CHAPTER II

THEORIES AND PRINCIPLES OF VISCOSITY

CHOKYUN RHA
Dept. 0/ Nutrition and Food Science, Massachusetts Institute o/Technology, Cambridge, Mass., U.S.A.

Viscosity is a transport phenomenon. Viscosity is the transport of momentum due to

a velocity gradient. The beginning of the phenomenological studies of viscosity goes
back to the ancient Greeks and later the Romans characteristically applied what they
had learned in practical ingenious ways [1]. Modern theories of viscosity of liquids
are based on continuum mechanics and molecular theory.
Since Maxwell's prediction of viscosity based on the kinetic theory, many theories
of viscosity were developed. Although it has been several decades since the first
development of the theory of viscosity, obtaining the numerical values for the theoret-
ical equations, or confirmation of the theories by experimental results has been con-
fined to only a few monoatomic or diatomic fluids. The application of the theories of
viscosity to the complex poly-atomic associating food components is still far away.
Nevertheless, these theories help us to visualize the viscosity phenomena at the molec-
ular level and with molecular forces.

1. Theories of Viscosity

The theories of viscosity will be discussed here rather superficially. The three main
theories of viscosity discussed here are molecular theory, the rate process theory and
diffusional theory.

1.1. MOLECULAR THEORY

The molecular theory attempts to relate the viscosity to two factors. One is the distri-
bution of the nearest molecules surrounding a given molecule and the other, the
intermolecular potential between this pair of molecules.
The molecules in a liquid are coupled to each other by intermolecular attraction.
Therefore, if two adjacent layers of fluid move with different velocities, each will tend
to drag the other due to this intermolecular attraction. This drag will dissipate the
velocity gradient within the liquid. As a result of the drag exerted on one another by
molecules in adjacent layers of the fluid moving with different velocities, the molecular
structure of the fluid becomes deformed. The configuration of the molecules sur-
rounding a given molecule effected by such drag is more ellipsoidal than the usual
radial distribution. Principle axes of this ellipsoidal distribution are determined by the
local velocity gradient, and the degree of deformation of the molecular structure
determines the magnitude of the coefficient of viscosity [2, 3, 4].

ChoKyun Rha (ed.). Theory. Determination and Control of Physical Properties of Food Materials, 7-24.
Copyright © 1975 by D. Reidel Publishing Company, Dordrecht-Holland. All Rights Reserved.
8 CHOKYUNRHA

Starting from this concept, Born and Green [4] gave an approximate solution for
the viscosity by the following equation:

11 = 0.48 ~ [mcf>a(r)r/2 exp [- _1 cf>(r)]

v kT
11 = viscosity
r = distance between the centers of two adjacent molecules;
v = molecular volume;
m = mass per molecules;
cf> a (r ) = attractive component of the pair potential cr - 6 ;
cf> (r ) = mutual potential energy of a pair of molecules at distance r;
k = Boltzman constant;
T = absolute temperature.

1.2. THE RATE-PROCESS THEORY

The rate-process theory is similar to very familiar rate theory governing the kinetics
of chemical reactions. The key aspect of this theory is that a molecule has to pass over
a potential barrier in order to flow. Figure I shows the cross-section of an idealized
liquid illustrating the fundamental rate process involved in viscous flow [5]. In order
to move into an unoccupied site, a molecule passes through a potential energy bottle-

o o
F------..~

0 0 0--.
o 0--.· o 0 1
>-
(.!)
0::
o 0 000 ACTIVATED STATE
W
Z
W
-I
«
I- /WITHOUT IMPRESSED
Z SHEARING FORCE, F
W
I- /-WITH IMPRESSED
o SHEARING FORCE, F
a..

01 STANCE
Fig. 1. Activation for flow.