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Sep 29, 2014

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Mass Transfer

© All Rights Reserved

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Mass Transfer

© All Rights Reserved

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Systems

9 MassTransfer.key - January 10, 2014

Molar Fluxes in Binary Systems

N = N

A

+N

B

v

M

=

N

c

=

N

A

+N

B

c

= x

A

v

A

+x

B

v

B

Ficks law is a MODEL for J

A

(has limitations!)

D

AB

= D

BA

J

A

= -J

B

For C > 2 components, everything changes!

(graduate school, anyone?)

A species A in mixture of A & B.

N

A

molar ux of A.

v

A

velocity of A.

x

A

mole fraction of A.

c mixture molar concentration.

N total molar ux.

v

M

mixture molar-averaged velocity.

J

A

- molar diffusive ux of A relative to a

molar averaged velocity. (motion of A

relative to the mixture motion)

Diffusive uxes are only dened relative

to a convective and total ux!

Diffusive and convective uxes are NOT

independent (they must sum to N

A

).

N

A

= cx

A

v

A

molar convective

ux of A

(carried by v

M

)

molar diffusive

ux of A

(relative to v

M

)

J

A

= N

A

cx

A

v

M

J

A

= cD

AB

x

A

Ficks Law

J

A

= cD

AB

dx

A

dz

N

A

= cx

A

v

M

cD

AB

dx

A

dz

= x

A

N cD

AB

dx

A

dz

N

B

= x

B

N cD

AB

dx

B

dz

Here we have assumed 1-D.

We could use vectors for

uxes & velocities...

Often we know something about x

A

(z)

and v

M

. Ficks law lets us get N

A

.

SHR 3.1.1

10 MassTransfer.key - January 10, 2014

Mixture Velocities

Motorcycle:

Dump Truck:

u

m

= 50

u

t

= 30

If there are n

m

motorcycles and n

t

trucks

on the road, what is the average velocity?

Number averaged:

Mass averaged: v =

n

m

m

m

v

m

+n

t

m

t

u

t

n

m

m

m

+n

t

m

t

v

#

=

n

m

v

m

+n

t

u

t

n

m

+n

t

u

t

= v

#

+v

#

t,di

u

m

= v

#

+v

#

m,di

u

t

= v +v

t,di

u

m

= v +v

m,di

N

A

= c

A

v

M

+J

A

= x

A

cv

M

+J

A

= x

A

N +J

A

Molar ux

(analogous to number ux)

what if

n

m

=n

t

?

what if

n

m

=n

t

and

m

t

!m

m

?

v

A

=

N

A

c

A

=

N

A

cx

A

v

M

=

N

c

=

N

A

+N

B

c

v

A,di

=

J

A

/c

A

Ficks Law gives us a relationship between J

A

& x

A

.

11 MassTransfer.key - January 10, 2014

Steady-State Diffusion in Binary Systems

SHR 3.3.1

Be careful with areas!

(ux vs. ow rate)

If there is no bulk ow (N

= 0) then

N

A

= cD

AB

dx

A

dz

= D

AB

dc

A

dz

(if c is constant)

Planar system with constant N

A

(or n

A

):

Concentric cylinders with constant n

A

:

N

A

= x

A

(N

A

+N

B

)

| {z }

N

+J

A

Note: in cylindrical & spherical

coordinates, constant nA does

not imply constant NA.

n

A

= 2LD

AB

c

A

2

c

A

1

ln (

r

2

/r

1

)

A

:

N

A

= D

AB

c

A

2

c

A

1

z

2

z

1

c

A

2

c

A

1

c

A

1

c

A

2

n

A

= 4r

1

r

2

D

AB

c

A

2

c

A

1

r

2

r

1

J

A

= cD

AB

dx

A

dz

n

A

= x

A

(n

A

+n

B

)

| {z }

n

+AJ

A

12 MassTransfer.key - January 10, 2014

The Molar Balance Equations (Again)

c

i

t

= N

i

+S

i

c

i

t

= (c

i

v

M

) J

i

+ S

i

J

A

= cD

AB

x

A

For a binary system of A and B:

Integral Forms

Differential Forms

In terms of total

species uxes:

In terms of convective and

diffusive species uxes:

In terms of total

species uxes:

In terms of convective and

diffusive species uxes:

N

i

= c

i

v

M

+J

i

= x

i

N+J

i

d

dt

Z

V

c

i

dV =

Z

S

N

i

adS +

Z

V

S

i

dV

d

dt

Z

V

c

i

dV =

Z

S

x

i

cv

M

adS

Z

S

J

i

adS +

Z

V

S

i

dV

13 MassTransfer.key - January 10, 2014

Ficks Law Example: Equimolar Counter-diffusion

Assume:

T, p are constant

No reaction

domain boundaries z = 0, z = L.

z = 0 z = L

Equimolar counter-diffusion: for

every mole of A that moves to the

left, a mole of B moves to the right.

x

A

= x

0

A

z = 0

x

A

= x

L

A

z = L

Total ux must be zero (closed

system, constant T, p).

Therefore, N = cv

M

= 0 so v

M

= 0.

N

A

= x

A

N +J

A

= J

A

= cD

AB

dx

A

dz

pseudo-

steady state

vM = 0 no reaction

a = z

a = z

Tube sides:

Tube face at z=0:

Tube face at z=L:

Z

S

J

A

adS = 0

Note: we could have done this integral balance on

any segment of the tube and arrived at the same

conclusion regarding JA. Therefore, it must be

constant! Since JA = NA, NA is also constant!

