Mass Transfer

CHEG 324 – Spring 2024

3 - Interphase Mass Transfer
Faisal Abdulla AlMarzooqi
MONDAY, MARCH 11, 2024
Single-Phase Mass Transfer and Interphase Mass Transfer:

In the previous sections we went through mass transfer within one phase and calculated the flux in gas or liquid
(Sections 1 and 2). In this part we consider diffusion through phases, therefore we need to establish equilibrium
relationships:

Gas-Liquid systems:

Raoult’s law:
Pa
for Raoult's , m= p
At equilibrium and constant pressure and temperature, for ideal gases and liquids for Henry's m =
H or
H
, p

!! " = $! "! !! and $! = compositions of component A in gas and liquid phases

" = Total pressure of the system
"! = Vapour pressure of A at the system temperature

If the liquid is not ideal: !! " = %! $! "! %! = activity coefficient of A

check its units !

For dilute solutions, Henry’s law is applied: always
↑ dimensionless :

pressure : Pa = Hea
Ya HxA
=

&! = !! " = '$! &! = partial pressure of A ' = Henry’s constant 2

Single-Phase Mass Transfer and Interphase Mass Transfer:

Liquid-Liquid systems:

Distribution law:

(!"#$%#&' = )(!"#$%#&( ) = distribution coefficient

3
Two-Resistance Theory

In Interphase Mass Transfer there are three distinct regions: 1) Phase 1 , 2) Interface and 3) Phase 2

yA,i and xA,i are in equilibrium but …

Concentration of
yA,G and xA,L are not, if they are then bulk mass transfer
diffusing component A
will not occur from gas to liquid.
yA,G Interface
Mass transfer coefficient in each phase is different due
to the difference in chemical potential. xA,i
Gas phase Liquid phase
Mass transfer occurs: yA,i
1. From bulk gas (yA,G) to interface (yA,i)
2. Through interface (yA,i, xA,i)
3. From interface (xA,i) to bulk liquid (xA,L) absorption xA,L
1 2 3
At steady-state (no accumulation): NA1 = NA2 = NA3 Distance
GAS : CCA ,
Why not use the previous model in section 2? yAi and xAi ?
LIQUID TO
Stripping Ya , a

G As TO LIQUID :
absorption Ya GTCA L
because concentration gradient is based different phases ,
,

not just one

,
now our on two
4
Two-Resistance Theory (Lewis and Whitman)

Lewis and Whitman assumed that:

1. Interface has zero thickness because at the interface there is equilibrium ,
so the flux is zero

2. Interface has zero resistance to mass transfer Since the thickness is not there ,
it doesn't interfere w/mass transfer,
so there is zero resistance

…and they called this theory the “Two Resistance Theory” - two resistance of mass transfer in the two phases only

-.! )#$ -)#%

Consider A diffusing through stagnant B: *! = +) !!* − !!# = ++ $!# − $!, ⟶ ."
= +#& -+#%
Note: this is for mass transfer from Gas to Liquid
Concentration of
diffusing component A
yA,G Yac
Interface
KAL

xA,i
Gas phase Liquid phase - Yai
Kai
yA,i

xA,L
1 2 3
5
Distance
Overall Mass Transfer Coefficient

To calculate *! = +) !!* − !!# = ++ $!# − $!, we need to either know +) and ++ or measure !!# and $!# .
Measuring !!# and $!# is almost impossible, so if +) and ++ are not available we define a new mass transfer
coefficient called “Overall Mass Transfer Coefficients”, .) and .+ : *! = .) !!* − !!∗ = .+ $!∗ − $!,
* Valid if Ya MIA
=

