466 MASS TRANSFER BASICS

➢ Time of exposure of eddies is assumed to be

constant, that is, u is constant.
& Denckwerts surface renewal theory.
➢ Assumption of constant exposure time for fluid

elements by penetration theory is not realistic and

eddies are exposed for varying lengths of time in a
random way (random distribution of periods of
FIGURE 15.5 Schematic representation of the situation at the
contact).
interface.
➢ Mass transfer between the gas phase and the fluid

elements takes place at the interface.

kc 1 DAB : ð15:39Þ ➢ As rate of mass transfer depends upon expo-

sure time, average rate for unit surface area

➢ In actual cases, must be determined by summation of individ-
ual values.
2=3
kc 1 DAB : ð15:40Þ
p
➢ In general, KLav ¼ ðDAB SÞ ð15:42Þ

kc 1 DnAB ; ð15:41Þ and rate of mass transfer,

where values of n are ranging from 0.5 to 2/3.
➢ For laminar flow conditions, film theory might
represent, to an approximation, close prediction of
mass transfer coefficients.
➢ For turbulent conditions, film theory gives results
far from realistic.
& Higbie’s penetration theory.
➢ Time of exposure to mass transfer is short, so
concentration gradient of film theory, characteris-
tic of steady state would not have time to develop.
➢ For example, rising gas bubble in a liquid (Fig-
ure 15.6): Particle of liquid, initially at top of
bubble, is in contact with gas for time u required
for the bubble to rise a distance equal to diameter
of the bubble.
p
NAav ¼ ðCAi CAo Þ ðDAB SÞ: ð15:43Þ
➢ S is the surface renewal factor/fractional rate of
replacement of eddies at the surface, u1.
➢ Eddy is swept to the surface (e.g., gas bubble) and
undergoes unsteady-state diffusion and then swept
away to the interface and so on (Figure 15.7).
& Film–penetration theory.
➢ Principles of both film and penetration theories are
incorporated.
➢ Whole of resistance to mass transfer is assumed to
be lying within a laminar film at the interface as in
two-film theory. But mass transfer is considered as
an unsteady-state process.
➢ It is assumed that fresh surface is formed at

intervals from the fluid that is brought from bulk

FIGURE 15.6 Rising gas bubble in liquid. FIGURE 15.7 Gas–liquid contacting.

