Mass Transport and Operations

LECTURE 4
CHMT 3039A
Prof. Geoffrey S. Simate
Interphase Mass Transfer
School of Chemical and Metallurgical Engineering
University of the Witwatersrand, Johannesburg

Prof. Geoffrey S. Simate

Room RW 119
RW 517

Mass transfer across interphase

Introduction

The theories presented in the previous lectures have shown mass transfer from
one point to another in a single phase or in a homogeneous medium using

PART I  Equations of molecular diffusion

 Phenomenological mass transfer coefficients

In most of the existing operations, however, material is transferred from one

phase to another across a phase boundary
The Film Theory
Example of mass transfer across the boundary

 In distillation, a vapour and a liquid are brought into contact where the more
volatile material transfers from the liquid to the vapour phase and the less volatile
material transfers, in the opposite direction, from the vapour to the liquid.

 In gas absorption the soluble gas diffuses from the bulk of the gas to the gas-
liquid interface, dissolves in the liquid, then diffuses in the bulk of the liquid.

3 How can we calculate the rate of mass transfer in a two phase system?
 Mass transfer across interfaces Film theory
How can we calculate the rate of mass transfer in a two phase system? Entire resistance to mass transfer in a given turbulent phase is in a thin, stagnant
region of that phase at the interface, called a film.
Since mass transfer occurs in both phases, we need to make use of two mass
transfer coefficients – one for each phase Liquid
For the system shown, gas is taken as film
The driving force is not merely the difference in the concentrations of the solute in pure component A, which diffuses into
the two phases. The driving force is rather measured by how far the phases are non-volatile liquid B.
pA
away from equilibrium
In reality, there may be mass transfer
If two phases are at equilibrium, there is no net transfer of solute from one phase resistances in both liquid and gas phases. Bulk
CAi
So we need to add a gas film in which gas liquid
to the other
is stagnant. Gas
If the two phases are not in equilibrium, mass transfer from phase-I to phase-II CAb
occurs as long as the concentration of the solute in phase-II is lower than the
equilibrium concentration. The extent of deviation from the equilibrium state is a
z=0 z=δ
measure of the ‘driving force’ for mass transfer. Similar arguments apply if there
are more than two phases in contact Mass transport

5 6

The two-film theory The two-film theory: Concentration profile

There are two stagnant films (on either side of the fluid-fluid interface).

Each film presents a resistance to mass transfer Interface Interface

Gas Liquid
Concentrations in the two fluid at the film film
interface are assumed to be in phase Gas Liquid Gas Liquid
phase phase phase phase
equilibrium (e.g., pAi and CAi are in Liquid pAb pAb
equilibrium) Gas film film
pAi pAi
Gas Liquid
phase phase CAi CAi
For ideal gas-liquid or vapour-liquid pAb CAb CAb
system, the equilibrium relationship
pAi
obeys the Raoult’s law CAi Mass transport Mass transport
Equilibrium data for many non-ideal CAb
Concentration gradients for More realistic concentration
gas-liquid systems at low
the film theory gradients
concentrations can be expressed by Mass transport
the Henry’s law 7 8
 Two-film theory applied at steady state Derivation of the overall mass transfer coefficient
Mass transfer from one phase (e.g., gas phase, G) to another phase (e.g., liquid Interface
Gas Liquid film
phase, L) involve the following sequential steps:
film
 The solute (A) is transported Gas phase Liquid
from the bulk of the gas phase Interface Liquid phase
Gas pAb
(G) to the gas-liquid interface film
film yAb pAi
Gas
phase Liquid x*Ab yAi
 The solute (A) is picked up or CAi
absorbed by the liquid phase (L)
phase CAb
pAb xAi
at the gas-liquid interface xAb
yAb pAi y*Ab
x*Ab yAi
 The absorbed solute (A) is CAi
CAb Mass transport, NA
transported from the interface to xAi
xAb
the bulk of the liquid (L)
y*Ab Consider the gas-liquid interface in the above figure
The first & third step are facilitated by Assume that a stagnant film exists near every interface
Mass transport, NA
turbulence in the fluid medium Gas on the left is being transferred into the liquid in the right side

