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## EKB 2113 MASS

TRANSFER
Lecture 3 Diffusion in gases

Overview
Diffusion of gases A & B + convection
Diffusion of A through stagnant, non- diffusing B
Diffusion through a varying cross-sectional area
Diffusivities of gases

## Mathematical modelling of steady-state

one dimensional diffusion + convection

## Ficks Law of diffusion

J A DAB

dC A
dz

.1

The molar rate of transfer of A, per unit area due to molecular motion is
given by:
dx

J A* C.DAB

dz

## Where, C is total concentration of(A and B) kmol/m3

xA is the mole fraction of A in the mixture

.2

## Diffusion of gases A & B plus convection

We have considered Ficks law for diffusion in a stationary fluid; i.e. there has been no net
movement or convective flow of the binary mixture of A and B.
The flux NA can be converted to velocity of diffusion of A by:

m kgmolA
J * A (kgmolA / s.m 2 ) v Ad C A

3
s
m

.3

## where vAD is the diffusion velocity of A in m/s.

Now consider that the whole liquid is moving in bulk (or convective flow).

The average molecular velocity of the whole fluid relative to a stationary point is
vM (m/s).
Expressed mathematically, the overall velocity of A relative to a stationary point
is the sum of the diffusion velocity and the convective velocity:

v A v Ad vM

.4

VA

VM

v A v Ad vM

## Multiply the above equation by CA

v Ac A v Ad c A vM c A

.5

## CA vA,total = CA vA,diffusion + CA vconvective

Each of the three terms represents a flux.
The first term is NAT (kmol A / s.m2), -Total flux of A relative to a stationary point.
The second term is NA is the diffusion flux
The third term is the convective flux of A.

N AT J

vM c A

.6

## Diffusion of gases A & B plus convection

Let NT be the total convective flux of the whole stream relative to a stationary point.

NT cvM N AT N BT
Then solve it for VM

N AT N BT
vM
C

## Substituting the above equation into

N AT

.8

N AT J * A vM c A

CA
N AT N BT
J A
C
*

.7

We get

.9

Since

J C.DAB
*
A

## is Ficks law, then:

N AT C.DAB

dx A
dz

dx A C A
N AT N BT .10a

dz
C
or

N AT DAB

dC A C A
N AT N BT

dz
C

.10b

Diffusion plus convection when the flux NA is used relative to a stationary point.
for Component B

dxB C B
N AT N BT
N BT C.DBA

dz
C
dC B C B
N AT N BT
N BT DBA

dz
C

.11a

.11b

nA
pA
(12a)
CA =
=
V
RT

nT
V

CT =

P
=
RT

(12b)

Total pressure

NA = -

DAB
RT

dpA
dz

pA (N + N )
A
B
+
P

(..13)

10

## Summary equations for (one dimensional) flow in z direction

In terms of concentration of A:
NA = -DAB dCA
dz

CA (N + N )
A
B
+
CT

(..14)

## In terms of partial pressures (using pA = CART and P = CTRT):

DAB dpA
pA (N + N )
(.15)
A
B
NA = +
RT
dz
P
In terms of molar fraction of A (using xA = CA /CT):
NA = -CT DAB dxA + xA (NA + NB)
dz

(.16)

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Air (B)

12

## Examples: evaporation of pure liquid

benzene (A) at the bottom of a
narrow tube where large amount of
inert or non-diffusing air (B) is
passed over the top.
The benzene vapour (A) diffuses
through air (B) in the tube.

z2 z1

## The boundary at the liquid surface

(at point 1) is impermeable to air (B),
since air is insoluble in benzene.

1
Liquid
Benzene
(A)

## Hence, B cannot diffuse into or

away from the surface.
Therefore, NB = 0
At point 2, the partial pressure of air,
pA2 = 0, since a large volume of air
is passing by.

