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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

Objectives of the slides that follow:

Mathematical modelling of steady-state


one dimensional diffusion + convection

Diffusion of gases A & B plus convection

JA is the diffusive flux described by Ficks law, and we have


already studied about it.

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

Where vA is the overall velocity of A.

Diffusion of gases A & B plus convection

VA
VAD

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

Diffusion of gases A & B plus convection


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

Let us introduce partial pressure pA into (10b):


nA
pA
(12a)
CA =
=
V
RT

nT
V

CT =

P
=
RT

(12b)

Total number of moles

Total pressure

Using (12a) and (12b), equation (10b) can be written as


NA = -

DAB
RT

dpA
dz

pA (N + N )
A
B
+
P

(..13)

Diffusion of gases A & B plus convection:

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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Objectives of the slides that follow:

Diffusion of A through stagnant, nondiffusing B

A diffusing through stagnant, non-diffusing B

Air (B)

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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.

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Substituting NB = 0 in equation (15), we get


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 )]

Equation (18) is therefore written as follows:


NA =

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

(.19)

15

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

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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 )

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

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

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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

(0.250x10-4 m2/s)(1x1.01325x105 Pa)(0.0231 - 0) atm

(8314 J/kmol.K) (293 K) (0.1524 m) (0.988 atm)

= 1.595 x 10-7 kmol/m2.s

19

Objectives of the slides that follow:

Diffusion through a varying crosssectional area

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.

Diffusion through a sphere to a surrounding medium.

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

Since r2 >> r1, 1/r2 0. Substituting PBM into Eq. (25),

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

Dr. TVN. Padmesh

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

Objectives of the slides that follow:

Diffusivities / Diffusion coefficients for


gases

Diffusion coefficients for Gases


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

(a) Experimental diffusivity data

(b) Estimation of Gas-Phase Diffusion


Coefficients
Observations from the kinetic theory of gases:
Observation

Explanation

DAB a T3/2

As T, molecules move faster

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

As MA or MB, heavier molecules move slower

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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