CH6702-TRANSPORT PHENOMENA 2018-2019

UNIT I

TRANSPORT PHENOMENA BY MOLECULAR MOTION

Transport Phenomena

A transport phenomenon is any of various mechanisms by which particles or quantities move

from one place to another.

Three main categories of transport phenomena:

a. Heat (energy) transport
b. Mass transport, and
c. Fluid dynamics (or momentum transport)
Transport Processes

Momentum Transport – transfer of momentum which occurs in moving media (fluid flow,
sedimentation, mixing, filtration, etc.)

Heat Transport – transfer of energy from one region to another (drying, evaporation,
distillation)

Mass Transport – transfer of mass of various chemical species from one phase to another
distinct phase (distillation, absorption, adsorption, etc.)

Levels of Analysis

Macroscopic Level : It gives Overall assessment of a system

Microscopic Level :

 Small region/volume element is selected

 Use of equations of change
 Velocity, temperature, pressure and concentration profiles are determined

Molecular Level:

 Molecular structure and intermolecular forces become significant

 Complex molecules, extreme T and P, chemically reacting systems

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Analogous nature of transfer process

All the three transfer operations, Momentum Transport, Energy Transport and Mass Transport
are governed by the rate law similar to the Electrical energy transmission

Rate = Driving Force / Resistance

Phenomenon Rate Driving Force Resistance

Electrical Energy Current density Potential Difference

Impedance

Momentum Transport Momentum Flux Velocity Gradient

Viscous resistance

Energy Transport Heat Flux Temperature

Thermal conductivity
Difference

Mass Transfer Mass Flux Concentration

Diffusivity
Difference

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CONSERVATION LAWS IN TRANSPORT PROCESSES

The most widely applicable laws in our universe are

 Law of conservation of mass

 Law of conservation of energy
 Law of conservation of momentum

[Input] + [sources] = [output] + [sinks] + [accumulation]

Momentum Balance

The momentum balance equation for the steady state flow is written as

{Rate of momentum in} - {Rate of momentum out} + {Sum of forces acting on system} = 0

Forces that will be concerned are

• the pressure forces that act on surfaces and

• gravity forces which act on the volume as a whole.

Heat Balance

• For determining the Thermal flux distribution and temperature distribution in solids and
in laminar flow, an elemental thin shell is considered and thermal energy balance is made
on that.

• Shell energy balance equation for steady state can be written as follows

{Rate of thermal energy in} – {Rate of thermal energy out} + {Rate of thermal energy
production} = 0

• Thermal energy may enter or leave the system by the mechanism of heat conduction
according to Fourier’s law.

• Thermal energy may also enter or leave the system by virtue of the over all fluid
motion;(convective transport) and the energy entering and leaving this way is commonly
called the sensible heat in and out.

• Thermal energy may be ‘produced’ by the degradation of electrical energy, by the

slowing down of the neutrons and nuclear fragments liberated in the fission process, by
the degradation of the mechanical energy(viscous dissipation) and by conversion of
chemical energy into heat. It should be emphasized that this energy balance equation is
restricted as no mention is made of kinetic energy, potential energy or work.

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Mass Balance

• Shell Mass balance equation for a specific chemical species can be written as follows

Rate of mass of ‘A’ in} – {Rate of mass of ‘A’ out} + {Rate of production of mass of
‘A’ by homogeneous chemical reaction} = 0

CONTINUUM CONCEPT

• At the microscopic level, the description of the motion of a fluid involves a study of the
behaviour of all the discrete molecules, which make up the fluid.

• However, when dealing with problems in which some characteristic length in the flow is
very large compared with molecular distances, it is convenient to think of a lump of fluid
sufficiently small from macroscopic point of view, but large enough at the microscopic
level so as to contain a large number of molecules, and to work with the average
statistical properties of such large number of molecules.

CONTINUOUS CONCEPT

• In such a case, the detailed molecular structure is washed out completely, and is replaced
by a continuous model of matter having appropriate continuum properties, so defined as
to ensure that on the macroscopic scale, the behaviour of the model resembles with the
behaviour of the real fluid.

• When the characteristic length in the flow is not large, compared with the molecular
distances, the continuum model is invalid, and the flow must be analysed on the
molecular scale.

• The smallest lump of fluid material, having sufficiently large number of molecules, to
allow statistically of a continuum interpretation, is here called a “fluid particle”.

REFERENCE FRAMES

• Reference frames are said to be the approaches, in which the coordinates of the transport
properties are fixed in the fields by the observer, who is attempting the above said
transport problem.

