Diffusion and MT Coefficient

BITS, PILANI K. K.
BIRLA GOA CAMPUS
Molecular Diffusion in
Fluids
-Dr.S.S.Baral
2/14/2017 BITS, PILANI K. K. BIRLA GOA 1

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Molecular Diffusion in Fluids
It is concerned with the movement of individual

molecules through a substance by virtue of their thermal
energy
The rate of diffusion
is very slow due to highly zig-zag travel path of
molecules
Net distance in a particular direction in a given time

is a small fraction of its actual path
Increases by T ( Molecular velocity increases)
Decreases by p(Reducing the collisions

between particles)
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Molecular Diffusion in Fluids
The phenomenon of molecular

diffusion ultimately leads to
completely uniform concentration
of substance throughout a solution
Ex: CuSO4 in water ( Blue
solution)

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Rate of Diffusion
It is described in terms of Molar Flux

(mol/ area time), area is measured in a
direction normal to the diffusion
Two ways to define the Flux
N Flux of a constituent relative to the
fixed location in space
J Flux of a constituent relative to the
average molar velocity of all
constituent
Ex: fisherman

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Rate of Diffusion
Ficks First Law Negative sign emphasizes that

diffusion occurs in the direction
of drop in concentration
C A x A
J A DAB cDAB
z z
Flux
Diffusivity or Concentrati
on Gradient
Diffusion
Coefficient Function of (T,P,C, Medium)
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Rate of Diffusion
2 kg
1 kg 1 kg Water + Ethanol
Water Ethanol of 50 wt %
(A) (B) concentration
Net mass movement to the right
If direction to the right is taken as positive
Flux NA relative to the fixed position P +ve
Flux NB relative to the fixed position P -ve
Net Flux (N) = NA + NB
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Rate of Diffusion
NA = N xA + JA
NA = (NA + NB) xA + JA
NB = (NA + NB) xB + JB
JA = - JB
NA - NB

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Steady State Molecular Diffusion in Fluids
at Rest And in Laminar Flow
c A
N A N A N B DAB
cA
c z
NA and NB constant (Steady
State)
DAB is constant
dc A 1
dz
N Ac c A N A N B cDAB
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On integration
and putting z = (z2-z1)
NA c A2

NA DABc N A N B c
NA ln
N A NB z NA

c A1
N A NB c

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Molecular Diffusion in Gases
cA p A
yA
c pt NA
y A2
NA DAB pt N A N B
NA ln
N A N B RTz NA
y A1
Catalytic Reaction N A NB
CH4 C + 2H2 NB = -2 NA
(A) (B) (NA / NA+NB ) = -1
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Steady State Diffusion of A through nondiffusing B

NB = 0,
p p
t
A t
p B2 NA
DAB pt
RTz p B , M

p A1 p A2
P
r pB
e
s p B1
s p B 2 p B1
u p A1 pA p B,M
r p B2
e ln

p A2 B1
p
z Distance, z
1 z 2

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Problem 1
Oxygen (A) is diffusing through carbon monoxide

(B) under steadystate conditions, with the
carbon monoxide nondiffusing. The total pressure
is 1 x 105 N/m2, and the temperature 0 C .The
partial pressure of the oxygen at two planes 2.0
mm apart is, respectively, 13 000and 6500 N/m2.
The diffusivity is 1.87 x 10-5 m2/s. Calculate the
rate of diffusion of oxygen in kmol/s through each
square meter of two planes.

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Solution of the Problem
5
DAB 1.87 10 m / s, 2 pt 10 N / m5 2
T 273K ;
R 8314 N.m / kmol.K , z 0.002 m ,
p B 2 p B1
p B,M
p A,1 13 10 ,
3
NA
DAB pt
RTz p B , M

p A1 p A2 p B2
ln

p A, 2 6500 , B1
p

93.5 87 103
pB , 2 10 6500

5
pB ,1 10 13 10
5 3
ln 93.5
93.5 10 , 3 87
87 10 , 3
90 200 N 2
m
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Contd
NA
DAB pt
RTz p B , M

p A1 p A2
(1.87 105 )(105 )(13 6.5)(103 )

