TRANSPORT PROCESSES AND

TRANSPORT COEFFICIENTS
Introduction
From the earliest days of the profession, chemical engineering education has been characterized by an
exceptionally strong grounding in both chemistry and chemical engineering. Over the years the approach
to the latter has gradually evolved; at first, the chemical engineering program was built around the
concept of studying individual processes (i.e., manufacture of sulfuric acid, soap, caustic, alcohols etc.).
This approach, unit processes, was a good starting point and helped to get chemical engineering off to a
running start.

After some time it became apparent to chemical engineering educators that the unit processes had many
operations in common (heat transfer, distillation, filtration, etc.). This led to the concept of thoroughly
grounding the chemical engineer in these specific operations and the introduction of the unit operations
approach.
Once again, this innovation served the profession well, giving its practitioners the understanding to cope
with the ever-increasing complexities of the chemical and petroleum process industries.

As the educational process matured, gaining sophistication and insight, it became evident that the unit
operations in themselves were mainly composed of a smaller subset of transport processes (momentum,
energy, and mass transfer). This realization generated the transport phenomena approach-an approach
that owes much to the classic chemical engineering text of Bird, Stewart, and Lightfoot.

Its purpose is to thoroughly ground the student in basic principles (the transport processes); then to move
from theoretical to semi-empirical and empirical approaches (carefully and clearly indicating the rationale
for these approaches); next, to synthesize an orderly approach to certain of the unit operations; and,
finally, to move in the important direction of engineering practice by dealing with the analysis and design
of equipment and processes.

THE PHENOMENOLOGICAL APPROACH: FLUXES, DRIVING FORCES, SYSTEM

COEFFICIENTS

In nature, “changes” occur in response to imbalances or driving forces.

For example:
1. Heat (energy in motion) flows from one point to another under the influence of a temperature
difference.
2. Flow of (respectively) mass, momentum, electrons, and neutrons.
FLUX:
1. A “flux” occurs when there is a “driving force”.
2. The flux is related to a gradient by some characteristic of the system itself - the “system” or
“transport coefficient”.
( )( )
( )( )
Example of gradient:
The gradient for the case of temperature for one-dimensional (or directional) flow of heat is
expressed as:

Lecture by: Engr. Renato C. Ong 1

Schematic of a flux

Flux illustration on Heat Transfer

 The flux equations can be derived by considering simple one-dimensional models. Consider, for example,
the case of energy or heat transfer in a slab (originally at a constant temperature, T1) shown in Figure
below.
 One of the opposite faces of the slab suddenly has its temperature increased to T2. The result is that heat
flows from the higher to the lower temperature region. Over a period of time the temperature profile in the
solid slab will change until the linear (steady-state) profile is reached.

Temperature profile development (unsteady state to steady state)

 At this point the rate of heat flow Q per unit area A will be a function of the system's transport coefficient
(k, thermal conductivity) and the driving force (temperature difference) divided by distance.

( )( )
( )( )

( )
( )( ) ( )
( )

If the above equation is put into differential form, the result is the one-dimensional form known as “Fourier’s Law”
or gases and liquids:
( )

For solids, it is the one-dimensional form of Fourier’s Law which also has y and z components

Since Heat flux, ( ) is a vector, units are :

Lecture by: Engr. Renato C. Ong 2

Flux illustration on Momentum Transfer (Flow of Fluid)
Let us consider another situation: a liquid at rest between two plates as shown below. At a given time the bottom
plate moves with a velocity V. This causes the fluid in its vicinity to also move. After a period of time with unsteady
flow we attain a linear velocity profile that is associated with steady-state flow. At steady state a constant force F is
needed.
Velocity profile development for steady laminar flow:

( )( )
( )( )

Let as flux of momentum [ because force = d(momentum)/dt].

where µ is the fluid‘s viscosity (i.e., transport coefficient).