• There are two ways to set up a transport problem: the Eulerian approach in which the
coordinates are fixed in the reference frame of the observer; and the Lagrangian
approach, in which the coordinates are fixed in the reference frame of the transported
fluid.

• In general the Eulerian approach is the commonly used one. However, a number of
formulations of quantum transport theory are expressed in terms of Lagrangian variables

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FIELD AND REFERENCE FRAMES

• The term “field” refers to a quantity, defined as a function of position and time
throughout a given region.

• There are two different forms of representation for fields in transport phenomena,
namely, the Lagrange’s form and, the Euler’s form.

• The difference between these approaches lies in the manner, in which the position in the
field is identified.

• In the Lagrangian approach, the physical variables are described for a particular element
of fluid, as it traverses the flow.

• This is the familiar approach of particle, and rigid-body dynamics. The coordinates (x, y,
z) are the coordinates of the element of fluid, and, as such, are functions of time.

The coordinates (x, y, z), are therefore, dependent variables in the Lagrangian form.

The fluid element is identified by its position in the field at some arbitrary time, usually, t =
0. The velocity field in this case is written in the functional form as follows:

v = v (a, b, c, t),

where, the coordinates (a, b, c) refer to the initial position of the fluid element. The other
fluid flow variables, being functions of the same coordinates, may be represented in a similar
manner.

The Lagrangian approach is seldom used in transport phenomena, since the type of
information desired is usually the value of a particular fluid variable at a fixed point in the
flow, rather than the value of a fluid variable, experienced by an element of fluid along its
trajectory.

For example, the determination of the force on a stationary body in a flow field requires that
we know the pressure, and shear stress at every point on the body.

The Eulerian form provides us with this type of information.

The Eulerian approach gives the value of a fluid variable at a given point at a given time.

In functional form, the velocity field is written as follows: v = v (x, y, z, t), where x, y, z, and
t are all independent variables.

For a particular point (x1, y1, z1), and t1, the above equation gives the velocity of the fluid at
that location at time t1.

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In transport phenomena, the Eulerian approach will be followed exclusively.

REFERENCE FRAMES

• Reference frames are said to be the approaches, in which the coordinates of the transport
properties are fixed in the fields by the observer, who is attempting the above said
transport problem.

• There are two ways to set up a transport problem: the Eulerian approach in which the
coordinates are fixed in the reference frame of the observer; and the Lagrangian
approach, in which the coordinates are fixed in the reference frame of the transported
fluid.

• In general the Eulerian approach is the commonly used one. However, a number of
formulations of quantum transport theory are expressed in terms of Lagrangian variables

BOUNDARY CONDITIONS

• Differential equation resulting from the differential conservation balance describes what
is happening within the system.

• “boundary conditions”, mathematically describe the physical phenomena occurring at the

boundaries of the system.

• Solutions to differential equations can be either “general”, or “particular”.

• General solution is said to be a “family of solutions”, and is accompanied by arbitrary

constants (or constants of integration).

• Values of the arbitrary constants are determined by the specification of the boundary
conditions.

• Number of arbitrary constants is dictated by the order of the differential equation, and
therefore, the number of specified boundary conditions must be equal to the order of the
differential equation.

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• As engineers we typically deal with specific problems, and consequently, the boundary
conditions are every bit as important as modeling the physical system to obtain the
applicable differential equation.

• In transport phenomena, we look to the physical phenomena occurring at the boundaries

of the physical system, in order to specify the boundary conditions for a given transport
problem.

• It is important to realize that these conditions must have an assignable numerical value, in
order to be viable boundary conditions.

• Either the dependent variable (temperature, concentration, or velocity) and / or their

derivatives (fluxes) must be specified.

• We must be able to assess, what is happening at the physical boundaries of the system,
and then to specify numerical values for the dependent variables and / or their
derivatives.

• Sometimes, the numerical values at the boundaries are given symbols, so that specific
numerical values can be substituted as they become available.

• The engineering task is to evaluate the physical phenomena and to then decide, what the
realistic boundary condition is.

METHODS OF ANALYSIS

• Equations for laminar, or turbulent flow are, in general, so complex that in most practical
cases, exact solutions are impossible.

• Relationships between variables must be established empirically, rather than analytically.

• If there are many variables, as usually is the case, the resulting correlations in terms of
any one variable are hopelessly complex; however, if variables are grouped in a logical
manner, the correlations are considerably simplified.

• Experience has shown that, dimensionless groups of variables are the most useful tools in
correlating the experimental data.

