UNIT -I

TRANSPORT PHENOMENA BY MOLECULAR MOTION

PART A (2 MARK)

(1) What is the importance of Transport Phenomena?

Ans: The continuum approach adopted in Transport Phenomena makes it of more immediate
interest to Engineering students. The Transport Phenomena places more importance on basic
principles than on the blind use of empiricism. Even though the subject matter is sufficiently
basic cutting across the individual topic lines, it ranks along with Thermodynamics, Mechanics
and Electromagnetism as one of the key Engineering Sciences.

(2) Explain the analogous nature of the different divisions of Transport

Phenomena.
Ans: 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;
The different terms in the above phenomena are as given in the table below
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 [1/ Heat Transfer
Difference Coefficient] or 1/ k
Mass Transfer Mass Flux Concentration 1 / Diffusivity
Difference

(3) What is substantial time derivative?

Ans: Substantial time derivative can be very well illustrated with an example of a person
getting into a canoe and allows himself to float along the river and observe the fish
concentration. Now the velocity of the observer is the same as the velocity of the river v. When
the change of fish concentration with time is reported, the numbers would depend upon the
local stream velocity. This derivative is a special kind of total time derivative and is called the
‘substantial time derivative’ or sometimes more reasonably called the ‘derivative following the
motion’. It 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 components of the local fluid velocity v.

(4) What do you mean by reference frames?

Ans: 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.

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 Broadly speaking, 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.

(5) Compare Newton’s law of Viscosity with Hook’s law of elasticity

Ans: Newton’s Law of Viscosity states that the shear stress in a flowing fluid is directly
proportional to the negative velocity gradient  yx = - µ [d v x / dy ] Which means that
the shear stress imparted by the fluid is directly proportional to the negative velocity gradient,
the proportionality constant being the viscosity of the fluid.
Hook’s Law of elasticity states that: Stress is directly proportional to the resultant strain, the
proportionality constant being the young’s modulus of elasticity.

(6) What is the science of Rheology?

Ans: The characteristics of flow of various fluids which obey New ton’s law, Bingham fluid law,
Power law etc and the science regarding the determination of these factors such as viscosity
of a Newtonian fluid and such other parameters and the influence of temperature Pressure
etc. on these factors are grouped under the name of Science of Rheology. In other words
Rheology is the ‘Science of deformation and flow’ and it includes the study of the mechanical
properties of gases, liquids, plastics, asphalts and crystalline materials. Rheology comprises
Newtonian Fluid Mechanics at one end of the spectrum of the subject material and Hookean
elasticity at the other end.

(7) What are the units of dynamic viscosity and kinematic viscosity?
Ans: Viscosity or coefficient of Dynamic Viscosity has units of [=] gm/cm.Sec.(Poise) and
(Newton.Sec) / m2.
Kinematic Viscosity is define as  =  /  and has units [=] m2 / Sec

(8) Define Newtonian Fluids.

Ans: 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 v x / dy
].
This shows that there is a linear relationship between shear stress and the velocity gradient

(9) What is a pseudo plastic?

Ans:The steady state behavior of fluids can be expressed by a generalized form  yx=-[dv
x/dy ] where  may be expressed as a function of either [d v x/dy] or  yx. The flow regions in
which  decreases with increasing rate of shear stress - [d v x / dy ] the behavior is termed
pseudoplastic.

(10) What is Bingham plastics?

Ans: 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

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A Substance that follows this above two parameter model is called Bingham Plastic which
remains when the shear stress is of smaller magnitude than the yield stress  o but flows
some what like a Newtonian fluid when the shear stress exceeds  o .
(11) Define Viscosity.

Ans: According to Newton’s Law of Viscosity a plot of  yx versus - [d v x / dy ] for a given

fluid should give a straight line passing through the origin and the slope of this line is called
the viscosity of the fluid at the given temperature and pressure. Experiments have shown
that  yx is indeed proportional to - [d v x / dy ] for all gases and for homogeneous non-
polymeric liquids. The propor- tionality constant ‘µ’ is called viscosity of the fluid. All the
industrially important materials that do not obey the Newtons’ Law of viscosity are termed as
non-Newtonian fluids.

(12) What is meant by Thixotrophic fluid?

Ans: 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 . in regions where η
decreases with the rate of shear (- dvx / dy) the fluid is termed pseudoplastic and where η
increases with the increasing rate which of shear (- dvx / dy) the fluid is termed dilatant.
Fluids that show a limited decrease in η with time under suddenly applied constant stress
are called Thixotrophic. And those fluids show an increase in with time are called
Rheopectic.

(13) What is the difference between dilatant and pseudoplastic fluids?

Ans: The steady state behavior of most fluids 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.
The flow regions in which  decreases with increasing rate of shear stress - [d v x / dy ] the
behavior is termed pseudoplastic and the flow regions in which  increases with increasing
rate of shear stress - [d v x / dy ] the behavior is termed dilatant.

(14) Define non-Newtonian fluids.