9 10

Derivation of the overall mass transfer coefficient
Consider the gas liquid interface in the previous figure
Assume that a stagnant film exists near every interface
Gas on the left is being transferred into the liquid in the right side
 The mass transfer flux in the gas phase is
N A = k y (y Ab  y Ai ) (1)
Derivation of the overall mass transfer coefficient
 We can not determine the interfacial composition (p Ai or y Ai and x Ai or
CAi ), so such a representation may not be useful. Instead the bulk driving
force can be used, i.e., the composition of the gas phase (y*Ab ) in
equilibrium with the bulk concentration of the liquid phase (x Ab ) or the
liquid composition (x*Ab ) in equilibrium with the bulk gas phase (y Ab )

N A = K y (y Ab  y* ) (3)
 Because the interfacial region is thin, the mass transfer flux across it will Ab
(on the basis of mole fraction of the gas phase)
be in steady state, and the mass transfer flux in the gas will equal that in the
liquid phase
N A = K x (x*  x Ab ) (4)
Ab
N A = k x (x Ai  x Ab ) (2) (on the basis of mole fraction of the liquid phase)

 In order to determine K y in terms of k y and k x , Eqn (3) is rearranged as

11 12
follows:
 Derivation of the overall mass transfer coefficient Derivation of the overall mass transfer coefficient
 In order to determine K y in terms of k y and k x , Eqn (3) is rearranged as 1 1 (yA i  y*A b )
= + (7)
follows: Ky ky k x (x A i  x A b )

1 (y Ab  y* )  Plotting y A versus x A gives the equilibrium curve to which

= Ab
Ky NA (y Ai  y*Ab )/(x Ai  x Ab ) is the slope m (see Figure below)

(y A b  y A i ) (y A i  y*A b ) 1 1 m
1  = + (8)
 = + (5) Ky ky kx
Ky NA NA
( giving the overal gas-side mass transfer coeffiecient)

 Substituting Eqn (1) and (2) into Eqn (5) yields:

 Similarly, the overall liquid-side mass transfer coefficient is given as
1 (yA b  yA i ) (yA i  y*A b )
= + (6) 1 1 1
Ky k y (yA b  yA i ) k x (x A i  x A b ) = +
K x mk y k x
(9)

1 1 (yA i  y*A b )  Eqns (8) & (9) lead to the concept of controlling resistance in mass
 = + (7)
Ky ky k x (x A i  x A b ) 13 transfer resitance 14

Graphical determination of interfacial concentrations Mass transfer resistance

slope of the chord = m'
 Eqns (8) & (9) lead to the concept of controlling resistance in mass
slope of the chord = m''
transfer resitance

slope = -kx/ky
 Since K y in Eqn (8) is the overal mass transfer coefficient, its inverse
1/K y is the overal mass transfer resistance on the gas-phase basis. It is
the sum of the individual mass transfer resistances of the two phases as
yAb P
described below:

gas-phase
equilibrium curve
1
driving force = individual gas-phase mass transfer resitance
ky
yAi
N m
 individual liquid-phase mass transfer resitance (on gas-phase
y*Ab kx
XAb XAi X*Ab basis)

liquid-phase
16
driving force
 Mass transfer resistance Mass transfer resistance
 Similarly is the message of Eqn (9):  Similarly (on the basis of overal liquid side mass transfer coefficient)
1
= individual liquid-phase mass transfer resitance The fractional resistance offered by the gas-phase
kx
resistance offered by the gas-phase 1/mk y
1 =  (12)
 individual gas-phase mass transfer resitance (on liquid-base total resistance of the two phases 1/K x
mk y
basis)
The fractional resistance offered by the liquid-phase
resistance offered by the liquid-phase 1/k x
Also (on the basis of overal gas side mass transfer coefficient) =  (13)
total resistance of the two phases 1/K x
The fractional resistance offered by the gas-phase
resistance offered by the gas-phase 1/k y
=  (10)
total resistance of the two phases 1/K y

The fractional resistance offered by the liquid-phase

resistance offered by the liquid-phase m/k x
=  (11)
total resistance of the two phases 1/K y 17 18

