1

Module 4:
Multicomponent Transport

Lecture 33:
Multi-component Mixtures

NPTEL,IITKharagpur,Prof.SaikatChakraborty,DepartmentofChemicalEngineering

Multi-component equations in terms of fluxes

a) Continuity for each chemical species
mass flux relative to mass average velocity

D i
= i ( .v ) . ji + ri
(3.7.1)
Dt
i = 1, 2,...., n

g/cm3-s

Summing over i one obtains:

Conservation of Total Mass

+ ( . ) = 0 (3.7.2)
t

b)

Equation of Motion
body force per unit mass

n
D
= ( + p ) + i gi (3.7.3)
Dt
i =1

c)

Equation of energy

NPTEL,IITKharagpur,Prof.SaikatChakraborty,DepartmentofChemicalEngineering

n
D 1 2

U
.
U
.
q
.
.
ni .g i (3.7.4)

+
=

Dt
2

i =1
mass flux

( )

Multicomponent energy
flux relative to

Mass Average Velocity

For a complete description of a system, one needs:

a)

A thermal equation of state p = p ( , T , X i )

b)

A caloric equation of state U = U ( , T , X i )

c)

Information on reaction kinetics (ri term in 3.7.1)

d)

Explicit expressions for the fluxes ji , q, in terms of the gradients and

transport coefficients.
Equations (3.7.1), (3.7.3) and (3.7.4) can also be written in terms of fluxes,
defined with respect to a coordinate system fixed in space, i.e.,

ni = wi + ji

i = 1, 2,...., n

= +

e = U + 2 + q + .
2

Then, we get the Equations of

Continuity:

i
= ( .ni ) + ri (3.7.6)
t

NPTEL,IITKharagpur,Prof.SaikatChakraborty,DepartmentofChemicalEngineering

(3.7.5)

Motion:

n
( )
= . + i .g i (3.7.7)
i =1
t

n
1 2
Energy: U + = [.e] + ni .g i (3.7.8)
t
2

i =1

Note: There is no need to add a term describing thermal energy release by

homogeneous chemical reactions. This is included implicitly in U in equations
(3.7.4)and (3.7.8).

Multi-component Fluxes

According to the thermodynamics of irreversible processes, there will be a contribution to

each flux due to each driving force in the system. This coupling can occur only between
flux force pairs that are tensors of equal order or which differ in order by two.
NPTEL,IITKharagpur,Prof.SaikatChakraborty,DepartmentofChemicalEngineering

Therefore,
a) The momentum flux depends only on the velocity gradients. For Newtonian fluids,

2
3

= + ( ) + k ( . ) (3.7.9)

Dyadic

Transpose

Viscosity

Bulk Viscosity ( zero)

of ( )
b) The energy flux depends on thetemperature gradient (Conduction), the
interdiffusion of the various species present , and the Dufour or diffusion
thermo effect . Thus,
c
d
x
q = q ( ) + q ( ) + q ( ) or

q = k T +

H
i =1

j i + q ( ) (3.7.10)
x

Partial molal enthalpyquite complex for multi-component systems .

Usually negligible
Note: Equation (3.7.10) neglects radiant energy flux and ji in this equation is the
mass flux of the i-th species defined w.r.t. the mass average velocity.
c) Mass flux depends on three mechanical driving forces that tend to produce
movement of a species relative to the mean fluid motion (i.e., (i) concentration
NPTEL,IITKharagpur,Prof.SaikatChakraborty,DepartmentofChemicalEngineering

gradient, (ii) pressure gradient, and (iii) external force acting unequally on the
various species), as well as on (iv) the temperature gradient (thermo diffusion or
Soret Effect)
d) Thus the total flux : ji = j i ( ) + j i ( ) + j i ( ) + j i ( ) (3.7.11)
x

With
(i) Ordinary (Concentration) Diffusion
Partial molal Gibbs free enegy

ji

(X )

C2
=
RT

n
G i

M i M j Dij X j
X k (3.7.12)

X
j =1
k =1
k T1 P1 xs
s j ,k
k j

Multi-component diffusion coefficients

(ii) Pressure diffusion (important in centrifuge separations)

ji ( p ) =

C2
RT

M M
j =1

Vj 1
D
X
M
p (3.7.13)

j ij
j
j
M

(iii) Forced diffusion (important in ionic systems; Force = (charge) x (electric

field))
NPTEL,IITKharagpur,Prof.SaikatChakraborty,DepartmentofChemicalEngineering

ji ( ) =
g

C2
RT

M
M
D
X
M
g
g k (3.7.14)

i
j ij
j
j j
j =1
k =1

If gravity is the only external force, then ji ( g ) = 0

(iv) Thermal diffusion(usually small)

ji ( ) = DiT ln T (3.7.15)
T

Multi-component thermal diffusion coefficients

The above equations can be derived from an entropy balance equation.

For n>2 Dij D ji , andthere are

n ( n 1)
independent diffusivities.
2

____________________________

NPTEL,IITKharagpur,Prof.SaikatChakraborty,DepartmentofChemicalEngineering