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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)

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

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.

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)

Diffusion takes place with any external force. It is very fast process .

Ex. Diffusion of NaCl solution in Water with agitation.

Ujvala Christian

LChE, IDS

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

Molar Flux =

MolarRateofDiffusion

unitArea unitTime

(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)

Ujvala Christian

LChE, IDS

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

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.

Ujvala Christian

LChE, IDS

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

Ujvala Christian

LChE, IDS

[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)

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

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

Ujvala Christian

LChE, IDS

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

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

NA = - NB

_______(13)

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

Ujvala Christian

LChE, IDS

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

(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

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

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)

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)

(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)

Ujvala Christian

LChE, IDS

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

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

Table 1 Force constant of gases as determined from viscosity data

Ujvala Christian

LChE, IDS

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

VA = solute molalal volume at NBP m3/kmol

= 0.756 for water as solute. May be estimated from table 2 except for water

= 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 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

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

= 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

Ujvala Christian

LChE, IDS

= 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

Ujvala Christian

LChE, IDS

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