Henry’s law Example 1

 Equilibrium is assumed to exist across the interface, so from Henry's law The equlibrium distribution of a solute A between air & H 2 O at low
p Ai =HCAi (14) concentration at a particular temperaure is given below
y=1.2x
 The 'pseudo' partial pressure, p*Ab , is the partial pressure in equilibrium At a certain point in a mass transfer device, the concentration of solute
with the liquid bulk concentration A in the bulk air is 0.04 mole fraction & that in the bulk aqueous phase
p*Ab =HCAb is 0.025. In which direction does the transport of the solute A occur (i.e.,
(15)
from the gas to the liquid or from the liquid to the gas)? Calculate the
overall gas-phase & the overall liquid-phase driving forces for mass
 The 'pseudo' concentration, C*Ab , is the concentration in equilibrium with transfer
the bulk gas partial pressure At the same point, the local individual mass transfer coefficients for the
C*Ab =H-1p Ab (16) transport of A are k y =7.2 kmol/(h)(m 2 )(y) & k x =4.6 kmol/ (h)(m 2 )(x).
Calculate
 There are two limiting cases of interest:
(a) the interfacial concentrations in both the gas-phase & liquid-phase;
(b) the overal mass transfer coeffcients, K x &K y ; and (c) the local flux, N A .
(1) A highly soluble gas (H<<1): Ky = ky (17)
19 Which resistance controls the role of mass transfer? 20
(2) A sparingly soluble gas (H>>1): Kx = kx (18)
 Solution Solution
 Bulk concentration of A in the gas-phase, y b = 0.04;  The overall driving force:
equilibrium relationship: y = 1.2x
 The corresponding equilibrium (or saturation) liquid-phase On the gas-phase basis:
concentration, y b  y*b  0.04  1.2x b  0.04  (1.2)(0.025)  0.01
y 0.04
x*b = b =  0.0333
1.2 1.2 On the liquid-phase basis:
x*b  xb  0.0333  0.025  0.0083
 The actual concentration of the solute in the bulk liquid is x b =0.025
which is less than the equilibrium value,x*b = 0.0333

 The transport of solute A will occur from the gas-phase to the liquid-
phase

21 22

Solution Solution
(a) Given: k y = 7.2 kmol/(h)(m 2 )(y); k x = 4.6 kmol/(h)(m 2 )(y).
Similarly, the overal liquid-phase coefficient
At steady state, the local flux is
1 1 1 1 1
N A = k y (y b  yi ) = k x (x i  xb ) = +  +  0.1157  0.2174  0.3331
K y mk y k x (1.2)(7.2) 4.6
 7.2(0.04  yi ) = 4.6(x i  0.025) (1)

1
Also yi = 1.2x i (assuming interfacial equilibrium) (2) Kx = =3.002 kmol/(h)(m 2 )(x)
0.3331

 Solving the two equations, the interfacial concentrations are: (c) The local mass flux
x i = 0.03044 and yi = 0.03653
N A = k y (y b  yi )=7.2(0.04  0.03653)=0.025 kmol/(h)(m 2 )

(b) The overal gas-phase coefficient

1 1 m 1 1.2
= +  +  0.1389  0.2609  0.3998
K y k y k x 7.2 4.6
1
Ky = = 2.501 kmol/(h)(m 2 )(y) 23 24
0.3998
 Solution Example 2
The equilibrium solubility of SO2 in water at 30°C is given in the table below:
 The controlling resistance:
pSO2, mm Hg 0.6 1.7 4.7 8.1 11.8 19.7 36 52 79
g SO2 per 100 g H2O 0.02 0.05 0.10 0.15 2.0 0.3 0.5 0.7 1.0
Fraction of the total mass transfer resistance in the gas-phase
resistance offered by the gas-phase 1/k y 1/7.2 At a point in an absorption column operating at a total pressure of 4.5 bar, the
=  = = 0.347
total resistance of the two phases 1/K y 1/2.501 bulk concentrations in the liquid and gas-phase are x = 0.0014 and y = 0.02,
respectively. The individual liquid-phase and gas-phase mass transfer coefficients
Fraction of the total mass transfer resistance in theliquid-phase are kx = 0.80 kmol/(h)(m2)(Δx) and ky = 0.15 kmol/(h)(m2)(Δy)
resistance offered by the liquid-phase 1/k x 1/4.6
=  = = 0.653 Calculate (a) the interfacial concentrations at the particular locations, (b) the
total resistance of the two phases 1/K x 1/3.002
overall mass transfer coefficients and the rate of absorption, (c) the individual and
overall driving forces at the location in terms of Δx and ΔC, and (d) what fraction
 The mass transfer resistance of the liquid phase is higher so it controls
of the total resistance is offered by the gas phase? What should have been the
the role of mass transfer
value of the coefficient ky, if the gas-phase offered 60% of the total resistance to
mass transfer (for the given liquid-phase coefficient)?