8314(273)(0.002)(90.2 10 ) 3
5
2.97 10 kmole 2
m .s
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Steady State Diffusion
in multi component mixtures
Molecular Diffusion in Gases
NA
y A2
NA DAB pt N A N B
NA ln
N A N B RTz NA
y A1
N A NB
For multi component Mixtures
n
NA + NB is replaced by
DAB is replaced by Effective DA, m
N
i A
i

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n
N A y A Ni
Effective diffusivity
D A, m n
i A

1
yi N A y A N i
i A D A ,i
Where DA, i are the binary diffusivities
Special Case
All Ns except NA are zero
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1 yA
D A, m n
yi

i B D A ,i
1
D A, m n ,
yi

i B D A ,i
,
where y i mole fraction of
the component i on an A - free basis
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Problem 2
Recalculate the rate of diffusion of

oxygen (A) in Problem 1, assuming
that the no diffusing gas is a mixture
of methane (B) and hydrogen (C) in
the volume ratio 2:1.
The diffusivities are estimate to be
DO2 H 2 6.99 10 5 , DO 2CH 4 1.86 x 10 5 m 2 / s.

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Solution 2
DAm pt
p t 10 N / m
5 2
NA p A1 p A2 T 273K ;
RTz p i ,M z 0.002 m ,
p A,1 13 10 3 , p A, 2 6500 , R 8314 N.m / kmol.K ,
pb , 2 105 6500
pb ,1 10 13 10
5 3
93.5 87 103 93.5 103 ,

87 103 ,
p B,M
p B , 2 p B ,1
p B,2

ln 93.5
87

ln
p 90 200 m 2
N
B ,1
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D A, m
1 yB 2 / 2 1 0.067,
yB / DAB yC / DA,C
yc 1 0.667 0.333,
1

0.667 / 1.86 10 5

0.333 / 6.99 10 5

5
2.46 10 m / sec 2
NA
2.46 10 13000 6500
5
3.91 10 5 2
kmol / m .s
83142730.00290 200
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Contd

Steady State Equimolal counter diffusion
DAB
NA = -NB = const NA p A1 p A 2
NA RTz
y A2
NA DAB pt N A N B p p
NA ln P t t
N A N B RTz NA r
y Ae1 p A1 p B2
N A NB s pA pB
s
u
r
N A N A N B
p A DAB d p A e p B1 p A2

pt RT dz z Distance, z
1 z 2

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Diffusivity of Gases
Diffusivites of Gases at 1 atm
System Temp, C Diffusivity, m2/sec x 105

H2 CH4 0 6.25
O2 N2 0 1.81
CO O2 0 1.85
CO2 O2 0 1.39
Air NH3 0 1.98
Air H2O 25.9 2.58
Air Ethanol 0 1.02
Air Aniline 25.9 0.74
59.0 0.90
Air Toluene 25.9 0.86
22
59.0 0.92
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Estimation of Diffusivity of Gases
Based on kinetic theory of

Gases
1 1 3
1 1
4

10 1.0894 0.249 T 2

MA MB MA MB
DAB
2 kT
pt rAB f
AB
Where,
rAB Molecular Separation at collision, nm = (rA + rB)
/2.0
AB energy of molecular attraction = (A B )0.5
k Boltzmanns Constant
f Collision Function
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Estimation of Diffusivity of Gases
Empirical correlations are also available to calculate the values of r and
1
r 1.18 3

1.21Tb

Where is the molal volume of liquid at normal boiling point
Tb is normal boiling point in K

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Problem 3
Estimate the diffusivity of ethanol vapor,C2 H 5OH , A

through air (B) at 1 std atm pressure, 0C
T 273 k , pt 101.3kN / m , 2
M A 46.07, M B 29
for air,
B / k 78.6, rB 0.3711mm
for ethanol,
v A 20.0148 60.0037 0.0074 0.0592

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Problem 3
rA 1.180.0592 0.46mm.
1
3
Tb , A 351 .4 and A / k 1.21351 .4 425 .