If the above equation is put into differential form, the result is the one-dimensional form of Newton’s Law of
Viscosity:
By Converting to a shear stress τ

( )

Since Momentum flux, ( ) is a tensor, units are :

Lecture by: Engr. Renato C. Ong 3

 * Note: The shear stress is subscripted with two letters. The reason for this is that momentum transfer is
not a vector (three components) but rather a tensor (nine components). As such, momentum transport,
except for special cases, differs considerably from heat transfer.

Flux illustration on Mass Transfer:

For the case of mass transfer because of concentration differences we cite Fick’s First Law for a binary system:

( )
where
JAy = molar flux of component A in the y direction, a vector with units:
DAB,= the diffusivity of A in B (the other component), is the applicable transport coefficient,

*As with Fourier’s Law, Fick’s First Law has three components and is a vector.

THE TRANSPORT COEFFICIENTS

We have seen that the transport processes ( heat, momentum and mass) each involve a property of the system
namely:
Transport Process Property of the System (Transport Coefficient)
Heat Transfer Thermal conductivity (k)
Momentum Transfer Viscosity (µ)
Mass Transfer Diffusivity (D)

*Transport coefficients as system properties are functions of temperature and pressure.

Expression/Determination of Transport Coefficients:

A. Low Density Gases:
Expressions for the behavior of these properties in low-density gases can be derived by using two approaches:
1. Approach using the kinetic theory of gases
2. Approach using the molecular interactions (Chapman-Enskog theory).
Using the Kinetic theory of gases approach:
The molecules are rigid, non-attracting, and spherical. They have
1. A mass m and a diameter, d
2. A concentration n (molecules/unit volume)
3. A distance of separation that is many times d.
This approach gives the following expression for viscosity, thermal conductivity, and diffusivity:

Thermal Conductivity √ ( )

Viscosity √
⁄
⁄ ⁄ ⁄
( ) ( )
Diffusivity ( )
* Subscripts A and B refer to gas A and gas B
Where: *K or KB is the Boltzmann constant. or
(Boltzmann's constant,K or KB, is a bridge between macroscopic and microscopic physics)

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Using the molecular interactions (Chapman-Enskog theory).
If molecular interactions are considered (i.e., the molecules can both attract and repel) a different set of relations are
derived. This approach involves relating the force of interaction, F, to the potential energy . The latter quantity is
represented by the Lennard-Jones
( ) [( ) ( ) ]
 The Lennard-Jones potential (also referred to as the L-J potential, 6-12 potential, or 12-6 potential) is a
mathematically simple model that approximates the interaction between a pair of neutral atoms or
molecules.
 A mathematical approximation that illustrates the energy of interaction between two nonbonding atoms or
molecules based on their distance of separation.
Where:
( )
σ = collision diameter (characteristic diameter), finite distance at which inter-particle potential is zero
ϵ = characteristic energy of interaction , the depth of the potential well and a measure of how strongly the
two particles attract each other.
(see Table below for values of σ and ϵ)
r = distance between the particles

The Lennard-Jones potential predicts weak molecular attraction at great distances and ultimately strong repulsion
as the molecules draw closer.
Lennard-Jones model potential energy function.

Resulting equations for viscosity, thermal conductivity, and diffusivity using the Lennard-Jones potential are:
√ ⁄ k in ;
Thermal σ in ;
Conductivity
*(for monoatomic gas) ( ) ( )
;
T in ;
√
Viscosity σ in ;
M is Molecular weight
( ) ( )

P in Atm
√ ( )
( )
Diffusivity
√( ) ( )

( )

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Intermolecular Force Parameters and Critical Properties

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Functions for Prediction of Transport Properties of Gases (Low Density)

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Sample Problems:
1. The viscosity of isobutane at 23°C and atmospheric pressure is . Compare this value to
that calculated by the Chapman-Enskog approach.
Solution:
√

Using Intermolecular Force Parameters and Critical Properties,

( )

Using Functions for Prediction of Transport Properties of Gases (Low Density)

1.634 (by interpolation)
√

√ ( )
( ) ( )

2. Calculate the diffusivity for the methane-ethane system at 104°F and 14.7 psia.

Solution:
√ ( )

Let A = Methane and B= Ethane

( ) ( )