25 26

Solution Solution
Convert the equilibrium data so that it is in terms of x and y: (A) Plot the equilibrium data (x,y) as shown in the figure below:

For example:

data set p = 52 mm Hg and liquid concentration = 0.7 g SO2 per 100 g H2O
P (0.0014,0.02)
 Total pressure, P = 4.5 bar = (4.5)(760/1.013) mm Hg
52 mm Hg
 y= = 0.0154
(4.5)(760/1.013) mm Hg
102 y
Slope of PM =-kx/ky
M (0.00206, 0.0164)
 Molecular weight of SO 2 = 64; H 2O = 18
0.7/64
 x= = 0.001965
(0.7/64) + (100/18)
Equilibrium curve, y* = f(x)
The calculated equilibrium data is given below:
103 x
103x 0.0562 0.1403 0.280 0.422 0.564 0.842 1.403 1.965 2.79
pSO2, mm Hg 0.6 1.7 4.7 8.1 11.8 19.7 36 52 79
102y 0.0178 0.0504 0.139 0.24 0.35 0.584 1.07 1.54 2.34 The bulk concentrations of the two phases are given: xb = 0.0014; yb = 0.02

 locate point P (0.0014,0.02) on the x-y plane

27 28
 Solution Solution
k
 A line PM of slope  x = 
80
=  5.33 is drawn through the point P 1 1 m 1 1 1
= + (Eqn. 8) and = + (Eqn. 9)
ky 15 Ky ky kx K x mk y k x
so as to meet the equilibrium line at M.
1 1 m 1 5.65
 The point M gives the interfacial concentration of the phases:  = +  +  0.1373
K y k y k x 15 80
 x i = 0.00206, yi = 0.0164
 K y  7.28 kmol/(m 2 )(h)(y)

(B) The overall coefficients:

1 1 1 1 1
In the region near the interfacial concentration, the equilibrium line is almost  = +  +  0.0243
K x mk y k x (5.65)(15) 80
linear.
 The slope (m or m) is determined as = 5.65  K x  41.1 kmol/(m 2 )(h)(x)

Use equation (8) and (9) to solve for Ky and Kx

 Absorption flux, N A :
1 1 m 1 1 1 NA = k y (y b  yi ) = 15(0.02  0.0164)
= + (Eqn. 8) and = + (Eqn. 9)
Ky ky kx K x mk y k x
29
 N A = 0.054 kmol/(m 2 )(h) 30

Solution
(C) This part is left as an exercise

(D) This part is left as an exercise

PART II

Material Balance

(Note: develop mathematical expressions for

the concentration profile or operating lines
using material balance learnt in first year)
31
 Material balance in a contacting equipment Steady-state counter current mass transfer
G
Notation Gs B
The concentration differences in the previous lectures were those existing at one 1 y 2
G1 = rate of input of phase G at
position section 1, mol/time G1 Y G2
G2 = rate of output of phase G at GS GS
In a steady-state process, because of the transfer of solute from one phase to the y1 y2
section 2, mol/time
other, the concentration within each phase changes as it moves through the Y1 Y2
GS = rate of flow of phase G on
equipment. In batch processes the concentration changes with time solute-free basis, mol/time
L1 L2
G = rate of flow of phase G at any
LS LS
section, mol/time
x1 x2
The following are some of the modes of contact: y1,y2,y = mole fractions of solute 1 X2
X1
in phase G at respective sections 2 LB
Countercurrent contact in which the phases move in opposite direction Y1,Y2,Y = mole ratios of solute in LS
phase G at respective sections x
Cocurrent contact in which the phases move in the same direction
X Fig.1. Mass
L1 = rate of output of phase L at section 1, mol/time balance for
Crosscurrent contact in which phase G flows from one stage to the next
steady state
L2 = rate of input of phase L at section 2, mol/time
sequentially & an amount of fresh L phase is added to each stage & the countercurrent
LS = rate of flow of phase L on solute-free basis, mol/time
phases are brought into intimate. The phases leaving a stage are then L = rate of flow of phase L at any section, mol/time
separated x1,x2,x = mole fractions of solute in phase L at respective sections
X1,X2,X = mole ratios of solute in phase L at respective sections

