Concentration, Velocity and Flux

p. 530-532
i: mass concentration of species i, in kg/m3 or lb/ft3.
n

: total mass concentration of all species in a solution, in kg/m3 or lb/ft3.    i

i1
i
wi: mass fraction of species i in a solution. wi 

n
ci: molar concentration of species i, in kmol/m3 or lbmol/ft3. c   ci
i 1
c: total molar concentration of all species in a solution, in kmol/m3 or lbmol/ft3.
ci
xi: mole fraction of species i in a solution. xi 
c
ui: velocity of species i in a given direction in m/h or ft/h.

ni = i * ui: mass flux of species i in the given direction, in kg/(m2 * h) or lb/(ft2 * h).

Ni = ci * ui: molar flux of species i in the given direction, in kmol/(m2 * h) or lbmol/(ft2 * h).

1
 Theory of Diffusion p. 527-528

The molar flux of a species (JA) relative to an observer moving with the molar average
velocity is proportional to the concentration gradient of the species.
dc A dc A dy A
Fick's first law of diffusion: J A   Dv   cDv
db db db
JA = molar flux of component A, mol/(cm2*s)
Dv = diffusivity, cm2/s
cA = concentration (mole per unit volume), mol/cm3
b = distance in direction of diffusion, cm
c = concentration of the mixture = P/(RT) for ideal gas , mol/cm3
yA = mole fraction of A (gas phase)
cA
According to Fick's first law of diffusion, the dc A
0
diffusion only happens when the concentration db
gradient existing.

Eqn (17.2) should be: J A   Dv c A  cDv y A

The minus signs are missing. b 2
 Molar Average Velocity and Diffusion
uA - u0
cA, uA p. 530-532
c Au A  c B u B
Molar average velocity: u0   x Au A  x B u B
u0  x Au A  xB uB c A  cB
mol cm mol
Molar flux of component A: N A  c Au A     
cm 3 s cm 2  s
cB, uB Molar flux of component B: N B  cB uB
uB - u0
Total molar flux: N A  N B  c AuB  cB uB  c  x AuB  xB uB   cu0
c  c A  cB

Molar flux of component A:

dc A
N A  c Au A  c A  u A  u0   c Au0  J A  x Acu0   DAB  xA  N A  N B 
db
Diffusion velocity Diffusion flux Bulk-flow flux

N A  N B   J A  J B    x A  xB  N A  N B   J A  J B  0
dc A dc
P  DAB  DBA B  0  DAB  DBA  Dv
For ideal gas: c  c A  cB   d  c A  cB   0 db db 3
RT
 Fick's Laws
c A  x, t  Accumulation = Input - Output
The first law: J Ax   Dv
x
z c A  x, t 
 xyz   J Ax  yz  x  x  J Ax  yz  x x x
t

c A  x, t  J  x  x   J Ax  x  J
JAx JAx   lim Ax   Ax
t x 0 x x
z
 2 c A  x, t 
y  Dv The second law
x x 2
The Penetration Theory
x x+x x
c A  x, t   2 c A  x, t 
y  Dv
t x 2
Initial Condition: t  0, c A  c Ab
Gas
Boundary Condition 1: x  0, c A  c A0
A
Boundary Condition 2: x  , c A  c Ab

DAB
N Ax   c A0  c Ab  tc: contact time
c Ab
x 0
t c 4
 Analogies with Momentum and Heat
Transfer p. 529

dv x  d v x  d  v x 
Newton's law of viscosity:  yx     
dy  dy dy
yx = shear stress (shearing force per unit area), (g*cm/s2)/cm2 = (g*cm/s)/(cm2*s)
= momentum flux
 = viscosity, g/(cm*s) = poise,  = kinematic viscosity, cm2/s
vx = momentum per unit volume, (g*cm/s)/cm3

Fourier's law of heat conduction: q y   k

dT

k d Cˆ pT    

d Cˆ pT 
dy Cˆ p dy dy
qy = heat flux, cal/(cm2*s)
k = conductivity, cal/(cm*s*C), Cˆ p = heat capacity per unit mass, cal/(g*C)

