UNIT I

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:
 Heat (energy) transport
 Mass transport
 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

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

NEWTON’S LAW OF VISCOSITY

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
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

dVx
Where,  can be expressed as a function of either or y x
dy
Bingham model:
 Two parameter model, to describe the deformation and flowing nature of Bingham fluid.
 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.

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]
Problem No :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
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
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 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.
Chemical Composition
The viscosity of liquids generally depends upon the size, shape and chemical nature of their molecules.
It is greater with larger than with smaller molecules; with elongated than with spherical molecules.
Large amounts of dissolved solids generally increase viscosity. Small amounts of electrolytes lower the
viscosity of water slightly.
Colloid Systems:
The viscosity of lyophilic colloid solution is generally relatively high.
Suspended Material:
Suspended particles cause an increase in the viscosity. The viscosity of blood is important in relation to the
resistance offered to the heart in circulating the blood. The heart muscle functions best while working
against a certain resistance. The viscosity of blood is due largely to the emulsoid colloid system present in
plasma and to the great proportion of suspended corpuscles.
Concentration:
 Concentration is the amount of substance that is dissolved in a specific volume.
 An increase in concentration will usually result in an increase in viscosity.

Fick’s first law

An empirical relation for the diffusional molar flux, first postulated by Fick and, accordingly, often referred
to as Fick’s first law, defines the diffusion of component A in an isothermal, isobaric system. For diffusion
in only the Z direction, the Fick’s rate equation is

where DAB is diffusivity or diffusion coefficient for component A diffusing through component B, and dCA
/ dZ is the concentration gradient in the Z-direction
Types of diffusion:
Molecular Diffusion: is a mechanism of mass transfer in stagnant fluids / moving in laminar flow. Molecular
diffusion is concerned with the movement of individual molecules through a substance by virtue of their
thermal energy. The phenomenon of molecular diffusion leads to a completely uniform conc. throughout a
solution.
Eddy Diffusion : is a mechanism in which the mechanical agitation produces rapid movement of relatively
large chunks /eddies ,of fluid characteristics of turbulent motion ,which have carried salt with them .( method
of solute transfer).
Knudsen diffusion is a means of diffusion that occurs when the scale length of a system is comparable to or
smaller than the mean free path of the particles involved. For example in a long pore with a narrow diameter
(2–50 nm) because molecules frequently collide with the pore wall
Diffusivity in Gases:
Pressure dependence of diffusivity is given by

And temperature dependency is according to

Diffusivity of a component in a mixture of components can be calculated using the diffusivities for the
various binary pairs involved in the mixture. The relation given by Wilke is
Where D 1-mixture is the diffusivity for component 1 in the gas mixture; D 1-n is the diffusivity for the binary
pair, component 1 diffusing through component n; and is the mole fraction of component n in the gas
mixture evaluated on a component –1 – free basis, that is

Diffusivity in Liquids
This characteristic of liquid diffusion often limits the overall rate of processes accruing in liquids (such as
reaction between two components in liquids).
In chemistry, diffusivity limits the rate of acid-base reactions; in the chemical industry, diffusion is
responsible for the rates of liquid-liquid extraction. Diffusion in liquids is important because it is slow.
Certain molecules diffuse as molecules, while others which are designated as electrolytes ionize in solutions
and diffuse as ions. For example, sodium chloride (NaCl), diffuses in water as ions Na + and Cl-. Though
each ions has a different mobility, the electrical neutrality of the solution indicates the ions must diffuse at
the same rate; accordingly it is possible to speak of a diffusion coefficient for molecular electrolytes such as
NaCl. However, if several ions are present, the diffusion rates of the individual cations and anions must be
considered, and molecular diffusion coefficients have no meaning. Diffusivity varies inversely with viscosity
when the ratio of solute to solvent ratio exceeds five. In extremely high viscosity materials, diffusion
becomes independent of viscosity.
Diffusivity in solids
Typical values for diffusivity in solids are shown in table. One outstanding characteristic of these values is
their small size, usually thousands of time less than those in a liquid, which are in turn 10,000 times less than
those in a gas.
Diffusion plays a major role in catalysis and is important to the chemical engineer. For metallurgists,
diffusion of atoms within the solids is of more importance.
The diffusion coefficient in solids at different temperatures is generally found to be well predicted by the
Arrhenius equation:

Where
D is the diffusion coefficient (m2 / s)
D0 is the maximum diffusion coefficient (at infinite temperature; m2 / s)
EA is the activation energy for diffusion in dimensions of (J mol−1)
T is the temperature (K)
k is the Boltzmann constant
Heat Energy and Heat Transfer
Heat is a form of energy in transition and it flows from one system to another, without
transfer of mass, whenever there is a temperature difference between the systems. The process
of heat transfer means the exchange in internal energy between the systems and in almost every
phase of scientific and engineering work processes, we encounter the flow of heat energy.
Importance of Heat Transfer
Heat transfer processes involve the transfer and conversion of energy and therefore, it
is essential to determine the specified rate of heat transfer at a specified temperature difference.
The design of equipments like boilers, refrigerators and other heat exchangers require a detailed
analysis of transferring a given amount of heat energy within a specified time. Components like
gas/steam turbine blades, combustion chamber walls, electrical machines, electronic gadgets,
transformers, bearings, etc require continuous removal of heat energy at a rapid rate in order to
avoid their overheating. Thus, a thorough understanding of the physical mechanism of heat
flow and the governing laws of heat transfer are a must.
Modes of Heat Transfer
The heat transfer processes have been categorized into three basic modes: Conduction,
Convection and Radiation.
Conduction – It is the energy transfer from the more energetic to the less energetic particles
of a substance due to interaction between them, a microscopic activity.
Convection - It is the energy transfer due to random molecular motion a long with the
macroscopic motion of the fluid particles.
Radiation - It is the energy emitted by matter which is at finite temperature. All forms of matter
emit radiation attributed to changes m the electron configuration of the
constituent atoms or molecules The transfer of energy by conduction and
convection requires the presence of a material medium whereas radiation does
not. In fact radiation transfer is most efficient in vacuum.
All practical problems of importance encountered in our daily life Involve at least two,
and sometimes all the three modes occuring simultaneously When the rate of heat flow is
constant, i.e., does not vary with time, the process is called a steady state heat transfer process.
When the temperature at any point in a system changes with time, the process is called unsteady
or transient process. The internal energy of the system changes in such a process when the
temperature variation of an unsteady process describes a particular cycle (heating or cooling of
a budding wall during a 24 hour cycle), the process is called a periodic or quasi-steady heat
transfer process.
Heat transfer may take place when there is a difference In the concentration of the
mixture components (the diffusion thermoeffect). Many heat transfer processes are
accompanied by a transfer of mass on a macroscopic scale. We know that when water
evaporates, the heal transfer is accompanied by the transport of the vapour formed through an
air-vapour mixture. The transport of heat energy to steam generally occurs both through
molecular interaction and convection. The combined molecular and convective transport of
mass is called convection mass transfer and with this mass transfer, the process of heat transfer
becomes more complicated.
Thermodynamics and Heat Transfer-Basic Difference
Thermodynamics is mainly concerned with the conversion of heat energy into other
useful forms of energy and IS based on (i) the concept of thermal equilibrium (Zeroth Law),
(ii) the First Law (the principle of conservation of energy) and (iii) the Second Law (the
direction in which a particular process can take place). Thermodynamics is silent about the heat
energy exchange mechanism. The transfer of heat energy between systems can only take place
whenever there is a temperature gradient and thus. Heat transfer is basically a non- equilibrium
phenomenon. The Science of heat transfer tells us the rate at which the heat energy can be
transferred when there IS a thermal non-equilibrium. That IS, the science of heat transfer seeks
to do what thermodynamics is inherently unable to do.
However, the subjects of heat transfer and thermodynamics are highly complimentary.
Many heat transfer problems can be solved by applying the principles of conservation of energy
(the First Law)
Table 1.1 Dimensions and units of various parameters
Parameter Dimension Unit
Mass M Kilogram, kg
Length L metre, m
Time T seconds, s
Temperature Kelvin, K, Celcius oC
Velocity L/T metre/second,m/s
Density ML–3 kg/m3
Force ML–1T–2 Newton, N = 1 kg m/s2
Pressure ML2T–2 N/m2, Pascal, Pa
Energy, Work ML2T–3 N-m, = Joule, J
2 –3
Power ML T J/s, Watt, W
–1 –1
Absolute Viscosity ML T N-s/m2, Pa-s
Kinematic Viscosity L2T–1 m2/s
Thermal Conductivity MLT–3 –1
W/mK, W/moC
Heat Transfer Coefficient MT–3 –1
W/m2K, W/m2oC
Specific Heat L2 T–2 –1
J/kg K, J/kgoC
Heat Flux MT–3 W/m2