Using Intermolecular Force Parameters and Critical Properties,

( ) ( )

√( ) ( ) √( )( )

Using Functions for Prediction of Transport Properties of Gases (Low Density)

1.125 (by interpolation)

√ ( ) √( ) ( )
( )( ) ( )

The actual value is

Lecture by: Engr. Renato C. Ong 8

B. High Density Gases and mixture of Gases:
 If gaseous systems have high densities, both the kinetic theory of gases and the Chapman-Enskog theory
fail to properly describe the transport coefficients' behavior.
 Furthermore, the previously derived expression for viscosity and thermal conductivity apply only to pure
gases and not to gas mixtures.
Empirical relations for the estimation of Viscosity of monoatomic gases:
( ) ⁄
(̂ ) ⁄

⁄ ⁄

( ) ⁄

Where:

̂
Empirical relations for the estimation of viscosity ( ) and thermal conductivity ( ) of mixtures of
gases at low densities:

∑
∑

∑
∑

⁄ ⁄
[ ( ) ( ) ]
⁄
[ ]
√
Empirical relations for the estimation of viscosity ( ) and thermal conductivity ( ) of mixtures of
gases at high densities using pseudocritical method:

∑ ∑

Where:

. These values are then used to determine the

and values needed to obtain ( ) from the above figure.

*The same approach can be used for the thermal conductivity using above figure if data are available or by using
√ ⁄
a value determined from equation,

*Behavior of diffusivities is not as easily handled as the other transport coefficients. The combination ( ) is
essentially a constant up to about 150 atm pressure. Beyond that, the only available correlation is the one developed
by Slattery and Bird. This, however, should be used only with great caution because it is based on very limited data

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Figures below give the correlation for viscosity and the thermal conductivity of monoatomic gases
 One set are plots of the reduced viscosity ( ) , where is the viscosity at the critical point or
reduced thermal conductivity ( ) versus ( ) , reduced temperature, and ( ) reduced pressure.
 The other set are plots of viscosity and thermal conductivity divided by the values ( ) at
atmospheric pressure and the same temperature.

Reduced viscosity as a function of reduced pressure and temperature

Modified reduced viscosity ( ) as a function of reduced temperature and pressure

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Reduced thermal conductivity (monatomic gases) as a function of reduced temperature and pressure

Modified reduced thermal conductivity as a function of reduced temperature and pressure

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Sample Problem:
o
1. Compare estimates of the viscosity of CO2 at 114.6 atm and 40.3 C using:
a. Figure above and an experimental viscosity value of 1800 x 10 -8 Pa-sec for CO2 at 45.3 atm and 40.3oC
b. The Chapman-Enskog relation and Figure above.

Solution:
a.
From: Intermolecular Force Parameters and Critical Properties

For P = 45.3 atm and T = 40.3 oC (Experimental Value)

( )

From: Modified reduced viscosity ( ) as a function of reduced temperature and pressure

For P = 114.6 atm and T = 40.3 oC (Estimated Value)

( )

From: Modified reduced viscosity ( ) as a function of reduced temperature and pressure

( )( )
b.
From: Intermolecular Force Parameters and Critical Properties
M= 44.01
( )

Using Functions for Prediction of Transport Properties of Gases (Low Density)

1.264 (by interpolation)
√

√( )( )
( ) ( )

Since

( )( )

*The Percent error for case a vs. case b is 3.54%.

Lecture by: Engr. Renato C. Ong 12

2. Estimate the viscosity of gas mixture of CO2 (y=0.133); O2(y=0.039); N2(y=0.828) at 1 atm and 293 by using :
a. Reduced viscosity as a function of reduced pressure and temperature and pseudocritical concept
b. Empirical relations equation for mix gases given the viscosities of pure component as:

Solution:
a. Using Intermolecular Force Parameters and Critical Properties,

304.2 72.9
154.4 49.7
126.2 33.5

( )( ) ( )( ) ( )( )
[( )( ) ( )( ) ( )( )] 39.37 atm
[( )( ) ( )( ) ( )( )]