Cˆ pT = energy per unit volume, cal/cm3

 = thermal diffusivity, cm2/s

5
 Four Types of Diffusion p. 529-530

• One-way diffusion: only one component A of Gas Gas Liquid Liquid

the mixture is transferred to the interface. Gas Phase Film Film Phase
absorption is a typical example. yA
• Equimolal diffusion: the diffusion of
y Ai
component A in a mixture is balanced by an
equal and opposite molar flow of component yA*
x Ai
B. Distillation is the typical example.
xA
• Diffusion of A and B takes place in opposite
directions, but the molar fluxes are unequal.
Chemical reaction on a catalyst surface is the
typical example.
O 2 g   2C s   2CO g  2N O2   N CO Interface
• Two of more components diffuse in the same
direction but at different rates, such as:
membrane separation.
6
Equimolal Diffusion p. 533

dc A
N A  J A  y A  N A  N B    DAB  yA  N A  N B 
db

Eqimolal assumption: N A  N B  0

c n P
y A  A , c  M  For ideal gas:  M 
c V RT
dy A BT y
N A  J A   Dv M   N Adb    Dv M dy A
db 0 yi

BT
Assuming that Dv and M are constant, and the molar
flux is also constant at steady state.
Dv M  yi  y 
N A  BT  0    Dv M  y  yi   N A  J A 
BT

7
 One-way Diffusion p. 534

dc A
N A  J A  y A  N A  N B    DAB  yA  N A  N B 
db
One-way assumption: NB  0

dy A y D 
1  y A  N A   DAB M
BT
  N Adb    AB M dy A
db 0 yi 1  y
A

N A  BT  0   Dv M ln
1 y
 NA 
Dv M 1  y 
ln  JA
BT
1  yi  BT 1  yi 
Dv M
uA - u0 JA   yi  y 
cA, uA BT
u0  y Au A  y B uB
ln
1 y
ln
1 y
 uB NA 1  yi  1  yi  1
NA  JA
   1
JA  yi  y  1  y   1  yi  1  y  L
cB, uB

uB - u0 = 0
1  y  L  1 , since logarithmic mean of (1-y)<1 and (1-yi)<1 is
8
always less than 1.
 (a) For the diffusion of solute A through a layer of gas to an absorbing
Ex 17.1 liquid, with yA=0.20 and yAi = 0.10, calculate the transfer rate for one-way
diffusion compared to that for equimolal diffusion. (b) What is the value
of y, halfway through the layer for one-way diffusion?

yA = 0.2
p. 534-535
yA = ??
ln
1  y 
yAi = 0.1 N A  one  way  N A
 
1

1  yi 
N A  equimolal  J A 1  y  L 1  y   1  yi 
0 BT/2 BT b
ln
1  y A  ln
1  0.2 
1  y Ai  1  0.1
  1.18
1  y A   1  y Ai  0.1  0.2
Assuming that the diffusion is at the steady state, NA=constant.

Dv M 1  0.1 D 1  y A 
NA B  ln  N A B 2  v M ln
T
BT 1  0.2  T
BT 2 1  0.2 

ln
1  y A   1 ln 1  0.1  y  0.1515
1  0.2  2 1  0.2  A

In the case of equimolal diffusion, yA = 0.15. 9

 Mass Transfer Coefficient
dc A The molar flux cannot be calculated when the bulk flow term
N A   DAB  xA  N A  N B 
db is too complex. From the observation, we can conclude:

WA  AC A 
WA
 N A  k c C A The molar flux is proportional to the concentration
A driving force.
WA: molar flow rate, A: contact area, CA the difference in concentration,
kc: the proportionality constant

NA molar flux
kc  
C A concentration driving force

10
 Analogue to Omh's Law
V voltage driving force
I   current
R resistance

where I is the current through the conductor in units of amperes, V is the voltage
(driving force) measured across the conductor in units of volts, and R is the
resistance of the conductor in units of ohms.

C A concentration driving force

N A  k c  C A    molar flux
1 kc resistance

yA
where NA is the molar flux through the gas film,
CA is the concentration difference (driving
force) measured across the film, and 1/kc is the y Ai
Gas
resistance of the film.
Film

11
 Film Theory p. 542-543
Dv M
NA  JA   y Ai  y A   k y  y Ai  y A   kc  c Ai  cA 
BT
1. The ky and kc are the mass transfer coefficient with different
units. kc [=] cm/s, ky [=] mol/(cm2*s)
2. Since the thickness (BT) of the film cannot be measured, the
mass transfer coefficients are determined experimentally.
3. The molar flux (JA) and the concentration difference (cAi-cA),
aka driving force of mass transfer, can be measured.
JA JA P
kc  , ky  , k y  kc
BT
 c Ai  c A   y Ai  y A  RT
4. The mass transfer coefficients are based on the equimolal flow.