!!∗ = /$!, ; !!* = /$!∗ ⟶ for linear equilibrium relationship

*! = +) !!* − !!# = ++ $!# − $!,

>
- capital K in book
*! = .) !!* − !!∗ = .+ $!∗ − $!,

!!* − !!∗ = !!* − !!# + !!# − !!∗

= !!* − !!# + / $!# − $!,

0# 0# 0# 2 ' ' 2
= + ⟶ = +
1" ." .! 1" ." .!
!!∗
Overall resistance = gas phase resistance + liquid phase resistance
"!∗
to find/ resistance in liquid phase :

% same
way for gas
6
Overall Mass Transfer Coefficient
2
if m <<< 1 i.e. (A) very soluble in liquid, then <<< 1 ∴ the liquid phase will have minor resistance and most of the
.!
' ' '
resistance will be from the gas phase ∴ ~ ⟶ .) = +)
." 1" ."

For .+ :
'
=
'
+
' to find/ resistance in liquid phase :
""
1! .! 2."
to find/ resistance in gas phase
:
"I wil,
'
if m >>> 1 i.e. very large m (A) almost insoluble in liquid <<< 1 ∴ the gas phase will have minor resistance and
2."
' ' '
most of the resistance will ve from the liquid phase ∴ ~ ⟶ .+ = ++
.! 1! .!

For equimolar counter diffusion the same equations apply, by applying∴ +)3 and ++3 instead of +) and ++
respectively.

7
Example:

Solute (A) is being absorbed from a binary 0.4

P

gas mixture in a tower with liquid flowing Yag = 0 .

38

downward along the tower wall (liquid does 0.35

↑
not evaporate to enter gas phase, and
component (B) in the gas phase is insoluble 0.3
in the liquid). At a point, the mol fraction of
A in the bulk of gas phase, yAG = 0.38 and in 0.25
the bulk of liquid phase, xAL = 0.1. The tower
is at 298K and 1 atm. Equilibrium data is 0.2197

y
M
Yai20 .

given. For A: ky = 2.066×10-3 kgmol/s.m2

mol frac, and kx = 2.399×10-3 kgmol/s.m2 0.15
mol frac
0.1
Find the interface composition (yAi, xAi), flux
of NA, and overall MTC (RX and RY). Note that 0.05 Y XAL= 0 I
.

ky and kx are given for (A) diffusing (B) non-

diffusing case. 0 aiv0 . 258 xA
*

0 0.05 0.1 0.15 0.2 0.25 0.3 0.35 0.4

x 8
Example:

Solute (A) is being absorbed from a binary 0.4

gas mixture in a tower with liquid flowing
kx/ky the 399/2
2
downward along tower066wall (liquid doesC 0.35
-

161 =
1
slope y mx ;
-

= = +
= .
.
-

not 0.evaporate
38 1 1 16)(0 to
= -
1) centerc gas
. 0 496 phase,
.
y +
and
16x 496 - = .
= -
1 .
+ 0 .

component (B)Min (Kai

plot to get point the Yai)
gas phase
10 258 0 is insoluble
197) ,
=
.

,
.
0.3
in the liquid). At a point, the mol fraction of
A in the bulk of gas phase, yAG = 0.38 and in 0.25
the bulk
Na of ky(Yaa
liquidYai)
phase, xAL = 0.1.
kx(xai CAL)The tower =
- -

is at 298K and 13)(0atm. 197)

(2 066x10 Equilibrium data is
3 78x10- "kmol/m2s 0.2
-

y
=
. . 38 -

0 .
= .

given. For A: ky = 2.066×10-3 kgmol/s.m2

mol frac, and kx = 2.399×10-3 kgmol/s.m2 0.15
Na Ry (Yaa ya) Rx(x* Ca) =
-

mol frac
= -

4
NA
-

3 78x10
=
145x103kmol/m2s 0.1
.

Ry 1
= =

yaG y * 0 38 0 05
- .
-

. .

Find the interface

=
NA
composition
3 78x10 (yAi, xAi), flux
512x10-3 kmol/m2s
=
.
-
4

Rx * xA x 0
=
1

of NA, and overall MTC (RX and RY). Note that

35 0 1
- .

