Dr. R.

Nagarajan
Professor
Dept of Chemical Engineering
IIT Madras

Advanced Transport Phenomena
Module 1 Lecture 1
Overview & Bulb Blackening Example
COURSE OUTLINE
This advanced course in Transport Phenomena deals
with the transport of:
Energy,
Mass, and
Momentum
in chemically reacting fluids.

The basic principles of these fields are here generalized
and reformulated so as to be able to deal with
chemically-reacting flow systems of current and future
Engineering interest.

Principles are developed and illustrated here for the
rational design of Engineering equipment
chemical reactor analysis,
separation processes,
multiphase transport, etc.

Emphasis is placed on the use of fundamental laws, and
on a judicious blend of experimental, analytical and
numerical methods to develop:
required understanding, and
necessary mathematical models
for solving Engineering problems involving transport
processes.

COURSE OUTLINE CONTD
CONTENTS
Introduction:
Examples; Types/Uses of Control
Volumes; Notion of Conservation Principles and
Constitutive Laws; Illustrations of Use
Conservation Principles:
Mass, Momentum, Energy,
Entropy; Alternative Forms; statement of Assumptions
Constitutive Laws:
Diffusion Flux Laws/
Coefficients, general constraints; Momentum/ Energy/
Mass Diffusion Laws; Multi-component mass diffusion;
Reaction rates, mechanisms, time-scales
Momentum Transport Mechanisms, Rates &
Coefficients in Chemically Reacting Flow Systems
(CRFS)
Energy Transport Mechanisms, Rates & Coefficients
in CRFS
Mass Transport Mechanisms, Rates & Coefficients in
CRFS
Analogies & Similitude Analyses with Application to
CRFS
Problem-Solving Techniques, Aids, Philosophy
CONTENTS CONTD
Textbook:
Transport Processes in Chemically Reacting Flow
Systems, Rosner, Daniel E., Dover 2000

References:
Chemically Reacting Flow: Theory and Practice,
Robert J. Kee, Michael E. Coltrin, Peter Glarborg,
Wiley, 2003
Transport Phenomena, R. Byron Bird, Warren E.
Stewart and Edwin N Lightfoot, 2nd Edition, Wiley,
2001
TEXTBOOKS AND REFERENCES
STUDY OF TRANSPORT PHENOMENA: WHY?
In the known universe, systems and surroundings co-
exist in dynamic equilibrium, from macro-scale to
molecular-scale.

The fundamental quantities of mass, momentum, energy
and entropy are constantly being generated and
consumed, and being exchanged between the system
and its surroundings

To characterize and quantify these exchange rates, we
need to study the underlying transport processes.

EXAMPLES


IMPORTANCE OF STUDYING TRANSPORT
PHENOMENA
BULB BLACKENING
INCANDESCENT LAMPS
Oldest known light source
e.g., candle, kerosene lamp, gas lights
High temperature achieved by chemical reaction
Light emitted by particles brought to incandescence

1879: Edison constructs carbon filament lamp
Filament electrically heated
Carbon evaporates at a high rate
Bulb blackens within days
CARBON FILAMENT LAMP
Tungsten FILAMENT LAMP
1906: Tungsten used first in vacuum lamps
Tungsten has lower melting point than carbon, but has a
vapor pressure lower than that of carbon by 5000X at
filament temperatures
Evaporation rate further reduced by operating filament in
gaseous atmosphere
e.g., nitrogen, inert gases
Tungsten FILAMENT IG BULB COMPONENTS

1. Outline of Glass bulb
2. Low pressure inert gas (argon,
neon, nitrogen)
3. Tungsten filament
4. Contact wire (goes out of stem)
5. Contact wire (goes into stem)
6. Support wires
7. Stem (glass mount)
8. Contact wire (goes out of stem)
9. Cap (sleeve)
10. Insulation
11. Electrical contact
HALOGEN CYCLE LAMPS
Conceived in order to bring evaporated Tungsten back to
filament
Suitable reactive environment provided
Tungsten depositing on bulb wall reacts with
halogen,
Forms a volatile Tungsten halide,
Circulates back through bulb, and
Decomposes to W and halogen near or at hot
filament
Perfect cycle results in absence of bulb-blackening,
infinite lifetime of filament
Till it breaks!
All current incandescent bulbs have the halogen cycle
XENON HALOGEN LAMP
BULB BLACKENING: TRANSPORT
PHENOMENA INVOLVED
Mass transfer:
Tungsten to bulb wall, Tungsten halide back to
filament
Heat transfer:
From hot filament to cold bulb wall, setting up a
temperature distribution
Momentum transfer:
Collision of evaporated Tungsten atoms with inert-gas
& halogen molecules
Entropy transfer:
As a result of chemical reactions that drive towards a
thermodynamic equilibrium
All are intricately coupled, and must be solved
simultaneously
Tungsten EVAPORATION PROCESS
Vapor pressure of Tungsten is given by:
(Elenbaas, 1972)