In general, the mass transfer in the gas phase is expressed by the difference of partial pressure
of species A (pAi-pA). J  k  p  p   k P  y  y   k  k P
A G Ai A G Ai A y G

The mass transfer in the liquid phase is expressed by the concentration difference (cAi-cA).

J A  k L  c Ai  c A   k L c  x Ai  x A   k x  k L c  k L x
M 12
 Effect of one-way diffusion p. 544

NA 1 k y'  y Ai  y A  ky
   k y' 
J A 1  y  L k y  y Ai  y A  1  y  L

yA = 0.1
1-yA = 0.9
1
0.9  1  y  L  0.99  1.11   1.01
1  y  L
yAi = 0.01
1-yAi = 0.99

0 BT b
13
 Vapor Liquid Equilibrium
Dalton's law: [Link]
V
PAV  y A P
A+B
Raoult's law: [Link]

B
A+B PAL  x A p*A  T  log10 p*A  A 
T C
L
Antoine equation: [Link]
Acitivity Coefficient
At VLE: PAV  PAL  y A P  x A p*A p*A  A
y A P A  x A p A  A  y A  x A
*
 mx A
P A
Ideal Gas Mixture Ideal Solution
Fugacity Coefficient
The fugacity coefficient can be estimated by the equation of state, e.g., Peng-Robinson (PR)
or Redlich-Kwong (RK) .

The acitivity coefficient can be estimated by the excess functions, e.g., Non-Random Two-
Liquid (NRTL).
14
 Equilibrium Between Phases
H2O + SO2 Phase Rule: dof = c – p + 2 = 3 – 2 + 2 = 3
ya xa
At the constant temperature and pressure, given the mole fraction of
SO2 (xA) in water, and the mole fraction of SO2 (yA) in air is determined.
SO2

yb xb
Air + SO2

The low temperature help the SO2 absorption.

15
 Raoult's and Henery's Law
For an ideal solution, the equilibrium partial pressure of A can be written as:

PAL  x A  p*A  T  pA*(T) is the vapor pressure of A at the given temperature T.

For many non-ideal solution at low concentrations (xA0), the equilibrium partial
pressure of A can be described as:
H(T) is the Henery's law constant, determined by equilibrium
PAL  x A  H T 
experimental data.

 A T  x A  H T 
L *
P x p
yA 
* A
 A
or Ptot is the total pressure of the system.
Ptot Ptot Ptot

16
 Two-Film Theory
p. 547
(EXTREMELY IMPORTANT)
Gas Gas Liquid Liquid
Phase Film Film Phase
y Ab
The phase equilibrium is only
assumed at the interface.
y Ai
y Ai  m  x Ai
yA* Not in the bulk phases.
x Ai
y Ab  m  x Ab
x Ab

The molar flux of species A across films at s.s.:

N A  k y  y Ab  y Ai   k x  x Ai  x Ab   K y  y Ab  y *A 
Since the interface is a imaginary boundary, the interfacial
Interface composition yAi is unmeasurable. Therefore, the overall driving
y *A  m  x A force (yAb - yA*) is used where yA* is the composition of the vapor
that would be in equilibrium with the bulk liquid composition. 17
 Overall Mass Transfer Coefficient, Ky
p. 548
Gas Gas Liquid Liquid N A  k y  y A  y Ai   k x  x Ai  x A   K y  y A  y *A 
Phase Film Film Phase
 y A  y *A   y A  y Ai    y Ai  y *A 
NA
Ky
yA
NA N N
y Ai    mx Ai  mx A   A  m A
ky ky kx
yA* 1 1 m
MEASURABLE x Ai  
K y k y kx
xA
1 Overall mass transfer resistance.
Ky Ref: p.11
1
MEASURABLE Gas phase mass transfer resistance.
ky
Interface m
Liquid phase mass transfer resistance.
kx
If m is large, the gas is easily slipped from the liquid, or the solubility of gas is low, the mass
transfer rate is controlled by the liquid-phase resistance, such as: oxygen is absorbed by water.
On the other hand, m is small, the gas is easily absorbed by the liquid, the mass transfer is gas-
phase controlled, for example: ammonia is absorbed by water. 18
 Absorption and Desorption
When the absorption is happening, NA > 0

N A  k y  y Ab  y Ai   k x  x Ai  x Ab   K y  y Ab  y *A   0

y Ab  y Ai , x Ai  x Ab , y Ab  y *A

The operating point M (xAb, yAb) is above the

equilibrium line. At the limiting case, NA = 0 that will
be used to determined the minimum liquid flow rate
(Lmin).