Break the surface integral into pieces:

" Tube mole

balance gives:

N

A

dz = cD

AB

dx

A

Z

L

0

N

A

dz =

Z

x

L

A

x

0

A

cD

AB

dx

A

Find ux through the tube.

N

A

Z

L

0

dz = cD

AB

Z

x

L

A

x

0

A

dx

A

N

A

=

cD

AB

L

x

L

A

x

0

A

A

c

J

L

A

A

c

J

0

A

= 0

J

0

A

= J

L

A

Z

S

J

A

adS = A

c

J

L

A

Z

S

J

A

adS = A

c

J

0

A

SHR 3.1.3

d

dt

Z

V

c

i

dV =

Z

S

x

i

cv

M

adS

Z

S

J

i

adS +

Z

V

S

i

dV

14 MassTransfer.key - January 10, 2014

z = 0 z = L

We previously showed:

N

A

= J

A

(no bulk ow/convection)

N

A

is constant (so J

A

is constant)

What is the species mole fraction prole through the tube?

J

A

= cD

AB

dx

A

dz

= !

dx

A

=

cD

A

B

dz

Z

x

A

x

0

A

dx

A

=

cD

A

B

Z

z

0

dZ

x

A

x

0

A

=

cD

A

B

z

Note: to determine !, we can use x

A

(L) = x

L

A

x

A

= x

0

A

+

x

L

A

x

0

A

z

L

15 MassTransfer.key - January 10, 2014

Bulb Balances

z = 0 z = L

N

A

=

cD

AB

L

x

L

A

x

0

A

bulb as a function of time.

Pseudo-steady state:

The tube is at steady state (adjusts to the

slowly changing bulb compositions quickly).

For the

left bulb:

vM = 0 no reaction

V

0

dx

0

A

dt

=

A

c

D

AB

L

x

L

A

x

0

A

to steady-state conditions:

cx

0

A

V

0

+cx

L

A

V

L

| {z }

at time t

= cx

A

(V

0

+V

L

)

| {z }

at t=

x

L

A

= x

A

(1 +

V

0

/V

L

) x

0

A

V

0

/V

L

dx

0

A

dt

=

A

c

D

AB

V

0

L

A

x

0

A

(1 +

V

0

/V

L

)

= D

AB

A

x

0

A

We need to eliminate x

L

A

A

c

V

0

L

1 +

V

0

V

L

Geometry factor

x

0

A

= x

A

+

x

0

A,0

x

exp(D

AB

t)

Separate

& solve...

A nice way to determine D

AB

experimentally!

d

dt

Z

V

c

i

dV =

Z

S

x

i

cv

M

adS

Z

S

J

i

adS +

Z

V

S

i

dV

0 2000 4000 6000 8000 10000

0

0.1

0.2

0.3

0.4

0.5

(s/m

2

)

x

A 0

D

ab

= 0.01

D

ab

= 0.001

D

ab

=0.0001

D

ab

= 1e05

t

cV

0

dx

0

A

dt

= N

0

A

A

c

16 MassTransfer.key - January 10, 2014

Example: Evaporation from a Beaker

(Unimolecular Diffusion)

Benzene (A)

& air (B)

Determine x

A

(z).

What do we know about N

A

& N

B

?

N

A

= x

A

N +J

A

N

A

= x

A

N

A

+ J

A

=

J

A

1 x

A

N

A

=

cD

AB

1 x

A

dx

A

dz

(1-xA) accounts for bulk ow.

In very dilute systems (xA!0),

this effect is small relative to JA.

N

A

=

cD

AB

z z

0

ln

1 x

A

1 x

0

A

or

1. Estimate gas-phase composition of benzene at the

vapor-liquid interface (from equilibrium thermo).

2. Determine N

A

from x

A

at z=0.

3. Determine x

A

(z).

SHR 3.1.4

N

A

cD

AB

Z

z

z

0

dz =

Z

x

A

x

0

A

dx

A

1 x

A

x

A

= 1 (1 x

0

A

) exp

N

A

(z z

0

)

cD

AB

DAB=0.0905 cm

2

/s

Note: from x

A

(z) and N

A

you

can determine anything else

about the system (e.g. J

A

(z)).

17 MassTransfer.key - January 10, 2014

The Log-Mean

N

A

=

cD

AB

z z

0

ln

1 x

A

1 x

0

A

(1 x

A

)

LM

= (x

B

)

LM

=

(1 x

A

2

) (1 x

A

1

)

ln

h

1x

A

2

1x

A

1

i

=

x

A

1

x

A

2

ln [

(1x

A

2

)

/(1x

A

1

)]

N

A

=

cD

AB

(1 x

A

)

LM

x

A

z

This makes things look a bit cleaner and allows

us to express N

A

in terms of !x

A

.

You will see this used more when we start

dealing with Mass-Transfer Coefcients (soon)...

Log-mean of x

A

at

the two ends of

the diffusion path.

18 MassTransfer.key - January 10, 2014

Comments on Ficks Law

In this class, we typically assume that the total molar

concentration, c, is constant.

This is usually reasonable for isothermal, isobaric systems or for liquid

systems.

We have only considered binary systems.

For multicomponent systems, things become considerably more complex.

Other driving forces:

other species can cause strange diffusion (push a species against its

gradient) for C > 2 components.

pressure gradients (centrifugation)

thermal gradients (Soret effect)

In general, the chemical potential is the correct driving force for diffusion.

19 MassTransfer.key - January 10, 2014

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