Ubbelohde and d ) S c h u r z and I ~ n m e r g u tv i s c o m e t e r w i t h a
velocity rate.

F i g . 5 : Couette viscometer ( f o r R1, R2, h, a,see the text)

 Nevertheless, d e t e r m i n a t i o n o f t h e v i s c o s i t y by use o f c a p i l l a r y tubes
r e q u i r e s c a r e . F i r s t , temperature must be c o n t r o l l e d w i t h a p r e c i s i o n of
0.01' C i n o r d e r t o have a c c u r a t e v i s c o s i t y measurements. The c a p i l l a r y
s h o u l d be r i g o r o u s l y v e r t i c a l . C l e a n i n g t h e v i s c o m e t e r between each measurement
i s a must. I t i s necessary t o make 3 o r 4 d e t e r m i n a t i o n s f o r each sample.The
r e p r o d u c i b i l i t y i s o f t h e o r d e r of 0 . 1 %,

b. R o t a t i n g v i s c o r n e t e r ~ ' ~: t h e t e s t e d l i q u i d i s p l a c e d between two

s u r f a c e s s u s c e p t i b l e of r o t a t i n g one w i t h r e s p e c t t o t h e o t h e r around a common
a x i s of symnetry, i .e. c o n c e n t r i c c y l i n d e r s o r c o n e - p l a t e systems. I f one of
t h e surfaces r o t a t e s w i t h a c o n s t a n t v e l o c i t y , i t communicates a movement t o
t h e 1 i q u i d which, owing t o t h e v i s c o u s f r i c t i o n f o r c e s , tends t o make t h e o t h e r
s u r f a c e r o t a t e . The measurement of t h e t o r q u e a p p l i e d t o t h i s second s u r f a c e
p e r m i t s d e t e r m i n a t i o n o f t h e v i s c o s i t y . T h i s t y o e o f v i s c o m e t e r was f i r s t
concieved by Couette. I t i s shown F i g . 5. The v i s c o s i t y , when t h e g r a d i e n t of
v e l o c i t y i s c o n s t a n t i s g i v e n by t h e r e l a t i o n :

where T i s t h e t o r q u e measured by means o f t h e t o r s i o n w i r e , R is 'the angular

v e l o c i t y o f t h e c y l i n d e r c o n t a i n i n g t h e l i q u i d ; For R1, R2, h (see F i g . 5 ) .
The g r a d i e n t o f v e l o c i t y i s t a k e n as t h e a r i t h m e t i c mean o f t h e g r a d i e n t s
on each o f t h e faces o f t h e c y l i n d e r s and i s equal t o :

I n s t e a d o f t h e t o r q u e , t h e shear s t r e s s T i s used t o g i v e t h e r e l a t i o n
7 = ? D mentioned p r e v i o u s l y . The advantages o f t h e r o t a t i n g v i s c o m e t e r s as
compared t o c a p i l l a r y tubes may be summarized as f o l l o w s :

- t h e measurements i n a r o t a t i n g v i s c o m e t e r may be made i n s t e a d y s t a t e

conditions ;
- t h e same sample may be used f o r d i f f e r e n t values o f g r a d i e n t o f v e l o c i t y ;
- t h e v i s c o s i t y v a r i a t i o n may be f o l l o w e d d u r i n q t h e t i m e .
 - f o r non-Newtonian f l u i d s , i t i s i m p o r t a n t t o m a i n t a i n t h e g r a d i e n t of
v e l o c i t y constant.

c . F a l l i n g b a l l v i s c o m e t e r s : t h e s e v i s c o m e t e r s a r e based on t h e Stokes
relation :

where F i s t h e f r i c t i o n f o r c e e x e r t e d on a sphere h a v i n g a r a d i u s R, f a l l i n g
i n a l i q u i d o f v i s c o s i t y ~ w i t ha v e l o c i t y v.
When the movement o f t h e f a l l i n g sphere takes p l a c e under g r a v i t y , F
may be expressed by :

4 3
F = -3T R ( P - Po)g (58)

where p and po a r e t h e s p e c i f i c g r a v i t i e s o f t h e sphere and t h e l i q u i d

respectively.
I n steady s t a t e . c o n d i t i o n s ?) may be d e r i v e d f r o m (57) and ( 5 8 ) :

I f R, p , po and g a r e f i x e d , 12 i s deduced f r o m t h e v e l o c i t y o f f a l l
o f t h e sphere. However, c o r r e c t i o n s must be made t o t a k e i n t o
account the i n f l u e n c e o f the p r o x i m i t y o f the w a l l s .

d. Other t e c h n i q u e s : among t h e m i c r o v i s c o s i t y methods, t h e n i t r o x i d e s p i n -

l a b e l t e c h n i q u e was a p p l i e d 7 6 t o sucrose s o l u t i o n s . The ESR s p e c t r a account f o r
t h e m o b i l i t y o f t h e w a t e r around t h e s o l u t e . T h i s t e c h n i q u e p e r m i t s 77 f i n d i n g
t h a t the v a r i a t i o n of the c o r r e l a t i o n time ( l i f e t i m e o f the l a b e l - s i n g l e t a t a
g i v e n l e v e l o f e n e r g y ) as a f u n c t i o n o f t h e sucrose c o n c e n t r a t i o n i s s i m i l a r t o
t h a t o f t h e v i s c o s i t y . The measurement of u l t r a s o n i c v e l o c i t i e s 7 8 and a c o u s t i c
a b s o r p t i o n c o e f f i c i e n t s 7 ' i n aqueous s o l u t i o n s o f sugars p e r m i t t e d d e t e r m i n a t i o n
o f t h e amounts o f h y d r a t i o n w a t e r and were c o r r e l a t e d w i t h v i s c o s i t y d a t a .
 B. II4DUSTRIAL MEASUREMENTS

The p r i n c i p l e s o f the v i s c o m e t e r s used i n t h e i n d u s t r y a r e t h e same as

those d e s c r i b e d f o r t h e l a b o r a t o r y measurements. H o w e v e r , c a p i l l a r y v i s c o m e t e r s
a r e n o t used f o r e m p i r i c a l d e t e r m i n a t i o n s i n t h e sugar f a c t o r y . Most o f t h e
measurements i n t h e sugar i n d u s t r y a r e o b t a i n e d by use o f r o t a t i n g v i s c o m e t e r s ,
o r i n some cases t h e v i b r a t i n g ones d i r e c t l y f i x e d on t h e vacuum Pan.
A g u i d e t o v i s c o s i t y measurements has been given8' f o r t h e chemical
i n d u s t r y . I t s p e c i f i e s t h e p r a c t i c a l use o f the d i f f e r e n t viscometers.
81
V i s c o s i t y measurements and t h e i n t e r p r e t a t i o n o f v i s c o s i t y d a t a were r e v i e w e d
r e c e n t l y f o r p h a r m a c e u t i c a l p r o d u c t s . I n d u s t r i a l v i s c o s i t y measurements a r e
g e n e r a l l y adapted t o t h e s p e c i f i c problems posed by t h e f l o w of a p a r t i c u l a r
m a t e r i a l . The methods are, hence, d e v i sed t o s u i t t o t h e m a t e r i a1 ; i.e. t h e
o i p e l i n e method f o r massecuites. T h a t i s why we s e p a r a t e t h e l a b o r a t o r y measure-
ments d e a l i n g w i t h t h e m o l e c u l a r s t r u c t u r e f r o m t h e i n d u s t r i a l measurements
concerned w i t h t h e p r a c t i c a l problems posed i n t h e c r y s t a l l i z a t i o n s t a t i o n
( f l o w , e x h a u s t i o n o f molasses,. ..) .
1. R o t a t i n g v i s c o m e t e r s .
The most used v i s c o m e t e r s i n t h e sugar i n d u s t r y a r e t h e C o u e t t e - t y p e
v i s c o m e t e r s . The t h e o r y i s t h e same as d e s c r i b e d above f o r l a b o r a t o r y measure-
ments. G e n e r a l l y t h e c y l i n d e r c o n t a i n i n g t h e sample i s f i x e d and t h e c o a x i a l
i n t e r n a l c y l i n d e r r o t a t e s . The r o t a t i n g s p i n d l e has g e n e r a l l y d i f f e r e n t s i z e s
and shapes adapted t o t h e m a t e r i a l i n v e s t i g a t e d . A c o m p a r a t i v e s t u d y l o o f
molasses v i s c o s i t y by use o f t h e rook field^ v i s c o m e t e r s (RVF u n i t m o d i f i e d t o
have a h i g h e r t o r q u e 5X-HBF) and t h e HSPA r o t a t i n g c y l i n d e r v i s c o m e t e r was made.
I t was concluded t h a t accuracy o f t h e r e s u l t s o b t a i n e d w i t h t h e B r o o k f i e l d
i n s t r u m e n t s may be improved by use o f s p i n d l e s f a b r i c a t e d i n t h e f a c t o r y and
s p e c i a l l y a j u s t e d t o t h e m a t e r i a l . However, molasses d i f f e r f r o m a f a c t o r y t o
a n o t h e r by t h e s o l i d s i n suspension and t h e entrapped gases t h e y may c o n t a i n .
Another c o l l a b o r a t i v e s t u d y on molasses v i s c o s i t y d e t e r m i n a t i o n was r e p o r t e d
9
i n t h e M o n t r e a l ICUMSA m e e t i n g .
The r o t a t i n g c y l i n d e r v i s c o m e t e r s used were
t h e B r o o k f i e l d 5X-HBT, t h e HSPA r o t a t i n g c y l i n d e r (HawaTan Experimental s t a t i o n ) ,
the R16 Weissenberg Rheogoniometer and t h e Contraves Rheomat 15. The r e s u l t s
o b t a i n e d w i t h t h e d i f f e r e n t r o t a t i n g c y l i n d e r v i s c o m e t e r s were found s a t i s f a c t o r y
and t h e method was adopted as an o f f i c i a l standard f o r determining the v i s c o s i t y

a
Mention o f a trademark o f an i n s t r u m e n t does n o t i m p l y i t s a p p r o v a l t o t h e
e x c l u s i o n o f o t h e r p r o d u c t s t h a t may a l s o be s u i t a b l e .
o f molasses. I t must be p o i n t e d o u t t h a t t h e Schneider e l a1 .llvalues adopted
by I C U M S A ~ ' i n 1966 were o b t a i n e d w i t h a r o t a t i n g c y l i n d e r v i s c o m e t e r ( R o t o v i s k o
o f Haake). The range o f v i s c o s i t i e s covered by r o t a t i n g v i s c o m e t e r s to
5 Pa. s ) seems t o be c o n v e n i e n t t o t h e d e t e r m i n a t i o n o f sugar syrups and
10
molasses v i s c o s i t i e s . Some o f t h e i n s t r u m e n t s 1 ike t h e B r o o k f i e l d i n s t r u m e n t
p r e s e n t t h e advantage o f b e i n g p o r t a b l e . Other v i s c o m e t e r s l i k e t h e Contraves
and Haake apparatus may be used i n a wide temperature range ( - 60" C t o 2000" C ) .
Accuracy o f r o t a t i n g v i s c o m e t e r s may be t e s t e d 8 3 by use o f s i l i c o n e s t a n d a r d s
w i t h known a b s o l u t e v i s c o s i t i e s . I t i s , then, p o s s i b l e t o choose t h e s p i n d l e
and t h e s h e a r r a t e w h i c h y i e l d s t h e most a c c u r a t e a b s o l u t e v i s c o s i t y v a l u e s .