Following are the different methods of analysis, which are encountered under practical
situations in transport phenomena:

1. Differential methods of analysis

2. Integral methods of analysis and

3. Experimental methods of analysis.

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a) Inspection analysis,

b) Dimensional analysis

c) Modeling analysis.

Differential Methods of Analysis

• The goal here is to derive differential equations, which describe the conservation of
energy (heat), mass, and momentum at a point.

• Equations, which apply at a point, are then capable of producing solutions to a wider
variety of problems, that is, by solving the differential equations over the region of
interest.

• In order to derive a differential equation from the general conservation equation, it is

necessary to apply it to a differential volume element.

• In differential analysis, detailed balances to quantify the conservation of a property

(energy, mass, moles, and momentum) have been made on a differential element in the
system.

• Thus, the first task is to decide what this element should look like.

• The construction of the element will not only depend on the geometry of the system
being analyzed, but also on the anticipated direction of the transport

• The next step in the differential analysis is to apply the conservation equation to the
differential element over some time period.

• The final step in the differential analysis is to divide the entire conservation equation by
the volume of the element, and the differential time increment, and then let the
differential quantities approach zero in the limit.

• After simplification of the entire conservation equation, the result was integrated in order
to obtain the velocity, temperature, and concentration distributions for specific
geometries, and boundary conditions.

Integral Methods of Analysis

• For many cases, such detailed information as given in differential method of analysis is
not necessary and, in fact, is impossible to obtain because of the complexity of the
equations, and the nature of the boundary conditions.

• The complexity of the system is often due to the presence of a turbulent flow in a
complex flow geometry, together with heat and / or mass transfer.

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• Much of the complexity can be eliminated, if the principle of conservation of property is

applied to the system on an integral (overall, or macro) basis, rather than on a differential
(micro) basis.

• Balance equations can be applied over a finite volume of the system, thereby obtaining
the overall balance of mass, momentum, and energy (heat).

• Since the overall balance equations represent an integration over a volume, they can give
no information as to conditions inside the system.

• Since the details of the flow are not needed in the integral analysis, the equations apply
equally well for both turbulent, and laminar flow. However, the nature of the flow will
have an effect at both the entrance and the exit.

NEWTON’S LAW OF VISCOSITY

Let us consider two parallel plates located in a continuous media of fluid. These plates may
be separated by a small distance ‘Y’ Let us consider that both these plates are initially at rest.

At, t = 0 the lower plate is set in motion. At the final state of steady motion, a constant force ‘F’ is
required to maintain the motion of the lower plate. This force may be expressed as follows:
[Laminar flow]

F/A =  [V/Y] {(F/A) = -  [(0 – V) / (Y – 0)]} [1]

i.e. The force per unit area is proportional to the velocity decrease in the distance y; the constant
of proportionality is  called Viscosity of the fluid. This can be expressed in a an explicit form:
The fluid in the layer immediately next to the wall is kept in that steady state of motion by the
lower plate which is at Y = 0. This layer in turn keeps the layer above that in motion and so on.
Or the shear stress exerted in the x-direction on a fluid surface of constant y by the fluid in the
region of lesser y is designated as yxand the x-component of the fluid vector is designated.

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Thus yx = -  [dvx /dY] [2]

This states that the shear force per unit area is proportional to the negative of the local velocity
gradient; this is known as Newton’s law of Viscosity, and fluids that behave in this fashion are
termed Newtonian Fluids. All gases and most simple liquids are described by Eqn.[2] Fluids that
do not obey this simple law(primarily pastes, slurries and high polymers) are called non-
Newtonian Fluids.

Another way the eqn. [2] can be interpreted. In the very neighborhood of the moving surface at
y=0 the fluid acquires certain x-momentum. This fluid, in turn, imparts some of its momentum to
the adjacent layer of liquid causing it to remain in motion in the x-direction. Hence x-momentum
is transmitted through the fluid in the y-direction. Consequently, yxmay also be interpreted as the
viscous flux of x-momentum in the y-direction.

It can be seen from eqn.[2] that the viscous momentum flux is in the direction of the negative
velocity gradient., i.e. the momentum tends to go in the direction of decreasing velocity. In other
words, the momentum travels “downhill” in the sense that it coasts from a region of higher velocity
to a region of lower velocity. [ e.g. like a sled going downhill from a region of high elevation to a

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region of low elevation or heat flows from a hot region toward a colder one] A velocity gradient
can thus be thought of as a “driving force” for momentum transport.