Steady-state counter current mass transfer Steady-state counter current mass transfer
Assume phase L & G are mutually immiscible and are the ‘carriers’ of solute A At steady state,

Let single component A diffuse from phase G to phase L during their contact  Rate of input = Rate of out put
LSX 2 + GSY=LSX + GSY2
Material balance over envelop 1 (the molar flow rates of phases, GS & LS, are
taken on a ‘solute-free basis, i.e., these are simply the flow rates of the carrier GS (Y  Y2 )=LS (X  X 2 ) (1)
phases; GS & LS remain constant through since it is assumed that they are
Eqn (1) represents a straight line having a slope LS/GS and passing through the
immiscible)
point X2,Y2. This eqn is called the equation of the operating line
 The total rate of input of the solute (with both the phases)
The operating line relates the bulk concentrations (X,Y) of the two phases at any
= LSX 2 + GSY
section in the mass transfer equipment with terminal concentrations ( i.e., it gives
the general relationship between concentration in the phases at any
 The total rate of output of the solute (with both the phases)
section)
= LSX + GSY2
X2 & Y2 are the concentrations of the two phases at the terminal of the equipment
At steady state, while X & Y are the concentrations at any location within the equipment

 Rate of input = Rate of out put

 Steady-state counter current mass transfer Steady-state counter current mass transfer
Material balance over envelop 2

Concentration in phase G mole A/mole non-A=Y

Equilibrium curve Yi=f(Xi)
 The total rate of input of the solute (with both the phases)
operating line,
= LSX 2 + GSY1 Q
slope=Ls/Gs
(X1,Y1)
(transfer from G to L)

 The total rate of output of the solute (with both the phases) M
Y N'' S
= LSX1 + GSY2 (X2,Y2)
M'
N' operating line,
At steady state, P slope=Ls/Gs (transfer from L to G)
(X2,Y2)
Line MN''= local overall driving force line
LSX 2 + GSY1 = LSX1 + GSY2 for phase L; Line MN'= local overall
R
(X1,Y1) driving force line for phase G

GS (Y1  Y2 )= LS (X1  X 2 ) (2) X

Concentration in phase L mole A/mole non-A=X

Eqn (2) indicates that the point (X1, Y1) satisfies Eqn (1). So the operating line Fig. 2. The operating line for a counter current contact (concentrations are in mole
joins the points (X1, Y1) & (X2 , Y2) ratio units)

Steady-state counter current mass transfer Material balance using mole fractions
Figure 2 shows the operating line PQ on the X-Y plane. The equilibrium curve is The entire exercise can also be done using the concentrations of the phases in
also shown on the figure the mole fraction unit instead of the mole ratio unit

Point M on line PQ represents the bulk concentration of the phases at any section
Material balance over envelop 1
of the equipment

Line MN' represents the overall driving force at this section for phase G. Similarly,
 Rate of input = Rate of out put
line MN'' represents the overall driving force for phase L.
L 2 x2 + Gy = Lx + G 2 y2

A line of slope -kX/kY through M meets the equilibrium curve at a point M' that
Gy  G 2 y2 = Lx  L 2 x2 (3)
gives the interfacial concentrations of the phases at this section

If another set of values of the terminal concentrations (X1, Y1) & (X2 , Y2), There is a major difference between Eqn (3) & Eqn (1). The quantities G & L (i.e.,

represented by the points R & S, are chosen such that the operating line is total flow rates of phases – carrier & solute) are not constant. Transfer of solute

represented by RS (lying below the equilibrium curve) then there will be a from G to L increases L until the value of L1 at the exit is reached. The flowrate of