2. P i p e f l o w v i s c o m e t e r s .
Although t h e r o t a t i n g v i s c o m e t e r s seem t o be adapted t o t h e determina-
t i o n o f mol asses v i s c o s i t i e s ( e s s e n t i a l l y because o f t h e Newtonian behaviour
o f most o f t h e m o l a s s e s ) , t h e p i p e l i n e v i s c o m e t e r s were found9 more s u i t a b l e
f o r massecui t e v i s c o s i t y . I n s t r u m e n t s employing t h e p r i n c i p l e o f t h e r a t e of
f l o w o f a f l u i d under p r e s s u r e t h r o u g h a p i p e l i n e can measure a wide range of
viscosities (lo-' to lo1' Pa. s . ) . They may be compared, as f o r t h e i r o r i n c i ~ l e s
t o t h e c a p i l l a r y v i s c o m e t e r s . The a p p l i c a t i o n o f a p i p e f l o w v i s c o m e t e r t o
84b
massecuites was discussed84a and compared t o a B r o o k f i e l d RVT model by Ness .
The dimensions ( d i a m e t e r D and l e n g t h L ) o f t h e tube have t o be known,
as w e l l as t h e a p p l i e d a i r p r e s s u r e ( a P) and t h e w e i g h t o f massecuite
84b
c o l l e c t e d i n a measured i n t e r v a l t i m e (see F i g . 6 ) . These raw d a t a p e r m i t
e v a l u a t i o n o f t h e shear s t r e s s rWand shear r a t e Y w a t t h e t u b e w a l l . The
D AP
?=--x,
7

Yw = (2:s)
v i s c o s i t y o f t h e f l u i d i s g i v e n by :
$
l o g - l o g p l o t of
, rw
w i t h 7, = - and
V b e i n g t h e average f l o w v e l o c i t y and n l t h e s l o p e o f t h e
rwvs. 8V/D. F o r a Dower l a w f l u i d t h i s p l o t i s a s t r a i g h t
1ine84b and n1 i s a c o n s t a n t u s u a l l y w r i t t e n asl'n". C o r r e c t i o n s o f v i s c o s i t i e s
determined by t h i s method have been s t u d i e d 8 5 i n o r d e r t o account t h e p r e s s u r e
l o s s e s due t o end e f f e c t s and e x i t l o s s e s as w e l l as w a l l s l i p e f f e c t s .

The f l o w p r o p e r t i e s o f massecuites were i n v e s t i g a t e d 8 6 b y use of an o r i f i c e

v i s c o m e t e r . The t e c h n i q u e c o n s i s t s i n measuring t h e head l o s s across an o r i f i c e
f o r a g i v e n f l o w r a t e . No s i g n i f i c a n t d i f f e r e n c e was observed between t h e o r i f i c e
and p i p e l i n e v i s c o m e t e r s .

3. V i b r a t i n g v i s c o m e t e r s .
The measured f a c t o r i n v i b r a t i n g instruments, l i k e t h e Bendix
U l t r a v i s c o s o n , i s t h e r a t e of damping o f v i b r a t i o n o f a probe. The probe may be
a m e t a l l i c s t r i p o r a sphere d i r e c t l y immersed i n t h e l i q u i d o r t h e massecuite.
The v i s c o s i t y of massecuites measured by U l t r a s o u n d viscometer was found87 t o
be l e s s i n f l u e n c e d b y t h e amount o f c r y s t a l s t h a n t h e Couette-type v i s c o s i t i e s .
 - I Ternoerature
c o n t r o l l e r and

sample
ontai ner water
2 L. bath @ 1 1
f I
I 1
I '
pressure I I

gauge L- ,
- - - -- ---- -- - , -51 1I

Ai r Removable t u b e w i t h

II I I
I

water j a c k e t

Fig. 6 ! P i p e l i n e viscometer ( f r o m r e f . 130)

F i g . 7 : Recording o f a f i r s t s t r i k e m o n i t o r i n g w i t h an u l t r a s o n i c v i s c o m e t e r
(from r e f . 87)
The v a l ue in d i c a t e d by t h e i n s t r u m e n t i s t h e p r o d u c t of v i s c o s i t y by the densi t~
of t h e mother l i q u o r . T h i s f a c t was n o t f o r the monitoring
t h e b o i l i n g as t h e o p t i m a l process has t o be r u n a t a c o n s t a n t supersaturation
o f t h e mother l i q u o r .

C . ON LINE CONTROL USING VISCOMETERS.

Automatic pan b o i l i n g was r e c e n t l y revieweda8. The use o f viscometers f o r
c o n t r o l o f c r y s t a l 1iz a t i on was r e p o r t e d 8 8 t o g i v e good r e s u l t s . The r e g u l a t i o n
o f t h e sugar c r y s t a l l i z a t i o n process by use o f r o t a t i n g v i s c o s i ~ Y - C O ~ S ~ S ~ ~ ~ C Y

i n s t r u m e n t s was analyzed8' ' i n d e t a i 1 . The s e n s i t i v i t y o f t h e d e v i c e s was o b t a i n e d

f r o m e x p e r i m e n t a l curves d u r i n g t h e c o n c e n t r a t i o n phase which preceds t h e
seeding. The problems posed by an i m p o r t a n t amount of c r y s t a l s when a r o t a t i n g
c y l i n d e r v i s c o m e t e r i s used a r e d i s c ~ l s s e d a g . The use o f a v i s c o s i t y - c o n s i s t e n c y
t r a n s m i t t e r was describedg0. The S i p m p n s - t r a n s m i t t e c e s p e c i a l l y adapted t o t h e
sugar i n d u s t r y , in v o l ves t h r e e measurement s c a l e s d e l i v e r i n g s t a n d a r d s i g n a l s
i n o r d e r t o m o n i t o r t h e b o i l i n g process. I n t h e f i r s t phase o f c o n c e n t r a t i o n o f
t h e syrup, t h e f l u i d i s Newtonian and t h e a m p l i f i e d s i g n a l d e l i v e r e d by t h e
r o t a t i n g v i s c o m e t e r on t h e f i r s t s c a l e ( 0 - 10 mA) corresponds t o a 0 - 400 c ~ .
range. The second s c a l e ( 1 0 - 20 mA) f o r a c o n s i s t e n c y o f 400 - 1500 cp.
corresponds t o t h e b o i l i n g phase i n t h e c r y s t a l l i z a t i o n process. A s e p a r a t e
t h i r d s c a l e o f measurement r a n g i n g f r o m 0. t o 20 mA ( s t a n d a r d s i g n a l ) i s
e s p e c i a l l y a d a ~ t e dt o t h e s e e d i n g c o n c e n t r a t i o n s t a g e and corresponds t o
s u p e r s a t u r a t i o n r a n g i n g f r o m 0 . 9 t o 1.4.
Process v i s c o m e t e r s must be chosen c a r e f u l l y and s e t up a t a s u i t a b l e
p l a c e i n t h e vacuum pan. O t h e r r e q u i r e m e n t s o f process viscometers a r e g i v e n by
~aram". V i s c o s i t y c o n t r o l may a l s o be d e r i v e d f r o m t h e power consumption i n
a pan equipped w i t h a mechanical s t i r r e r a 8 . The r e c o r d o f a f i r s t s t r i k e b o i l e r
c o n t r o l by t h e ~ l t r a v i s c o s o ni ~s ~shown i n Fig.7. The curve i s s i m i l a r t o t h e
c o n d u c t i v i t y c u r v e r e p o r t e d i n K n $ v l and ~ ~ l l r eev i erw .~ Washing o f t h e probe
i s necessary because o f t h e development of sugar c r y s t a l s on t h e s t r i p o f
measure, o r t h e r o t a t i n g body.
R o t a t i n g body v i s c o m e t e r s have a l s o been usedg1 i n t h e c o n t r o l o f low-
grade ~ r ~ ~ t a l l i z a st t ia ~ t i onn s . The temperature l o w e r i n g programme and t h e
d i l u t i o n b e f o r e c e n t r i f u g i n g may be m o n i t o r e d b y v i s c o s i t y o f massecuites. The
r o t a t i o n a l v i s c o m e t e r s used f o r t h i s purpose must be a d j u s t e d r e g u l a r l y by
comparison w i t h l a b o r a t o r y measurements. Recent use o f comauters i n process
c o n t r o l may be h e l p f u l because i t p e r m i t s s t o r a g e o f data, and p r o c e s s i n g of
t h e s e d a t a i n such a way t h a t t h e programme c o u l d be adapted t o t h e raw m a t e r i a l ,
i.e. frozen sugar b e e t s , o r b e e t s o f d i f f e r e n t o r g a n i c / a s h r a t i o , Moreover,...
t h e c o m p u t e r i z a t i o n o f t h e c o n t r o l of t h e c r y s t a l l i z a t i o n workshop a l l o w s
o p t i m i z a t i o n of t h e p r o c e s s . The temperatures may be programmed i n such a way
t h a t t h e power consumption by t h e s t i r r e r s i s minimized and t h e e x h a u s t i o n
maxinii zed.

