Mass Transport

Steven A. Jones
BIEN 501
Friday, April 13, 2007

Louisiana Tech University Slide 1

Ruston, LA 71272
 Mass Transport

Major Learning Objectives:

1. Obtain the differential equations for mass
transfer.
2. Compare and contrast these equations
with heat transfer equations.
3. Apply the equations to nitric oxide
transport in the body.

Louisiana Tech University Slide 2

Ruston, LA 71272
 Mass Transport

Minor Learning Objectives:

1. Review Continuum.
2. Describe various definitions of concentration.
3. Write down the equation for conservation of mass for a
single species and a multi-component system.
4. Obtain the solution for 1-dimensional diffusion of a
substance with a linear reaction.
5. Linearize a nonlinear partial differential equation.
6. Apply the Laplace transform to a partial differential
equation.

Louisiana Tech University Slide 3

Ruston, LA 71272
 Continuum Concept
Properties are averaged over small regions of space.

The number of blue circles moving left is larger

than the number of blue circles moving right.
We think of concentration as being a point value,
but it is averaged over space.
Louisiana Tech University Slide 4
Ruston, LA 71272
 Time Derivative
The Eulerian time derivative still applies.

dB B
  v  B 
dt t

1. For mass transport, B is usually a concentration.

2. There are various ways to refer to concentration.

Louisiana Tech University Slide 5

Ruston, LA 71272
 Expressions for Concentration
Mass per Unit Volume.   A  g/cm3
Moles per Unit Volume. c A  moles/cm3
Example: NO has molecular weight of 30 (one nitrogen,
molecular weight 14 g/mole, one oxygen, molecular
weight 16 g/mole). A 1 mg/liter solution of NO has a
molar concentration of 1 mg/liter / 30 mg/mmole, or 33
nmole/liter.
Mass fraction.   A is the mass of species A divided by the
total mass of all species.
Molar fraction x(A) is the number of moles of species A
divided by the total number of moles of all species.
Louisiana Tech University Slide 6
Ruston, LA 71272
 Expressions for Concentration

To convert mass concentration to molar concentration, it is

necessary to divide by the molar mass of the species.
Two species may have the same mass concentration, but
vastly different molar concentrations (e.g. NO vs. a large
protein. If they had the same mass concentration, the
molar concentration of the protein would be much smaller
than the molar concentration of the NO).
If we have a pure solution of something, then the mass
fraction is 1.
Similarly, molar fraction may be vastly different from the
mass fraction.
Louisiana Tech University Slide 7
Ruston, LA 71272
 Properties of a Multicomponent
Mixture

Density:      A
A1

1 N N  A N

Mass-Averaged Velocity: v      A v  A  v  A    A v  A
A1 A1  A1

Molar-Averaged Velocity: v   x A  v  A 
o

A1

Rate of reaction (rate of production): r A  g/(cm3-s)

Louisiana Tech University Slide 8

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 Density of the System
N

To convince yourself that      A

A1

Consider the following thought experiment. Add 1 liter of

water to 1 liter of another liquid with density 1.2 g/cm3.
Although the density of water is 1 g/cm3, the density of
water in the mixture is (1 liter x 1 g/cm3)/(2 liters). I.e., in
the mixture, there is 0.5 g/cm3 of water. Similarly, there is
0.6 g/cm3 of the other liquid. The density of the mixture is
then 0.5 g/cm3 + 0.6 g/cm3, or 1.1 g/cm3, as expected.
It is important to remember that (A) is the density in the
mixture (0.5 g/cm3 for water), not the density of the
substance itself (1 g/cm3).
Louisiana Tech University Slide 9
Ruston, LA 71272
 Density

+ =

1 Liter 1 Liter 2 Liter

Mass 1 Kg Mass 1.2 Kg Mass 2.2 Kg

=1 Kg/L =1.2 Kg/L =1.1 Kg/L

a =1 Kg/(2 L) = 0.5 Kg/L
b =1.2 Kg/(2 L) = 0.6 Kg/L
 = a + b

Louisiana Tech University Slide 10

Ruston, LA 71272
 Conservation of Mass
In terms of mass-averaged velocity, for a single species:
  A c A
     A v  A   r A    c A v  A   
r A
t t M  A