13

NA = -

DAB
RT

dpA
dz

pA (N + 0)
A
+
P

(.17)

## Rearranging and integrating

NA (1 - pA/P) = -

DAB
RT

z2

N dz =
A

z1

NA =

dpA
dz
pA2

DAB
RT

pA1

dpA
(1 - pA/P)

DAB P
P - pA2
ln
RT(z2 z1)
P pA1

(.18)

14

## Introduce the log mean value of inert B as follows:

Since P = PA1 + PB1 = PA2 + PB2;
PB1 = P PA1, and PB2 = P PA2, which is defined as follows:

pB,LM =

(pB2 pB1 )
ln(pB2 /pB1 )

(P pA2 ) (P pA1 )
ln[(P - pA2 )/ (P - pA1 )]

(pA1 pA2 )
ln[(P - pA2 )/ (P - pA1 )]

NA =

DAB P
(pA1 - pA2 )
RT(z2 z1) pB,LM

(.19)

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## Using xA = CA /CT, pA = CART and P = CTRT,

equation (18) can be converted to the following:
DAB CT ln 1 - xA2
(.20)
NA =
(z2 z1)
1 xA1
Introduce the log mean value of inert B as follows:
xB,LM =
=

(xB2 xB1 )

ln(xB2 /xB1 )

(1 xA2 ) (1 xA1 )

## ln[(1 - xA2 )/ (1 - xA1 )]

(xA1 xA2 )
ln[(1 - xA2 )/ (1 - xA1 )]

## Therefore, equation (20) becomes the following:

DAB CT
NA = (xA1 - xA2 )
(z2 z1) xB,LM

(.21)

16

Example:
Diffusion of water through stagnant, non-diffusing air:
Water in the bottom of a narrow metal tube is held at a constant
temperature of 293 K. The total pressure of air (assumed to be dry)
is 1 atm and the temperature is 293 K. Water evaporates and
diffuses through the air in the tube, and the diffusion path is 0.1524
m long. Calculate the rate of evaporation at steady state. The
diffusivity of water vapour at 1 atm and 293 K is 0.250 x 10-4 m2/s.
Assume that the vapour pressure of water at 293 K is 0.0231 atm.
Answer: 1.595 x 10-7 kmol/m2.s

17

## Solution: The set-up of Example is shown in the

figure. Assuming steady state,
DAB P
NA =
(pA1 - pA2 )
RT(z2 z1) pB,LM

Air (B)

where

pB,LM =

z2 z1

(pA1 pA2 )

## Data provided are the following:

10-4

m2/s;

DAB = 0.250 x
P = 1 atm; T = 293 K;
Water (A)
z2 z1 = 0.1524 m;
pA1 = 0.0231 atm (saturated vapour pressure);
pA2 = 0 atm (water vapour is carried away by air at point 2)
R = 8314.34 m3.Pa/kg mol.K

18

## Substituting the data provided in the equations

given, we get the following:
pB,LM =

NA =

(0.0231 0 )

ln[(1 - 0 )/ (1 0.0231 )]

= 0.988 atm

19

20

## Diffusion through a varying cross-sectional Area

At steady state we have considered NAT or JA or NA as constants.
In these cases the cross-sectional area A (m2) through which the diffusion has
been constant with varying distance z.
In some situations (like a sphere) the area A may vary.
This situation appears often in cases as the evaporation of a drop of liquid,
the evaporation of a ball of naphthalene, and the diffusion of nutrients to a
spherical-like microorganism in a liquid.

21

In the below Fig we see a sphere of fixed radius r1 (m) in an infinite gas
medium. Component (A) at partial pressure pA1 at the surface is diffusing
into the surrounding stagnant medium (B), where pA2 = 0 at some large
distance away. Steady-state diffusion will be assumed.

