Tutorial/HW Week #7

WRF Chapters 22-23; WWWR Chapters 24-25

ID Chapter 14

Tutorial #7
WWWR# 24.1, 24.12, 24.13,
24.15(d), 24.22.

To be discussed on March
7, 2017.
By either volunteer or
class list.
 Molecular Mass Transfer
Molecular diffusion
Mass transfer law components:
Molecular concentration:
A nA p A
cA
MA V RT
Mole fraction:
cA (liquids,solids) , cA
xA yA (gases)
c c
 p A RT p A
For gases, y A
P RT P
n n
Velocity: v i i i vi
mass average velocity, v i 1
i 1
n

i
i 1
n

c v i i

molar average velocity, V

i 1
c

velocity of a particular species relative to mass/molar average is

the diffusion velocity.
mol
 Flux:
A vector quantity denoting amount of a particular species that
passes per given time through a unit area normal to the vector,
given by Ficks First Law, for basic molecular diffusion

J A DAB c A
or, in the z-direction,
dc A
J A, z DAB
dz
For a general relation in a non-isothermal, isobaric system,
dy A
J A, z cDAB
dz
 Since mass is transferred by two means:
concentration differences
and convection differences from density differences
For binary system with constant Vz,
J A , z c A (v A , z V z )
Thus,
dy A
J A, z c A (v A, z Vz ) cDAB
dz
Rearranging to
dy A
c Av A, z cDAB c AVz
dz
 As the total velocity,
1
Vz (c A v A, z c B v B , z )
c
Or

c AVz y A (c Av A, z cB vB , z )

Which substituted, becomes

dy A
c Av A, z cDAB y A (c A v A , z c B v B , z )
dz
 Defining molar flux, N as flux relative to a fixed z,
N A c A v A
And finally,
dy A
N A, z cDAB y A ( N A, z N B , z )
dz
Or generalized,

N A cDABy A y A (N A N B )
 Related molecular mass transfer
Defined in terms of chemical potential:
d c DAB d c
v A , z Vz u A
dz RT dz
Nernst-Einstein relation

DAB d c
J A, z c A (v A , z Vz ) c A
RT dz
 Diffusion Coefficient
Ficks law proportionality/constant
J A, z M 1 L 2
DAB ( 2 )( )
dc A dz L t M L 1 L
3
t
Similar to kinematic viscosity, , and
thermal diffusivity,
 Gas mass diffusivity
Based on Kinetic Gas Theory
1
DAA* u
3
= mean free path length, u = mean speed
2T 3 / 2 3 N 1/ 2
DAA* 3/ 2 2 ( )
3 A P M A
Hirschfelders equation:
1/ 2
1 1
0.001858T 3/ 2

M M B
DAB A

P AB D
2
 Lennard-Jones parameters and from tables,
or from empirical relations
for binary systems, (non-polar,non-reacting)
A B
AB AB A B
2

Extrapolation of diffusivity up to 25
atmospheres
3/ 2
P1 T2 D T1
DABT2 ,P2 DABT1 ,P1
P2 T1 D T2
Binary gas-phase Lennard-Jones
collisional integral
 With no reliable or , we can use the Fuller
correlation,
1/ 2
1 1
3
10 T 1.75

DAB MA MB

P v A v B
1/ 3

1/ 3 2

For binary gas with polar compounds, we

calculate by
0.196 2
D0 *
AB
T
 where
1 .94 10 P
3 2
A B ,
1/ 2
AB
VbTb
T T / AB
*

1/ 2
AB A B


/ 1.181 1.3 Tb
2

A C E G
D0
T
* B * * *
exp(DT ) exp(FT ) exp(HT )
and 1/ 3
1.585Vb
AB A B 2
1/ 2

1 1.3

For gas mixtures with several components,

1
D1 mixture '
y2 / D1 2 y3' / D13 ... yn' / D1 n
with
y2
y
'
2
y2 y3 ... yn
2
 Liquid mass diffusivity
No rigorous theories
Diffusion as molecules or ions
Eyring theory
Hydrodynamic theory
Stokes-Einstein equation
T
DAB
6r B
Equating both theories, we get Wilke-Chang eq.
DAB B 7.4 10 B M B
8 1/ 2

T VA0.6
 For infinite dilution of non-electrolytes in
water, W-C is simplified to Hayduk-Laudie eq.
DAB 13.26 10 5 1.14
B V 0.589
A

Scheibels equation eliminates B,

DAB B K
1/ 3
T VA
3V 2 / 3
K (8.2 10 8 ) 1 B
VA
 As diffusivity changes with temperature,
extrapolation of DAB is by
n
( DABT1 ) Tc T2

( DABT2 ) Tc T1
For diffusion of univalent salt in dilute solution,
we use the Nernst equation
2 RT
DAB
(1 / 1 / ) F
0 0
 Pore diffusivity
Diffusion of molecules within pores of porous
solids
Knudsen diffusion for gases in cylindrical pores
Pore diameter smaller than mean free path, and
density of gas is low

Knudsen number Kn
d pore
From Kinetic Theory of Gases,
u 8NT
DAA*
3 3 M A
 But if Kn >1, then

d pore d pore 8NT T

DKA u 4850d pore
3 3 M A MA
If both Knudsen and molecular diffusion exist, then
1 1 y A 1

DAe DAB DKA
with
NB
1
NA
For non-cylindrical pores, we estimate

D DAe
'
Ae
2
Example 6
Types of porous diffusion. Shaded areas represent nonporous solids
 Hindered diffusion for solute in solvent-filled
pores
A general model is

DAe D F ( ) F2 ( )
o
AB 1

F1 and F2 are correction factors, function of pore

diameter, d
s
d pore
F1 is the stearic partition coefficient
(d pore d s ) 2
F1 ( ) (1 ) 2

d pore
2
 F2 is the hydrodynamic hindrance factor, one
equation is by Renkin,

F2 ( ) 1 2.104 2.09 3 0.95 5

Example 7
 Convective Mass Transfer
Mass transfer between moving fluid with
surface or another fluid
Forced convection
Free/natural convection
Rate equation analogy to Newtons cooling
equation
N A kc c A
Example 8
 Differential Equations
Conservation of mass in a control volume:

c.s. v n dA t c.v. dV 0
Or,
in out + accumulation reaction = 0
 For in out,
in x-dir, n A, x yz x x n A, x yz x

in y-dir, n A, y xz y y n A, y xz y

in z-dir, n A, z xy z z n A, z xy z

For accumulation,
A
xyz
t
 For reaction at rate rA,
rA xyz

Summing the terms and divide by xyz,

nA, x x x nA, x x nA, y y y nA, y y nA, z z z nA, z z A

rA 0
x y z t

with control volume approaching 0,

A

n A, x n A, y n A , z rA 0

x y z t
 We have the continuity equation for
component A, written as general form:
A
nA rA 0
t
For binary system,
A B
n A nB
rA rB 0

t

but n A n B A v A B v B v
and rA rB
 So by conservation of mass,

v 0
t
Written as substantial derivative,
D
v 0
Dt
For species A,
D A
j A rA 0
Dt
 In molar terms,
c A
NA RA 0
t
For the mixture,
c A cB
N A NB ( RA RB ) 0
t
And for stoichiometric reaction,
c
cV ( RA RB ) 0
t