FALLSEM2023-24 BCHE207L TH VL2023240100110 2023-04-24 Reference-Material-I

BCHE207L Mass Transfer I
Instructor: Dr. Monash P.

School of Chemical Engineering (SCHEME)
Vellore Institute of Technology, Vellore
Date: 24 April 2023
Course Content
• Module:1 Diffusion - 6 hours
• Module:2 Molecular diffusion in Fluids - 6 hours
• Module:3 Mass transfer coefficients - 6 hours
• Module:4 Theories of mass transfer - 5 hours
• Module:5 Humidification - 7 hours
• Module:6 Drying - 7 hours
• Module:7 Crystallization - 6 hours
• Contemporary issues - 2 hours
Total Lecture hours - 45 hours

Dr. Monash Purushothaman BCHE207L Mass Transfer I 2
Text Books
• B.K. Dutta, Principles of Mass transfer and Separation
Processes, 2010, 1st ed., PHI, India.
• R.E. Treybal, Mass-Transfer Operations, 2017, 3rd ed.,
McGraw-Hill Inc., USA.
Reference Books
• E.L.Cussler, Diffusion: Mass Transfer in Fluid Systems,
2017, 3rd ed., Cambridge University Press, United Kingdom.
• Christie J, Geankoplis, Transport processes and Unit
Operations, 2003, 4th ed., Prentice Hall India Pvt. Ltd., India.
• N.Anantharaman, K.M.Meera Sheriffa Begum, Mass
transfer-Theory and practice, 2011, Prentice-Hall of India,
New Delhi, India.
Course Objectives (COB’s)
• To understand the fundamentals of diffusion and the theories
of mass transfer.
• To impart the knowledge of humidification, drying and
crystallization
• To solve application oriented problems using separation
techniques.

Course Outcomes (CO’s)
• Apply Steady state molecular diffusion in fluids under
stagnant and laminar flow conditions.
• Interpret the theories of mass transfer and relate individual
and overall mass transfer coefficients.
• Describe the principle of humidification and designing the
cooling tower.
• Comprehend the need and application of dryers in a
chemical process and its classification based on the material
dried.
• Select and learn the types of Crystallizers used in practice
and its principle.

Assessment Method
Assessment Date Max. Weightage Remarks
Type Marks
Digital Assignment 24/06/2023 10 10 Question and rubrics will be

given separately
Continuous 28/05/2023 50 15 As per the circular by Dean
Assessment Test I Academics
(CAT – I)
Quiz 1 16/06/2023 10 10 10-20 minutes test during class
(Tentative) hour
Continuous 30/06/2023 50 15 As per the circular by Dean

Assessment Test II Academics
(CAT – II)
Quiz 2 14/07/2023 10 10 10-20 minutes test during class
(Tentative) hour
Final Assessment 17/07/2023 100 40 Schedule will be announced by

Test (FAT) the CoE, VIT Vellore.

VTOP - Course Assessment Configurations

Module I – Diffusion
Topics covered
• Introduction to Mass transfer operation
• Fick's law of diffusion
• Steady state molecular diffusion in fluids under stagnant and
laminar flow conditions
• Diffusion coefficient measurement and prediction

Diffusion
• Mass transfer could occur by the following three ways:
 Diffusion is the net transport of substances in a stationary solid or
fluid under a concentration gradient.
 Advection is the net transport of substances by the moving fluid. It
cannot therefore happen in solids. It does not include transport of
substances by simple diffusion.
 Convection is the net transport of substances caused by both
advective transport and diffusive transport in fluids.
• Diffusion is the macroscopic result of random thermal motion

on a micoscopic scale (Brownian motion).
• It occurs even when there is no concentration gradient (but
there will be no net flux).

Modes of mass transfer

• Mass transfer by diffusion occurs when a component in a
stationary solid or fluid goes from one point to another driven
by a concentration gradient of the component.