Simple model of halogen cycle:
W + X WX (low T)
WX W + X (high T)

Simplified condition for zero Tungsten flux:

2
10
44770
log ( / ) 12.81
W
p N m
T
=
( ),
( ),
'
W b
W
W f WX
p
D
where D s are Fick diffusivities
p D
=
HEAT-TRANSFER MODELING IN INERT
GAS INCANDESCENT LAMPS
Langmuir heat-conduction model:

where

and power-law heat conductivity

with boundary conditions:

Temperature distribution in annular geometry is given by:



where rs represent cylindrical radii.


( '') 0 div q

=
'' q grad T

=
(0.5 1) kT

= s s
( ) , ( )
f f b b
T r T T r T = =
( )
( )
1
1
1 1 1
( ) / ln ln
f
f b f
b f
r
r
T r T T T
r r

+
+ + +
(
| |
| |
= +
( |
|
|
( \ .
\ .

MASS-TRANSFER MODELING IN INERT
GAS INCANDESCENT LAMPS
Mass diffusion of Tungsten vapor is described by:


with


where





''
( ) 0
w
div j

=
( )
''
/
W W W W W IG
j D grad T grad T e e o

= +
W IG
mass density of inert gas
thermal diffusion coefficient

For the bulb geometry, the solution is found to be:

where A and B are constants evaluated by applying the bcs:



With this, mass loss of Tungsten wire per unit length may be
estimated.


2
( ) ' ' T A T B T
| o
e e
+
= = +
( )
( ) , ( ) 0
W f
W
f b
IG
IG
p T
m
T T
m
p
e e
| |
=
|
\ .
MASS-TRANSFER MODELING IN INERT
GAS INCANDESCENT LAMPS CONTD
MASS-TRANSFER MODELING IN HALOGEN
INCANDESCENT LAMPS: SPECIES VIEW

Equation to be satisfied by chemical species becomes:


with


where

and are Fick and thermal diffusion coefficients,
respectively, of species i

''
( )
i i
div j r

=
( )
''
/
i i i i i
j D grad T grad T e eo

= +
i
D
i
o
Assumption of local thermo-chemical equilibrium (LTCE)
leads to law of mass action:



where are number of atoms of type in compound

Resulting system of highly nonlinear PDEs are solved
numerically using a finite-difference procedure.

( ),
,
1
( , )
l i
l
v
m
i c i i
l
K T p e e
=
= [
MASS-TRANSFER MODELING IN HALOGEN
INCANDESCENT LAMPS: SPECIES VIEW
CONTD
( ), l i
v
l
i
For each element, we have:



where





''
( )
( ) 0
k
div j

=
( ) ( ) ( )
''
( ) ( )
[ / ]
k k k
k k
j D grad T grad T e e o

= +
MASS-TRANSFER MODELING INHALOGEN
INCANDESCENT LAMPS: ELEMENT VIEW
with element diffusivities being weighted sums of bearer
species diffusivities:




Element mass concentrations can be solved for as:


where A and B can be obtained by applying bcs
( ),
( ),
( ) ( )
( ), ( ) ( ),
k i i i i
i k i i
i
k k
k i i k k i i
i
D
D grad
D
grad D w
e e o
e e
o
e e e

= =

( ) ( )
2
' '
( ) ( ) ( )
( )
k k
k k k
T A T B T
| o
e
+
= +
MASS-TRANSFER MODELING IN HALOGEN
INCANDESCENT LAMPS: ELEMENT VIEW
CONTD

Radial diffusion flux of k
th
element is given by:



When this is equated to zero, we obtain the zero element
flux (i.e., no bulb blackening) condition:

' '
( )
0
k
j

( )
( ) ( )
' '
( ) ( )
/
k
k k
k k
d
dT
j D T
dr dr
e
e o

(
= +
(
(

MASS-TRANSFER MODELING IN HALOGEN
INCANDESCENT LAMPS: ELEMENT VIEW
CONTD
REMARKS
This case-study from everyday life is a classic illustration
of the interplay between various transport phenomena in
chemically-reactive environments.

A seemingly-complex problem can be greatly simplified
by identifying conserved and invariant quantities in such
systems, and focusing our analysis on such quantities.

In the next lecture, well review another illustration of
these principles.