TYPES OF FLUIDS

NEWTONIAN FLUIDS:
A fluid which obeys Newton’s law of Viscosity is called Newtonian Fluid. The
relationship between shear stress and the velocity gradient is given by: yx = - µ [d vx /dy]

This shows that there is a linear relationship between shear stress and the velocity gradient.
Draw the graph [sketch] between shear stress yx , and velocity gradient - [d v x / dy] and show
how the Newtonian fluids plot is straight line passing through the origin with viscosity µ as
its slope.

According to Newton’s law of viscosity given by: yx = - µ [d vx /dy] , a plot of yx
shear stress and the velocity gradient -(dv x /dy) for a given fluid should give a straight line
through the origin.
NON-NEWTONIAN FLUIDS :
Those fluids that do not follow this law are called non-Newtonian fluids. For these fluids, the
steady state behavior can be expressed by a generalized form:
yx = -  [d v x / dy] where  may be expressed as a function of either [d v x / dy] or yx.
1)Time Independent Fluids

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a) Bingham plastics: A finite shear stress (yield stress) is needed to initiate the flow.
Examples: Tooth Paste

b) Pseudoplastic (shear thinning) fluids

Apparent viscosity decreases with increase in shear rate. Examples: paper pulp in
water, latex paint, syrup, molasses, ketchup, whipped cream, nail polish

c) Dilatant (shear thickening) fluids

Apparent viscosity increases with increase in shear rate.Examples: suspensions of
corn starch or sand in water

2)Time Dependent Fluids

a)Thixotropic fluids: Apparent viscosity decreases with increase in duration of

stress.Examples: Honey, many gels or colloids, gelatin, cream, shortening, salad dressing.

b)Rheopectic fluids : Apparent viscosity increases with increase in duration of

stress.Examples: beating and thickening of egg whites,

3)Viscoelastic Fluid displays both elastic and viscous properties. Part of deformation is
recovered upon the removal of stress. A true visco-elastic fluid gives time dependent
behaviour. Examples: polymers, metals at temperature close to their melting point

PHENOMENOLOGICAL BEHAVIOUR (Or) RHEOLOGICAL MODELS TO

CHARACTERIZE NON-NEWTONIAN FLUIDS:

Rheology is the science of “deformation and flow”, and it include the study of the
mechanical properties of gases, liquids, plastics, plasticizers and crystalline
materials, for non-newtonian fluids.

The steady state behavior of most fluid can be expressed by a generalized form as
given in the following equation.
dVx
yx  
dy
Where,  can be expressed as a function of either dVx
or  y x
dy
Bingham model:
 Two parameter model, to describe the deformation and flowing nature of
Bingham fluid.

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 The substances that follow this model is called Bingham plastics or Bingham
fluids, and these types of fluids can resist a small shear stress but flows easily
somewhat like a Newtonian fluid under larger shear stress.
 At low shear the viscosity is infinite (No movement of Bingham fluid) and at
higher shear stress the  is decreases.
Eg: toothpaste, jellies, sewage sludge etc.

The same plot as shown above between shear stress yx and velocity gradient -[dvx/ dy]
for the Bingham model fluid is to be drawn. The Bingham model is given by:
yx = - µ [d v x / dy] + 0 if |yx| > o and
[d v x / dy] = 0 if |yx| < o
A Substance that follows this above two parameter model is called Bingham Model
Plastic which remains when the shear stress is of smaller magnitude than the yield stress
 o but flows somewhat like a Newtonian fluid when the shear stress exceeds o .

i) Power law model {Oswald-de Waale model}:

The shear stress- Velocity gradient equation for general type of fluid can be written as:
yx= - η (dvx / dy)
If η is constant then the fluid is deemed to be Newtonian Fluid and takes the terminology
Viscosity . η may be expressed as a function of either (dvx / dy) or yx .
yx = - m |(dvx / dy)|n-1 (dvx / dy)
This two parameter equation is also known as Power law model. For n=1 it reduces
to Newton’s law of viscosity with m=µ; thus the deviation of n from unity indicates the
degree of deviation from Newtonian behaviour.

ii) Eyring model:

The Eyring model, given by:
yx = A arcsinh [-(1/B)(dvx / dy)]
is a two parameter model for the rheological characterization of different fluids and is
derivable by the Eyring Kinetic Theory of liquids. It predicts pseudoplasticbehaviour at
finite values of yx but reduces asymptotically to Newton’s law of viscosity with µ =
A/B as yx approaches zero.

iii) The Ellis model:

All the rheological models can be expressed by the same plot as above.
- (dvx / dy) = [0 +1|yx| -1 ] yx

This model contains three adjustable positive parameters:

0 ,1 and . If  is chosen greater than unity, the model approaches Newton’s law for
small yx ; on the other hand if is chosen less than unity.

