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1CHA01 Mass Transfer-I

MOLECULAR DIFFUSION IN FLUIDS


Definition :
Movement of individual molecules through a substance by virtue of their thermal
energy is termed as molecular diffusion.
What does molecular diffusion leads to?
The molecular diffusion leads to a completely uniform concentration of substance
through out a solution which may initially have been non-uniform.
Kinetic Molecular Theory of Gases:
This theory gives better understanding of molecular diffusion in gases. Ideal gas
law tells us how ideal gases behaves, but not explain us why it behaves in that
way. The molecular basis of this law is provided by the kinetic-theory of gases.
According to this Theory,
(i)
(ii)
(iii)
(iv)

Ideal gas consist large number of molecules, which are in continuous


random motion
These molecules are very small so volume of all molecules is negligible
(In equation PV=nRT we consider only bulk volume of ideal gas)
Energy can be transferred between the molecules during their collisions.
This energy is in form of kinetic energy due to motion of molecules.
1
mv 2 , is function of Temperature.
2
v= velocity of individual molecule, m= mass of molecule

Kinetic energy of a given molecule =

As number of molecules are very large,


Average Kinetic energy of a given molecules = =

1
mu 2
2

3RT
Mw
As Temperature increases, average kinetic energy of molecules will
increase so molecules movement is more which results in more diffusion.
Thus, mass transfer of species from higher concentration to lower concentration is
accomplished by the actual migration of molecules.

u=root mean square speed of molecules =

Classification of Diffusion:
(i) Laminar Diffusion or Simple molecular diffusion:
Diffusion takes place without any external force. It is very slow process .
Ex. Diffusion of NaCl solution in Water without agitation.
(ii)

Eddy diffusion or turbulent diffusion :


Diffusion takes place with any external force. It is very fast process .
Ex. Diffusion of NaCl solution in Water with agitation.
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LChE, IDS

1CHA01 Mass Transfer-I


Rate of Diffusion: Rate of diffusion is expressed in terms of Molar Flux.
Molar Flux =

MolarRateofDiffusion
unitArea unitTime

Two type of molar flux:


(i)N-type It is a local flux of A
(ii)J-type It is an Average flux of A
Ficks Law: Steady State Rate of molecular diffusion:
Molar Flux = (Constant) (Concentration Gradient)
C A
J A D AB
___________ [A]
Z
Where, JA =Average flux of A with respect to all other components.(Kmol/m2 sec)
DAB = Diffusivity of A in B (m2/sec)
C A
=Concentration gradient of A in z- direction.
Z
Negative (-ve) sign indicates that diffusion occurs in the direction of drop in
concentration
Diffusivity: Is ratio of molar flux to concentration gradient.
DAB = F (Temperature, Pressure, concentration, physical state of the substance,
nature of the constitutes)

Prove that for Binary gas mixture, DAB = DBA :

Figure 1 Diffusion in a binary solution

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LChE, IDS

1CHA01 Mass Transfer-I

A & B both diffuses


Net diffusion relative to fixed position Partition =N = NA + NB ________(1)
Movement of A is made of two parts
1) Relative to fixed position (XA, fraction of N)
2) Resulting from diffusion JA
Thus, NA = XA*N + JA ________ (2)
Where XA is mole fraction of component A=CA/C and
Substituting N from eq. (1) and JA from eq.[A]
C
C A
_______________(3)
N A ( N A N B ) A D AB
C
Z
Similarly for B
C
C B
________________(4)
N B ( N A N B ) B DBA
C
Z
Diffusion occurs only in Z direction,
C A dC A
C dC


and B B
Z dZ
Z dZ
Adding equation (3) and (4)
C CB
dC
dC
N A N B ( N A N B ) A
D AB A D BA B __________(5)
C

dZ
dZ

But , total concentration, C = CA + C B ________ (6)


dC dC
0 A B
dZ dZ
dC
dC
A B ____________ (7)
dZ
dZ
From eqn. (5)(, (6) & (7)
dC
dC
( N A N B ) ( N A N B ) D AB A D BA B
dZ
dZ
______________(8)
D AB DBA
From eqn. (8) & [A]
JA = -JB
STEADY STATE DIFFUSION IN FLUIDS AT REST & LAMINAR FLOW
Assumptions :
Steady state diffusion i.e. NA, NB constant, CA, CB and C do not change with
time
Isothermal condition. DAB constant
Total concentration C = CA +CB constant mole/liter i.e. No reaction
Concentration gradients in other directions (except Z) are zero.
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LChE, IDS

