MASS TRANSFER OPERATIONS

MODULE 1
MODULE1 -SYLLABUS
 Molecular diffusion - mass fluxes JA and NA - Fick’s law -
diffusivity and estimation - steady state diffusion of A through
stagnant B and equimolar counter diffusion in binary gases,
liquids and multi component gas mixtures. Mass transfer
coefficients, dimensionless groups - analogy between mass,
heat and momentum transfer. Basic concepts and assumptions
involved in theories of mass transfer: penetration and surface
renewal theories - interphase mass transfer - equilibrium -
diffusion between phases - two-film theory - local and overall
k-type coefficients.
INTRODUCTION
 In chemical process industries raw materials undergo transformation
into useful products
 The materials undergo different operations that may be physical or
chemical operations
 Separation processes consume more money and time than the
chemical conversion reactions in an industry
 Separations can be of two type: mechanical separations and diffusional
separations
 Mechanical separations are used for separating one phase from other
eg: filtration, sedimentation etc
 Diffusional separations are used for separating homogeneous mixtures
 Diffusional separations are also known as mass transfer operations
Driving force
 Heat transfer between two planes stops when the temperature of the
planes become equal
 Hence, temperature difference is the true driving force for heat transfer
 But in mass transfer between two phases, at equilibrium the
concentration in two phases need not be same.
 Thus concentration difference is not the true driving force for mass
transfer
 At equilibrium, the chemical potentials of the components in the
different phases should be equal
 Concentration difference is a measure of driving force , but not the true
driving force
 True driving force is the difference in chemical potentials of species in
different phasess
Molecular diffusion
 Primary mechanism of mass transfer
 Molecular diffusion is concerned with the movement of
individual molecules through a substance due to their
thermal energy
 In a homogenous mixture, the molecules move from region
of higher concentration to lower concentration till
equilibrium is established
 Eg: adding dye in a beaker of water, adding sugar to coffee
 Interphase mass transfer
 In interphase mass transfer, molecular diffusion occurs from first phase to
interphase and then from the interphase to second phase
 Eg: absoption of ammonia from air- ammonia mixture using water
 Rate of mass transfer is governed by the rate of diffusion
 Extent of mass transfer is governed by phase equilibrium
 Criterion for phase equilibrium is the equality of chemical potential and not
the uniformity of concentration
 The concentrations are related to chemical potential in different ways for
different phases
 Criterion for chemical equilibrium will be satisfied even when the
concentrations of the components in different phases are not equal
 The true driving force for mass transfer between phases is the difference in
chemical potential of the components in different phases
 The difference in concentration can be treated as the true driving force in
individual phase
 Composition of the mixture
 concentration: mass concentration (ρ) and mole concentration
(C)
 Mass concentration: amount in kg per unit volume: kg/m3: ρ
=∑ ρ i
 Mole concentration: amount in moles per unit volume:
moles/m3 C= ∑ C i , C i = ρ i /Mi, Mi- M.W
 Mass fraction ωi= ρ i / ρ
 Mole fraction xi= Ci/C
Velocity of mixture
 Mass average velocity: This is Mass fraction weighted average of the
velocities of the components in the mixture

 Molar average velocity : This is mole fraction weighted average of the

velocities of the components in the mixture

Diffusion velocity
Velocity of a particular component relative to the average velocity of the
mixture is termed diffusion velocity
 ui’= ui-u, (relative velocity w.r.t mass average velocity)
 Ui’= ui-U (relative velocity w.r.t molar average velocity)
 ui – absolute velocity of species i
 ωi- mass fraction of species i
Flux
 Amount of the species (mass or moles)that pass per unit
area normal to the direction of transfer in unit time
 Flux is a vector quantity, unit is kg/m2h or kmol/m2h
 Flux= concentration x velocity
 Flux can be of two type:
 JA= flux of component A relative molar average velocity
 NA= flux of component A relative to stationary observer
 NA = C A u A
 JA = C A U’ A
 NA =JA + xA N
 N- Total rate of transfer of the fluid by bulk flow
 Ficks’law of diffusion

 Molar flux of diffusion in the z direction of component A in solution with

component B is directly proportional to concentration gradient
 JA is the molar flux of component A in the z direction relative to molar
average velocity of fluid in kmol/m2h or kmol/m2s
 CA- concentration of A in kmol/m3
 dC A/dZ =concentration gradient in z direction
 DAB- Diffusion Coefficient or mass diffusivity of component A in a mixture
of A and B
 Diffusivity is a characteristic of a constituent and its environment ( T, P,
whether it is liquid, gas etc), Unit of DAB is m2/s or m2/h

 The negative sign indicate that the diffusion occurs in the direction of
decreasing concentration
 DAB is a function of nature of A, composition, pressure,
temperature as well as B
 The value of diffusivity is higher for gases
 Gases- 5x10-6 to 10-5 m2/s
 Liquids- 10-10 to 10-9 m2/s
 Solids- 10-14 to 10-10 m2/s
Fick’s law of diffusion in stationary
coordinates
 NA =JA + xA N