0.46 0.3711 AB
rAB 0.416 42578.6 170.7
2 k
kT 273
1.599 kT 1 1
AB 170.7 f 0.595 0.237
AB MA MB
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Problem 3
3

10 1.084 02490.237 273 2 2.237
4

D AB

101.3 10 0.416 0.595
3 2
5
1.05 10 m / s 2

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Molecular Diffusion in Liquids
NA
x A2
NA DAB N A NB
NA ln
N A N B z M av NA
x A1
Where N A NB
Solution Density
M Molecular Weight
Steady State Diffusion of A through non diffusing B.
xB 2 xB1
x A1 x A2
DAB
NA where xBM
zxBM M av ln
xB 2
2/14/2017 BITS, PILANI K. K. BIRLA GOA xB1 28
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Molecular Diffusion in Liquids
Steady State Equimolal counter diffusion.
NA
DAB
c A1 c A2
z
DAB
x A1 x A 2
z M av
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Problem 4
Calculate the rate of diffusion of acetic acid

(A) across a film of nondiffusing water (B)
solution 1 mm thick at 17C when the
concentrations on opposite sides of the film
are respectively, 9 and 3 wt% acid. The
diffusivity of acetic acid in the solution is
9
0.95 10 2
m /s

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Solution to Problem 4
xB 2 xB1
x A1 x A2
DAB
NA where xBM
zxBM M av ln
xB 2
xB1
z 0.001m, M A 60.03, M B 18.02
Density of the 9 wt% solution is 1012 kg/m3
Density of the 3 wt% solution is 1003.2
kg/m3
0.09 / 60.03 0.0015
X A1 0.0288
0.09 / 60.03 0.91 / 18.02 0.0520
X B1 1 0.0288 0.9712 Mole fraction Water
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1 1012
M 19.21Kg / kmol 52.7 kmol / m 3
0.0520 M 19.21
Similarly
x A2 0.0092, xB 2 0.9908,
M 18.40, and / M 54.5
52.7 54.5 0.9908 0.9712

53.6 kmol / m x BM 0.980
3
M av 2 ln 0.9908 / 0.9712
0.95 10 9
NA 53.6 0.0288 0.0092 1.018 10 6 kmol / m 2 .s
0.0010.980
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Estimation of Diffusivity of Liquids
Empirical correlationship of Wilke-Chang
for dilute solutions of nonelectrolytes
D 0

117 x10 M
18
B
0.5
T
v A0.6
AB
Where
0
DAB Diffusivit y of A in very dilute solution in solvent B, m 2 /s
M B Molecular weight of the solvent, kg/kmol
T Temperature, K
Solution Viscosity, kg/m s
v A Solute molal volume at normal boiling point, m 3 /kmol
association factor for solvent
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Estimation of Diffusivity of Liquids
association factor for solvent

2.26 for water as solvent
1.9 for methanol as solvent
1.5 for ehanol as solvent
1.0 for unassociated solvent e.g. benzene and ethyl ether

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Problem 5
Estimate the diffusivity of mannitol,
in dilute solution in water at 20 deg C. Compare
with the observed value, 0.56x10-9m2/s
0
DAB
117 x10 M
18
B
0.5
T
v A0.6
2.26, M B 18.02, T 293K
A 0.01486 0.003714 0.00746 0.185
For dilute solution, the viscosity ( )may be taken

as that for water, 0.001 005 kg/m.s
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117.3 10 2.2618.02 293

18 0.5
DAB
0.0010005 0.185
0.6
0.601109 m 2 / s

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Problem 6
6. Estimate the diffusivity of mannitol in
dil. Water solution at 70C and
compare with the observed Value ,
1.56 x 10-9 m2/s.
( at 70C = 0.4061 X 10-3 kg/m.s)

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Stefans Experiment
Used to find diffusivity from
experimental Data.
NA= DABPT (PA1-PA2)
RTZPBM
DAB= LRTPBM x z22-z12
mLPt(PA1-PA2) 2t

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Problem 7 (based on Stefans)
A tube of small diameter was filled with
acetone of density 0.79gm/cc upto
1.10cm. From the top and maintained at
a Temp. of 20C in a gentle current of
Air. After 5 hrs. the level of liquid fell to
2.05cm from the top. Calculate the
diffusivity of acetone In air if the
barometer pressure was 750 mm Hg .
Vapor Pr. Of acetone at 20C is 180 mm
Hg. (R=882.06 cc.atm/gmmol K)
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Ficks second Law
Navier-stokes equation
(u(u/x)+v(u/y)+w(u/z)+u/t)=
-p/x+gx+(2u/x2+2u/y2+2u/z2)
FOR MASS TRANSFER
(ux(CA/x)+uy(CA/y)+uz(CA/z)+CA/)=
DAB(2CA/x2+2CA/y2+2CA/z2)+RA
FOR HEAT TRANSFER
(ux(T/x)+uy(T/y)+uz(T/z)+T/)=
(2T/x2+2T/y2+2T/z2)+Q/CP