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iv) The Reiner-Philippoff Model:

It is another three parameter rheological model as expressed below:
- (dvx / dy) = yx[1 /[(µ) +{ (µ0 - µ)/[1 + (yx /s)]2 }]
This model as said above contains three adjustable parameters µ0 , µand s. At very low
and high shearing rates Newtonian behaviour has been observed the above model has
been set up to reduce to Newton’s law of Viscosity with µ = µ0 and µ = µ respectively
in these two limiting cases. The plot of yx versus [d v x / dy] has inflexion points located
at yx=  [3 µ0 /µ]

SUBSTANTIAL TIME DERIVATIVE:

Suppose that we get into a canoe, and, not feeling energetic, we simply float along counting fish.
Now the velocity of the observer is just the same as the velocity of the stream (v). When we report
the change of fish concentration with respect to time, the numbers depend on the local stream
velocity. This derivative is a special kind of total time derivative, and is called the “substantial
derivative”, or sometimes (more logically) the “derivative following the motion”.
The substantial derivative is related to the partial time derivative as follows:
[Dc/Dt] = [c/t] + vx[c/x] + vy[c/y] + vz[c/z],
in which vx, vy, and vz are the t] is the derivative at c/ components of the local fluid velocity
(v). Here, [ a fixed point in space, and [Dc/Dt] is a derivative computed by an observer floating
downstream with the fluid.

TOTAL DERIVATIVE:

Instead of standing on the bridge and observing the fish concentration if the observer gets
into a speed boat and sped around the river , sometimes upstream and sometimes down stream and
sometimes across the current. Thus if one reports the change of fish concentration with respect to
time , the numbers reported should reflect the motion of the boat. This, called total time derivative
is given by:
dc / dt = c /t + (c /x) (dx/dt) + (c /y) (dy/dt)+ (c /z) (dz/dt)
in which dx/dt, dy/dt and dz/dt are the velocity components of the boat.

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PARTIAL TIME DERIVATIVE, c/t

Suppose we stand on a bridge and note how the concentration of fish just below us changes with
time. We are observing then how the concentration changes with time at a fixed position in
space. Hence by c/t mean the ‘partial of c with respect to t, holding x,y,z constant’.

Problem No :1

1. Toluene is contained between two identical and parallel plates each of area 5m2. The top
plate is pulled in minus x direction by a force of 0.083 N at a velocity of 0.3 m/s. The
bottom plate is pulled in the opposite direction by a force of 0.027N at a velocity of 0.1
m/s as shown in fig. The plates are 10mm apart. Calculate the viscosity in centipoise.

Solution:
U = - 0.3 m/s
F = -0.083N

10 mm

A = 5m2 , du = V2-V1

= -0.3 – 0.1
= -0.4 m/s

(-0.083 – 0.027) /5 = = -0.022 m/s

= -0.022/ (-0.4/0.01)

= 5.5 x 10-4 Ns/m2

Convert this unit in to centipoise using the conversion 0.001kg/ms = 1cP

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Problem No : 2(EXERCISE)

2. The distance b/w two parallel plates is 0.00914m. The lower plate is being pulled at a
relative velocity of 0.360 m/s greater than the top plate. The fluid is soya bean oil with
viscosity 0.4 x 10-2pa.s at 303K.

(i) Calculate shear stress and shear rate

(ii) If glycerol at 293K having a viscosity of 1.069 kg/m.s is used instead of soyabean oil.
What relative velocity is needed using the same distance between the plate that the
same shear stress is obtained as (i) and what is the new shear rate.

EFFECT OF TEMPERATURE AND PRESSURE ON VISCOSITY

Viscosity of a gas at low density increases with increasing temperature,

Viscosity of a liquid decreases with increasing temperature.

Reduced viscosity as a function of reduced temperature for several values of the reduced
pressure

if critical p-V-T data are available, then c, may be estimated from these empirical
relations:

For N-component fluids with mole fractions x, the "pseudocritical" properties are:

EFFECT OF TEMPERATURE

Viscosity of any fluid depend upon two factors

• Inter molecular cohesive forces

• Transfer of molecular momentum

For Liquids:

• Intermolecular cohesive forces predominates molecular momentum transfer and hence

viscosity of liquids primarily depends upon the magnitude of intermolecular cohesive

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forces with increase of temperature the cohesive forces decrease rapidly resulting in
decrease of viscosity of liquid.