  A
if n  A     A  v  A     n  A   r A 
t
For a the entire system:
 N
The last equality is a result
    v    r A   0
t A1 of conservation of mass.
Consequence of the individual It would not hold for molar
mass balances, not an concentration.
independent equation.
Louisiana Tech University Slide 11
Ruston, LA 71272
 Species Velocity
c A
   c A v  A   
r A
In t M  A

The difference between species velocity and mass

averaged velocity adds an increased level of complexity.
Consider two species, where one is dominant.
N
v    A v  A  1 v 1   2 v  2
A1

 
 1 v 1  1  1 v  2  v 1 because  2  0
v 1  1 v 1 v (1) 1  1 
 v 2    v 1
1    
1
1  1  I.e. velocity of both species
will be about the same.
Louisiana Tech University Slide 12
Ruston, LA 71272
 Mass Flux
With respect to a fixed coordinate system.

With respect to a mass-averaged velocity.

j A     A  v  A   v  Tells us how rapidly

substance A is moving
Which leads to with respect to the
other substances.
  A
     A v     j A  r A
t
  A
Compare to slide 11:      A v  A   r A
t

Louisiana Tech University Slide 13

Ruston, LA 71272
 Subtle Point
If I have the following:

z=0
Will there ever be any NO
upstream of z=0?

Louisiana Tech University Slide 14

Ruston, LA 71272
 Fick’s Law of Diffusion
  A
In      A v     j A  r A
t

Use Fick’s Law j A   D o

 AB  A

  A
To get      A v     DoAB   A   r A
t

Louisiana Tech University Slide 15

Ruston, LA 71272
 Fick’s Law of Diffusion
If density and diffusion coefficient are constant:

  A
     A v     D o
 AB    A   r A
t
 
     A v   DoAB  2  A  r A
Becomes  A
t
Which is like the equation for heat transfer. In many
cases, the mass-averaged velocity will be uncoupled
from the mass transport, so the equations can be
solved independently of one another.
Louisiana Tech University Slide 16
Ruston, LA 71272
 Sources of Nonlinearity
1. Reaction rates may be nonlinear. I.e., reaction
may depend on higher powers of concentration.

r A  k 2
 A

2. When concentrations are high, changes in mass

fractions may affect the overall density. E.g. for a
2-component system:
 B 
   
 B    x B    1   A   
1   A

Louisiana Tech University Slide 17

Ruston, LA 71272
 Fick’s Law of Diffusion
Then:

 A  1  

     A v       A
D AB  A   r A
o

t  1 
 
 A  


Louisiana Tech University Slide 18

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 Example – Transport of NO
Consider the diffusion of Nitric Oxide from a monolayer
of platelets:

c NO 0, z   0

2nd order reaction depends on O2
NO  O2  ONOO 
concentration.
NO

J NO t,0  J 0 ut  (where J0 is constant)

Louisiana Tech University Slide 19

Ruston, LA 71272
 Example – Transport of NO
The reaction between NO and O2- is nonlinear in that it is
the product of the NO concentration and the O2-
concentration, and as NO is consumed, so is O2-.

 
rA  k1 O2 NO

However, if we assume that the O2- concentration is

constant, then we can “linearize” the equation such that:

 
k  k1 O2  rA  k NO

Louisiana Tech University Slide 20

Ruston, LA 71272
 Transport of NO
Modeling Assumptions

1. Platelets adhere in a monolayer along a wall placed at z=0 and

simultaneously begin to produce NO with constant flux in the positive
z – direction.
2. Diffusion obeys Fick’s law.
3. All densities and diffusion coefficients are constant.
4. The wall is infinite in width and height so that diffusion occurs in the
z – direction only.
5. No convection.
6. Consumption of NO by O2- follows a first order reaction (not really).
7. Constant flux of NO from the monolayer.
8. Initial NO concentration is zero.
9. Concentration of NO at infinity is zero.

Louisiana Tech University Slide 21

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 Fick’s Law of Diffusion
General Law:

J  Dc
One-dimensional Diffusion:

c
J  D
z

Louisiana Tech University Slide 22

Ruston, LA 71272
 Fick’s Law of Diffusion
Conservation of Mass:

C A (t , z )  2 C A (t , z )
 D AB  kCA (t , z )
t z 2

Rate of increase r A 
Diffusive transport

Louisiana Tech University Slide 23

Ruston, LA 71272
 Initial and Boundary Conditions
1. Initial concentration of NO throughout the medium is zero:

C (0, z )  0

2. The concentration must go to zero for large values of z.

C (t , )  0
3. The flux of NO through the surface at z=0 is constant and
equal to J0 for all t > 0, i.e.:
C (t ,0)
 D AB  J 0 u t  at z  0.
z
Where u(t) is the unit step function.

Louisiana Tech University Slide 24

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 Laplace Transform Property

Recall that:

 df t 
L   sL  f t   f 0 
 dt 
We will use L(s,z) to represent the Laplace transform
of CA(t,z).

Louisiana Tech University Slide 25

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Solution to the Governing Equation
Use the Laplace transform to transform the time
variable in the governing equations and boundary
conditions. The governing PDE transforms from:

C A (t , z )  2 C A (t , z )
 D AB  kCA (t , z )
t z 2

To: sL( s, z)  C(0, z)  DAB L( s, z )  kL( s, z)

sk
Or: L( s, z )    L( s, z )  0 d 2 Ls, z 
 DAB  L( s, z ) 
dz 2
Louisiana Tech University Slide 26
Ruston, LA 71272
 Transformed BC’s
1. Initial condition was already used when we transformed
the equation.

2. The concentration must go to zero for large values of z.

C(t, )  0  Ls,   0
3. The flux of NO through the surface at z=0 is constant and
equal to J0 for all t > 0, i.e.:

C (t ,0) Ls,0
 J 0 ut   D AB
J0
 D AB 
z z s
or Ls,0  
J0
D AB s

Louisiana Tech University Slide 27

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 Match Boundary Conditions
 sk   sk 
With: L( s, z )  A exp   z   B exp  z
 


 D AB   D AB 

The 2nd term will go to infinity for infinite z, so B=0.

 sk 
Thus: 
L( s, z )  A exp   z 
D AB 
 
To apply constant flux, we must differentiate:
s k
sk z
J0 J0
L( s; z )   A   A
DAB
e
DAB DAB s s DAB s  k
z 0

Louisiana Tech University Slide 28

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 Invert the Laplace Transform
The solution for the Laplace transform is:
sk
z
J0
L( s, z ) 
D AB
e
s DAB s  k

So the solution for the concentration is the inverse

Laplace transform:
  z sk 
J0 
1 e
D AB

C A (t , z )  L  
D AB s s  k 
 
Louisiana Tech University Slide 29
Ruston, LA 71272
 Invert the Laplace Transform
In the Laplace transform, division by powers of s is the
same as integration in the time domain from 0 to t. The
result of this application is:

  z s k    z s k 
 DAB
 t
 DAB

C A t , z  
J0 e K e
0  s  k
1 1
L   L  du
D AB s s  k  D AB  
   

Louisiana Tech University Slide 30

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 Invert the Laplace Transform
Now we can use the time shifting property of Laplace
transforms:
L 1
F ( s  k )  e ktL 1 F ( s)
 z s 
t
 DAB

C A t , z  
J0 e
0
ku 1
e L   du
D AB  s 
 

Louisiana Tech University Slide 31

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 Invert the Laplace Transform
Compare the form of the inverse Laplace transform in:
 z s 
t
 DAB

C A t , z  
J0 e
0
ku 1
e L   du
D AB  s 
 
To the following form from a table of Laplace transforms:

a2

1
 e a s 
e 4t
with a 
z
L  
 s  t D AB

Louisiana Tech University Slide 32

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 Invert the Laplace Transform
Then:
 z s  
z2

 e DAB
 e 4 DABt
L1  
 s  t
 
So:
 z2 
 ku  

t  4 D u
AB 
J0 e
C A (t , z ) 
D AB 
0 u
du

Louisiana Tech University Slide 33

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 Example Concentration Profiles

0.006
5s
0.005
Increasing time
0.004
uM

0.003

0.002

0.001

0
1 10
3
0.1 1 10 100
um

Louisiana Tech University Slide 34

Ruston, LA 71272