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Special case(when velocity=0 and no
chemical reaction takes place)
CA/=DAB(2CA/x2+2CA/y2+2CA/z2 )
Ficks second Law

equation
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Problems:8
A test tube , 1.5cm in diameter and 12cm tall, is
partly filled with a solution of alkaline
pyrogallate . The depth of the empty space
above solution is 5cm. The temp. is 25C and
total pressure is 1 atm. Air may be assumed to
contain 21%O2 and 79%N2. The diffusivity of
O2 in N2 at given condition is 0.21 cm2/s.
Calculate: The rate of absorption of O2 from air
in the solution at steady state if air flows gently
over the open end of the test tube.

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Problem 9:
Q2. Two large vessels are connected by a tube 5cm in
diameter and 15cm in length. Vessel1 contains
80%N2(A) and 20%O2(B); Vessel2 contains 20%N2
and 80%O2.The temperature is 20C and total
pressure is 2atm. Calculate:
The steady state flux and the rate of transport of N2
from vessel1 to vessel2
The steady state flux and the rate of transport of O2
from vessel1 to vessel2
The net mass flux with respect to stationary observer
Given: DN2-O2 = 0.23 cm2/s at 316K and 1atm.

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Problem 10:
An open cylindrical tank is filled within 2m to the
top with pure CH3OH. The tank is tapered as shown
in Fig. The air within the tank is stationary but
circulation of air immediately above the tank is
adequate to assume negligible concentration of
CH3OH at this point. The tank and air space are at
77C and 1atm . Diffusivity of CH3OH in air at 77C
and 1 atm=0.6 m2/s. Calculate the rate of loss of
methanol from the tank at steady state.
BITS, PILANI K. K. BIRLA GOA 44

2/14/2017 CAMPUS
Figure
4m
2m
methanol
6m
Assume Vapour pressure of CH3OH AT 77C=135mmHg

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Problem 11:
5.Ammonia gas (A) and nitrogen (B)
are stored in 2 large storage tanks
respectively. The tanks are
maintained at constant pressure of
1.0132bar pressure and
temperature of 298K.A uniform tube
0.1m long connects the 2 tanks,
A Z2-Z1 B
1 2

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The partial pressure of A at pt.1 is
PA1=0.1013bar and at pt.2,
PA2=0.0507bar. The diffusivity
DAB=0.23cm2/s.R=8314m3.Pa/k
g-mol.K.
a) Calculate the flux JA at steady
state.
b) Repeat for JB

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Mass Transfer Coefficients

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What is Mass Transfer Coefficient?
When a fluid flows past a solid surface

Turbulent region and laminar sublayer
Eddies move rapidly from one position to
the other and mass transfer is also rapid
and much more than that
molecular diffusion in the laminar sublayer
Mechanism of mass transfer in the turbulent
region is not thoroughly understood
Whereas mechanism of the molecular
diffusion is well known.

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Mass Transfer coefficient
NA = kc CA = kc (CA1 CA2 ) (3)

kc is the liquid-phase mass-transfer coefficient
based on a concentration driving force.
CA1 A&B
What is the unit of kc?

NA
CA2
February 14, 2017 BITS, PILANI K. K. BIRLA GOA 50
50
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Mass Transfer coefficient
NA = kc CA = kc (CA1 CA2 ) (4)
CA1 = pA1 / RT; CA2 = pA2 / RT
Equation (4) can be written as
NA = kC (pA1 pA2) / RT = kG (pA1 pA2) (5)
where kG = kc / RT (6)
kG is a gas-phase mass-transfer coefficient based on a
partial-pressure driving force.

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Convective mass transfer
Diffusion
Molecular Eddy diffusion / convective mass

diffusion(eg.w transfer(eg.water+sugar,stirred)
ater+sugar ,
unstirred)
Free convection Forced

convection

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In case of eddy diffusion.
How to calculate the rate of mass
transfer in the presence of turbulent
motion?
How can we calculate convective

mass transfer?

