Topic 2: Molecular

Transport
DR. MANAL ISMAIL
DR.NUR TANTIYANI ALI OTHMAN
Mass Transfer KKPK2342
Program Kejuruteraan Kimia,
UKM

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Transport Phenomena Laws
• Transport phenomena laws are developed based on the observation of the
Molecular Diffusion and Convection Mass Transfer :

The basic mass

transfer law Mass Transfer:

Fick’s Law

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General Equation : Overall Mass Balance

(Rate of property In) + (Rate of Generation of property) =

(Rate of property Out) + (Rate of accumulation of property)

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Mass Transfer
• General balance
 Rate of   Rate of   Rate of   Rate of 
Mass   Mass   Mass   Mass 
       
 IN  GENERATION  OUT   ACCUMULATI ON 

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Molecule arrangement

solid Liquid Gas

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Mass Transfer

• Mass transfer (or mass transport)

• Occurs when a component in a mixture migrates in the
same phase or phase to phase because of a difference in
concentration between two points.
• Examples
• Sugar dissolves and diffuses in a cup of tea or coffee
• Water evaporates from a container into the still air.

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Flux relative to the total molar flux, NA
The component may be transferred simultaneously by
2 different mechanisms:

 Concentration difference as described by Fick’s law

 Convective mass transfer due to density difference

that causes the concentration gradient

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Mass Transfer

• Mass transport mechanisms:

• Molecular Diffusion

• Convective mass transfer

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Diffusion

(2)
A
Mass transfer occurs when there are
B 2 or more components.
B
B
B B Mass transfer in terms of molecular
B motion is known as molecular
B B diffusion.
B
B

A
(1)

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Diffusion

The component diffuses from

a high concentration region to
the low concentration region

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Diffusion

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Fick’s Law
• The driving force for the mass transfer in the diffusion process is the
concentration gradient (or concentration difference).

• Mass transfer across a surface area with respect to time is known as

mass flux.

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Fick’s Law
• Example: Mass transfer of binary mixture of
molecule A diffusing through B molecules by
means of diffusion in the x-direction based on
the Fick’s law can be written as:
dC A dx A
J A,x  D AB ; J A , x  CD AB
dx dx

• DAB is the diffusion coefficient and subscript

“AB” represents the diffusion of molecule A
through molecules B

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Fick’s Law
• Mass flux

d A d A
jA , x  D AB ; j A , x  D AB
dx dx

• Ref: Welty et al.

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Diffusion Coefficient
• Fick’s law depends on the mass transfer coefficient or the diffusion
coefficient, DAB

• DAB, gives a correlation between the mass flux and the concentration
gradient.

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Diffusion coefficient

substance DAB values (cm2 s-1)

Gas 0.1 - 1.0

Liquid 1x10-7 - 1x10-5

Solid 1x10-12 - 1x10-7

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Diffusion coefficient
substance Pressure Temperature

Gas  

Liquid 
-

Solid 
-

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 Diffusion Coefficient (gas)
 1 
3 1
 T    
  MA MB   Chapman-Enskog
DAB  0.0018583  
 p AB
2
 D , AB 
kinetic theory

 
 

• where DAB (cm2/s),

• T (K), p (atm),
• AB Lennard-Jones collision parameter(Angstrom)
• AB, collision integral
• MA , MB relative molecular masses, g mol-1

* Please refer to the Lennard-Jones parameter table in Welty et al. and Bird et al.

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 Diffusion coefficient (gas)
• Fuller-Schettler-Giddings is a semi-empirical correlation with some
simplifications from the Chapman-Enskog correlation:

1/ 2
 1 1 
0.001T 1.75

M  M 

DAB   
 
A B

P  A    B 
1/ 3 1/ 3 2

A = The sum of structural volume increments of the molecular

species ,
P = atm
MA, MB = molecular weight A and B, g mol-1
DAB = units in cm2/s
This equations permits the DAB evaluation when reliable Lennard-
Jones parameters are unavailable.
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Diffusion coefficient (gas)
(Fuller-Schettler-Giddings correlation)

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 Equimolar Counterdiffusion in Gases