1CHA01 Mass Transfer-I

We have for components A and B diffusing relative to a fixed position


NA + NB = N _____________ (1)
Also, N A X A N J A ______________(2)
C
C A
= N A N B A D AB
_______ (3)
C
Z
As the diffusion is only in Z direction the equation becomes
C
dC A
N A ( N A N B ) A D AB
C
dZ
dC A
N AC ( N A N B )C A CD AB
dZ
dC A
________ (4)
N AC ( N A N B )C A D AB C
dZ
Integrating equation (4)
CA

2
dC A
dZ

D AB C C A N A C ( N A N B )C A
Z1

Z2

where 1 indicates the beginning of diffusion path (high CA) and 2 indicates the end of
diffusion path (low CA)
under isothermal condition DAB = constant and C = constant
Because of Steady State condition NA and NB are constants
CA2

(Z 2 Z1 )
1

lnN A C ( N A N B )C A
D AB C
NA NB
CA1

N AC ( N A N B )C A2
1
ln

N A N B N AC ( N A N B )C A2
Now , take Z 2 Z1 Z
NA
C

A2

(N N B )
Z
1

ln A


NA
C A1
D AB C N A N B

C
( N A N B )

_________(5)

NA

C A2 / C

N A .D AB C
N NB

ln A
________________(6)
N A

( N A N B )Z N A
C A1 / C
N A N B

Equation (6) is the general relation of diffusion rate of component A.

Ujvala Christian
LChE, IDS

1CHA01 Mass Transfer-I


[A] Steady State Laminar Flow Diffusion For Gases:
Applying ideal gas law,
P
P
C A A and C t ___________ (7)
RT
RT
Where, PA = Partial Pressure of component A & Pt = Total pressure
From Equation (6) and (7)
NA

PA2 / Pt

N A D AB Pt
N NB


N A
ln A
N A N B RTZ N A
PA1 / Pt
N A N B

NA

Pt PA2

N A D AB Pt
N NB
_____________(8)

N A
ln A
N A N B RTZ N A
P PA1
N A N B t

Relationship between NA & NB should be known to use the above equation no.(8)

Now, lets consider some special cases for gaseous diffusion:


Specific cases:
CASE-I Steady State Diffusion of A through non diffusing B
Here, As B is non diffusing NB = 0 ( N A N B N A )
NA

1 ____________(9)
NA NB
Hence equation (8) becomes
D P P PA2
N A AB t ln t
RTZ
Pt PA1

Also Pt PA2 PB 2 and Pt PA1 PB1


D AB Pt PB 2
ln
___________(10)
RTZ
PB1
P PB1
Now, PBM B 2
___________(11)
PB 2
ln

PB1

NA

D P ( P PB1 )
N A AB t B 2

RTZ PBM

But,
( PB 2 PB1 ) ( PA1 PA2 )

NA

D AB Pt
PA1 PA2 _______(12)
RTZ PBM
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LChE, IDS

1CHA01 Mass Transfer-I


The equation 12 is shown graphically in the figure 2 below.

Figure 2 Diffusion of A through Non diffusing B


CASE-II : Equimolar counter diffusion of gas A and gas B:
NA = - NB

_______(13)

We know that, (from eqn.(2) & (3)


NA XA N JA
C
dC A
N A ( N A N B ) A D AB
C
dZ
For equi molar counter diffusion NA = -NB
D AB dPA
_________(14)
NA
RT dZ

D AB
N A dZ
RT
Z1
Z2

N AZ

D AB
PA1 PA2
RT

PA2

dP

PA1

OR

D AB
PA PA2 _________(15)
RTZ 1
The equation (15) is graphically shown in the figure 3 below.
NA

Figure 3 Equimolar counter Diffusion


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LChE, IDS

1CHA01 Mass Transfer-I

[B] Steady State Laminar Flow Diffusion For liquids:


Lets discuss special cases for liquid-liquid diffusion,
Case-I Diffusion of A through non diffusing B.
Here, NB=0
From eqn. (6)
NA

C A2 / C

N A .D AB C
N NB

ln A
N A
( N A N B )Z N A
C A1 / C
N A N B

Taking Concentration C as an average molar density and DAB as constant equation


(6) becomes
1 X A2
D
N A AB ln
________ (16)
Z M av 1 X A1
where XA2 and XA1 are mole fractions of A at point1 and point2 of diffusion path
D
N A AB ln X B2 X B1
Z M av
X B2 X B1
D
AB
Z M av X B X B ln XX B2
2
B

DAB

(1 X A2 ) (1 X A1 )
X BM Z M av
D AB
NA
X A1 X A2 ___________(17)
X BM Z M av

Case-II Equimolal Counter Diffusion of A and B:

N A N B
We know that,(from eqn.(2) & (3))
NA XA N JA
C
dC A
N A ( N A N B ) A D AB
C
dZ
For equi molal counter diffusion NA = -NB
dC A
C
N A N A N B A D AB
dZ
C
D AB
NA
dC A
dZ

Ujvala Christian
LChE, IDS

1CHA01 Mass Transfer-I


Z2

C A2

Z1

C A1

N A dZ DAB

dC

C A2
A

DABCA
C A1

N A Z DAB (C A1 C A2 )
D AB C A1 C A2

Z
C
C
D
N A AB X A1 X A2
Z M av

NA

______(18)

STEADY STATE DIFFUSION IN MULTI COMPONENT MIXTURE


n

D A1m

N A Y A Ni
i A

__________(19)
1
Yi N A Y A N i

i A D Ai
DA1m Effective diffusivity of A relative to other components
Ni = flux of components Ai, Bi, Ci..
Yi = Mole fraction of component i
If only component A diffuses & other are non diffusing
NB, NC . = 0
Ni N A
D A1m

N A N AYA
n
Yi

i B D Ai

___________ (20)

Empirical equations for estimation of diffusivity:

[A] Diffusivity of Gases:


(I) GILLILANDS METHOD:
According to this method the equation to estimate diffusivity of gases is,
3
1
1
0.043T 2

MA MB
D AB
1
1 2
Pt V A 3 V B 3
Where, DAB = Diffusivity ()
MA and MB = Molecular Weight of A and B
VA and VB = Molar Volume of A and B
Pt=Total Pressure (atm)

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LChE, IDS

1CHA01 Mass Transfer-I

(II) Wilke-Lee equation for diffusivity of Gases:


DAB

10 4 1.084 0.249

1
MA

1
MB

3/ 2

1
MA

1
MB

Pt AB f KT / AB
DAB = diffusivity m2/s
T = Abs. Temperature K
MA, MB = Molecular weight of A & B respectively kg/kmol
Pt = absolute pressure N/m2
AB = Molecular separation at collision, nm = A B 2
2

AB = energy of molecular attraction = A B


K = Boltzmanns Constant
f(KT/ A B) = Collision function given by figure 3
Value of and listed in Table 1
Also
v = Molal vol. of liquid at normal BP m3/kmol
=1.18 v1/3
From Table 2
E/K = 1.21 Tb
Tb = NBP in Kelvin

Figure 3 Collision function for Diffusion


Table 1 Force constant of gases as determined from viscosity data

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LChE, IDS

1CHA01 Mass Transfer-I

Table 3 Atomic and molecular volumes

2.Diffusivity of Liquids

Do AB

117.3 10 M
18

0.5

VA

0.6

35
DoAB =Diffusivity of A in very dilate solution in solvent B m2/s
MB = Mole wt of solvent kg/kmol
T
= Temperature 0K

= solution viscosity kg/m.s


VA = solute molalal volume at NBP m3/kmol
= 0.756 for water as solute. May be estimated from table 2 except for water

= Association factor for solvent


= 2.26 for water
= 1.9 for Methanol
= 1.5 for Ethanol
= 1.0 for unassociated solvent e.g. Benzene

D AB D 0 BA A

D
XA

B 1
XB

AB

d logYA

d log X A

D AB = Diffusivity of A at infinite dilution in B


D 0 BA = Diffusivity of B at infinite dilution in A
PA
YA = activity coefficient =
X A PA
PA = partial pressure in real system
PA = vapour pressure at given condition of temperature
0

Ujvala Christian
LChE, IDS

1CHA01 Mass Transfer-I

Empirical equation for estimation of diffusivity:


Diffusivity of liquids:
For dilute solutions of non-electrolytes, the empirical correlation of Wilke and Chang is
used which is as follows:

Do AB
35
DoAB =
MB
T

VA

117.3 10 M
18

0.5

VA

0.6

Diffusivity of A in very dilate solution in solvent B m2/s


= Mole wt of solvent kg/kmol
= Temperature 0K
= solution viscosity kg/m.s
= solute molal volume at NBP m3/kmol
= 0.756 for water as solute. May be estimated from table 2 except for water
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LChE, IDS

1CHA01 Mass Transfer-I

= Association factor for solvent


= 2.26 for water
= 1.9 for Methanol
= 1.5 for Ethanol
= 1.0 for unassociated solvent e.g. Benzene and ethyl ether.

Ujvala Christian
LChE, IDS

1CHA01 Mass Transfer-I

Ujvala Christian
LChE, IDS