Diffusion
• Liquids A and B are separated from

each other.
• Separation removed.
• A goes from high concentration of A
to low concentration of A.
• B goes from high concentration of B
to low concentration of B.
• Molecules of A and B are uniformly
distributed everywhere in the vessel
purely due to diffusion.
• Equilibrium is reached
Concentration
• Mass and molar concentration:

Velocity
• Mass average velocity:
• Molar average velocity

Frames of Reference

Flux
• Mass flux:
• Molar flux:

Diffusion
• Diffusion is the movement of an individual component
through a mixture from a region of high concentration to low
concentration at fixed temp & pressure with or without the
help of external force.
• Diffusion stops once equilibrium is attained.
Types of diffusion
• Molecular diffusion
• Eddy or turbulent or convective diffusion

Fick’s first law
• Adolf Fick (1955) first described the molecular diffusion in an
isothermal, isobaric binary system of components A and B.
• “Molar flux of a species relative to an observer moving with
the molar average velocity is proportional to the
concentration gradient of the species”.
where, DAB is the proportionality constant called the 'diffusion

coefficient' or the 'diffusivity' of A in a mixture of A and B.
The diffusional flux JA is a positive quantity by convention, Since diffusion occurs

spontaneously in the direction of decreasing concentration ie. dCA/dz < 0, the
negative sign is incorporated in equation to make it consistent with respect to sign
Fick’s First Law of Diffusion
• For mass transfer occurring only in z-direction
• If the concentration gradient is expressed as the gradient of

mole fraction and in three dimensional cases, the molar flux
can be expressed as

Defination
• Flux
 It is defined as the amount of species that crosses per unit area per
unit time
• Molar Flux(J)
 It is defined as moles of species that passes through a unit area per
unit time
• Diffusivity(D)
 It is the ratio of molar flux to the concentration gradient.

Derivation of DAB = DBA under certain conditions
• Equimolar counter-diffusion in gases
• Consider steady-state diffusion in an ideal mixture of 2 ideal
gases A & B at constant total pressure and temperature.
• Molar diffusive flux of A in B: (1)
• Molar diffusive flux of B in A: (2)

• Since the total pressure remains constant, there is no net
mass transfer. That is, . (3)
• For an ideal gas mixture at constant pressure
• Therefore, . (4)
• Substituting (3) and (4) in (1) and (2), we get

. (5)
• Therefore, (1) and (2) give
Note: It is applicable
to stationary
• This is known as equimolar counter diffusion. medium or a fluid in
streamline flow
• This describes the mass transfer arising solely from the
random motion of the molecules (i.e., only diffusion).
Treybal Book – Derivation DAB = DBA

Steady state molecular diffusion in fluids under
stagnant and laminar flow conditions

Mathematical modelling of steady-state one
dimensional convective mass transfer
• Diffusion of gases A & B plus convection.
• Diffusion is the net transport of substances in a stationary
solid or fluid under a concentration gradient.
• Advection is the net transport of substances by the moving
fluid, and so cannot happen in solids. It does not include
transport of substances by simple diffusion.
• Convection is the net transport of substances caused by
both advective transport and diffusive transport in fluids.
JA is the diffusive flux described by Fick’s law, and we have already
studied about it.
Let us use NA to denote the total flux by convection (which is diffusion

plus advection).
Molar diffusive flux of A in B: (1)
The velocity of the above diffusive flux of A in B can be given by

JA (mol/m2.s)
vA,diffusion (m/s) = (2)
CA (mol/m3)
The velocity of the net flux of A in B can be given by

NA (mol/m2.s)
vA,convection (m/s) = (3)
CA (mol/m3)
The velocity of the bulk motion can be given by
(NA + NB) (mol/m2.s)

vbulk (m/s) = (4)
(CT) (mol/m3)
Total concentration
vA,convection = vA,diffusion + vbulk
Multiplying the above by CA, we get
CA vA,convection = CA vA,diffusion + CA vbulk
Using equations (2) to (4) in the above, we get
NA = JA + CA (NA + NB) (5)

CT
Substituting JA from equation (1) in (5), we get
NA = -DAB dCA (NA + NB)

+ CA (6)
dz CT

Let us introduce partial pressure pA into (6) as follows:
nA pA
CA = = (7a)
V RT
nT P
CT = = (7b)
V RT
Total pressure
Total number of moles
Using (7a) and (7b), equation (6) can be written as
DAB dpA pA (N + N )
NA = - + A B (8)
RT dz P

Let us introduce molar fractions xA into (13) as follows:
NA CA (9)
xA = =
(NA + NB) CT
Using (16), equation (13) can be written as
NA = -CT DAB dxA + xA (NA + NB) (10)

dz

Summary equations for (one dimensional)
flow in z direction
In terms of concentration of A:
NA = -DAB dCA CA (N + N )
+ A B
dz CT
In terms of partial pressures (using pA = CART and P = CTRT):

DAB dpA pA (N + N )
NA = - + A B
RT dz P
In terms of molar fraction of A (using xA = CA /CT):
NA = -CT DAB dxA + xA (NA + NB)

dz

Diffusion of A through stagnant non-diffusing B
Air (B) • Evaporation of a pure liquid (A) is
at the bottom of a narrow tube.
2 • Large amount of inert or non-
diffusing air (B) is passed over
the top.
z2 – z1 • Vapour A diffuses through B in
the tube.
• The boundary at the liquid
surface (at point 1) is
1 impermeable to B, since B is
insoluble in liquid A.
Liquid
Benzene • Hence, B cannot diffuse into or
(A) away from the surface.
• Therefore, NB = 0
DAB dpA pA (N + N )
Substituting NB = 0 in NA = - + A B
RT dz P
DAB dpA pA (N + 0)
we get NA = - + A
RT dz P
Rearranging and integrating
DAB dpA
NA (1 - pA/P) = -
RT dz
z2 pA2
N ⌠dz ⌠
DAB dpA
A
⌡ = - ⌡
RT (1 - pA/P)
z1 pA1
DAB P P - pA2
NA = ln (1)
RT(z2 – z1) P – pA1
Introduce the log mean value of inert B as follows:
(pB2 – pB1 ) (P – pA2 ) – (P – pA1 )
pB,LM = =
ln(pB2 /pB1 ) ln[(P - pA2 )/ (P - pA1 )]
(pA1 – pA2 )
=
ln[(P - pA2 )/ (P - pA1 )]
Equation (1) is therefore written as follows:
DAB P
NA = (pA1 - pA2 ) (2)
RT(z2 – z1) pB,LM
The above equation is most widely used form to find the

diffusion of A through stagnant non-diffusing B.
Using xA = CA /CT, pA = CART and P = CTRT,
equation (1) can be converted to the following:
NA = DAB CT ln 1 - xA2 (3)

(z2 – z1) 1 – xA1
Introduce the log mean value of inert B as follows:

(xB2 – xB1 ) (1 – xA2 ) – (1 – xA1 )
xB,LM = =
ln(xB2 /xB1 ) ln[(1 - xA2 )/ (1 - xA1 )]
(xA1 – xA2 )
=
ln[(1 - xA2 )/ (1 - xA1 )]
Therefore, equation (20) becomes the following:
DAB CT
NA = - (xA1 - xA2 ) (4)
(z2 – z1) xB,LM

Partial pressure distribution of A in non-
diffusing B

Treybal Book – Derivation steps in detail
N A = J A + Nx A → (1)
NA = JA + ( NA + NB ) x A
dCA CA
N A = - D AB + ( NA + NB )
dz C
dCA
N A C = - C D AB + ( N A + N B ) CA → (2)
dz
dCA
N A C - ( N A + N B ) CA = - C D AB
dz
CA 2 Z2
- dCA 1
∫
C A1
N A C - ( N A + N B ) CA
=
C D AB ∫ dz
Z1
→ (3)

CA 2 Z2
- dCA 1
∫
C A1
N A C - ( N A + N B ) CA
=
C D AB ∫ dz
Z1
→ (3)
Here Z = Z2 - Z1
1 N A C - ( N A + N B ) CA2 Z
ln =
N A + N B N A C - ( N A + N B ) CA1 C D AB
1 N A C - ( N A + N B ) CA2 Z NA
ln = ×
N A + N B N A C - ( N A + N B ) CA1 C D AB NA
N A C D AB N A C - ( N A + N B ) CA2
NA = ln → (4)
NA + NB Z N A C - ( N A + N B ) CA1

N A C D AB ln N A + ln C - ln CA2 + ln ( N A + N B ) 
NA =
N A + N B Z ln N A + ln C - ln CA1 + ln ( N A + N B ) 
N A C D AB ln N A - ln ( N A + N B ) − [ ln CA2 − ln C ]
NA =
N A + N B Z ln N A - ln ( N A + N B ) − [ ln CA1 − ln C ]
 NA CA2 
−
 (N + N ) C 
N A C D AB
NA = ln  A B
 → (5)
NA + NB Z  NA C
− A1 
 ( NA + NB ) C 
 
For molecular diffusion in gases
CA pA
= = yA
C pt
 NA 
−
 ( N + N ) A2 y
N A p t D AB
NA ln  A B
 → (6)
N A + N B RTZ  NA
− yA1 
 ( NA + NB ) 
 
 NA  
  p t − pA2 
N A p t D AB   ( NA + NB )  
NA ln   → (7)
N A + N B RTZ  N 
 A
 p t − pA1 
  ( N A + N B )  
steady state diffusion of A through nondiffusing B
NA
=1
NA + NB

D AB p t  p t − pA2 
NA ln   → (8)
RTZ p
 t − pA1 
We re-write the above equation in terms of

Flux = coefficient × driving force
[  This is required to explain mass transfer cofficient]
D AB pt  p t - p A2  p A1 - p A2
NA ln   × → (9)
RTZ p -
 t A1 p p A1 - p A2
For binary diffusion, p A + p B = p t ,we can write the above equation as
 p B2 
ln  
D AB pt p
 B1 
NA = ( pA1 - pA2 ) → (10)
RTZ p A1 - p A2
p 
ln  B2 
D AB pt  p B1 
NA ( pA1 - pA2 ) → (11)
RTZ p B2 - p B1
p 
ln  B2 
D AB pt  p B1 
NA ( pA1 - pA2 ) → (12)
RTZ p B2 - p B1
p B2 - p B1
 p BLM =
 p B2 
ln  
p
 B1 
D AB pt
NA ( pA1 - pA2 ) → (13)
RTZ p BLM
Flux of component A = Coefficient × driving force → (14)

Derivation for diffusion of gas A in in non-
diffusing gas B – Alternate approach
N A = J A + Ny A → (1)
N A = J A + ( N A + N B ) yA
dCA
N A = - D AB + ( N A + N B ) yA
dz
D AB dp A pA
NA = - + ( NA + NB ) → (2)
RT dz pt
NA + NB = N
pA pA
 CA = & yA = NB = 0
RT pt
0 N = NA
 pA  D AB dp A pA
1 −  NA =
- + NB → (3)
 pt  RT dz pt
 pt - pA  D AB dp A
  NA = -
 pt  RT dz
 pt - pA  D AB dp A
  NA = -
 pt  RT dz
Z2 PA 2
D AB pt dp A
N A ∫ dz = - ∫P p t - pA
Z1
RT A1
Here Z = Z2 - Z1
D AB pt  p t - p A2 
NA ln   → (4)
RTZ p -
 t A1 p

D AB pt  p t - p A2 
NA ln   → (4)
RTZ p -
 t A1 p
We re-write the above equation in terms of

Flux = coefficient × driving force
[  This is required to explain mass transfer cofficient]
D AB pt  p t - p A2  p A1 - p A2
NA ln   × → (5)
RTZ  p t - p A1  p A1 - p A2
For binary diffusion, p A + p B = p t ,we can write the above equation as
 p B2 
ln  
D AB pt p
 B1 
NA = ( pA1 - pA2 ) → (6)
RTZ p A1 - p A2
 p B2 
ln  
D AB pt p
 B1 
NA ( pA1 - pA2 ) → (7)
RTZ p B2 - p B1
 p B2 
ln  
D AB pt p
 B1 
NA ( pA1 - pA2 ) → (8)
RTZ p B2 - p B1
p B2 - p B1
 p BLM =
 p B2 
ln  
p
 B1 
D AB pt
NA = ( pA1 - pA2 ) → (9)
RTZ p BLM
Flux of component A = Coefficient × driving force → (10)