• For a binary gas mixture of A and B diffusing at steady state and at constant total
pressure, P, in order to achieve the concentration gradient, the partial pressure, pA1>pA2
and pB2>pB1
(see Fig.6.2-1 Geankoplis)

• For counterdiffusion:
P = pA1 + pB1 is equal to P = pA2 + pB2

dC A dC B
J A,x  D AB  J B, x  D BA
dx dx

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Equimolar counterdiffusion in Gases

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Flux relative to the total molar flux, NA
Binary system:

NA  M J AZ  x A (N A  N B )

dxA
N A  CD AB  xA ( N A  N B )
dz

Total flux of
Diffusion flux of A Convective flux
component A relative
relative to the fluid relative to the main
to the stationary
motion stationary point
point
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 Diffusion of A through stagnant,
nondiffusing B
 It is the case where one boundary at the end of the diffusion path
of A is impermeable (cannot pass through) to component B.
 Example : Gas A is insoluble in gas B.

 General equation for this case where NB = 0:

N A   CD AB
dxA
dz

CA
C
N A  0 Equation 6.2-16
Geankoplis

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 Diffusion of A through stagnant,
nondiffusing B
 Substituting C = P/RT, pA = xAP and CA/C = pA/P into equation 6.2-16
yield:
DAB d p A pA
NA    NA
RT dz P
Integrating the equation with respect to x ( taking limits x1 to x2) and pA
(limits pA1 to pA2), the equation 6.2-16 becomes:

DAB P P  p A2
NA  ln
RT  z 2  z1  P  p A1

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 Diffusion of A through stagnant,
nondiffusing B
• Total Pressure P :
P = pA1 + pB1 is equal to P = pA2 + pB2

rearrange that gives:

pB1 = P – pA1 and pB2 = P – pA2

Taking log mean value pBM for pB1 and pB2 :

p B 2  p B1 p A1  p A 2
p BM  
lnp B 2 p B1  lnP  p A 2  P  p A1 

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 Diffusion of A through stagnant,
nondiffusing B

• The general equation for diffusion of A through nondiffusing B is:

Equation 6.2-22 Geankoplis

NA 
DAB P
 p A1  p A 2 
RT z1  x2  pBM

• Please study Eg. 6.2-2 on Diffusion of Water through non-stagnant, non-diffusing Air

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Fick’s Law
Flux
dCA
v J AZ   DAB Flux relative to the volumetric
dz average velocity

Flux relative to the molar

dxA
M J AZ  CD AB average velocity
dz
d A
m J AZ   DAB
Flux relative to the mass
average velocity
dz

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Fick’s law
Mass average velocity Molar average velocity Volumetric average
velocity

i
n

 c
n
 v   i i (
n

 i i i i )
m  i 1 M  i 1
n
i 1 Mi
c
n


i 1
i
i 1
i

vi = Velocity of the species i relative to the fixed coordinate

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Comparison of Flux
Phenomena Law Mathematical Coefficient
Equation
Newton’s Law of d vx  
 yx   
Viscosity dy 
Fourier’s Law dT k k
q y  k
''

dy C P
Fick’s Law dx A DAB DAB
N A, x  CD AB
dx

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Example 1
• Ammonia gas (A) is diffusing through a uniform tube 0.10m long (Δx = 0.10) containing N2 gas (B)
at 1.0132 x 105 Pa total pressure and 298 K at an equimolar counterdiffusion. The partial
pressures of A are:
pA1 = 1.013 x 104 Pa ; pA2 = 0.507 x 104 Pa

The diffusivity DAB = 2.30 x 10-5 m2 s-1.

(a) Calculate the flux JA,x at steady state (Ans = 4.70 x 10-4 mol m-2 s-1)
(b) Repeat for JB, x (Ans = - 4.70 x 10-4 mol m-2 s-1 , the negative sign means the flux JB,x goes from
point 2 to point 1 )

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Example 2
• Normal butanol (A) is diffusing through air (B) at 1 atm abs. Using the Fuller et al.
method, estimate the diffusivity , D AB at temperature 0 o C.

Ans = 7. 73 × 10 -6 m 2 s -1

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