‘negative driving force’ for the transfer of solute from phase G to L. So, in effect, G also changes likewise. The operating line (L/G) will keep on changing along the

transfer of solute from phase L to phase G will occur equipment thus it is no longer a straight line, but a curve drawn on the x-y plane
(Fig 3). However, if the concentrations of the phases are low, the variations in the
flow rates will be small. In such a case, the operating line will be nearly straight
 Material balance using mole fractions Steady-state cocurrent mass transfer
The figure below shows the schematic of the cocurrent contacting apparatus. The
operating line
Q(x1,y1)
(transfer from G to L) notation used for the phase flow rates and concentrations have the same
significances as in Figure 1 G
GS B
1 y 2
y Y G2
equilibrium curve G1
GS GS
P y1 y2
(x2,y1) 1
Y1 Y2

L2
x
L1 LS
LS x2
x1 X2
Fig. 3. The operating curve for a counter current process (concentrations are in
X1 2 LB
mole fraction) LS
x
X
Fig.4. Mass balance for steady state cocurrent

Steady-state cocurrent mass transfer Steady-state cocurrent mass transfer

Flowing the procedure used in the previous section, the steady state material Material balance over envelop 2
balance equation (with the concentrations expressed in mole ratio unit) over At steady state,
envelope 1 may be written as
LSX1 + GSY1 = LSX2 + GSY2
 Rate of input = Rate of out put
LSX1 + GSY1 = LSX + GSY GS (Y1  Y2 )= LS (X 2  X1 ) (5)

GS (Y1  Y) = LS (X  X1) (4) Eqn (5) indicates that the operating line Eqn (4) is satisfied by the point (X2, Y2).
So in the case of cocurrent contact also, the operating line joins the points
Eqn (4) represents a straight line of slope (–LS/GS) & passing through the point representing the terminal concentrations of the two phases
(X1,Y1) The eqn relates the bulk concentrations (X,Y) of phases at any section
inside the apparatus with the terminal concentrations at (X1,Y1) at one end ( i.e., it
gives the general relationship between concentration in the phases at any
section)

Eqn (4) is the equation of the operating line for cocurrent contact
 Steady-state cocurrent mass transfer Steady-state cocurrent mass transfer
Figure 5 shows the operating line PQ on the X-Y plane together with the
equilibrium curve
(solute transfer Point M on line PQ represents the bulk concentration of the phases at any section
from G to L)
slope =-LS/GS of the equipment

Line MN' represents the overall gas-phase driving force and line MN'' represents
P
(X1,Y1) M (X,Y)
the overall liquid-phase driving force at this section.
N''
(X2,Y2)
Y Q slope =-LS/GS If a line of slope -kX/kY is drawn through M & meets the equilibrium curve at point
S (solute transfer
Slope = -kX/kY F M', it gives the interfacial concentrations of the phases at this section
from L to G)
M'(Xi,Yi) If the phases are allowed to reach equilibrium, the equilibrium concentration will
N' R
be given by F

If the point representing the concentrations of the phases at the inlet lies on the
X other side of the equilibrium curve, the operating line is represented by line RS.
Fig. 5. Operating lines for cocurrent contact (concentrations in mole ratio unit) As the sign of the driving force changes, transfer of solute occurs from L to G

The material balance can also be written using mole fraction unit & as in the case
of countercurrent, the operating line will be a curve

Steady-state crosscurrent mass transfer Steady-state crosscurrent mass transfer

Figure 6 shows a cross-flow cascades which may be used in processes such as Figure 7 shows the operating lines for each stage
adsorption, leaching, drying and extraction but rarely in others It can be seen that both the slope and the driving force change with the stage
Each circle represents a stage because x decreases with successive stage

Concentration in phase G mole A/mole non-A=Y

L11 LS1 L22 LS2 L33 LS3
x1 X1 x2 X2 x3 X3
G0, GS G1, GS G2, GS G3, GS
1 2 3
y0, Y0 y1, Y1 y2, Y2 y3, Y3 Y1
L20 LS2 L30 LS3 Y2
L10 LS1 x0 X0 -Ls/Gs2
x0 X0 x0 X0 Y3 Slope=-Ls/Gs1
-Ls/Gs3

Yo

Fig.6. Flow arrangement in a crosscurrent contact X3 X2 X1 X0

Concentration in phase L mole A/mole non-A=X

Fig. 7. Concentration in phase G, moles A/mole non-A

Example (Refer to Treybal: Illustration 5.2)