I V . RESULTS AND DISCUSSION

Since t h e 1 4 t h s e s s i o n of ICUMSA i n 1966, s c h n e i d e r l 1 e t a l ' s d a t a were

adopted i n o r d e r t o complete t h e N a t i o n a l Bureau o f S t a n d a r d ' s valuesg2 f o r
h i g h c o n c e n t r a t i o n s and l o w temperatures. Numerous v i s c o s i t y r e s u l t s a r e g i v e n
i n t h e l i t e r a t u r e e i t h e r f o r pure and impure s o l u t i o n s . Our aim i n t h i s r e v i e w
i s n o t t o c a t a l o g u e these d a t a i n t a b l e s , b u t r a t h e r t o i n t e r p r e t them i n t h e
l i g h t of r e c e n t concepts on t h e h y d r a t i o n and m o l e c u l a r a s s o c i a t i o n i n aqueous
sugar s o l u t i o n s i n o r d e r t o e l u c i d a t e some sugar f a c t o r y problems l i k e molasses
f o r m a t i o n and e x h a u s t i on.

A. VISCOSITY OF PURE SOLUTIONS

Pure sucrose s o l u t i o n s a r e g e n e r a l l y used as s t a n d a r d l i q u i d s f o r c h e c k i n g

viscometePs. R e l a t i v e l y a c c u r a t e r e s u l t s a r e known f o r pure s o l u t i o n s f o r a l o n g
t i m e . However, t h e d a t a and i n t e r p r e t a t i o n on a m o l e c u l a r l e v e l of m i c r o v i s c o -
s i t y determined d i r e c t l y ( b y v i s c o m e t e r s ) o r d e r i v e d i n d i r e c t l y f r o m s p e c t r o s -
c o p i c measurements a r e r e l a t i v e l y s c a r c e . I n t h e range of c o n c e n t r a t i o n s between
i n f i n i t e d i l u t i o n ( C = 0) and s a t u r a t i o n (C,), i t was foundg3 t h a t t h e
m o l e c u l a r i n t e r a c t i o n s ( b y hydrogen bonds) a r e dominated by w a t e r - w a t e r
i n t e r a c t i o n s from z e r o c o n c e n t r a t i o n t o 1/3 o f s a t u r a t i o n c o n c e n t r a t i o n , w a t e r -
sugar from 1/3 t o 2/3 Cs and sugar-sugar above 2/3 Cs. I t i s , t h e r e f o r e ,
i m p o r t a n t t o have s t r u c t u r a l i n f o r m a t i o n i n o r d e r t o i n t e r p r e t v i s c o s i t y r e s u l t s .

1. D i l u t e s o l u t i o n s .
The hydrodynamic c h a r a c t e r i s t i c , d e r i v e d f r o m t h e v i s c o s i t y measurement
o f d i l u t e solutions, i s the i n t r i n s i c v i s c o s i t y [12] . I t has t h e dimension o f a
volume p e r gram ( d l .g-l) and r e p r e s e n t s t h e r e a l volume under which a gram of
d i s s o l v e d substance i s opposed t o t h e f l o w o f t h e s o l u t i o n . The i n t r i n s i c
[~ki
(-v
viscosity
= o
:-c O
s o b t a i n e d f r o m t h e t r i p l e e x t r a p o l a t i o n o f t h e reduced v i s c o s i t y
) the i n h e r e n t v i s c o s i t y (Log % /c) and t h e d i f f e r e n t i a l

('e)
viscosity towards c = o a t a g i v e n t e m p e r a t ~ r e ~ w h e r e and T o a r e t h e
v i s c o s i t i e s of s o l u t e and s o l v e n t o b t a i n e d w i t h a c a p i l l a r y v i s c o m e t e r . The
g r a p h i c a l method o f d e t e r m i n a t i o n o f [ q ] - i s shown i n f i g u r e 8. A c c u r a t e r e s v l t s
were obtainedg4 by t h i s method f o r d i f f e r e n t mono- and d i s a c c h a r i d e s among which
i s sucrose. T h e o r e t i c a l c a l c u l a t i o n s 4 ' have shown t h a t t h e d i f f e r e n t i a l v i s c o s i t y
helps i n determining [ q ]w i t h a good accuracy. I t may be seen ( F i g . 8) t h a t t h i s
f u n c t i o n g i v e s a means o f v e r i f i c a t i o n o f e x p e r i m e n t a l r e s u l t s . Indeed, t h e
t h e o r y p r e d i c t i n g t h a t i n h e r e n t v i s c o s i t y i s equal t o h a l f
 t h e sum o f s p e c i f i c and d i f f e r e n t i a l v i s c o s i t i e s i s v e r i f i e d e x p e r i m e n t a l l y .
The i n t r i n s i c v i s c o s i t y [ q ] was a1 so derived1' from measurements u s i n g a
I r o t a t o r y v i s c o m e t e r ( C o u e t t e ) . The e x p e r i m e n t a l r e s u l t s were found t o agree w i t h
E i n s t e i n ' s e q u a t i o n m o d i f i e d by vandZ1 f o r c o n c e n t r a t i o n s r a n g i n g up t o
30 - 40 % (w/w). Above t h i s c o n c e n t r a t i o n a t r a n s i t i o n occurs f r o m sugar-water
i n t e r a c t i o n s ( h y d r a t i o n ) t o sugar-sugar a s s o c i a t i o n . T h i s t r a n s i t i o n a t
30 - 40 % (w/w) c o n c e n t r a t i o n i s a p p a r e n t on f i g u r e 9 showing v i s c o s i t y as a
f u n c t i o n o f c o n c e n t r a t i o n . The t h r e s h o l d of 30 - 40 % may be t a k e n as t h e
threshold o f d i l u t e solutions, f o r which t h e o r i e s l i k e t h a t o f E i n s t e i n o r i t s
m o d i f i e d forms,may be a p p l i e d . I n t h i s range o f c o n c e n t r a t i o n s , molecules of
sugar c o u l d be c o n s i d e r e d as spheres o r e l l i p s o i d s surrounded by a h y d r a t i o n
( she1 1 . The number of molecules o f h y d r a t i o n may be determinedg5 f r o m i n t r i n s i c
I
v i s c o s i t y and t h e a p p l i c a t i o n o f E i n s t e i n - S i m h a e q u a t i o n . T h i s number i s
g e n e r a l l y e s t i m a t e d t o be 5 m o l e c u l e s o f w a t e r p e r m o l e c u l e o f sucrose. I t was
found15 t o i n t e r f e r e i n t h e c r y s t a l l i z a t i o n process.
The second hydrodynamic parameter w h i c h i s i m p o r t a n t t o know f o r d i l u t e
s o l u t i o n s , i s k ' t h e Huggins c o e f f i c i e n t , a l s o c a l l e d g 5 t h e i n t e r a c t i o n
coefficient. It i s d e r i v e d f r o m Huggins e q u a t i o n developed t o t h e 2nd t e r m :

The v a r i a t i o n o f k ' i s g i v e n F i g . 9 i n f u c t i o n o f ? sp. I t was demonstrated 96

t h a t k ' may be o b t a i n e d f r o m eq. 9 and t h e e q u a t i o n o f Schultze-Blaschke :

9 s ? / c = [y] ( 1 * k 12 sp)
and expressed by :

where k , t h e S c h u l t z e - B l a s c h k e c o n s t a n t i s independent o f t h e c o n c e n t r a t i o n .
The v e r i f i c a t i o n o f t h e 1 i n e a r i t y o f r e l a t i o n ( 6 1 ) was p o s s i b l e g 7 f o r s o l u t i o n s
o f l o w i n t e r a c t i o n e f f e c t s ( p o l y s t y r e n e i n benzene).
I t i s seen i n F i g . 1 0 t h a t
a1 though t h e o r d i n a t e a t t h e o r i g i n i s 2, t h e s l o p e o f k ' i s s e n s i t i v e t o a g i n g
This i s p a r t i c u l a r l y e v i d e n t f o r g l u c o s e s o l u t i o n s ( F i g . l o ) , where 24 hours
a r e needed b e f o r e t h e anomeric e q u i l i b r i u m i s reached.

2. Concentrated s o l u t i o n s .
The v i s c o s i t y o f h i g h - c o n c e n t r a t i o n sugar s o l u t i o n s was determined
e x p e r i m e n t a l l y 92y11 o r c a l c u l a t e d35y98. Data r e l a t i v e t o pure s o l u t i o n s , a t
d i f f e r e n t temperatures and c o n c e n t r a t i o n s , may be found i n books
o r i n t h e s e l e c t e d t a b l e s of p h y s i c a l D r o ~ e r t i e sof sugar s o l u t i o n s e d i t e d by
~ 0 r r i s t - i ~Most
~ . of t h e have as t h e i r o r i g i n t h e N.B.S. circular
Fig.8:Determinationofintrinsicviscosity Fig.9:Viscosityofsucrose
by the t r i p l e e x t r a p o l a t i o n s o l u t i o n s i n cp. i n
method4' f u n c t i o n of c o n c e n t r a -
t i o n a t 20' C .
( f r o m r e f . 94)

F i g . 10 : Dependence o f Huggins c o n s t a n t k ' on s p e c i f i c v i s c o s i t y 15 m i n . and

24 hours a f t e r d i s s o l u t i o n of sucrose ( S ) and glucose ( G ) .
( f r o m r e f . 94)
 ~440". The Schneider e t a1 .I1
r e s u l t s were adopted a t t h e 1 4 t h . s e s s i o n of
ICUMSA and published8' f o r t h e range o f c o n c e n t r a t i o n s ( 7 5 - 86 % (w/w) and
temperatures ( 5 - 80" C ) which complements t h e N.B.S. d a t a g 2 . V i s c o s i t i e s of
c o n c e n t r a t e d sugar s o l u t i o n s ( 6 0 - 74 % (w/w) weremeasuredloo a t temperatures
below 0" C . T h i s range o f c o n c e n t r a t i o n s and temperatures down t o -20" C were
I i n v e s t i g a t e d by d i f f e r e n t a u t h o r s 101y102 i n t e r e s t e d i n t h e amorphous f r o z e n
s o l u t i o n . I t was found t h a t , even a t such low temperatures, c o n c e n t r a t e d
sucrose s o l u t i o n s showed a Newtonian b e h a v i o u r . The v a r i a t i o n o f t h e v ' i s c o s i t y
of s u p e r s a t u r a t e d p u r e sucrose s o l u t i o n s was i n v e s t i g a t e d b y ~i
khomiroff103. It
was found t h a t t h e v i s c o s i t i e s decrease i n f u n c t i o n o f t i m e and s u p e r s a t u r a t i o n .
The t i m e a f t e r which t h e v i s c o s i t i e s a r e s t a b i l i z e d , i s a f u n c t i o n of t h e
s u p e r s a t u r a t i o n . No v a r i a t i o n o f v i s c o s i t y was observed f o r a s u p e r s a t u r a t i o n
equal o r less than 1 . 2 . F o r h i g h e r v a l u e s , swarms o f sucrose molecules a r e
formed i n a s t e p p r e c e d i n g t h e n u c l e a t i o n process c a l l e d " p r e n u c l e a t i o n " . The
103
" p r o t o n u c l e i " s e t t l e down c a u s i n g t h e decrease o f d e n s i t y and v i s c o s i t y .
Many nomograms have been e s t a b l i s h e d , f o r use i n t h e sugar i n d u s t r y , t o
g i v e v i s c o s i t i e s of p u r e sucrose s o l u t i o n s , a t d i f f e r e n t temperatures and
c o n c e n t r a t i o n s i n OBrix. s i l i n l o 4 g i v e s a nomogram based on t h e e x p e r i m e n t a l
d a t a of B e n n e t t and ~ e e s ' ' ~ , Spenqler and ~ a n d t " ~and on t h e r e l a t i o n ( 2 0 ) o f
~ a g a n o v ' ~ .More r e c e n t l y , ~ a l o h l ' ~p u b l i s h e d a s e t o f diaqrams, summarizing t h e
most i m p o r t a n t p h y s i c a l p r o p e r t i e s of sugar s o l u t i o n s , amonq w h i c h dynamic and
k i n e m a t i c v i s c o s i t i e s as a f u n c t i o n of c o n c e n t r a t i o n .

3. I n t e r p r e t a t i o n .
V i s c o s i t y o f sucrose s o l u t i o n s g i v e s i n f o r m a t i o n on t h e t r a n s p o r t
p r o p e r t i e s of t h e sugar i n t h e aqueous medium. The r e l a t i o n s h i p between
viscosity 7 and t h e d i f f u s i o n c o e f f i c i e n t D i s g i v e n b y t h e S t o k e s - E i n s t e i n
equation :

where r i s t h e r a d i u s of t h e p a r t i c l e , k t h e Bol tzman c o n s t a n t and T t h e

absolute temperature.
Eq. 62 was f o u n d 108y109 t o be inadequate f o r t h e b e h a v i o u r o f sucrose
s o l u t i o n s , p r o b a b l y because o f t h e s t r o n g i n t e r a c t i o n amongst t h e components
o f the solution.

a. H y d r a t i o n : m o l e c u l a r a s s o c i a t i o n was reviewedl10 i n t h i s journal,

w i t h p a r t i c u l a r r e f e r e n c e t o t h e e f f e c t o f h y d r a t i o n o f t h e sucrose molecule
on t h e t r a n s p o r t p r o p e r t i e s i n aqueous s o l u t i o n s .
More r e c e n t l y 1 5 , a model o f
h y d r a t i o n of t h e sugar m o l e c u l e was proposed and i t s e f f e c t on t h e
 crystal1 i z a t i o n of low purity syrup discussed. The hydration numbers given
i n the l i t e r a t u r e vary with the method of determination. The blunt modification
of the v a r i a t i o n of i n t r i n s i c viscosity in function of weight concentration
around 30 t o 40 % has been assigned1' t o the transformation of sugar hydrates
t o a s s o c i a t e s . Moreover, i t was showng3 from an X-ray study t h a t , in the range
of concentrations below 22.3 %, the hydrogen bonding i n aqueous sucrose s o l u t i o n
occurs p r e f e r e n t i a l l y between water molecules i n i n f i n i t e chains including
water-sugar bonds of an open (with no intramolecular H-bonds) sucrose molecule.
That i s why, except an increase of the hydrodynamic volume of the s o l u t e
molecule due t o the hydration s h e l l , the sucrose s o l u t i o n s obey the E i n s t e i n ' s
r e l a t i o n in t h i s range of concentrations.

b. Molecular Association : v a r i a t i o n of v i s c o s i t y of supersaturated

aqueous solutions was i n t e r p r e t e d l o 3 i n terms of molecular association (sugar-
sugar) leading t o the formation of "proto-nuclei" ; i . e . Swarms of Sucrose
molecules j u s t preceding the nucleation process. A t high concentrations, there
i s a polymer formation and c r y s t a l l i z a t i o n develops only when a s u f f i c i e n t
number of hexamers a r e present111. The a s s o c i a t e s formed i n supersatured

-
solutions a r e not completely anhydrous and probably obey an e q u i l i b r i m of
dehydration, s i m i l a r t o what was proposed by Culp 112 ..

I S(H2OIn S(H20), - 1 ,
- S(H20),, - ....
When temperature i s decreased, t h e complexity of t h e sol ute-solute and s o l u t e -
solvent associates i s manifested in the metastable character of the hemipenta-
3 . - I
and hemiheptahydrates formed"'.

6. VISCOSITY OF IMPURE SOLUTIONS

I t i s generally admi t t e d , t h a t the rheological behaviour of pure sucrose

solutions i s Newtonian i n the whole range of concentrations and temperatures
~ r a c t i c e din sugar f a c t o r i e s . However, t h e impure syrups and molasses diverge
from the Newtonian behaviour and show pseudo-plastic or v i s c o e l a s t i c v i s c o s i t i e s
depending on t h e i r o r i g i n (cane o r beet) and the impurities they contain
(dextrans, p e c t i n s , . . . ) .
1 . Viscosity of molasses.
The e f f e c t o f temperature on nol lasses v i s c o s i t y was expressed62 by t h e
r e l a t i o n s h i p of F r e n k e l :

where i s t h e v i s c o s i t y , T i s t h e a b s o l u t e temperature, A and 6 a r e c o n s t a n t s .

The e f f e c t o f t h e n a t u r e of t h e i m p u r i t i e s on t h e v i s c o s i t y was found t o be
i m p o r t a n t i n cane molasses, where a r e l a t i v e l y h i g h amount of o r g a n i c macromole-
cules (dextrans , gums) i s f o u n d . Macromolecular components of cane molasses were
obtained114 a f t e r d i a l y s i s o f t h e s y r u p . The o t h e r f r a c t i o n s s t u d i e d f o r their
i n f l u e n c e on t h e v i s c o s i t y o f m i l l syrups were t h e sediment o b t a i n e d a f t e r
c e n t r i f u g a t i o n of a 20" B r i x s o l u t i o n and t h e low and medium m o l e c u l a r w e i g h t
components o b t a i n e d i n t h e d i a l y s a t e f r o m t h e syrup, as w e l l as s a l t s , amino-
a c i d s and s u g a r s . The m i x t u r e o f t h e f o u r f r a c t i o n s equals 85 % o f t h e v i s c o s i t y
o f t h e sucrose s y r u p . The macromolecular f r a c t i o n was found t o have t h e b i g g e s t
e f f e c t on v i s c o s i t y . The d e x t r a n o f b a c t e r i a l (Leuconostoc mesenteroides) o r i g i n
has an enormous e f f e c t . I t s m i x t u r e w i t h sucrose has a v i s c o s i t y of o v e r twenty-
f i v e times t h a t of a c o r r e s p o n d i n g p u r e sucrose s o l u t i o n . The i n c r e a s e i n
v i s c o s i t i e s o f molasses due t o d e x t r a n s has been in v e s t i gated115 and e x p r e s s i o n s
of such an i n c r e a s e were proposed. F o r a t y p i c a l m o l e c u l a r w e i g h t of d e x t r a n
6
equal t o 20 x 10 , t h e v i s c o s i t y i n c r e a s e i s g i v e n by :

where p DEX = v i s c o s i t y o f d e x t r a n c o n t a i n i n g s o l u t i o n
PTS = v i s c o s i t y o f t h e same t o t a l s o l i d s b u t z e r o d e x t r a n
C = c o n c e n t r a t i o n o f d e x t r a n ( g / d e c i lit r e )

The f l o w behaviour, caused i n p u r e sucrose s o l u t i o n by a d d i t i o n o f dextran,was

s l i g h t l y p s e u d o - p l a s t i c , w h i l e , i n molasses, t h e non-Newtonian e f f e c t was more
n o t i c e a b l e 1 1 5 . Flow anomalies were studied6' i n 62 samoles o f cane sugar
molasses. I t was found t h a t t h e p s e u d o - p l a s t i c b e h a v i o u r o f t h e s e molasses was
n o t dependent on c o n c e n t r a t i o n , b u t a c o r r e l a t i o n may be d e r i v e d between
pseudopl a s t i c i t y and temperature.
The e f f e c t o f temperature and c o n c e n t r a t i o n on beet-sugar molasses v i s c o s i t y
was studied116 by comparison t o p u r e sucrose s o l u t i o n s . I t must b e n o t e d t h a t
i n c r e a s i n g i n p u r i t y causes i n c r e a s e i n v i s c o s i t y and e x t r a p o l a t i o n f r o m
molasses t o impure syrups i s n o t f e a s d b l e . An i n c r e a s e o f a p p r o x i m a t l y 1 %
v i s c o s i t y f o r each 1 % p u r i t y i n c r e a s e has t o be accounted for1''. The v i s c o s i t -
i e s o f h i g h - c o n c e n t r a t i o n impure syrups, b e e t and cane molasses were r e p o r t e d 118 .
I t was found t h a t a l l b e e t molasses and a p a r t o f cane molasses i n c l u d e a i r and/or
o t h e r gases, and showed a Newtonian b e h a v i o u r . One cane molasses showed a
s t r u c t u r a l v i s c o s i t y , p r o b a b l y due t o gas b l i s t e r s , r e s u l t i n g f r o m M a i l l a r d
reaction. Two b e e t syrups w i t h h i g h p e c t i n c o n t e n t s showed s t r u c t u r a l v i s c o s i t y .
119
However, t h e d e v i a t i o n f r o m Newtonian b e h a v i o u r was o n l y s m a l l 18. Another work
on t h e e f f e c t 3f d i f f e r e n t non-sucrose components on molasses l e d t o t h e
c o n c l u s i o n t h a t molasses, 1 i k e sucrose s o l u t i o n s a r e Newtonian f l u i d s . The
p s e u d o - p l a s t i c b e h a v i o u r , t h e y may show, i s due t o macromolecules o f 100,000 t o
200,000 M.W. w h i c h a r e e l i m i n a t e d i n t h e p u r i f i c a t i o n process. The e f f e c t o f
i m p u r i t i e s i s expressed as f o l l o w s :
k = log r/c (65)

where : k = v i s c o s i t y i n d e x o f a g i v e n substance
r = r a t i o o f v i s c o s i t i e s o f t h e s o l u t i o n w i t h t h e non-sucrose (NS) t o
t h e s o l u t i o n w i t h zero NS
c = c o n c e n t r a t i o n o f NS by r e f e r e n c e t o w a t e r

k i s n o t i n f l u e n c e d by t h e i n i t i a l d r y substance c o n t e n t , b u t v a r i e s w i t h
temperature. The i n f l u e n c e o f temperature on t h e e f f e c t o f non-sucrose i s shown
1
i n t a b l e 2 f o r p u r e sucrose s o l u t i o n s ( S ) , cane (C) and b e e t ( R ) molasses. The
i n v e s t i g a t e d c o n c e n t r a t i o n i s 70' B r i x and t h e non-rsucroses a r e d i v i d e d i n t h r e e
groups :

group 1 : NS c a u s i n g a decrease i n sucrose s o l u t i o n v i s c o s i t y

group 2 : NS c a u s i n g an i n c r e a s e o f v i s c o s i t y l o w e r t h a n t h a t caused by t h e
same amount o f sucrose
group 3 : NS c a u s i n g an i n c r e a s e i n v i s c o s i t y h i g h e r t h a n t h a t caused by t h e
same amount of sucrose

An i n v e s t i g a t i o n l Z 0 o f t h e e f f e c t o f i m o u r i t i e s on U k r a i n i a n beet-sugar
molasses v i s c o s i t i e s d i d n o t p e r m i t a r e l i a b l e c o r r e l a t i o n . Tendancies were,
however, drawn as f o r t h e i n c r e a s e o f v i s c o s i t y w i t h t h e c a l c i u m i o n c o n t e n t ,
i t s decrease w i t h a1 k a l ine in o r g a n i cs and i n c r e a s e w i t h t h e c o l l o i d s o r e c i p i t a -
t e d i n a l c o h o l i c s o l u t i o n s . The B r a z i l i a n molasses were analyzed12' by use o f a
f a l l i n g b a l l v i s c o m e t e r . No c o r r e l a t i o n was found between t h e B r i x degree and
t h e v i s c o s i t i e s . The f a c t o r s a f f e c t i n g molasses v i s c o s i t y were discussed12' and
an e q u a t i o n was proposed i n o r d e r t o express i t i n terms of d r y substance,

found w i t h a '
t e m p e r a t u r e , p u r i t y and reduced sugar/ash r a t i o . The c a l c u l a t e d v i s c o s i t i e s were
20 % s t a n d a r d e r r o r and a maximum o f f 108 %.The a u t h o r s 122
c l a i m t h a t i t i s necessary t o i n c l u d e i n t h e e q u a t i o n f a c t o r s such as suspended
m a t t e r , c o l l o i d s , e t c . However, i t was r e p o r t e d l Z 2 t h a t molasses v i s c o s i t y
decreases w i t h an i n c r e a s e i n p u r i t y , which i s c o n s i s t e n t w i t h what i s
Table 2
V i s c o s i t y i n d e x o f d i f f e r e n t non-sucrose components a t d i f f e r e n t temperature.
___. ---- . -- - -- - -- A . A

Substance I Temperatures

1. Group
water
water

2. Groupe
NaN03
Betaine

KzC03
KzS04
K-glutamate
Glucose
NaCl
Na-Formi a t e
Dry-substance

I Sucrose

3. Group
Dry substance
Na-glutamate
Raffinose
Ca (N0312
SrC1
Ca-acetate
L i Cl
NaS04
Na-ci t r a t e

C : cane ; R : b e e t ; S : sucrose s o l u t i o n s .
g e n e r a l l y a d m i t t e d . Indeed, f o r b e e t molasses t h e r e l a t i o n s h i p between n u r i t y
and v i s c o s i t y were s t u d i e d l Z 3 . I t was found t h a t molasses v i s c o s i t y decreases
when p u r i t y i n c r e a s e s a c c o r d i n g t o t h e r e l a t i o n

where %= v i s c o s i t y o f a s o l u t i o n a t a ~ u r i t yP
= v i s c o s i t y o f n u r e sucrose s o l u t i o n
I
= v i s c o s i t y o f mol asses w i t h o u r i t y Pm
2
The v i s c o s i t y o f c o n c e n t r a t e d pure and impure sucrose s o l u t i o n s were i n v e s t i -
g a t e d l Z 4 . Equations were proposed i n o r d e r t o r e l a t e v i s c o s i t y and o u r i t y . The
effect o f temperature was a l s o s t u d i e d . An e m n i r i c a l r e l a t i o n was nrooosed :

where?: v i i c o s i t y i n Pa.s., t temoerature i n OC and n m o l e c u l a r c o n c e n t r a t i o n

I
Yolasses v i s c o s i t y has a l s o been s t u d i e d f r o m t h e p o i n t o f view o f i t s e f f e c t s
on t h e w o r k a b i l i t y o f low grade massecuites and c o n s e q u a n t l y on t h e e x h a u s t i o n
o f molasses. One o f t h e f a c t o r s i n f l u e n c i n g t h e v i s c o s i t y o f molasses and
c a u s i n g c o n t r o v e r s i a l i n t e r o r e t a t i o n s o f r e s u l t s i s t h e a e r a t i o n . The oresence
o f qases i n molasses was r e p o r t e d 7 ' t o produce v i s c o s i t y anomalies. A r e c e n t
in v e s t i q a t i o n l Z 5 o f molasses and massecui t e s v i s c o s i t i e s was concluded by
a s s i g n i n q a p s e u d o - p l a s t i c b e h a v i o u r t o molasses because o f t h e nresence o f a i r
and a Newtonian b e h a v i o u r , due t o t h e absence o f a i r , f o r massecuites. An
126
a t t e m o t t o determine t h e f a t e o f a i r i n e m u l s i f i e d molasses has been made .
A e r a t i o n g e n e r a l l y takes lace d u r i n g t h e m i x i hq o f massecuites, e s o e c i a l l y when
f e r m e n t a t i o n occurs i n immature o r f r o z e n b e e t s . The i n f l u e n c e o f a e r a t i o n on
molasses v i s c o s i t y has been studied127. R e s u l t s o f molasses c o n t a i n i n q 0, 10,
20 and 30 mL a i r % g were o b t a i n e d by use o f a t i o n p l e r v i s c o m e t e r and comoared
t o a s t a n d a r d molasses h a v i n q 44 p o i s e s v i s c o s i t y (see Table 3 ) .
These r e s u l t s show an i n c r e a s e i n v i s c o s i t y w i t h a i r c o n t e n t . An i o n exchanqe,
t t
l i k e t h a t o f t h e Q u e n t i n process ( ~ q " a g a i n s t Na and K ) , provokes an i n c r e a s e
o f molasses v i s c o s i t y 128,129
 Table 3
127
Molasses viscosity with d i f f e r e n t a i r contents

Air content in mL % q
Bri x T "C
0 10 20 30

2 . Viscosity of Massecuites.
I t i s more appropriate f o r massecuites t o consider t h e i r rheology
o r flow properties. The rheological curves of massecuites were found84a pseudo-
p l a s t i c , b u t approached Newtonian behaviour a t higher shear r a t e s . This r e s u l t
i s a t t r i b u t a b l e t o end and wall e f f e c t s of pipeline viscometers. The pipe used
must be of s u f f i c i e n t diameter, t h a t wall e f f e c t s a r e minimized and of a
s u f f i c i e n t l y l a r g e L / D r a t i o , so t h a t entrance e f f e c t s can be neglected130.
Thus, the pipeline method recommended by the l a s t ICUMSA meetings must be
improved. The v i s c o s i t y of massecuites depend on the c r y s t a l content, c r y s t a l
s i z e , s i z e d i s t r i b u t i o n and shape and on the viscosity of the molasses surround-
ing the c r y s t a l s q 2 ' . The r a t i o of massecuite t o molasses v i s c o s i t y in function
of c r y s t a l content has been determined by ~ iina65 l ( s e e Table 1 ) . The values
given in Table 1 a r e comparable t o recent determinations'". As the d i r e c t
determination of massecuite viscosity i s d i f f i c u l t and t h e i n d i r e c t r e s u l t
obtained by multiplying molasses v i s c o s i t y by t h e r a t i o of v i s c o s i t i e s
ell^'^'
u n s a t i s f a c t o r y , an approach l i k e t h a t of may be helpful. Considering
a massecuite a s a f l u i d i z e d bed of c r y s t a l s in the mother l i q u o r , he was able
t o c a l c u l a t e the velocity of flow through the bed and t o p r e d i c t t h a t f o r a
c r y s t a l content of 44 % the c r y s t a l will not be in separate motion and a t 48 %
a l l c r y s t a l s a r e in contact and the massecuite looses f l u i d i t y q 3 ' . I t was even
establ ishedq3'that c r y s t a l s may be more compressed i s massecuite than in
granulated dry sugar. However, the massecuite remains a two-phase ~ y s t e i n ~ ~ ~ u n t i l
the percentage of c r y s t a l s reaches 60 - 65 %.The viscosity of low-grade
massecuites was determinedq33 with a rheo-viscometer based on the Hoppler
principle. I t was found133 t h a t the v i s c o s i t y of C-massecuites obtained from
the double s u l p h i t a t i o n process t o produce white sugar was higher than what was
observed when simple defecation was applied t o produce raw sugar. Viscosity of
beet molasses and massecuites was extensively investigated by wagnerowski7. He
proposed'34 a modified Sil ina formula t o express the r a t i o of v i s c o s i t i e s :
where MC i s t h e massecui t e v i s c o s i t y , EM, t h e mother-1 i q u o r v i s c o s i t y ,
BMC, t h e massecuite B r i x and Cr t h e c r y s t a l c o n t e n t . F o r l o w grade massecuites,
7
a f o r m u l a was e s t a b l i s h e d t h a t p e r m i t t o c a l c u l a t e t h e v i s c o s i t y f o r a c r y s t a l
c o n t e n t o f 42 % a t a g i v e n temperature ( 6 ) , when t h e o p t i m a l c o o l i n g tempera-
ture ( 8 o p t . ) i s known :

0°pti2-540 t lo] x log t 0.315 ,g - 0.267 (69)

L O ~ " Z E ( C ( , ~=[) e+;1;
T h i s e m p i r i c a l f o r m u l a i s i m p o r t a n t f o r c o n d u c t i n g o f low-grade c r y s t a l l i z a t i o n .
7
R e s u l t s o b t a i n e d f o r P o l i s h b e e t massecui t e s w i t h t h i s f o r m u l a a r e summarized
i n the f o l l o w i n g t a b l e .

Table 4

Dependence o f massecuite v i s c o s i t y ( i n Pa.s) on c o o l i n g t e m p e r a t u r e a t d i f f e r e n t

f i n a l o b t i m a l temperatures and a c r y s t a l c o n t e n t o f 42 %

Optimal Temperature OC
f in a l Log
temperatureyMC(80) 80 75 70 65 60 55 50 45 40

Other r e l a t i o n s p r e d i c t i n g t h e v i s c o s i t y o f massecuites as a f u n c t i o n o f
68
temperature and c r y s t a l c o n t e n t have been proposed .
3. I n t e r p r e t a t i o n .
The r h e o l o g i c a l b e h a v i o u r o f molasses and massecuites was found t o
be e i t h e r Newtonian o r p s e u d o - p l a s t i c . F o r b o t h p r o d u c t s , we deal w i t h a v e r y
complex medium. Beside t h e s o l v e n t ( w a t e r ) and t h e main s o l u t e ( s u c r o s e ) , t h e r e
i s a g r e a t number o f o t h e r components i n t e r a c t i n g w i t h w a t e r and sucrose mole-
c u l e s . These components (see t a b l e 2) have d i f f e r e n t o r i g i n s , m o l e c u l a r w e i g h t s ,
hydration characteristics, etc... To t h e h e t e r o g e n e i t y o f c o m p o s i t i o n o f t h e
l i q u i d phase, one has t o add t h e h e t e r o g e n e i t y o f phases i n massecuites where
t h e s o l i d phase i s i t s e l f l a r g e l y heterogeneous. Indeed t h e s i z e and shape o f
c r y s t a l s a r e f a r from b e i n g homogeneous. These f e a c t u r e s i n f l u e n c e t h e r e s u l t s
of measurement o f v i s c o s i t y and t h e f l o w and a g i t a t i o n o f molasses and massecuites
 a . E f f e c t o f a d d i t i v e s : t h e non-sucrose components may be regarded
as a d d i t i v e s t o p u r e sucrose s o l u t i o n s and t h e i r e f f e c t on v i s c o s i t y be analyzed.
But, what i s g e n e r a l l y meant by a d d i t i v e s i s t h e t e n s i o a c t i v e p r o d u c t s used i n
sugar f a c t o r i e s t o improve t h e f l u i d i t y o f low-grade massecuites. The f i r s t
c l a s s o f a d d i t i v e s concerns a r t i f i c i a l impure s o l u t i o n s s t u d i e d i n t h e
l a b o r a t o r y 135'136. The e f f e c t o f added e l e c t r o l y t e s on t h e v i s c o s i t y of aqueous
sucrose s o l u t i o n s has been d i s c u ~ s e d ' i~n~ terms o f s t r u c t u r e - m a k i n g o r
s t r u c t u r e - b r e a k i ng . The in t e r a c t i ons by hydrogen b o n d i n g i n t h e t e r n a r y System
KC1-water-sucrose were d e r i v e d from v i s c o s i t y studies136. Comparison o f t h e
v i s c o s i t i e s of pure and impure s o l u t i o n s led137 t o c h a r a c t e r i z e t h e e f f e c t of
aMX
each e l e c t r o l y t e b y a c o n s t a n t d e r i v e d from t h e e q u a t i o n : Tz/Tc
= A.10 ,
where and T c are t h e v i s c o s i t i e s of impure ( c o n t a i n i n g t h e e l e c t r o l y t e )
and pure s o l u t i o n s r e s p e c t i v e l y ; M t h e m o l e c u l a r w e i g h t o f t h e e l e c t r o l y t e and
I X i t s m o l a r c o n c e n t r a t i o n ; A and a a r e c o n s t a n t s c h a r a c t e r i z i n g t h e e l e c t r o l y t e .
I
I The i n f l u e n c e o f d i f f e r e n t non-sugars on molasses v i s c o s i t y has been
i n ~ e s t i g a t e d al ~t ~t h e "normal" c o n d i t i o n s o f 82" B r i x , 40" C and 44 p o i s e s .
The i n c r e a s e of v i s c o s i t y b y added c a t i o n s was found i n t h e f o l l o w i n g o r d e r
K+ > ~ a '> cat' >~g'+ and by anions : NO3- >C1- > glutamic a c i d >acetic acid
>lactic a c i d . A1 1 t h e o p e r a t i o n s p r e c e d i n g t h e low-grade c r y s t a l l i z a t i o n , such
as d e c a l c i f i c a t i o n , Q u e n t i n process o r s u l p h i t a t i o n , e t c . . . must be t a k e n i n t o
account i n o r d e r t o i n t e r p r e t t h e r h e o l o g i c a l b e h a v i o u r o f molasses and C-
massecui t e s .
The second c l a s s o f a d d i t i v e s i s t h a t o f s u r f a c e a c t i v e chemicals used t o
reduce molasses v i s c o s i t y . T h i s t o p i c has been reviewed i n t h i s journal139. It
was r e p o r t e d t h a t s e v e r a l s u r f a c t a n t s a r e e f f i c i e n t i n r e d u c i n g molasses and
massecuites v i s c o s i t i e s , enhancing c r y s t a l y i e l d s and i n c r e a s i n g molasses
e x h a u s t i o n . However, i t has t o be n o t e d l 4 ' t h a t f o r each chemical, a c e r t a i n
optimum v i s c o s i t y r e d u c t i o n e x i s t s f o r an optimum dosage. I t m i g h t be s u f f i c i e n t
f o r c e r t a i n s u r f a c t a n t s t o employ 100 p.p.m. f o r r e d u c i n g molasses v i s c o s i t y
by about 30 %.

b. Flow o f non-Newtonian f l u i d s : t h e anomalies o f f l o w o f molasses

and massecuites may be an embarrassment t o t h e f a c t o r y For pumping and c e n t r i -
f u g i ng low-grade p r o d u c t s and i n t h e 1a b o r a t o r y when the p i p e f l o w v i scometer
i s used. Indeed, t h e more t h e s i z e o f t h e p a r t i c l e s d i s p e r s e d i n t h e l i q u i d
phase i s s m a l l , t h e more t h e c o n c e n t r a t i o n , a t which t h e d e v i a t i o n from the
Newtonian f l o w appears, i s l o w l 4 ' . H y d r a t i o n o f t h e i o n s , sugars and o t h e r com-
, ponents o f molasses as w e l l as t h e presence o f a i r a r e a t t h e o r i g i n o f t h e i r
p s e u d o - p l a s t i c b e h a v i o u r . When f l o w i n g , t h e p s e u d o - p l a s t i c substances e x h i b i t

I a decrease i n t h e i r i n t e r n a l f r i c t i o n , o r apparent v i s c o s i t y . T h i s phenomenon

i s due t o u n r a v e l i n g o f molecules, o r i e n t a t i o n i n t h e shear d i r e c t i o n and a
p o s s i b l e change i n t h e arrangement o f s o l v e n t m o l e c u l e s . The f a c t o r s g o v e r n i n g
t h e o u t f l o w o f massecuites through c i r c u l a r o r r e c t a n g u l a r a p e r t u r e s have been
determined6' f r o m r h e o l o g i c a l measurements. The v i s c o u s f l o w of molasses was
considered142 as a l a m i n a r f l o w f o r t h e c a l c u l a t i o n o f p i p e d i a m e t e r s .
V i s c o s i t y o f low-grade p r o d u c t s was c o n s i d e r e d as a dominant factor, t o c o n t r o l
c a r e f u l l y , i n o r d e r t o p e r m i t t h e i r pumping143 and c e n t r i f u g i n g o r t o o p t i m i z e
molasses exhaustion144. On t h e o t h e r hand, t h e w a l l e f f e c t s provoked by t h e
c r y s t a l number, s i z e and shape, i n p i p e f l o w and r o t a t i n g v i s c o m e t e r s r e n d e r s
t h e measurement o f massecuite v i s c o s i t y v e r y d i f f i c u l t e s p e c i a l l y i n t h e r e g i o n
of t r a n s i t i o n between Newtonian and p s e u d o - p l a s t i c f l o w s .

V . EFFECT OF VISCOSITY 014 SUGAR MANUFACTURING

The v i s c o s i t y o f sugar s o l u t i o n s p l a y s a d e c i s i v e r o l e d u r i n g t h e b o i l i n g
and c r y s t a l l i z i n g processes. Both v i s c o s i t y and s u r f a c e d i f f u s i o n a r e i n v o l v e d
i n t h e c r y s t a l l i z a t i o n o f sucrose. I t i s a l i m i t i n g f a c t o r i n t h e w o r k a b i l i t y
o f low-grade massecui t e s , hence i n t h e amount o f sugar o b t a i n e d . T h e o r e t i ca1
and p r a c t i c a l c o n s i d e r a t i o n s t e n d t o i n d i c a t e t h a t v i s c o s i t y may be used as a
good mean o f c o n t r o l i n vacuum pans and c r y s t a l 1iz e r s .

A. EFFECT ON CRYSTALLIZATION
The i n f l u e n c e o f v i s c o s i t y on t h e r a t e o f c r y s t a l l i z a t i o n i s n o t t h e
same i n p u r e and impure s o l u t i o n s . The r e l a t i v e imoortance o f d i f f u s i o n and
i n c o r p o r a t i o n o f sugar molecules i n t h e c r y s t a l and t h e i r a l t e r a t i o n b y an
i n c r e a s e i n v i s c o s i t y seem t o be c o n t r o v e r s i a l 104'145. F o r Van ~ o o k l ~i t~ ,
appears from a c t i v a t i o n e n e r g i e s t h a t v i s c o s i t y and d i f f u s i o n a r e f a s t e r
o p e r a t i o n s than growth i t s e l f . Thus t h e v i s c o s i t y i s n o t a c o n t r o l 1 i n a narameter
o f t h e r a t e o f c r y s t a l l i z a t i o n b u t r a t h e r some o r i e n t a t i o n and i n c o r p o r a t i o n
o f molecules i n t o t h e s e v e r a l faces o f t h e g r o w i n g c r y s t a l . Moreover, i t was
found145 t h a t c e r t a i n c o l l o i d s l i k e gum a c a c i a , p e c t i n s and s t a r c h i n c r e a s e
t h e v i s c o s i t y o f sucrose syrups tremendously b u t have l i t t l e e f f e c t on t h e
r a t e o f c r y s t a l l i z a t i o n o f sucrose f r o m t h e s y r u p . T h i s r e s u l t was c r i t i c i z e d
by s i l i n l o 4 who c o n s i d e r s t h a t t h e added c o l l o i d s i n c r e a s e t h e v i s c o s i t y b u t
a c t as "screens" f o r sugar molecules. Thus, d i f f u s i o n and c r y s t a l l i z a t i o n r a t e
a r e n o t r e s t r a i n e d . The c u r v e g i v i n g t h e e v o l u t i o n o f v i s c o s i t y d u r i n g t h e
course of a f i r s t s t r i k e i n a sugar b e e t f a c t o r y has been found146 v e r y s i m i l a r
t o t h a t o f s u p e r s a t u r a t i o n . I t was concluded t h a t t h e b o i l i n g process may be
c o n t r o l l e d i n a l l i t s stages by use o f a rheometer. I n d u s t r i a l c r y s t a l l i z a t i o n
was a l s o described14? as b e i n g dependent on a c i r c u l a t i o n c o e f f i c i e n t o r
s t i r r i n g i n t e n s i t y . The r e l a t i o n s h i p between f l u i d i t y ( r e v e r s e o f v i s c o s i t y )
and d i f f u s i o n c o e f f i c i e n t was studied148 as a f u n c t i o n o f t e m p e r a t u r e and
c o n c e n t r a t i o n . I t was found148 t h a t t h e d i f f u s i o n c o e f f i c i e n t decreases l e s s
I
than f l u i d i t y when t h e c o n c e n t r a t i o n i s i n c r e a s e d . The i n f l u e n c e o f v i s c o s i t y
I
on t h e n u c l e a t i o n process was i n v e s t i g a t e d by ~ i d o u x l ~He~ found
. t h a t the
f o r m a t i o n o f swarms o f sucrose m o l e c u l e s c a l l e d " p r o t o n u c l e i " t a k e s p l a c e i n
s u p e r s a t u r a t e d as we1 1 as i n u n d e r s a t u r a t e d s o l u t i o n s , p r o v o k i n g an i n c r e a s e
i n v i s c o s i t y as a f u n c t i o n of t i m e . When t h e v i s c o s i t y reachs i t s maximum, t h e
1 n u c l e a t i o n occurs spontaneously i n s u p e r s a t u r a t e d ( 0 2 1 . 3 ) s o l u t i o n s and under
t h e e f f e c t o f c e n t r i f u g a t i o n (15000 g ) i n s l i g h t l y s u p e r s a t u r a t e d s o l u t i o n s
( U = 1 . 1 3 ) . I t i s t o be n o t e d t h a t f o r a same B r i x degree, v i s c o s i t y i n c r e a s e s
when p u r i t y i s i n c r e a s e d and t h a t an i m p o r t a n t i n c r e a s e i n v i s c o s i t y i s
I observed150 f o r s a t u r a t e d s o l u t i o n s when t h e p u r i t y i s lowered. T h i s may be
i1 l u s t r a t e d by t h e f o l l o w i n g r e s u l t s a c c o r d i n g t o Maurandi (see F i g . 11).

F i g . 11. V i s c o s i t y o f s a t u r a t e d sucrose s o l u t i o n s a t 70' C as a f u n c t i o n of

purity150 (from r e f . 150).

These r e s u l t s a r e p a r t i c u l a r y i m p o r t a n t f o r t h e u n d e r s t a n d i n g o f low-grade
massecui t e s workabi 1 it y and molasses e x h a u s t i o n .
B. EFFECTS ON MOLASSES FORMATION AND EXHAUSTION
There a r e d i f f e r e n t t h e o r i e s c o n c e r n i n g molasses f o r m a t i o n . One o f t h e
e a r l i e s t c o n s i d e r s t h a t t h e g r o w t h of sugar c r y s t a l s i s i n h i b i t e d by v i s c o s i t y
w h i c h i n c r e a s e s when p u r i t y decreases. Another approach, which c o u l d be c a l l e d
t h e chemical approach, c l a s s i f i e s t h e non-sucrose components as p o s i t i v e l y ,
n e g a t i v e l y m e l a s s i g e n i c and n e u t r a l depending on t h e i r a s s o c i a t i o n w i t h sugar
molecules and p r e v e n t i o n o f c r y s t a l l i z a t i o n . I n f a c t , one has t o t a k e i n t o
account b o t h t h e o r i e s . Each non-su!Jar, even ifi t does n o t a s s o c i a t e w i t h
sucrose, c o n t r i b u t e s t o an i n c r e a s e i n t h e r a t e of f o r m a t i o n o f d r y substances,
and hence v i s c o s i t y . When such c o n d i t i o n as t h e "normal" molasses d e f i n e d by
S i l i n l O4 a r e adopted ( " B r i x = 82 a t 40" C, n = 44 p o i s e s ) , i t i s necessary t o
d i l u t e o r t o h e a t i n o r d e r t o m a i n t a i n these c o n d i t i o n s , which c o n t r i b u t e s t o
t h e decrease o f v i s c o s i t y . D u r i n g t h e c r y s t a l l i z a t i o n o f low-grade p r o d u c t s t h e
massecuite i s c o o l e d i n o r d e r t o a l l o w c r y s t a l l i z a t i o n o f a maximum o f sugar.
However, i t i s necessary t o m a i n t a i n v i s c o s i t y o f massecuites i n f e r l o r t o 1500
p o i s e s t o a l l o w i t s pumping143. The l i m i t of v i s c o s i t y p e r m i t t i n g t h e c e n t r i -
f u g a t i o n w i t h 1500 g i s 70 poises142. To l i m i t molasses f o r m a t i o n o r t o improve
144 in
i t s e x h a u s t i o n comes t o c o n t r o l i t s v i s c o s i t y . T h i s parameter was chosen
o r d e r t o o p t i m i z e t h e c r y s t a l 1iz a t i o n process : Rheometers were p l a c e d between
t h e c r y s t a l l i z e r s i n t h e p i p e s where massecuites f l o w . They m o n i t o r t h e a d d i t i o n
o f water f o r l o w e r i n g t h e v i s c o s i t y o f massecuites. However, Wagnerowski7 t h i n k s
t h a t v i s c o s i t y i s n o t a fundamental c r i t e r i a f o r t h e o p t i m i z a t i o n o f molasses
7
exhaustion*. I t i s e s p e c i a l l y remarked t h a t a d d i t i o n o f w a t e r i s n o t economical
and r a t i o n a l . I t i s more a d v i s a b l e t o reduce t h e c r y s t a l c o n t e n t b y a p r e l i m i n a r y
c e n t r i f u g a t i o n 1 5 1 , w h i c h reduces t h e v i s c o s i t y o f massecuites. Nevertheless, a
r e h e a t i n g i s necessary a t t h e end of t h e c r y s t a l l i z a t i o n , j u s t b e f o r e
.
c e n t r i f u g i n g 7 The s u p e r s a t u r a t i o n o f t h e r e h e a t e d m a s s e c u i t e must be 2 1 . 0 5
and t h e v i s c o s i t y o f t h e mother l i q u o r i s t h e n equal t o 40-50 p o i s e s , which i s
i n agreement w i t h S i l i n ' "normal " v i s c o s i t y . A t e s t o f c o n t r o l o f molasses
e x h a u s t i o n was developed152. I n t h i s t e s t , i t was recommended t o c e n t r i f u g e
a t t h e l o w e s t temperature p o s s i b l e , assuming t h a t t h e l i m i t o f v i s c o s i t y i s
70 poises f o r d i s c o n t i n u o u s c e n t r i f u g e s and 144 p o i s e s f o r c o n t i n u o u s ones.
153
The e f f e c t of v i s c o s i t y on e x h a u s t i b i 1it y o f mol asses has been reviewed
i n t h e c h a p t e r 14 o f H o n i g ' s book. The i n f o r m a t i o n s f o u n d i n t h i s r e v i e w 153
a r e s t i l l v a l i d and u s e f u l . The o p t i m a l c o n d i t i o n s o f work i n t h e low-grade
s t a t i o n have been studied154 and t h e a u t h o r recommends t o c o o l t h e massecuite
( p u r i t y 77.2) f r o m 75 t o 45' C, t h a n t o r e h e a t i t to54" C and t h i s y i e l d s
a molasses o f 58.7 % p u r i t y and 4 1 p o i s e s v i s c o s i t y . Thus, i t appears t h a t
o p t i m a l c o n d i t i o n s of molasses e x h a u s t i o n a r e d i r e c t l y o r i n d i r e c t l y dependent
on v i s c o s i t y .

C. EFFECT ON THE FLOW I N PIPES

The r h e o l o g i c a l p r o p e r t i e s s t u d i e s o f t h e sugar p r o d u c t s , i . e . , syrups,
molasses and massecuites, d e a l m a i n l y w i t h t h e dependence o f f l u i d b e h a v i o u r
on shear r a t e . They o n l y measure o r c a l c u l a t e t h e a p p a r e n t v i s c o s i t y w i t h o u t
t a k i n g i n t o account t h e p r e s s u r e c o n d i t i o n s found i n p i p e s , pumps, e t c . The
measurement o f t h e v i s c o s i t y o f molasses and massecuites w i t h t h e p i p e - f l o w
v i s c o m e t e r shows how c r i t i c a l i s t h e e f f e c t o f pressure, d i a m e t e r and l e n g t h o f
t h e p i p e . T h i s i s e s p e c i a l l y c o m p l i c a t e d when, as i t i s usual i n a f a c t o r y , t h e
 temperature i s n o t r i g o r o u s l y c o n s t a n t a l o n g t h e p i p e . The e f f e c t o f temperature
I
on t h e r h e o l o g i c a l p r o p e r t i e s o f sugar p r o d u c t s has been i n v e s t i g a t e d i n t h e
l a b o r a t o r y , b u t i t i s n o t always c o n s i d e r e d i n t h e f a c t o r y . Indeed, i t i s o f t e n
seen i n sugar f a c t o r i e s t h a t v e r y l o n g p i p e s o f molasses are n o t i n s u l a t e d . I t
I i s obvious t h a t h e a t c o n d u c t i o n i s n o t v e r y r a p i d i n such viscous medium,
b u t w a l l e f f e c t s , i n a p i p e , a r e more i m p o r t a n t when t h e temperature o f t h e w a l l i s
v a r i e d . The b a s i c r e l a t i o n s g o v e r n i n g v i s c o u s f l o w o f l i q u i d s w i t h v a r i a b l e
t r a n s p o r t p r o p e r t i e s has been considered155a. I t was found t h a t even i n t h e case
o f Newtonian f l o w under i s o t h e r m a l w a l l c o n d i t i o n s , a p p a r e n t l y non-Newtonian
b e h a v i o u r may r e s u l t . A n a l y t i c a l s o l u t i o n f o r non-Newtonian f l o w i n p i p e s was
li o b t a i n e d f o r t h e v e l o c i t y components, t h e f l o w r a t e , t h e p r e s s u r e d i s t r i b u t i o n
and t h e h e a t e f f e c t 1 5 5 b . From a p r a c t i c a l p o i n t o f view, t h e r h e o l o g i c a l
p r o p e r t i e s have been t a k e n i n t o account f o r t h e c a l c u l a t i o n o f diameters o f
I
p i p e s 1 4 and o r i f i c e s 6 ' o r f o r t h e c o n d i t i o n s o f work i n c r y s t a l l i z e r s and
~ e n t r i f u g e s ~The
~ . hydrodynamic problems posed by t h e f r i c t i o n i n p i p e s , e l bows,
I
I
v a l v e s ,. . . a r e a1 so v i s c o s i t y dependent. They go beyond t h e scope o f t h i s r e v i e w
and m e r i t t o be surveyed.
l
1 VI . CONCLUSION
I The b a s i c e q u a t i o n s r e l a t i n g v i s c o s i t y of sugar s o l u t i o n s t o c o n c e n t r a t i o n and
~
I

temperature show t h a t t h e t h e o r y was e s p e c i a l l y worked by polymer s c i e n c e people.

1 T h e i r c o n t r i b u t i o n t o s o l v e r h e o l o g y problems must be acknowledged, e s p e c i a l l y
f o r t h e f a t h e r o f r h e o l o g y , E.C. Bingham. I t was seen f r o m t h e i n t e r p r e t a t i o n
o f v i s c o s i t y r e s u l t s , t h a t t h e t r e a t m e n t o f v i s c o s i t y on a m o l e c u l a r l e v e l by
a c c o u n t i n g h y d r a t i o n , m o l e c u l a r a s s o c i a t i o n and shapes o f molecules h e l p s i n
u n d e r s t a n d i n g t h e r h e o l o g i c a l p r o p e r t i e s o f sugar s o l u t i o n s . Theory was found
t o be a good g u i d e t o p r a c t i c e and t h e day-to-day problems posed i n a f a c t o r y
make t h e t h e o r y advance b y f i n d i n g new s o l u t i o n s . A l l t h e q u e s t i o n s a r e f a r from
b e i n g s o l v e d . F o r example t h e r o l e o f v i s c o s i t y i n molasses e x h a u s t i o n , t o d i l u t e
massecuites w i t h water, o r w i t h molasses ? i s i t necessary t o have a maximum
t i g h t e n i n g o f massecuites i n t h e b o i l e r ? e t c . . . are t h e k i n d o f q u e s t i o n s which
o n l y f i n d e m p i r i c a l answers. T h i s i s p r o b a b l y due t o t h e d i f f e r e n t composition
o f sugar j u i c e s ( b e e t o r cane grown on d i f f e r e n t s o i l s ) . Thus, a l l i s n o t
p r e d i c t a b l e f r o m t h e m a t h e m a t i c a l t r e a t m e n t of r h e o l o g i c a l p r o p e r t i e s and a l o t
I
I
of work i s t o be done i n t h e l a b o r a t o r y t o improve t h e measurements, t o s t u d y
the e f f e c t o f impurities... as w e l l as i n t h e f a c t o r y .

SUFMARY
A r e v i e w of t h e t h e o r y and b a s i c V ~ S C O S ~r ~e lYa t i o n s i s presented. Most of
I t h e e q u a t i o n s r e p o r t e d a r e d e r i v e d from polymeb s c i e n c e s t u d i e s . I t i s shown
t h a t e m p i r i c a l r e l a t i o n s used i n t h e Sugar i n d u s t r y a r e g e n e r a l l y t h e a d a p t a t i o n
I o f b a s i c e q u a t i o n s of v i s c o s i t y The p r i n c i p l e s of t h e methods o f measurements
I
o f r h e o l o g i c a l p r o p e r t i e s a r e r e c a l l e d . A p p l i c a t i o n of r h e o l o g i c a l p r o p e r t i e s
of molasses and massecuites t o d e t e r m i n i n g t h e o p t i m a l c o n d i t i o n s of
C r y s t a l 1 iz a t i o n , molasses e x h a u s t i on and t r a n s p o r t i n p i p e s i s reviewed.

ACKNOWLEDGMENTS

The a u t h o r s a r e g r a t e f u l t o Professor Andrew Van Hook f o r h i s a d v i c e and

encouragement. We a l s o w i s h t o thank Dr. T. Morutsugu, f o r s u p p l y i n g some
documents. One o f t h e a u t h o r s (M.M.) i s i n d e b t e d t o D r . J. M e f f r o y and Dr.
A.M. M e f f r o y - B i g e t f o r p r o v i d i n g some u n p l i s h e d work on t h e i r r e c e n t
development o f t h e t h e o r y o f v i s c o s i t y .

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SUMARIO
Se p r e s e n t a una r e v i s i 6 n de l a t e o r i a y de l a s r e l a c i o n e s b a s i c a s de
v i s c o s i d a d . La mayori'a de l a s ecuaciones d e s c r i t a s s e derivan de e s t u d i o s en
pol imeros. Se demuestra que l a s r e l a c i o n e s empi'ricas u t i l i z a d a s en l a
i i n d u s t r i a del az;car son en general a d a p t a c i o n e s d e l a s ecuaciones b a s i c a s
de v i s c o s i d a d . Se recuerdan 10s p r i n c i p i o s de 10s m 6 t 0 d 0 ~de rnedida de l a s
propiedades r e o l o g i c a s . Se pasa r e v i s t a a l a a p l i c a c i o n de 10s v a l o r e s de
e s t a s propiedades en ~ n e l a z a sy rnasacochas para l a determincaihn de l a s

~
1
condiciones kptimas de c r i s t a l i z a c i g n , agotamiento de melazas' y t r a n s p o r t e
por t u b e r i a s .
Sugar Technology Reviews, 11(1984) 259
Elsevier Science Publishers B.V., Amsterdam -Printed in The Netherlands

CONTENTS OF VOLUME 11

Production of high fructose corn syrup in the U.S.A.

P.H. Blanchard and E.O. Geiger (San Francisco, CA, U.S.A.) ........... ...
A review of gas chromatography in the South African sugar industry. Development and
application of accurate methods for sugar analysis
K.J. Schaffler and P.G. Morel du Soil (Mount Edgecornbe, South Africa) .. ... . .. .... 95

Production of filter cake with low moisture content from carbonation mud
.
A. Fgns Johnsen (Nakskov, Denmark) . . . . . . . . . . . . . . . . . . . . . . .. . . . ... . 187

Viscosity of sugar solutions

M. Mathlouthi and P. Kasprzyk (Dijon, France). . . . . . . . . . . . . . . . . . . . . . . . . . . . 209