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Examples..
The dissolution of a solid coated on a flat
plate in a fluid flowing over it.
The absorption of gas in laminar liquid film

falling down a wall.
For complex situations like dissolution of

solid in mechanical stirred vessel/packed
bed absorption , calculation of mass transfer
rate is difficult.
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Mass Transfer coefficient :Types
Convective mass transfer can occur in gas or a
liquid medium: conc., mole fraction, partial
pressure
Different types of mass-transfer coefficient:

Where mass transfer occurs (gas or liquid phase)
Choice of driving force
Diffusion through stagnant film or equimolar
diffusion

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DIFFUSION OF A THROUGH NON-DIFFUSION B
Gas phase NA = kc (CA1 CA2 ) = kG (pA1 pA2 ) =
ky (yA1 yA2 )
Liquid phase : NA = kx (xA1 xA2 ) = kL (CA1 CA2 )
DAB P p A1 p A2
NA
What is kc and ky in terms
of kG?
RTz pB .m
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EQUIMOLAR COUNTER DIFFUSION
Gas phase NA = kc (CA1 CA2 ) = kG (pA1 pA2 ) =
ky (yA1 yA2 )
Liquid phase : NA = kx (xA1 xA2 ) = kL (CA1 CA2 )
D AB ( p A1 p A 2 )
NA What is kc and ky in
RT z 2 z1 terms of kG?

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Mass Transfer coefficient :Typical
magnitudes
Gas phase mass transfer coefficient: 102 m/s

for a film thickness ~ 1 mm
Liquid phase mass transfer coefficient: 105

m/s for a film thickness ~ 0.1 mm
What will the values of kG at 298 K? What will be the

liquid phase coefficient in a dilute aqueous solution?

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Estimation of mass transfer
coefficient
Change in mass over
time t = m
Molecular weight Mw
pAs T
Average molar flux: NA
{m / [(Mw t)(dp2)/4)}pAs
So what is
kG?

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What is Mass Transfer Coefficient?
NA c A2

NA DABc N A N B c
NA ln
N A NB z NA c
A1
N A NB c
(DABc/z) of the molar flux equation, is
replaced with F, a mass-transfer
coefficient. N c A
A2
NA NA NB c
NA F ln
NA NB NA c A1

NA NB c
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Equimolal Counter Diffusion
NA
DAB
RTz

p A1 p A2
DABc DAB pt
F k 'G pt k ' y
z RTz

N A k ' y y A,1 y A, 2 k 'G p A,1 p A, 2
Flux = (coefficient) (concentration difference)

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Steady State Diffusion of A
through nondiffusing B
p B 2 p B1
NA
DAB pt

p A1 p A2 p B,M
p B2
RTz p B , M ln

B1
p
Flux = (coefficient) (concentration difference)

N A k y y A,1 y A, 2 k G p A,1 p A, 2
DABc DAB pt ky
F kG p B , M p B,M
z RTz pt
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Problem 8
Determine the relation between mass
transfer coefficient KG and KY.
Ans: KY=(PB1PB2KG)/Pt

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Problem 9
The gas phase mass transfer coefficient
for the evaporation of a drop of ethyl
alcohol in a stream of air at 300K and
1.2bar pressure in
KG =2.4 X 10-6 kmol/s.m2.mmHg
Calculate the values of mass transfer
coefficients if the driving force is
expressed in terms of difference in:

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I. Mole fraction of alcohol
II. Mole ratio of alcohol
III.Concentration of alcohol
The diffusivity of alcohol in air is 0.102
cm2/s at 0C, Estimate the thickness of
the stagnant gas film. Vapor pressure of
alcohol = 0.0877bar @ 300K.

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Answers
I. Ky=2.161x10-3 kmol/s.m2
II. Ky=2.003x10-3 kmol/s.m2
III.KC=0.0449 m/s
DAB is proportional to T1.5/Pt
DAB @1.3bar and 300k=1.03x10-5m2/s
KG=1.8x 10-3kmol/m2s.bar.
z=0.24mm.

