MASS TRANSFER

Assoc. Prof. Dr. Emel AKYOL

Mass Transfer Using Film Mass-Transfer
Coefficients
and Interface Concentrations
 Mass transfer between phases

Concentration cA1 and cA2 are the bulk phase

concentrations in fluids 1 and 2, respectively, cAi is
the concentration of A at the interface, and NA is the
molar flux of A. For steady state conditions, we can
define the flux of A as

where
kc = individual mass transfer coefficient defined in terms
of the concentration difference in a single phase.
Kc = overall mass transfer coefficient defined in terms of
the overall difference in composition.
Figure 1. Concentration gradients near the interface between immiscible
fluids 1 and 2
 Equation (1) is analogous to that in heat transfer, where the individual coefficients h are related to the overall
coefficient U.
From equation (1),

In equation (1), the potential for mass transfer is exposed in terms of composition. However, this is not always the most
convenient way to express it. For example, if fluid 1 is a gas and fluid 2 a liquid, as in gas absorption, the potential in gas
phase is often expressed in terms of partial pressures, while that in the liquid phase may be expressed in terms of
concentrations. The expression for the molar flux is then written for the individual phases as:

where
kp = individual mass transfer coefficient for the gas phase with the potential defined in terms of partial pressures.
PAG , CAL = partial pressure and concentration of A in the bulk gas and liquid phases, respectively.
PAi , CAi = partial pressure and concentration of A, respectively, at the interface.
By varying this partial pressure of A at that fixed temperature,
we can vary the equilibrium concentration of A that would be
obtained in the liquid. These data points are usually plotted in
the form of an equilibrium curve, and fitted to a suitable model
that describes the compositions in equilibrium.

The key idea to grasp is that it is departure from equilibrium

that drives mass transfer. Thus, the partial pressure of A in the
bulk gas phase must be larger than , PAi for A to diffuse from the
bulk to the interface.

Likewise, for species A to diffuse from the interface to the bulk

liquid phase, there must be a concentration driving force.
We can write the molar flux of A in the gas film as

where kG is the mass transfer coefficient for partial pressure driving forces
in the gas phase. We assume steady operation so that this flux NA remains
constant throughout the gas “film.” This flux of A has to enter the liquid,
because A cannot accumulate at the interface, which has no volume. At
steady state, NA must remain constant throughout the liquid “film.” We can
write this molar flux of A that crosses over into the liquid phase as

using a liquid-phase driving force. We have adopted the convention that

this liquid-phase mass transfer coefficient should be designated kL to
maintain consistency with common notation in absorption problems, even
though the designation kC would be equally acceptable. Equating the
results for NA in the two phases yields

so that we find the slope of the straight line joining the two points
(CAL, PAG) and (CAi, PAi) to be given by
Overall mass transfer coefficients
Let us examine the equilibrium diagram again, but this time with
a couple of additional points marked on it.

You’ll notice that the additional points are (CAL, P*A) and (C*A, PAG). The
partial pressure P*A is the equilibrium partial pressure corresponding to
the bulk liquid phase concentration , CAL. Likewise, the concentration C*A is
the equilibrium concentration in the liquid that would correspond to the
partial pressure of A in the bulk gas phase, PAG.
Let us first consider P*A. This is a unique partial pressure that can be used
as an equivalent gas phase partial pressure corresponding to the bulk
liquid phase concentration, CAL. Thus, an overall driving force for mass
transfer can be written purely in gas phase partial pressures of A as
(PAG - P*A). We can now express the molar flux in terms of this overall
driving force for mass transfer and an overall mass transfer coefficient.

where KG is termed the “overall mass transfer coefficient based on gas

phase driving forces.” In an equivalent manner, we also can write
where KL is termed the “overall mass transfer
coefficient based on liquid phase driving
forces.
 Phase Rule and Equilibrium
In order to predict the concentration of a solute in each of two phases in equilibrium, experimental equilibrium data must
be available. Also, if the two phases are not at equilibrium, the rate of mass transfer is proportional to the driving force,
which is the departure from equilibrium. In all cases involving equilibria, two phases are involved, such as gas-liquid or
liquid-liquid. The important variables affecting the equilibrium of a solute are temperature, pressure, and concentration.
The equilibrium between two phases in a given situation is restricted by the phase rule:

F=C-P+2 (4)

Where
P is the number of phases at equilibrium,
C the number of total components in the two phases when no chemical reactions are occurring, and
F the number of variants or degrees of freedom of the system.
 For example,
for the gas-liquid system of
CO2-air-water, there are two phases and three components (considering air as one inert component).
F= C- P+2=3-2+2 =3

For ex: How many degrees of freedom has each of the following system?
a)Liquid water in equilibrium with its vapor.
b)Liquid water in equilibrium with a mixture of water vapor and nitrogen.
c) A liquid solution of alcohol in water in equilibrium with its vapor.

a)F=2-π+N=2-2+1=1 (At a given pressure water has one boiling point. T o rP, but not both, maybe specified.
b) F=2-π+N=2-2+2=2 (now T and P may be independently varied)
c) F=2-π+N=2-2+2=2 ( the phase rule variables are T, P and the phase composition)
 Henry's law.
Often the equilibrium relation between PA in the gas phase and xA can be
expressed by a straight-line Henry's law equation at low concentrations.

PA= H XA (5)

where H is the Henry's law constant in atm/mole fraction for the given
system. If both sides of Eq. (5) are divided by total pressure P in atm.

yA= H’xA (6)

where H' is the Henry's law constant in mole frac gas/mole frac
liquid and is equal to H/P. Note that H' depends on total
pressure, whereas H does not.
 EXAMPLE

What will be the concentratibn of oxygen dissolved in water at 298 K when the solution is in equilibrium with air at
1 atm total pressure? The Henry's law constant is 4.38 x 104 atm/mol fraction.

Solution:

The partial pressure PA of oxygen (A) in air is 0.21 atm. Using Eq. (5),
0.21 = HxA = 4.38 X 104xA
Solving, X,j = 4.80 X 10-6 mol fraction. This means that 4.80 x 10-6 mol O2 is dissolved in 1.0 mol water plus oxygen
or 0.000853 part O2 /l00 parts water.
Mass Transfer Using Film Mass-Transfer Coefficients
and Interface Concentrations
Mass Transfer Using Film Mass-Transfer Coefficients
and Interface Concentrations
EXAMPLE
Solution: Since the correlations are for dilute solutions, (1 – yA) İM and
(1 – xA) İM are approximately l.0 and the coefficients are the
same as k~ and k’x. The equilibrium data are plotted in graph.
Point P is plotted at yAG =0.380 and x AL = 0.1 00. For the
first trial (1 – yA) İM and (1 – xA) İM are assumed as 1.0 and the
slope of line PM is

A line through point P with a slope of 1.342 is plotted in graph.

intersecting the equilibrium line at M l' where yAi =0.183 and
xAi = 0.247.
For the second trial we use yAi and xAi i from the first trial to
calculate the new slope.
We obtain the new slope,

A line through point P with a slope of - 1.163 is plotted and intersects the
equilibrium line at M, where yAi=0.197 and xAi =0.257.
Using these new values for the third trial, the following values are
calculated:

This slope of -1.l60 is essentially the same as the slope of 1.163 for the
second trial. Hence, the final values are yAi = 0.197 and xAi = 0.257 and
are shown as point M.
To calculate the flux;
 EXAMPLE

For SO2 (g) dispersed in air and water within the dilute zone, equilibrium PA=2.5yA in an absorption column operating at
10 atm pressure. At a certain point in the tower the bulk gas concentration yAG = 0.01 mol fraction and the bulk liquid
concentration is xAL =0. If the film mass-transfer coefficient for A in the gas phase is predicted as ḱ́y = 8 kg mol/h.m2.mol
frac and for the liquid phase as ḱ́x = 10 kg mol/h.m2.mol frac., calculate the flux NA for below conditions?
a) For equimolar counter diffusion
b) steady state diffusion of SO2 through stagnant water
c) and calculate K’x