 JA = C A U’ A= CA (uA -U)
 C A u A = JA + C A U
 U=x A u A + x B u B = C A u A / C+ C B u B /C
 C A u A = JA + C A /C (C A u A +C B u B )
 C A u A = JA +x A (NA +NB )
Eddy diffusion
 Molecular diffusion is the mechanism of mass transfer in
stagnant fluids and fluids in laminar motion.
 It is a very slow process and requires long time to achieve
equilibrium or uniformity of concentration
 If turbulence is provided, mass transfer will be largely by
eddy diffusion and uniformity of concentration will be
achieved faster
 Large macroscopic aggregates of fluid called eddies carry
material from one location to another.
 The basic mechanism is still molecular diffusion, because in
each eddy uniformity is achieved by molecular diffusion
Steady state molecular diffusion in
gases
Equimolar counter diffusion
 In Equimolar counter diffusion, the number of moles of A moving
in one direction is equal to the number of moles of B moving in
the opposite direction
 With reference to a stationary observer , there is no net molar
flow in either direction
 Net motion of the entire phase is zero
 NA = - NB
Equimolar counter diffusion
concentration profile
Diffusion of A through stagnant B

Arnold diffusion cell

 One component of the mixture (A) diffuses through stagnant B

 Eg: absorption, humidification, evaporation etc
 Arnold diffusion cell:. Narrow tube with partially filled volatile
liquid A maintained at constant Temperature and Pressure
 Gas B is allowed to flow across the open end of the tube
 Assumptions: Liquid level is constant ii) solubility of B in the
liquid is negligible
Concentration profile
1. CO2 is diffusing through N2 at 0 0C and 1 atm pressure. The mole fraction of CO2 at
two points 3mm away are 0.2 and 0.02. diffusivity is 0.144 cm2/s. The gas phase as a
whole is stationary i.e., N2 is diffusing at the same rate as CO2 but in the opposite
direction. Determine a) the flux of CO2 in kmol/m2hr b) the net mass flux in
kg/m2hr
2. A tube 0.25 m long and having a diameter 1.5 mm connects two tanks one of which
is filled nitrogen and the other with hydrogen. The pressure is maintained constant at
101.2 kPa and the temperature at 298 K. Nitrogen and hydrogen diffuse in the
opposite direction. The mole fraction of nitrogen in the tanks were 0.7 and 0.25
respectively, at one particular instant during diffusion. The mass diffusivity of
nitrogen-hydrogen mixture is 7.84x10-5 m2/s. determine a) the rate of diffusion of
nitrogen in kmol/h and kg/h b) the velocity of species with reference to stationary
coordinates a s a function of concentration
3. Ammonia is diffusing under steady state conditions through a layer of stagnant air
film 2 cm thick. The gas contains 30% by volume ammonia on one side of the
stagnant layer. The diffused NH3 n the other side is immediately adsorbed in water,
the temperature is 30 0C and pressure 1 atm. Diffusivity for NH3 -air system is 60
cm2/hr. how much is NH3 absorbed in 10hrs?
4.Ethanol is diffusing through air under steady state condition,
with air non-diffusing, at temperature 313 K ad pressure
101.3 kPa. The partial pressure of ethanol at two planes 5
mm apart are 8 kPa and 4 kPa. The diffusivity of ethanol in
air is 1.45x10-5 m2/s. Calculate a) the rate of diffusion of
ethanol per unit area of the planes b) the mole fraction of
ethanol as a function of the distance along the direction f
diffusion .Evaluate the mole fraction at the centre of the tube
length
5.The diffusivity of benzene in air is measured by Stefan’s
method. A vertical glass tube is filled with benzene to a depth
of 20mm from the top open end. It took 190 hours for the
level to fall to 80 mm from the top. The tempertaureand
pressure are maintained at 298 K and 100kPa. Density of
liquid benzene is 875 kgm3 and the vapour pressure of
benzene is 12.6 kPa at 298 K. Calculate the diffusivity of
benzene in air at 298 K
Pseudo steady state diffusion of A through
stagnant B
 If the level of the liquid in the Arnold cell falls with time, a
pseudo steady state approximation is required

 If the liquid level falls by a height dz in time dt seconds

 Molar Flux
 DAB=DBA
 General Equation for steady state diffusion
 Diffusion in multicomponent mixtures

 Effective diffusivity

 DAi are the binary diffusivities

 Assuming that all the N except NA are zero (all but one
component is stagnant
Molecular diffusion in liquids
 Molecular diffusion in liquids is considerably slower than in gases
 Frequency of collision between molecules is more in liquid and
hence diffusion is slower
 Liquid diffusivities are smaller by 10-5 times than that of gases
 Rate of diffusion is smaller by 10-2 times because molar density of
liquid is 103 times that of gases
 The diffusivity and the total molar concentration of gaseous
components are nearly constant but not in the case of liquids,
where both vary with the concentration
 It is general practice to use the average concentration and best
average diffusivity as knowledge on diffusivity is limited
 For equimolar diffusion in liquids

 For diffusion through stagnant B

 For dilute solutions

Prediction of binary diffusivities
Gases
 Hirschfelder Bird Spotz equation
 Wilke-Lee Equation
 Fuller
Liquids
 Stoke-Einstein equation
 Wilke- Chang equation
 Hayduk and Minhas equation
Effect of temperature, Pressure and
composition on diffusivity of gas
 At low pressures where the gases can be assumed ideal, by Wilke-
Lee

 DAB varies as T 1.5 to T2

 DAB varies inversely with pressure for pressures upto about 1500
kPa
 At low pressures, the mass diffusivity s independent of
composition
 At high pressures, when the deviation of the gas from the ideal
behaviour is appreciable, small but definite changes in DAB with
composition were observed