Mechanism of Heat Transfer by Conduction

The transfer of heat energy by conduction takes place within the boundaries of a
system, or a cross the boundary of t he system into another system placed in direct physical
contact with the first, without any appreciable displacement of matter comprising the system,
or by the exchange of kinetic energy of motion of the molecules by direct communication, or
by drift of electrons in the case of heat conduction in metals. The rate equation which
describes this mechanism is given by Fourier Law
Q  kAdT / dx

where Q = rate of heat flow in X-direction by conduction in J/S or W,

k = thermal conductivity of the material. It quantitatively measures the heat conducting

ability and is a physical property of t he material that depends upon the composition of the
material, W/mK,
A = cross-sectional area normal to the direction of heat flow, m2,
dT/dx = temperature gradient at the section, as shown in Fig. 1 I The neganve sign IS
Included to make the heat transfer rate Q positive in the direction of heat flow (heat flows in
the direction of decreasing temperature gradient).

Fig 1.1: Heat flow by conduction

Thermal Conductivity of Materials
Thermal conductivity is a physical property of a substance and In general, It depends
upon the temperature, pressure and nature of the substance. Thermal conductivity of materials
are usually determined experimentally and a number of methods for this purpose are well
known.
Thermal Conductivity of Gases: According to the kinetic theory of gases, the heat
transfer by conduction in gases at ordinary pressures and temperatures take place through the
transport of the kinetic energy arising from the collision of the gas molecules. Thermal
conductivity of gases depends on pressure when very low «2660 Pal or very high (> 2 × 109
CH8791 Transport Phenomena 2020-2021

Pa). Since the specific heat of gases Increases with temperature, the thermal
conductivity Increases with temperature and with decreasing molecular weight.

Thermal Conductivity of Liquids: The molecules of a liquid are more closely spaced
and molecular force fields exert a strong influence on the energy exchange In the
collision process. The mechanism of heat propagation in liquids can be conceived as
transport of energy by way of unstable elastic oscillations. Since the density of liquids
decreases with increasing temperature, the thermal conductivity of non-metallic
liquids generally decreases with increasing temperature, except for liquids like water
and alcohol because their thermal conductivity first Increases with increasing
temperature and then decreases.
Thermal Conductivity of Solids (i) Metals and Alloys: The heat transfer in metals arise
due to a drift of free electrons (electron gas). This motion of electrons brings about
the equalization in temperature at all points of t he metals. Since electrons carry both
heat and electrical energy. The thermal conductivity of metals is proportional to its
electrical conductivity and both the thermal and electrical conductivity decrease with
increasing temperature. In contrast to pure metals, the thermal conductivity of alloys
increases with increasing temperature. Heat transfer In metals is also possible through
vibration of lattice structure or by elastic sound waves but this mode of heat transfer
mechanism is insignificant in comparison with the transport of energy by electron gas.
(ii) Nonmetals: Materials having a high volumetric density have a high thermal
conductivity but that will depend upon the structure of the material, its porosity and
moisture content High volumetric density means less amount of air filling the pores
of the materials. The thermal conductivity of damp materials considerably higher than
the thermal conductivity of dry material because water has a higher thermal
conductivity than air. The thermal conductivity of granular material increases with
temperature. (Table 1.2 gives the thermal conductivities of various materials at 0oC.)

St. Joseph’s College of Engineering 13 Department of Chemical Engineering