For Gases

• Molecular momentum transfer predominates the intermolecular cohesive forces, (because

in gases the molecules are widely spaced resulting in negligible intermolecular action).

• With increase of temperature the exchange of momentum of molecules increases

vigorously and resulting in increase of viscosity of gases.

Effect of Pressure

• Effect of pressure on viscosity is small.

• The viscosity under ordinary condition is not appreciably affected by change in pressure.

• Viscosity of gas and liquid has be found to increase with  in pressure at constant
temperature.

THEORIES OF TRANSPORT PROPERTIES OF GASES AND LIQUIDS

•
MOLECULAR THEORY OF VISCOSITY OF GASES AT LOW DENSITY:

Consider a pure gas composed of rigid, non-attracting spherical molecules of diameter d

and mass m, and the number density is taken to be n. The concentration of gas molecules
is presumed to be sufficiently small that the average distances between molecules is
many times their diameter d. In such a gas it is known that, at equilibrium the molecular
velocity are randomly directed and have an average magnitude given by,

u =(8kT/m)1/2
in which K is the Boltzman constant. The frequency of molecular bombardment
per unit area on one side of any stationary surface exposed to the gas is,

Z =u.n/4
The average distance traveled by a molecule between successive collisions is the
mean free path  is given by,
=1/[(21/2)d2.n]

on the average, the molecular reaching a plane will have experienced their last collision
at a distance a from the plane, where a is given roughly by,

a=2/3 

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The concept of the mean free path is intuitively appealing, but it is meaningful
only when  is large compared to the range of intermolecular forces. The concept is
appropriate for the rigid – sphere molecular model considered here.

The concept of the mean free path is intuitively appealing, but it is meaningful only
when  is large compared to the range of intermolecular forces. The concept is
appropriate for the rigid – sphere molecular model considered here.
To determine the viscosity of a gas in terms of the molecular model parameters, we
consider the behavior of gas when it flows parallel to the xy-plane with a velocity gradient
dvx/dy. The flux of x-momentum across any plane o constant y is found by assuming the
x – moments of the molecules that cross in the positive y direction and subtracting the x
– momenta of those that cross in the opposite direction, as follows,

yx =Z.my-a-Z.my+a

vxya = vxy  2/3dvx/dy

yx= -1/3u.mudvx/dy

This has the same form as Newton’s law of viscosity yx = dvx/dy. Comparing the two
equation gives an equation for the viscosity,
 =1/3n.m.u. =1/3u

By combining all the above equations,

=[2(mKT/)1/2]/[3.. d2] =[2(mKT)1/2]/[3(d)2]

This expression was obtained by Maxwell. The quantity d2 is called collision cross-
section.

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MOLECULAR THEORY OF THE VISCOSITY OF LIQUIDS:

A rigorous kinetic theory of the transport properties of monatomic liquids was

developed by kinkwood and co-workers. However this theory does not lead to easy to
use results. An older theory developed by Byring and co – workers, although less well
grounded theoretically, does not give a qualitative picture of the mechanism of
momentum transport in liquids and permits rough estimation of the viscosity from other
physical properties.

In a pure liquid at rest the individual molecules are constantly in motion.

However, because of the close parking, the motion is largely confined to a vibration
of each molecule within a “cage” formed by its nearest neighbors. This cage is
represented by an energy barrier of height in which is the molar free energy of
activation for escape from the cage in the stationary fluid. According to Eyring, a liquid
at rest continually undergoes rearrangements, in which one molecule at a time escapes
from its “cage” into an adjoining “hole”, and that the molecules thus move in each of the
co – ordinate directions in jumps of length a at a frequency  per molecule. The frequency
is given by the rate equation,

=KT/h.exp (-G0+/RT) (1)

in which, k and h are Boltzmann and Planck constants N is the avagadro number and
R= NK is the gas constant.

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In a fluid i.e. flowing in the x – direction with a velocity gradient dvx/dy, the frequency
of molecular rearrangement is increased. The effect can be explained by considering the
potential energy barrier as distorted under the applied stress so that,

-G+ =-G0+  (a/)(yxV/2) (2)

Where is the volume of a mole of liquid and is an approximation with the applied
shear stress or against the applied shear stress. + is the frequency of forward jumps and
- is the frequency of backward jumps. From (1) and (2),

 = KT/h exp (-G0+/RT) exp {ayxV/(2RT)} (3)

The net velocity with which molecular in layer A slips ahead of those in layer B is just the
distance traveled per jump (a) times the net frequency of forward jumps (+ - - ), is`
xA-xB=a (+--) (4)

The velocity profile can be considered to be linear over the very small distance
between the layers A and B, so that
-dx/dy =(a/f)(+--) (5)

Combining (3) & (5),

-dx/dy=(a/f) KT/h exp (-G0+/RT) exp {+ayxV/(2RT) - exp {-ayxV/(2RT)}

=(a/f) [KT/h exp (-G0+/RT)]{2 sinh (ayxV)/(2RT)}

This predicts the non-linear relation between the shear stress (momentum flux) and
the velocity gradient that is non- Newtonian flow.

