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Module 4:
Multicomponent Transport

Lecture 34:
Binary Systems

NPTEL,IITKharagpur,Prof.SaikatChakraborty,DepartmentofChemicalEngineering

For Binary Systems:


Using

DAB = DBA

(dGA )T , P = RTd (ln a A )

(where aA is the activity of A) and

defining thermal diffusion ratio as

DAT
kT = 2
,
C M A M B DAB

equation (3.7.11)-(3.7.15) yields

ln a A
M A B xA
x
g A gB

A
2

ln

x
RT
A T , P
C

jA = jB =
M A M B DAB

+ M A xA VA 1 p + k ln T
T
RT MA

(3.7.16)
Note: When kT is positive, component A moves to the colder region; when kT is negative,
component A moves to the warmer region.

EXPERIMENTAL THERMAL DIFFUSION RATIOS FOR LIQUIDS


AND LOW-DENSITY GASES
Liquids a
T ( K )

xA

kT

Gases b
Component
A B

C2 H 2Cl4 n C6 H14

298

0.5

1.08

Ne H e

C2 H 4 Br2 C2 H 4Cl2

298

0.5

0.225

C2 H 2Cl4 CCl4

298

0.5

0.060

Component
A B

N2 H 2

T ( K )

xA

kT

330

0.20

0.0531

0.60

0.1004

0.294

0.0542

264

NPTEL,IITKharagpur,Prof.SaikatChakraborty,DepartmentofChemicalEngineering

CBr4 CCl4

298

0.09

0.129

CCl4 CH 3OH

313

0.5

1.23

CH 3OH H 2O
CycloC6 H12 C6 H 6

313

0.5

313

0.5

0.775

0.0663

0.10

0.0145

-0.137

0.50

0.0432

0.100

0.90

0.0166

D2 H 2

327

Abstracted from R. L. Saxton, E. L. Dougherty, and H. G. Drickamer, J. Chem. Phys, 22, 1166-1168
(1954); R. L. Saxton and H. G. Drickamer, ibid., 1287-1288; L. J. Tichacek, W. S. Kmak, and H. G.
Drickamer, J. Phys. Chem., 60,660-665 (1956).
b
Abstracted from, tables givenby J. O. Hirschfelder, C. F. Curtiss, and R. B. Bird, Molecular Theory
of Gases and Liquids, Wiley New York (1954), .4.
Lets consider ordinary diffusion for a moment

( x)
A

ln a A
M A M B DAB
=
x A

ln x A T , P
C2

(3.7.17)

Compare with the usual form

jA( x ) =

C2

M A M B D AB x A

(3.7.18)

Thus,

AB

ln a A
= D AB

ln
x

A T ,P

For ideal systems (activity proportional to mole fraction), implying

D AB = DAB
For liquid systems, D AB has a stronger dependence on concentration than

DAB

NPTEL,IITKharagpur,Prof.SaikatChakraborty,DepartmentofChemicalEngineering

Ordinary Diffusion in Ideal Gas Mixtures


For an ideal gas mixture, eq., (3.7.12) becomes

ji =

C2

M M
i

j =1

Dij x j

, where i=1,2,3,,n

(3.7.20)

Note: In this subsection we are interested in ordinary (concentration) diffusion only. Items superscript
(X) has been dropped in (3.7.20).
For ideal gas mixtures, the relation between
mixture) and

Dij

Dij (the diffusivity of pair i-j in the multi component

(the diffusivity of the pair i-j in a binary mixture) is known.

Stefan Maxwell equation


It can be shown that equation (3.7.20) can be turned around as
n

Ci C j

j =1

C 2 Dij

xi =

(v

j vi ) =

1
( xi N j x j Ni )
CD
j =1
ij
n

(3.7.21)

These are known as the Stefan Maxwell equation.


The advantages of using (3.7.21) over (3.7.20) is that

Dij is virtual independent of gas composition

(which is not the case with D ij )

Note: From kinetic theory of gases

NPTEL,IITKharagpur,Prof.SaikatChakraborty,DepartmentofChemicalEngineering

1
1
T
+
M M
j
i
Dij = 0.0018583
p ij D ,ij
3

,
(3.7.22)

where Dij is in cm 2 / s, p is in atm and ij is in A 0 .

For some calculation it is convenient to define an effective binary diffusivity

Dim for diffusion of

component i into mixture m .

Ni = CDimxi + xi N j
j =1

(3.7.23)

Solving (3.7.23) for xi and using (3.7.21) one obtains

1
x j Ni xi N j )
(

j =1 CDij
n

1
=
CDim

Ni xi N j

(3.7.24)

j =1

Equation (3.7.24) is in general difficult to use because Dim depend on position. For certain simplified
cases, however, Dim becomes particularly simple. For example,
a) Trace components 2,3,n in nearly pure component 1.

Dim = Di1
NPTEL,IITKharagpur,Prof.SaikatChakraborty,DepartmentofChemicalEngineering

b)

Dij are all the same

=>

Dim = Dij

c) 2,3,.,n more with the same velocity =>

n
xj
1 x1
=
D1m
j = 2 D1 j

(3.7.25)

Figure showing the effect of activity on the product of viscosity and diffusivity for liquid
mixtures chloroform and ether. [Adapted from R. E. Powell, W. L. Roseveare, and Henry
Eyring. Ind. Eng. Chem. 33, 430-435 (1941)]

NPTEL,IITKharagpur,Prof.SaikatChakraborty,DepartmentofChemicalEngineering

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