On the other side, the desorption is happening, NA > 0

N A  k x  x ' Ab  x ' Ai   k y  y ' Ai  y ' Ab   K x  x ' Ab  x '*A   0

y ' Ab
x '*A 
m' x ' Ab  x ' Ai , y ' Ai  y ' Ab , x ' Ab  x '*A
The operating point M’ (x’Ab, y’Ab) is below the equilibrium line. 19
How to Measure Mass Transfer
p. 549
Coefficient ky (Gas Phase)
z+z V*y Input = Output
y NA: Absorption
by Liquid Vy  z  N A  2R  z  Vy  z z
Gas yi When y<10%, the constant molar flow
z Film can be assumed, i.e., V=constant.
V* y  y z z  y z 
V: gas molar flow (kmol/h)
lim  V   N A  2 R 
z  0
 z 

Wetted-wall dy 2 Rk y y2
dy 2Rk y L

Column   y  yi   y  y  yi     dz
dz V 1
V 0

y
V 1 dy V y1
2RL y2  y  yi  2 RL y2
y1 z 0  y2 z  L , k y   ln (y >> yi)

Assuming that the solute-free liquid is used, the interfacial mole fraction
of liquid is around zero, i.e., xi  0; therefore, yi  0. 20
 Mass Transfer in a Wetted-wall Column
In an experiment, benzene is absorbed from a stream of nitrogen in a wetted-wall column in
which the absorbent is a non-volatile mineral oil. Under the conditions, the liquid-phase mass
transfer resistance can be neglected. The mass flux of the feed gas is 13,500 kg/hm2 at 30 C
and 1 atm. Mole fractions of benzene in the inlet and outlet gases are 0.02 and 0.0052,
respectively. The interfacial concentration of benzene on the gas side is negligibly small. The
inner diameter of the column is 3.5 cm and the height of the wetted section is 3 m. Calculate
the gas-phase mass transfer coefficient ky.

ky 
V
ln
y1  V  R y
k y   2  ln 1
V2*y2 2 RL y2  R  2 L y 2
Mw1  0.02 * 78  0.98* 28  29
 0.035 2   0.02 
V1 13,500  kmol   471.6 *   *ln  
  465.5  2 
 2 *3   0.0052 
A 29  hm 
 kmol 
Mw2  0.0052 * 78  0.9948* 28  28.3  1.85  2 
 hm 
V2 13,500  kmol 
  477.7  2 
A 28.3  h  m 
V1*y1 V 1  kmol 
  465.5  477.7   471.6  2  21
A 2  hm 
 How to Measure Mass Transfer
Coefficient kL (Liquid Phase)
Q*cb Input = Output
h
cs Q * cb  h   N Aa  Ah  Q * cb  hh
A: cross-sectional area of the column
Particle
Surface a: specific surface area
Liquid cb
contact surface cm 2
h+h Film a   3
unit volume cm
Q*cb Assuming Q is a constant.
cb h h  cb h
lim Q  k L a  cs  cb  A
h  0 h
b2 c H
dcb k L aA dcb k L aA
  s b 
c  c    dh
cb 1  s
dh Q c  cb  Q 0

Packed-Bed  c  c  k aAH Q  c c 
 ln  s b 2   L  kL  ln  s b1 
Column  cs  cb1  Q aAH  cs  cb 2 
22
 Mass Transfer in a Packed Bed
Water at 25 C flows through a bed of benzoic acid (C6H5COOH) spheres of size dp = 8 mm
at a superficial velocity of 0.022 m3/sm2 of bed cross-section. The fractional void volume of
the bed is 0.4 ( = 0.4) and the depth of the bed is 0.7 m. If the inlet water is free from
benzoic acid and the outlet concentration of benzoic acid is 1.0 kmol/m3, calculate the liquid-
phase mass transfer coefficient kL and kx. The specific surface area is given by a = 6(1-)/dp
and the concentration of the liquid in contact with the surface of a sphere is 3.0 kmol/m3.

kL 
Q  c c 
ln  s b1  N A  k L  c Ai  c A   k L c  x Ai  x A 
aAH  cs  cb 2  
 k x  kLc  kL x
Q  m3  M
 0.022 
A  s  m 2 
  0.00283 
 cm 
*
1  g cm 3


1  1  0.4  
1  s  18  g mol 
a6 6  450  
dp 0.008 m  mol 
 1.57  104  2 
 c c   3   cm  s 
ln  s b1   ln    0.41

 s b2 
c c  3  1 

5  m 
3
0.022  cm 
kL  *0.41  2.83  10  2 
 0.00283  
450 *0.7  s  m   s  23