Ans: According to Newton’s law of viscosity given by:  yx = - µ [d v x / 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. 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.

(15) Explain Newton’s law of viscosity.

Ans: The relationship between shear stress and the velocity gradient is given by:
 yx = - µ [d v x / dy ].
This shows that there is a linear relationship between shear stress and the velocity gradient.
This is called the Newton’s law of viscosity. The proportionality factor µ is called the viscosity
of the fluid and this law obeying fluids are Newtonian.

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 (16) What is slip velocity?
Ans: If there is slip at the wall of a pipe then the velocity will not be zero at the wall. One
can obtain a modification of the Hagen-Poiseuille law by assuming the fluid to slip at the wall
of the cylinder. i.e., instead of assuming that vz=0 at r=R, we have to use the Boundary
Condition that .vz = -µ (d vz /dx) at r = R in which  is the coefficient of sliding friction. In
most fluid-flow problems slip is not important. The solution for flow around spheres with slip
has been used in connection with the hydrodynamic theories of diffusion. Also, slip appears
to be important in some non-Newtonian flow problems.

(17) State and explain power law of viscosity.

Ans: 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.

(18) List some models to characterize non-Newtonian fluids.

Ans: i] Bingham model, ii] Power law model {Oswald-de Waale model}; iii] Eyring model, iv]
The Ellis model, v] The Reiner-Philippoff model

(19) What are boundary conditions?

Ans: The differential equation resulting from the differential conservation balance
describes what is happening within the system. The “boundary conditions”, mathematically
describe the physical phenomena occurring at the boundaries of the system.
We know that the solutions to differential equations can be either “general”, or “particular”.
A general solution is said to be a “family of solutions”, and is accompanied by arbitrary
constants (or constants of integration). The values of the arbitrary constants are determined
by the specification of the boundary conditions.
The 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. 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.

(20) What is the velocity of fluid at the wall of a pipe?

Ans: The velocity of a fluid at the wall of a pipe is zero if the pipe is stationary and it will be
equal to the velocity of the pipe in case the pipe is moving. The is true under the hypothesis
“there is no slip at the wall”

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 PART B
1. Write short notes on (a) Conservation Laws, (b) Continuous concept, (c) Field and
reference frames, (d) Substantial Derivative, (e) Total derivative and (f) Boundary
conditions.

CONSERVATION LAWS IN TRANSPORT PROCESSES:

The conservation laws of mass, energy (heat), and momentum are the most widely
applicable laws in our universe.. The laws of conservation of mass, energy (heat), and
momentum will be expressed in an analogous fashion. The resultant generalized equation
is called the general property balance.

The general conservation equation can be expressed as follows:

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

This holds good for all conserved quantities (energy (heat), mass, and momentum).
One has to consider a typical differential volume element as the suitable system for one-
dimensional transport in different geometries.
The first two terms (INPUT) , (OUTPUT) in the conservation equation represent the flow
of material (mass , energy (heat), or momentum) across the boundaries of the system
(differential element). Because the basic laws of transport phenomena are all written in
terms of fluxes, and we will eventually need these laws to solve molecular transport
problems, it is common practice to specify these flow terms as fluxes.
[SOURCES] and [SINKS] in the conservation equation refer to the generation and
consumption of either energy (heat), mass, or momentum within the system (differential
element). In order to be considered as sources and sinks in the conservation equation, these
phenomena must occur uniformly throughout the physical system (differential element)
being analysed.
The [ACCUMULATION] term, which appears on the right-hand side of the conservation
equation, refers only to accumulation with time. In other words, it accounts for an increase
or decrease of the conserved quantity within the system (differential element), as time
increases. If there are no changes in any of the variables with time, the system is said to be
at “steady-state”.

The general laws of conservation are: Law of conservation of momentum; law of

conservation of energy and law of conservation of mass:

The general law of conservation can be written as:

{Rate of the Quantity in} + {Rate of the quantity out} + {Rate of generation of the
Quantity} = {Rate of accumulation of the quantity}

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For determining the Momentum Flux distribution and Velocity distribution in a flow situation
an elemental thin shell of fluid is considered and momentum balance is made on that. 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

Momentum may enter the system by momentum transfer according to Newtonian (or non-
Newtonian) expression for the momentum flux. Momentum may also enter by virtue of the
over-all fluid motion. The forces that one will be concerned with are the pressure forces that
act on surfaces and gravity forces which act on the volume as a whole.
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. Such 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;(This type of transport is sometimes referred to as 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.
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

CONTINUOUS CONCEPT:
In its most fundamental form, 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 one is 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.
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.

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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”.

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 (x 1, y1, z1), and t1,
the above equation gives the velocity of the fluid at that location at time t 1. 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.
Broadly speaking, 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 usedone. However, a number of
formulations of quantum transport theory are expressed in terms of Lagrangian variables.

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SUBSTANTIAL TIME DERIVATIVE:
The substantial derivative is the one, which has the property of being zero for a steady-
state problem, incompressible flow with no net velocity vector relative to the position of the
observer, who is attempting the given transport problem. It has a physical significance of
changes with time, as the observer moves with the fluid motion.
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 components of the local fluid velocity (v). Here, [c/t] is the
derivative at 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.
BOUNDARY CONDITIONS:

Whereas the differential equation resulting from the differential conservation balance
describes what is happening within the system, it is the “boundary conditions”, which
mathematically describe the physical phenomena occurring at the boundaries of the system.
We know that the solutions to differential equations can be either “general”, or
“particular”. A general solution is said to be a “family of solutions”, and is accompanied by
arbitrary constants (or constants of integration). The values of the arbitrary constants are
determined by the specification of the boundary conditions.
The 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. 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 realise that these conditions must have an assignable numerical
value, in order to be viable boundary conditions. That is, either the dependent variable

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(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.

2. What are the different methods of analysis adopted for experimental data?
Differentiate between Differential and Integral analysis.

METHODS OF ANALYSIS; DIFFERENTIAL, INTEGRAL AND EXPERIMENTAL METHODS:

The equations of the transport phenomena in laminar, or turbulent flow are, in general, so
complex that in most practical cases, exact solutions are impossible. In these situations,
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.
a) Inspection analysis, b) Dimensional analysis c) Modeling analysis.

Differential Methods of Analysis:

At this stage, the principles of the conservation of energy (heat), mass, and momentum,
and their applications to transport phenomena must be the familiar topics. These very same
conservation laws are used to describe transport phenomena, except the balances are taken
around the differential volume elements.
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. 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

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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.

Integral Methods of Analysis:

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. 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.
For many cases, such detailed information 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.
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.

i.e., the mass flow rate of helium per unit area is proportional to the mass fraction difference
by the plate thickness. Density is density of the helium-silica system, and the proportionality
factor is the diffusivity of the silica-helium system.

JAy = - DAB dWa/dy

Here WAy/A has been replaced by JAB, the molecular mass flux of helium in the positive Y-
direction.

3. Develop the concept of Viscosity for the Newtonian Fluids and the
corresponding rheological property terms for the Newtonian fluids.

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]

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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 yx and the x-component of
the fluid vector is designated.

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, yx
may also be interpreted as the viscous flux of x-momentum in the y-direction.

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 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 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.

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 v x / 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 v x / 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. 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.

NON-NEWTONIAN FLUIDS:

Those fluids that do not follow the Newton’s law of viscosity 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.

4. Write Short Notes on: a) Newtonian Fluids, b) Bingham plastics, c) Oswald De-
waele Model, d) The Ellis model, e) The Reiner-Philippof model.

MODELS TO CHARACTERIZE NON-NEWTONIAN FLUIDS:

i] Bingham model, ii] Power law model {Oswald-de Waale model}; iii] Eyring
model, iv] The Ellis model, v] The Reiner-Philippoff model

i) Bingham model:

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 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 .

ii) 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.

iii) 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 Eyeing Kinetic Theory of liquids. It predicts pseudoplastic
behaviour at finite values of yx but reduces asymptotically to Newton’s law of
viscosity with µ = A/B as yx approaches zero.

iv) 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.

v) 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 }]

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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]

Rheology:

The characteristics of flow of various fluids which obey New ton’s law, Bingham fluid
law, Power law etc and the science regarding the determination of these factors such as
viscosity of a Newtonian fluid and such other parameters and the influence of temperature
Pressure etc. on these factors are grouped under the name of Science of Rheology. In other
words Rheology is the ‘Science of deformation and flow’ and it includes the study of the
mechanical properties of gases, liquids, plastics, asphalts and crystalline materials. Rheology
comprises Newtonian Fluid Mechanics at one end of the spectrum of the subject material
and Hookean elasticity at the other end.

❖ 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 . in regions where
η decreases with the rate of shear (- dvx / dy) the fluid is termed pseudoplastic and
where η increases with the increasing rate which of shear (- dvx / dy) the fluid is termed
dilatant. Fluids that show a limited decrease in η with time under suddenly applied
constant stress are called Thixotrophic. And those fluids show an increase in with time
are called Rheopectic.

THEORIES OF TRANSPORT PROPERTIES OF GASES AND LIQUIDS

5. Discuss the theories of of viscosity of gases and liquids in respect of effect of

temperature and pressure.

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

14
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 

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

15
– 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.

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.

6. Discuss the theories of of thermal conductivity of gases and liquids in respect

of effect of temperature and pressure.

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

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 = 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,

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.

The heat flux qy across any plane of constant is found by summing the kinetic energies
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

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 K = nKu/2 = cvu. (11)

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

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

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.

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The velocity of low – frequency sound is,

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.

7. Discuss the theories of of diffusion of gases and liquids in respect of effect of

temperature and pressure.

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 M A 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]

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 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.

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,

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 DAB=KT (yA/FA) (1)

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

22