of the fluid to the interface by the action of eddy
currents.
➢ Mass transfer takes place as in penetration theory,
except resistance is confined to the finite film.
➢ Dobbins gives the following equation that repre-
sents combination of the film and penetration
theories:
p p
➢ KLav ¼ ½ð DAB SÞcoth½ ðSz2b =DAB Þ; ð15:44Þ
where zb is the depth of penetration.
. Define enhancement factor as proposed by Denckwerts
for gas–liquid mass transfer with chemical reaction.
& Enhancement factor, I.
I ¼ NA with reaction =NA without reaction
p p
¼ f ½DAB ðr þ SÞ= ðDAB SÞ½1 þ r=S1=2 :
ð15:45Þ
& r represents reaction rate.
. What is Marangoni effect? Explain.
& The phenomenon that liquid flows along a gas–liquid
or a liquid–liquid interface from areas having low
surface tension to areas having higher surface tension
is named the Marangoni effect.
& Solutal Marangoni convection is flow caused by
surface tension gradients originating from concen-
tration gradients, while thermocapillarity is flow
caused by surface tension gradients originating from
temperature gradients.
& The Marangoni convection increases the mass trans-
fer coefficient with respect to pure diffusive mass
transfer. Furthermore, the Marangoni effect can also
influence the shape and size of the mass transfer
interfacial area.
& Enhancement of Marangoni convection is largest for
systems in which the liquid-phase mass transfer
resistance is approximately equal to the gas-phase
mass transfer resistance, that is, the Biot number is
close to 1.
& Large interfacial gradients may result in rapid mo-
tion of liquid at the interface, creating interfacial
turbulence, called Marangoni effect. For example,
Ether–water system involve large interfacial
gradients.
. What is Marangoni number?
& Marangoni number (Mg) is a dimensionless number.
& Marangoni number may be regarded as proportional
to (thermal) surface tension forces divided by viscous
forces. It is, for example, applicable to bubble and
foam research and propellant behavior calculations
in spacecraft tanks.
THEORIES OF MASS TRANSFER 467
Mg ¼ ðds=dTÞð1=haÞLDT: ð15:46Þ
S ¼ surface tension; N=m: ð15:47Þ
L is the characteristic length, m, a is the thermal
diffusivity, m2/s, h is the dynamic viscosity, kg/(s m),
and DT is the temperature difference,  C.
. What is Rayleigh number and Rayleigh convection?
& Rayleigh number is defined as the product of the
Grashof number, which describes the relationship
between buoyancy and viscosity within a fluid, and
the Prandtl number, which describes the relationship
between momentum diffusivity and thermal
diffusivity.
& For free convection near a vertical wall, this number
is
Rax ¼ Gr Pr ¼ ðgb=yaÞðTs T1 Þx3 ; ð15:48Þ
where Rax is the Rayleigh number, Grx is the Grashof
number, Pr is the Prandtl number, g is the acceler-
ation due to gravity, x is the characteristic length (in
this case, the distance from the leading edge), Ts is the
surface temperature (temperature of the wall), T1 is
the Quiescent temperature (fluid temperature far
from the surface of the object), n is the kinematic
viscosity, a is the thermal diffusivity, and b is the
thermal expansion coefficient.
& Buoyancy, or Rayleigh convection, can occur at the
same time as Marangoni convection.
& The same concentration and temperature gradients
that are responsible for surface tension gradients, also
create density gradients. The intensity of the density
driven convection is characterized by the Rayleigh
number.
& Usually, the Rayleigh effect dominates the flow in
liquid layers with dimensions larger than 1 cm. The
Marangoni effect usually dominates when the char-
acteristic dimension is smaller than 1 mm.
. What are the causes for interfacial resistance for mass
transfer?
& Interfacial turbulence is attributed to hydrodynamic
instability caused by fluctuations in interfacial
tension associated with mass transfer across the
interface.
& Surface active agents concentrated at interface may
➢ partially block interface for solute transfer;
➢ make interfacial liquid layers more rigid;
➢ interact with solute.
& Net effect is reduction of mass transfer rates. For
example, addition of hexadecanol to open ponds of
water substantially reduce evaporation rates.
468 MASS TRANSFER BASICS
15.7 MASS TRANSFER WITH CHEMICAL
REACTION
. Name some important areas of application of mass
transfer with chemical reaction.
& Gas–Liquid Systems:
➢ Gas absorption and stripping for the removal
gaseous components from a mixture of gases.
Examples include CO, CO2, H2S, Cl2, SO2, SO3,
HCl, and so on.
➢ Manufacture of products such as H2SO4, HNO3,
nitrates, phosphates, and so on.
➢ Carrying out liquid-phase reactions such as oxi-
dation, halogenation, polymerization, sulfonation,
hydrogenation, and so on.
➢ Water pollution control processes such as aerobic
fermentation of sludges, biological waste treat-
ment, and so on.
& Liquid–Liquid Systems: Chemical reactions are used
in liquid–liquid systems to achieve the following
objectives:
➢ Nitration and sulfonation of aromatics, alkyl-
ation and hydrolysis of esters, oxidation of
cyclohexane, extraction of metals, and so on,
in which chemical reaction is may be part of a
process.
➢ Removal of acidic solutes from hydrocarbon sys-
tems in which chemical reactions are introduced
deliberately.
➢ Yields and rates of formation of many single-phase
reactions are increased by the controlled addition
of an immiscible extractive phase to extract a
product from the reactive liquid-phase extractive
reactions.
& Gas–Liquid–Solid Systems:
➢ The solid may be reactive as in the cases of
absorption of CO2 in limestone and thermal coal
liquefaction.
➢ The solid functions as a catalyst, for example,
when gases like hydrogen, water, ammonia,
or oxygen are involved resulting in the hydro-
genation, hydration, amination, or oxygenation.
. What are the advantages and attributes to be incorpo-
rated in equations for mass transfer with chemical
reaction?
& The main objective of coupling mass transfer and
chemical reaction is to enhance overall mass transfer
rates. Chemical reactions enhance the mass transfer
rate, because they take out the diffusing solute in the
region of the interface producing a steeper concen-
tration gradient. This has very important implications
for the design of gas absorbers and many mass
transfer devices.
& The general equation of mass transfer when accom-
panied by a chemical reaction is an unsteady-state
mass transport equation, that incorporates not only
diffusion but also convective mass transport and
chemical reaction contributions.
➢ The general equation can be written as
qCi =qt þ yrCi ¼ Di r2 Ci þ Ri ; ð15:49Þ
where y is the fluid velocity vector, y!Ci is the
convective mass transport contribution, Di!2Ci is
the molecular diffusion contribution, Ri is the
chemical reaction contribution, and Di is the dif-
fusion coefficient of i in the liquid.
➢ For steady state,
Di r2 Ci ¼ 0: ð15:50Þ
➢ If the medium is stationary,
y ¼ 0: ð15:51Þ
➢ The mechanism of steady-state diffusion with
reaction distributed homogenously throughout
the material is often adopted in the analysis of
cases of mass transfer and chemical reaction.
➢ There are, however, some reactions for which
the distinction between homogenous and het-
erogeneous systems is not sharp as in the cases
of
- enzyme–substrate reactions
- very rapid chemical reactions
& In multiphase systems, chemical reactions affect the
mass transfer rate in two distinct ways:
➢ At low reaction rate, it serves to change the bulk
concentration of the transferring solute, thus in-
creasing the driving force.
➢ On the other hand for reasonably fast reactions the
concentration gradient near the interface is affect-
ed leading to an enhancement of the mass transfer
rate.
& It is convenient to represent the effect of the chemical
reaction on mass transfer in terms of an enhancement
factor.
& The enhancement factor can be defined as the ratio of
the average rates of mass transfer in presence of
reaction to the average rate without reaction and is
given by the equation: