Fluxes in Multicomponent Systems

ChEn 6603

Taylor & Krishna 1.1-1.2

Saturday, January 7, 12

Outline
Reference velocities Types of uxes (total, convective, diffusive)
Total uxes Diffusive Fluxes

Example Conversion between diffusive uxes

Saturday, January 7, 12

Reference Velocities
Denote the velocity of component i as ui.
n

T&K Table 1.2

What assumptions have we made here?

Molar-Averaged velocity

u=
i=1 n

xi ui

xi is the mole fraction of component i.

Mass-Averaged velocity

v=
i=1 n

i ui

i is the mass fraction of component i.

Volume-Averaged velocity

u =
V i=1

i ui

ci Vi is the volume fraction of component i.

ci = xi c = i/Mi - molar concentration of i.

Vi - partial molar volume of component i (EOS).
n

Arbitrary reference velocity

ua =
i=1

ai ui
i=1

ai = 1 ai is an arbitrary weighting factor.

Why ai = 1? How do we dene ai such that ua = uj?

Saturday, January 7, 12 3

Types of Fluxes
Total Flux
Amount of a quantity passing through a unit surface area per unit time.

Convective Flux:
Amount of a quantity passing through a unit surface area per unit time that
is carried by some reference velocity.

Diffusive Flux:
Amount of a quantity passing through a unit surface area per unit time due
to diffusion. The difference between the Total Flux and the Convective Flux. Cannot be dened independently of the total & convective uxes!

Saturday, January 7, 12

Total Fluxes
Total Fluxes may be written in terms of a components velocity and specic density Mass Flux of component i:
ni = i ui i ui

Total Mass Flux:

n

n
i=1 n

ni = =
i=1 i ui ,

- mixture mass density

Molar Flux of component i:

Ni xi cui = ci ui

Total Molar Flux:

n

Nt

=
i=1 n

Ni ci ui
i=1

= = cu

Note: there is a typo in T&K eq. (1.2.5)

5

Saturday, January 7, 12

Diffusive Fluxes
Concepts:
The total ux is partitioned into a convective and diffusive ux. The convective ux is dened in terms of an average velocity. The diffusive ux is dened as the difference between the total and convective uxes. It is only dened once we have chosen a convective ux!
Mass diffusive ux of component i relative to a mass-averaged velocity. Total mass ux of component i Convective ux of component i due to a mass-averaged velocity

ji

= = =

ni iv v) i (ui ni i nt
6

Saturday, January 7, 12

Diffusive Fluxes
Diffusion uxes are dened as motion relative to some reference velocity. (Diffusion ux) = (Total Flux) - (convective ux) Diffusion Flux
ji
ju i
Ji
Jv i

Total Flux
ni ni
Ni Ni

Convective Flux
iv
iu

Comments
Mass diffusive ux relative to a mass-averaged velocity Mass diffusive ux relative to a molar-averaged velocity Molar diffusive ux relative to a molar-averaged velocity Molar diffusive ux relative to a mass-averaged velocity

ji

= = =

ni iv v) i (ui ni i nt

ci u ci v

Ji

= = =

Ni ci u ci (ui u) Ni xi Nt

Saturday, January 7, 12

T&K Table 1.3

Linear Dependence of Diffusive Fluxes

Appropriately weighted diffusive uxes sum to zero. Why? Total uxes are all independent. Convective uxes are not all independent.
For mass diffusive ux relative to mass-averaged velocity:
n

ji = 0
i=1

From the previous slide: ji = i (ui

n n

v)

ji
i=1

= =

( i ui
i=1 n

i v)

(i ui
i=1

i v),

= = =
n i i=1

v+ i ui v + v, 0.

Note: typo in table 1.3 (missing v superscript)

Saturday, January 7, 12

xi

Jv = 0 i
8

Example - Stefan Tube

Air
Species Mole Fractions

z=

At steady state (1D),

ni Ni = i =
i

1 0.8 0.6 0.4 0.2 0 0 Acetone(1) Methanol(2) Air(3)

Liquid Mixture

We will show this later...

z=0

0.05

0.1 0.15 z (m)

0.2

Molar, mass averaged velocities

1.6 1.5
velocity (m/s)

Species velocities ui =
3 x 10
3

x 10

ni i
Diffusive Fluxes for Acetone

Acetone diffusive uxes ji = i (ui

x 10 1.5
3

v)

Molar Average Mass Average

Species Velocities (m/s)

2.5 2 1.5 1 0.5 0 0 Acetone Methanol Air

j ju J Jv

1.4 1.3 1.2 1.1 0 0.05 0.1 0.15 z (m) 0.2 0.25

0.5

0.05

0.1

0.15 z (m)

0.2

0.25

0 0

0.05

0.1

0.15 z (m)

0.2

0.25
9

Saturday, January 7, 12

Conversion Between Fluxes

We can convert between various diffusive uxes via linear transformations.
Conversion between mass diffusive uxes relative to mass and molar reference velocities.

(ju ) = [B uo ](j) (j) = [B ou ](ju )

To form [Buo]-1 this must be an n-1 dimensional system of equations! (why?)

Derivation of [Bou]...
ju = i
n
i (ui

u)
n n i ui i=1 i u, i=1

ji =

i (ui

v)
add & subtract iu.

ju i
i=1

= = v

Lets try to get a jiu on the RHS

u, u.

ji

= =

i (ui

ju i
i=1

i (ui

ji = ju i
Saturday, January 7, 12

This is an n-dimensional set of !i ju equations. If we derive [Bou] j from this, it will not be full-rank. j=1
n X
10

ju i

v), u) + i (u

v)

Derivation of
ji = ju i !i
ji = ju i

ou] [B
n X xi i=1 i

(contd)
n 1

Eliminate ju from the above equation... n

!i 4 ju + n

j=1 2

n X

ju j

separate out ju n

n 1 X j=1

ju 5 j

ju i

=0

ju n

xi
i

xn

ju i

i=1

ju te n elimina

ji

= =

ju i

n 1 j=1

n 1 j=1

n xj u j j + ju , j xn j n xj xn j ju j

gather terms on ju n

ij

i 1

we have n-1 of these equations (i=1...n-1)

(j) = [B ou ](ju )
ou Bij

ij

i 1

n xj xn j

The inverse [Buo]=[Bou]-1 can be obtained from equations A.3.21-A.3.23 in T&K (note the typo in A.3.22).
[B]
1

= [A]

1 T

[A]
1

(u) (v) [A]

= 1 + (v) [A]
Saturday, January 7, 12

(u)
11