## It is then convenient to define NAT as

N AT N AT

A
4r 2

N AT

NAT = kg.mol/s

.22

Since this is a case of A diffusing through stagnant B, NAT will be equated to Eq. (22),
giving:

N AT

N AT
DAB
dPA

2
4r
RT 1 PA P dr

.23

Note that dr was substituted for dz. Rearranging and integrating between r1
and r2 (at a point a large distance away),

N AT
4

r2

r1

N AT
4

dr
DAB

2
r
RT

PA1

dPA
P 1 PA P
A2

1 1 DAB P P PA2

ln
RT
P PA1
r1 r2

.24

.25

23

N AT
4

1 1 DAB P P PA2

ln
RT
P PA1
r1 r2

## P PA2 PA1 PA2

ln
PBM
P PA1
N AT
DAB P PA1 PA2
N AT 1
2
4r1
RTr1
PBM

.26

. 27

This equation can be simplified further. If PA1 is small compared to P (a dilute gas
phase), PBM P.
Also, setting 2r1 = D1 diameter and CA1 = PA1/RT, we obtain

## DAB P PA1 PA2

N AT 1
D1 PBM
RT
2

24

2 DAB
N AT 1
PA1 PA2
RTD1

2 DAB
N AT 1
C A1 C A2
r1

. 28

. 29

This equation can also be used for liquids, where DAB is the diffusivity of A in the
liquid.

10/3/2016

## Example on Diffusion through a varying cross

sectional area
Q: A sphere of naphthalene having a radius of 2.0mm
is suspended in a large volume of still air at 318 K and
1.01325 x 105 Pa (1 atm). The surface temperature of
the naphthalene can be assumed to be 318 K and its
vapor pressure at 318 K is 0.555 mm Hg. The DAB of
naphthalene is air at 318 K is 6.92 x 10-6 m2/s.
Calculate the rate of evaporation of naphthalene from
the surface.

Solution:
DAB = 6.92 x 10-6 m2/s
P = 1 atm = 1.01325 x 105 Pa
PA1 = 0.555 mm Hg = 74.0 Pa
PA2 = 0
R = 8314.34 m3.Pa/kg mol.K
PB1 = P PA1=1.01251 x 105 Pa
PB2 = P PA2=1.01325 x 105 Pa
Since the PB1 and PB2 are close to each other,

PBM

PB 2 PB1

1.0129 105 Pa
2

DAB P PA1 PA 2
N AT 1
9.68 10 8 kgmolA / s.m 2
RTr1
PBM

27

gases

## Diffusion coefficients for Gases

The diffusion coefficients for gases can
be obtained by :
a) Experimental diffusivity data
b) Estimation using different correlation

## (b) Estimation of Gas-Phase Diffusion

Coefficients
Observations from the kinetic theory of gases:
Observation

Explanation

DAB a T3/2

DAB a (1/P)

## As P, molecules become more crowded &

increased collisions slow the movement down

DAB a (1/MA)1/2
DAB a (1/MB)1/2

## 1. Lennard-Jones Correlation (a binary

gas pair of A & B)
DAB

1.8583 10 7 T

2
PW D , ABs AB

3
2

1
1

MA MB

Units:
DAB = Diffusion coefficient (m2/s)
T = Temperature (K)
P = Absolute Pressure (atm)
MA, MB = Molecular weights of A and B, respectively
sAB = Collision diameter () = (sA + sB)/2
WD,AB = Diffusive collision integral (dimensionless)
sAB and WD = Lennard-Jones (L-J) parameters

2. Fuller-Schettler-Giddings
Correlation
When L-J parameters are not available then use

this method:
1/ 2

1.00 x 10
D AB

P v A

1.75

1/ 3

1
1

MA MB

vB

1/ 3 2

## = Sum of the structural volume increments.

Diffusivity of Gases

Example
Calculate the diffusivity of Butanol (A)
gas in air (B) at 1 atm abs using the
Fuller et al. method.
a) 0oC
b) 26oC
Ans 7.73x10-6 and 9.05x10-6 m2/s

Ans:
MA (butanol) = 74.1 (C4H10O)
MB (air) = 29
= 4 16.5 + 10 1.98 + 1 5.48 = 91.28

= 20.1
1/ 2

1.00 x 10
DAB

P v A

1.75

1/ 3

1
1

MA MB

vB

1/ 3 2

Diffusivities of Gases

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