Using Intermolecular Force Parameters and Critical Properties

(Using “low density limit” -line curve)

( )( ) ( )( )
b. Using the empirical equations,

∑
∑
⁄ ⁄
[ ( ) ( ) ]
⁄
[ ]
√

1.00 1.00 1.00 1.00

1.38 0.72 0.72 0.73
1.57 0.64 0.83 0.73
0.73 1.37 1.39 1.39
1.00 1.00 1.00 1.00
1.14 0.88 1.16 1.04
0.64 1.56 1.20 1.37
0.88 1.14 0.86 0.94
1.00 1.00 1.00 1.00

∑
∑
( )( ) ( )( )
[
( )( ) ( )( ) ( )( ) ( )( ) ( )( ) ( )( )
( )( )
]
( )( ) ( )( ) ( )( )

Lecture by: Engr. Renato C. Ong 13

 ( )( ) ( )( ) ( )( )
[ ]

*Actual experimental value of the mixture viscosity is . The % errors

are 3.10% and 4.41% respectively for Case a and Case b.

Transport Coefficients in Liquid and Solid Systems :

Understanding of Transport coefficients in gases >>>> Transport Coefficients for liquid system

Empirical Equations for the estimation of Pure Liquid Viscosities:

( )
( )
Where:
N = Avogadro’s number,
,
= a physical constant that is the quantum of action in quantum mechanics
= describes the relationship between energy and frequency
V = molar volume

Liquid viscosities. A centipoise is equal to 0.001 kg/m-sec.

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Coordinates for Use in Nomograph

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Gas viscosities. A centipoise is equal to 0.001 kg/m- sec.

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Coordinates for Use in Nomograph

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Empirical Equations for the estimation of Pure Liquid Thermal Conductivities:
̂ ⁄
( ) ( )
̂
Where:

√ ( )

̂
̂

*Note: For empirical equations for the estimation of Viscosities and Thermal Conductivities for mixtures of liquid, it
is recommended that the pseudocritical method be used where possible with liquid regions of the previous Figures.

Empirical Equations for the estimation of Pure Liquid Diffusivities:

Method 1
( )
Where:

Method 2 (For Dilute binary solutions only)

( ) ⁄
̂
( )
( )
Where:
̂

Association Parameters
Solvent System
Water 2.6
Methanol 1.9
Ethanol 1.5
Unassociated Solvents
1.0
(ether,benzene, etc)

**Note: Diffusivities for solid system are given from appendix section of various books.

Sample Problems:
1. Compare viscosity values for liquid water at as determined by:
a. The Eyring equation (the is 3.759 x J/kg mole)
b. Using the viscosity nomograph

Solution:
a. Using Eyring Equation

Lecture by: Engr. Renato C. Ong 20

 ( )
( )
( )
[ ]
( )( )
( )( )

b. Using the Nomograph,

Coordinate of water (10.2, 13)
Connecting with the coordinate point at the Nomograph
Viscosity reading,

*Note: Actual experimental viscosity value is 4.67x pascal sec, this clearly indicates that the Eyring
Method is only an approximation

2. Estimate the thermal conductivity of liquid carbon tetrachloride (CC1 4) at 20°C and atmospheric pressure if
( )

Solution:
̂ ⁄
Using ( ̂) ( )

( ) ( )

( )
( )
( )( )

Assume: ( )

√ ( ) √( )( )

( )( )
⁄
⁄
̂
( ) ( ) ( )( )
̂

*Note: The experimental value is 0.103 J/m-sec- oK. This gives a percent error of 8.74 %.

3. What is the diffusivity for a dilute solution of acetic acid in water at 12.5 oC? The density of acetic acid at its
normal boiling point is 0.937 g/cm3. The viscosity of water at I2.5 oC is 1.22 cP.

Solution:
Using the Wilke-Chang Equation,

( ) ⁄
̂
( )
( )

Lecture by: Engr. Renato C. Ong 21

 ̂

Association Parameter fpr water = 2.6

( ) ⁄ [( )( )] ( )

(̂ ) ( )

Lecture by: Engr. Renato C. Ong 22