0.05
-

. .

ky and kx are given for (A) diffusing (B) non-

diffusing case. 0
0 0.05 0.1 0.15 0.2 0.25 0.3 0.35 0.4
x 8
Local Mass Transfer Coefficient – General Case

In the previous pages we dealt with stagnant flow and equimolar counter diffusion cases, for the general case we
return to the general flux equation:

'#& (&
4#$ -)#% 4#& -+#& 4#$ -)#% 4#& -+#& 5' (
#$ $
*! = Ψ!* 7* ln = Ψ!, 7, ln ⟶ =
4#$ -)#$ 4#& -+#% 4#$ -)#$ 4#& -+#%

The equation above can be solved by:

1. If there is an algebraic relationship between !!# and $!# , !!# = : $!# , the two equations can be solved
'#& (&
4#$ -6 +#% 4#& -+#& 5' (
#$ $
simultaneously =
4#$ -)#$ 4#& -+#%
2. If the relation between !!# and $!# is available through an equilibrium distribution diagram, then plot
'#& (&
4#$ -)#% 4#& -+#& 5' (
#$ $
= on the same y and x diagram. The intersect would give us !!# and
4#$ -)#$ 4#& -+#%
$!# .

9
Material Balances

So far we have been considering systems of two immiscible phases with one component being transferred from one phase to the other.
Material balance of A from z1 to z2:

moles of A entering the device = moles of A leaving the device

L2 V2
4)5) + 7*8* = 4*5* + 7)8) x2 y2
X2 Y2
4 = TOTAL molar flowrate of phase V [molTotal/s] z = z2
7 = TOTAL molar flowrate of phase L [molTotal/s]
A
Material balance of A from z1 to any arbitrary z:
z
4)5) + 78 = 45 + 7)8) Phase L Phase V

Mole ratios (solute-free concentration unit): A

Y: moles of A in phase V per mole of A-free V (i.e. solvent, s) [molA/molS] z = z1

L1 V1
,! .! x1 y1
9+ = 5+ =
)-,! )/.!
X1 Y1
X: moles of A in phase L per mole of A-free L (i.e. solvent, s) [molA/molS]

!0 1
:+ = )-0 8+ = )/1! 10
!
Material Balances
L2 V2
42 = molar flowrate of solvent in phase V [mols/s]
Y
AKA solute-free vs = v,(1 y , )
-

vz(l ya)
= -

x2 y2
72 = molar flowrate of solvent in phase L [mols/s] flow rate us =
12(1 22) r , (1 x , )
-
= -

X2 Y2
z = z2

∴ we can re-write the material balance … 42 9) + 72 : = 42 9 + 72 :) A

z
3" . -. 3 4".#-3"1# Phase L Phase V
4"
= 1# -1 ⟶ 9 = 4" : + 4"
# "
A
3"
On an XY diagram, the above equation is a straight line with an slope. This line z = z1
4"
L1 V1
passes through (X1, Y1) and (X2, Y2). y1
x1
X1 Y1
This line is called the “operating line” and its equation is called the “operating line
equation” for countercurrent operation.

Y (A) Is transferred from V ⟶ L: Absorption Y (A) Is transferred from L ⟶ V: Stripping

Y1 Equilibrium curve
Operating line Equilibrium curve Yi vs. Xi
$ Yi vs. Xi
Slope = %!
!
Y2 M Operating line
operating line ABOVE $
equilibrium curve Slope = !
%!
Y2 operating line BELOW
equilibrium curve
v Y1
11
X X
X2 X1 X1 X2
Material Balances L2 V2
x2 y2
Why do we plot X and Y instead of x and y? Ls and Vs are constants while L X2 Y2
and V vary as solute is transferred from one phase to the other. z = z2
%A removed =

[1-eing]x0 A
Consider a case where solute (A) is being transferred from the vapour phase z
to the liquid phase, V ⟶ L
=

l 4 *I
-
=
X100
Phase L Phase V

In a typical process plant, the flowrate of the vapour phase (solute-free, i.e. A
solvent (Vs)) and the compositions y1, y2 and x2 are usually fixed. The solute- z = z1
free (i.e. solvent) liquid phase flowrate is a design variable. x1 changes as Ls L1 V1
is varied. x1 y1
X1 Y1
moving adown until moving down until
Ls and X1 are inversely proportional according to the operating line equation: we find tangent we touch the curve

3" .#-. 1 1
= Ls , min Y, -

Ya
4" 1#-1 -
X1 , max Xa
Vs
-

The minimum Ls, Ls|min gives the maximum possible X1, X1|max
Why a minimum and a maximum value of Ls and X1 exist?
At point P the diffusional driving force is zero (because equilibrium is
applies a line
S

achieved)

3 3 | 3
↳ oing below the
tangent means we
This gives us the minimum 4" ratio, " 4&'( the actual 4" ratio is usually enter equilibrium
" " " & then leave it ;
3"|&'( which needs a lot
specified as a multiple of 4 of energy
"
12
Material Balances
LS Y2I max- Y I
A similar analysis can be done for the case of solute (A) transfer from liquid to vapour, L ⟶ V Vs min
-
Xa X,
-

In this case there exists a minimum solute-free (i.e. solvent) vapour phase flowrate Vs|min leading to a maximum Y2|max.

NOTE: THE PHASES LEAVING THE UNITS IN THIS SECTION ARE NOT NECESSARILY IN EQUILIBRIUM

%A removed =

[1-eing]x0
L2 =l Y- =
* [,* ]x100 V2
x2 y2
X2 Y2
z = z2

A
z
Phase L Phase V

z = z1
L1 V1
x1 y1
X1 Y1

13
Equilibrium-Stage Operation

In the previous section we analysed a device in which two immiscible streams are brought into contact with only one component (component
A) being transferred from one phase to the other.

To enhance the separation and increase the transfer of A from one phase to the other, an assembly of multi-stages with a countercurrent flow
configuration is utilized and are usually called cascades.

Ideal Stages: each stage in the below multi-stage system is an ideal stage meaning that enough contact is achieved within each stage such that
the streams leaving the stage are in equilibrium, hence the name “Equilibrium-Stage Operations”.

Why countercurrent?

Are Y1 and XN in equilibrium?

because
no ,
they're not leaving
the same
stage

Since the cascade system overall is a countercurrent unit/device the same equations apply:

3" .)*#-. 3" 4".)*#-3"1) 3"

= ⟶ 9= : + operating line goes through (X0, Y1) and (XN, YN+1) with a slope of
4" 1)-1 4" 4" 4"

NOTE: Always stage 1 is the stage where the L phase enters regardless of the operation being absorption or stripping.
14
Equilibrium-Stage Operation

If the equilibrium and operating lines touch, the stages become

1
Ostripping
pinched and an infinite number of stages is required to achieve the 2

desired composition change.

N-1

This method gives us the number of ideal stages, if stages are not
Y4 - Y4
ideal then additional considerations needs to be taken. N

compositions entering stage 3 22 , Y4 &LB Y4

:
,

i
--
A not
moving

Stage 3 W
i
x2 15
Example

A waste airstream from a chemical process flows at the rate of 1.0 m3/s at 300 K and 1 atm, containing 7.4% by volume of
benzene vapors. It is desired to recover 85% of the benzene in the gas by a three-step process. First, the gas is scrubbed
using a nonvolatile wash oil to absorb the benzene vapors.

Then, the wash oil leaving the absorber is stripped of the benzene by contact with steam at 1 atm and 373 K. The mixture of
benzene vapor and steam leaving the stripper will then be condensed. Because of the low solubility of benzene in water,
two distinct liquid phases will form and the benzene layer will be recovered by decantation. The aqueous layer will be
purified and returned to the process as boiler feedwater. The oil leaving the stripper will be cooled to 300 K and returned to
the absorber.

The wash oil entering the absorber will contain 0.0476 mole fraction of benzene; the pure oil has an average molecular
weight of 198. An oil circulation rate of twice the minimum will be used. In the stripper, a steam rate of 1.5 times the
minimum will be used. The vapour pressure of benzene at 300 K is 0.136 atm and at 373 K is 1.77 atm.

Estimate the number of ideal stages in the absorber and stripper

Answer = 3.80 ideal stages (absorber)

Answer = 5.50 ideal stages (stripper)
16
Example YIA 0 136 atm 0 136 Cia
Yia
= >
- =
Pa
. .

VIA

Y from a chemical process flows at the rate of 1.0 m3/s at 300 K and 1 atm, containing 7.4% by volume of
A waste airstream
benzene vapors. It is desired to recover 85% of the benzene in the gas by a three-step process. First, the gas is scrubbed
using a nonvolatile wash oil to absorb the benzene vapors. 4
YN + 1 A

Then, the wash oil leaving

VN the absorber is stripped of the benzene by contact with steam at 1 atm and 373 K. The mixture of
+ /A

two distinct liquid phases

YNS
purified and returned toUns
as
benzene vapor and steam leaving the stripper will then be condensed. Because of the low solubility of benzene in water,
will form and the benzene layer will be recovered by decantation. The aqueous layer will be
the process as boiler feedwater. The oil leaving the stripper
3 will be cooled to 300 K and returned to
the absorber.

The wash oil entering the absorber will contain 0.0476 mole fraction of benzene;
2 the pure oil has an average molecular
weight of 198. An oil circulation rate of twice the minimum will be used. In the stripper, a steam rate of 1.5 times the I
minimum will
Ybe used. YN
The vapour pressure of benzene at 300 K is 0.136 atm and at 373 K is 1.77 atm.
+ 1S

Vn + 1S

Estimate the number

Pi (101 of ideal 0stages in the absorber and stripper
325)(1) .

Un + 1 A
=

RT
=
18 . 314)(300)
=
.
406kmol/s 0 48
. 0 91.

Vs
=
jN + 1 a(l -

yn + 11) = 0 . 406(1 -
0 .
074) = 0 038kmol/s
.

YN + 1
Answer
Yn = 3.80 YNideal stages (absorber)
A 0 074
.

Ls , min YN + IA YIA
-

0 08-0 012
0 0799 21s , min = 6 mol/s
= - =
Ls 10 038x103) 3 mol/s- Ls =
. .

= >
- =
11 1 1 min =
.

+ -
0 074 Vs XNa max- XoA
-
,
0 91
.

+1 A 0 05

Answer = 5.50 ideal stages (stripper)

.
-
.

, .

20A 0476 0
XoA Ya-Ya
=
.

= =
04998 =
0
1 201 1 0 0476 >
-
XNA 0 4807 ideal stages 4
=
- .
-
>
- =
no
XNA XoA
.
- .
.

Y(A =
0 . 85(1 -

YN + 11) = 0 . 08(1 -
0 . 85) = 0 012
.

16
Example YIA
Pa
=
1 77
.
atm >
-
Gia = 1 .
TTHia

VIA

Y
A waste airstream from a chemical process flows at the rate of 1.0 m3/s at 300 K and 1 atm, containing 7.4% by volume of
benzene vapors. It is desired to recover 85% of the benzene in the gas by a three-step process. First, the gas is scrubbed
using a nonvolatile wash oil to absorb the benzene vapors. 175 1 .