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Dimensionless numbers
Sherwood number: (kLl/DAB)
Schmidt number: (/DAB)
Nusselt number=hD/k
Prandtl number = CP/k
Stanton number = Nu/(RexPr)

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Peclet number = Re x Sc
Analogy with heat transfer

-1/2
Nu = Sh = f = 0.332 Rex
RexPr1/3 RexSc1/3 2

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Correlations for convective
mass transfer
o Laminar flow through circular tube(Re<=2100)
Sh=KLd/D=1.62[Re.Sc. d/L]1/3
o Turbulent flow through a tube

(4000<Re<60000),(0.6<Sc<=3000)
Sh=0.023Re0.83Sc0.33

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Correlations
o Boundary layer flow over flat plate
(Re<80000 , Re>5,00,000)
JD=0.664(Re)0.5
o Flow through wetted wall tower

(3000<Re<40,000) , (0.5<Sc<3)
JD=0.0328 Re-0.23
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Correlations
o Gas phase flow through packed bed
(10<Re<2500 )
JD=1.17Re-0.415
o Liquid flow through packed bed

(Re<55) JD=1.09Re-2/3
o 3<Re<1000 , Sh=2+1.1Re0.6Sc0.33
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Problem 9
A napthalene ball of 1 cm dia. Is suspended in
a stream of air flowing at velocity of 5m/s at
45C and 1 atm total pressure , Calculate the
time required for its diameter to be halved.The
following correlation can be used:
Sh=2+0.6Re0.5Sc0.33 Sublimation
pressure Of napthalene@45C=0.8654mmHg
DAB=6.92X10-6m2/s , @45C =1140kg/m3.
air=1.1kg/m3 ,air=1.92x10-5kg/m.s
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Ans=
t=3.84hrs.

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Thanks
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Diffusion and MT Coefficient

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BITS, PILANI K. K.

BIRLA GOA CAMPUS

2/14/2017 BITS, PILANI K. K. BIRLA GOA 1

It is concerned with the movement of individual

Net distance in a particular direction in a given time

Increases by T ( Molecular velocity increases)

Decreases by p(Reducing the collisions

The phenomenon of molecular

2/14/2017 BITS, PILANI K. K. BIRLA GOA 3

It is described in terms of Molar Flux

2/14/2017 BITS, PILANI K. K. BIRLA GOA 4

Ficks First Law Negative sign emphasizes that

2/14/2017 BITS, PILANI K. K. BIRLA GOA 7

2/14/2017 BITS, PILANI K. K. BIRLA GOA 9

Molecular Diffusion in Gases

Steady State Diffusion of A through nondiffusing B

2/14/2017 BITS, PILANI K. K. BIRLA GOA 11

Oxygen (A) is diffusing through carbon monoxide

2/14/2017 BITS, PILANI K. K. BIRLA GOA 12

2/14/2017 BITS, PILANI K. K. BIRLA GOA 15

Where DA, i are the binary diffusivities

Recalculate the rate of diffusion of

DO2 H 2 6.99 10 5 , DO 2CH 4 1.86 x 10 5 m 2 / s.

93.5 87 103 93.5 103 ,

2/14/2017 BITS, PILANI K. K. BIRLA GOA 21

System Temp, C Diffusivity, m2/sec x 105

Based on kinetic theory of

Empirical correlations are also available to calculate the values of r and

2/14/2017 BITS, PILANI K. K. BIRLA GOA 24

Estimate the diffusivity of ethanol vapor,C2 H 5OH , A

v A 20.0148 60.0037 0.0074 0.0592

Tb , A 351 .4 and A / k 1.21351 .4 425 .

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Steady State Equimolal counter diffusion.

Calculate the rate of diffusion of acetic acid

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52.7 54.5 0.9908 0.9712

association factor for solvent

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For dilute solution, the viscosity ( )may be taken

117.3 10 2.2618.02 293

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DAB= LRTPBM x z22-z12

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Ficks second Law

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Assume Vapour pressure of CH3OH AT 77C=135mmHg

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When a fluid flows past a solid surface

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NA = kc CA = kc (CA1 CA2 ) (3)

What is the unit of kc?

CA1 = pA1 / RT; CA2 = pA2 / RT

Equation (4) can be written as

NA = kC (pA1 pA2) / RT = kG (pA1 pA2) (5)

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