THEORY OF THERMAL CONDUCTIVITY OF GASES AT LOW DENSITY:

The thermal conductivity of dilute mono atomic gas is described by the kinetic theory
of gases at low density. We use the model of rigid, non-attracting spheres of mass m and
diameter d. The gas as a whole is at rest (V=0), but the molecular motions must be
amounted for.
For a rigid-sphere gas,
u = [8KT/(M)]1/2 (1)mean molecular speed

Z = nu/4 (2) wall collision frequency per unit area

= 1/[21/2.. d2.n]-1 (3) mean free path.

The molecules reaching any plane in the gas have had, on an average, their last collisions
at a distance a from the plane, where,

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A= 2 /3 (4)

In these equations K is the Boltzmann constants, n is the number of molecules per

unit volume and M is the mass of the molecule.

The only form of energy that can be exchanged in a collision between two
smooth and rigid spheres is translational energy; the mean translational energy per
molecule under equilibrium condition is,

u2/2 = 3KT/2 (5)

For such a gas, the molar heat capacity at constant volume is,

cv = (u/T)v = N d(Mu2/2)/dT = 3R/2 (6)

In which R is the gas constant. This equation is satisfactory for monoatomic gases
upto temperatures of several thousand degrees.
that cross the plane per unit time in the positive y direction and subtracting the kinetic
energies of the equal number that cross in the negative y direction,

Qy = Z (Mu2/2y-a - Mu2/2y+a )

= 3KZ(Ty-a-Ty+a)/2 (7)

The above equation is based on the assumption that all molecules have velocities
representative of their region of their last collision and that the temperature profile T (y)
is linear for a distance of several mean free paths.

T =T - 2 (dT/dy)/3 (8)

T = T + 2(dT/dy)/3 (9)

By combining the last three equations,

Qy= -n Ku (dT/dy)/2 (10)

This corresponds to Fourier’s law of heat conduction with the thermal conductivity
given by

K = nKu/2 = cvu. (11)

in which  is the gas density and cv = 3K/{2M}

Substitution for expressions & from (1) & (3),

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K=[{MKT/}^1/2](K/M)/(d2)=2[{MKT}^1/2]/(32d2).cv (12)

which is the thermal conductivity of a dilute gas composed of rigid spheres of

diameter d. This equation predicts that k is independent of pressure. This prediction is in
good agreement with experimental data up to about 10 atm for most gases.

THEORY OF THERMAL CONDUCTIVITY OF LIQUIDS:

A kinetic theory for the thermal conductivity of monoatomic liquids was developed
a half century ago, but it has not yet been possible to implement it for practical
calculations.

According to Bridgman’s simple theory of energy transport in pure liquids, the molecules
are arranged in a cubic lattice, with a center spacing given by (V/N )1/3 in which V/N
is the volume per molecule. He further assumed energy to be transferred from one
lattice plane

to the next at the sonic velocity for the given fluid. The development is based on
reinterpretation of rigid sphere gas theory,

K= cvu = cvuya (1)

The heat capacity at constant volume of monoatomic liquid is about the same as
for a solid at high temperature, which is given by Dulong and Petit formula,
The mean molecular speed in the y-direction, |uy|, is replaced by the sonic velocity vs.
The distance a that the energy travels between two successive collisions is taken to be
lattice spacing (V/N )1/3. Making these substitutions in (1) gives

K= 3(V/N )2/3 KVs (2)

which is Bridgman’s equation. Experimental data show good agreement with (2) even
for polyatomic liquids, but the numerical co-efficient is somewhat too high. Better
agreement is obtained if the co-efficient is changed to 2.80,

K = 2.80 (N/V )2/3KVs (3)

This equation is limited to densities well above the critical density, because of the tacit
assumptions that each molecule oscillates in a “cage” formed by its nearest neighbors.
The success of this equation for polyatomic fluids seems to imply that the energy transfer
in collisions of polyatomic molecules is incomplete, cv = 3(K/M) is less than the heat
capacities of polyatomic liquids.

The velocity of low – frequency sound is,

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Vs=[(cp/cv). (P/)T]

The quantity (P/)T may be obtained from iso thermal compressibility, measurements
or from an equation of state, and (cp/cv) is very nearly unity for liquids, except near the
critical point.

THEORY OF DIFFUSION IN GASES AT LOW DENSITY:

The mass diffusivity for binary mixture of non-polar gases is predictable within about
5 percent by kinetic theory. Considering a large body of gas containing molecular species
A and A, which are identical except for labeling. We wish to determine the self-diffusivity
DAA* in terms of the molecular properties on the assumption that the molecules are rigid
spheres of equal mass MA and diameter dA.

Since the properties of A and A* are nearly the same, the following results of kinetic
theory for a pure rigid sphere gas at low density in which the gradients of temperature,
pressure and velocity are small:
u=[(8KT)/(M)]1/2 (1)

Z=nu/4 (2)

=1/[21/2d2n] (3)

The molecules reaching any plane in the gas have on the average had their last
collusion at a distance a from the plane, where

A = 2/3

In these equations, n is the number density (total number of molecules per unit
volume). To predict the self diffusivity DAA, we consider the motion of species A in the y
direction under a mass fraction gradient dWA/dy, where the fluid mixture moves in the y
direction at a finite velocity, mass average velocity V throughout. The temperature T and
the total molar concentration are considered constant. The net mass flux of species A
crossing the plane in the positive y direction and subtracting the mass A crossing in the
negative Y direction;

(WAVy)y+[(uWA/4)y-a-(uWA)y+a]

Here, the first term is the mass transport in the y direction because of the mass motion
of fluid that is, the convective transport and the last two terms give the molecular
transport relative to VY.

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It is assumed that the concentration profile WA(y) is very nearly linear over distances
of several mean free paths

WAy a = WAy (2(dWA/dy)/3)

Combination of the last two equations then gives for the combined mass flux at plane y:

Ay = WA.Vy – [u(dWA/dy)]/3

= WA.Vy - DAA*( dWA/dy)

This is the convective mass flux plus the molecular mass flux, the latter being given by
(1). Therefore, we get the following expression for the self-diffusivity:

DAA*=u/3

From (1) and (3),

DAA*=2[(KT/MA)1/2]/(3dA2)n

= 2[(MAKT)1/2/dA2]/(3)

The development of a formula for D for rigid spheres of unequal masses and diameter is
considerably more difficult.

DAB=(2/3)(KT/)1/2 {(MA-1+MB-1)/2}1/2((dA+dB)/2)2n-1

That is 1/MA is replaced by the arithmetic average of 1/MA and 1/MB and dA by the
arithmetic average of dA and dB.

THEORY OF DIFFUSION IN BINARY LIQUIDS:

The kinetic theory for diffusion in simple liquid is not as well developed as that for
dilute gases, and it cannot presently give accurate analytical predictions of diffusivities.
As a result, our understanding of liquid diffusion depends primarily on the rather crude
hydro dynamic and activated-state models. These, in turn, have spawned a number of
empirical
Correlations, which provide the best available means for predictions. These correlations
permit estimation of diffusivities in terms of more easily measured properties such as
viscosity and molar volumes.
The hydrodynamic theory takes as its starting point the Nernst-Einstein equation,
which states that, the diffusivity of a single particle or solute particle A through a
stationary medium B is given by,

DAB=KT (yA/FA) (1)

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In which yA/FA is the “mobility” of a particle A. If the shape and size of A are known,
the mobility can be calculated by the solution of the weeping flow equations of motion.
Thus, if A is spherical and if one takes into account the possibilities of “slip” at the fluid-
solid interface, one obtains,

yA/FA =(3B+RAAB)/(2B+RAAB).(6ARA)-1 (2)

In which B is the viscosity of the pure solvent, RA is the radius of the solute particles and
AB is the “coefficient of sliding friction”. The limiting cases of AB =  and AB = 0 are
of particular interest.
a. AB =  (no slip condition)

In this case (2) becomes Stoke’s law and (1) becomes

DABB/KT =(6RA)-1 (3)

which is called the Stoke-Einstein’s equation.

b. AB = 0 (complete slip condition)

In this case, (1) leads to

DABB/KT =(4 RA)-1 (4)

If the molecules A and B are identical and if they can be assumed to form a cubic lattice
with the adjacent molecule just touching, then 2 RA=(VA/NA )1/3.

(DAAA)/(KT) = (NA/VA )1/3/2

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