YN + 1 A

Then, the wash oil leaving

VN the absorber is stripped of the benzene by contact with steam at 1 atm and 373 K. The mixture of
+ /A

benzene vaporY and steam leaving the stripper will then be condensed. Because of the low solubility of benzene in water,
two distinctXOSliquid phases will form and the benzene layer will be784 recovered by decantation. The aqueous layer will be
0
YNS
.

purified andLosreturned Uns

to the process as boiler feedwater. The oil leaving the stripper will be cooled to 300 K and returned to
the absorber. I

The wash oil entering the absorber will contain 0.0476 mole fraction of benzene; the pure oil 2 has an average molecular

weight of 198. An oil circulation rate of twice the minimum will be used. In the stripper, a steam rate of 1.5 times the
3
minimum XNS
will be used.
YN The vapour pressure of benzene at 300 K is 0.136 atm and at 373 K is 1.77 atm.
+ 1S
LNS Vn + 1S 4

Estimate the number of ideal stages in the absorber and stripper 5

Ls = 6 mol/s
20A 0 0476
XoA
.

XNS
= I =
0 04998
1 -

20A 1 -
0 0476
.
. =

Answer =YN3.80 0ideal

+ (pure stages
1 s
=
steam) (absorber) Ls
Vs , min
I
YNs , max-Yots
Xos-XNS
>
-
Vs, min = 6 (0 g3) 2 .
196mol/s - Vs = 1 . 5Vs , min
=
3 29 molls
.

Answer = 5.50 idealXOS

0 4807
X Na = .
stages (stripper)
= Ls YNS -

YN + 1S
Es
= >
-
YNs =
0 784 -
no. ideal stages =
5
Xos-XNS
.

16
Analytical determination of number of ideal stages

O
For special cases where the equilibrium curve is a straight line through the origin i.e. Yi = mXi MUST BE TRUE

An analytical solution was developed by Kremser:

3" Slope of operating line

Absorption factor, = = =
64" Slope of equilibrium line

For transfer from L to V (Stripping of L):

ideal
eno of stages
1+-1)
A = 1: C= ,
1)- )*#
&

,
-+. )*#
&
89 ,)*# )-+ /+
-). &
A ≠ 1: C= #
89 !

For transfer from V to L (Absorption into L):

.)*#-.#
A = 1: C=
.#-61+

, .&-+ # #
89 )*#
, .&-
)-! /!
# +
A ≠ 1: C=
89 +
17
Example

An absorber consisting of a cascade of 10 real stages is used to remove 99% of solute A from a gas stream
using pure liquid. The overall efficiency of the cascade is 62.4%. The equilibrium expression is Yi = 1.2Xi. The
gas enters the cascade at 100 mol/s, with a mole fraction of A of 10%. Calculate the flowrate of liquid
required for the specified fractional removal using this absorber.

n
=
Nidea -
Nideal
=
10 624) (10) = 6 24
. .

stage o

99 % removed >
-
X1 =
0 01 .
YN +

YN + 1
Yn + 1 =
1 -

yN + 1
I
8a = 0 111.
-
y, = 0 . 0110 111)
.
= 0 0111
.

YN+ 1 YI
-

0 111-0 00111
A=
assuming N 9976 24
.

1
.

- = =

y, -

10
mXo 0 0011/
.
= .

YN + 1 -
mXo
[ (1 1) t J
-

In
-
+
-
Y, -mXo
refor t
A
thus , A + 1 A = 1 85
- N = .

In (A)

Vs = Vn +, (1 -

yu 1)+
=
100(0 . 9) = 90 mol/s

A= m +
Ls =
AmVs =
(1 85)(1 2)(90)
. .
= 199 8 mol/s .

18
Co-current Flow

For a steady-state material balance of A:

VàL LàV

19
Batch Process

- Not steady state, the concentration changes with time

- The system approaches equilibrium with time (operating line touches the equilibrium line)

- The same equations and plots of the co-current apply here, with the difference that there is no flow, in and out of the system.

- If the two phases are kept for long enough in contact X2 and Y2 in the plot will be on the equilibrium line.

20