Similarly, the equation is solved for mole fraction, concentration terms in the basic equations
Derivation for Equimolar counter diffusion
of gas A and gas B
N A = J A + Ny A → (1)
N A = J A + ( N A + N B ) yA NA + NB = N
dCA 0 NA = -NB
N A = - D AB + ( N A + N B ) yA
dz NA + NB = 0
D AB dp A
NA = - → (2)
RT dz
pA
 CA =
RT
D AB dp A
NA - → (3)
RT dz
Z2 PA 2
D AB
N A ∫ dz = - ∫ dp A
Z1
RT PA1
Here Z = Z2 - Z1
D AB
NA ( p A1 - p A2 ) → (4)
RTZ
Comparing Diffusion of A in non-diffusing B and

Equimolar Counter diffusion
D AB pt D AB
NA = ( pA1 - pA2 ) NA ( pA1 - pA2 )
RTZ p BLM RTZ
Pt/ PBLM is the additional term in diffusion of A in non-difusing B

Steady state equimolar counter diffusion
• Take the example of a particle of carbon burning in air. We
visualize that the particle is surrounded by an 'air-film'
through which the molecules of oxygen diffuse and reach the
surface of the particle to sustain combustion.
• If a molecule of O2 diffuses to the surface, a molecule of CO2
is formed which diffuses out through the 'air-film' (provided
that CO2 is the only product of combustion) at steady state.
• So oxygen and carbon dioxide undergo 'equimolar counter
diffusion'.
• Separation of a liquid mixture containing the components A
and B by distillation may be cited as another practical
example.

• In distillation, the vapour rising through the distillation
column remains in intimate contact with the down-flowing
liquid.
• Exchange of mass occurs between the phases-the more
volatile component moves from the liquid to the vapour
phase and the less volatile one gets transported from the
vapour to the liquid phase.
• If the column is perfectly insulated against heat loss and the
molar heats of vaporization of the components are equal, the
mass exchange between the phases will occur in equimolar
counterdiffusion mode.

• This is the case for the diffusion of two ideal gases, where
an equal number of moles of the gases diffusing counter-
current to each other.
• In this case NB = -NA = constant and NA+ NB = 0.
• The molar flux equation at steady state can then be written
as
0
DAB dpA pA (N + N )
NA = - + A B
RT dz P
DAB dpA DABP dyA

NA = - or NA = -
RT dz RT dz

• Since NA remains constant for steady-state diffusion through
a constant area with the boundary conditions:
At Z = Z1 PA = PA1 or yA = yA1
At Z = Z2 PA = PA2 or yA = yA2
z2 pA2 z2 yA2
⌠
⌡
NA dz = - DAB
⌠
⌡ dp or N ⌠dz - DABP
⌠
z1
RT
pA1
A A
⌡ =
RT ⌡ dyA
z1 yA1
DAB (pA1 - pA2 ) DAB P

NA = or NA = (yA1 - yA2 )
RT(z2 – z1) RT(z2 – z1)
• It may be noted here also that molar latent heats of
v v
vaporization of A and B are equal. i.e. ΔHA = ΔHB.
Equimolar counter diffusion of A and B:
Partial pressure distribution with position

Diffusion coefficient
measurement and prediction

Experimental determination of the gas-
phase diffusion coefficient
• Use of the Stefan Tube
• Twin-bulb Method

Stefan Tube
• This method is suitable if, under the given set of
experimental conditions, one of the components (say A) is
available as a volatile liquid and the other component (B) is
a gas which is not soluble in A.
• The apparatus is
very simple. A
vertical glass tube,
sealed at the
bottom, is joined to
a larger diameter
horizontal tube to
form a tee (T) as
shown in Figure.

• The liquid A is taken in the narrow vertical tube and the gas
B is forced through the horizontal tube.
• Evaporated A diffuses through the mixture of A and B in the
vertical tube, reaches the top and is swept away by the
flowing stream of B.
• As B is insoluble in A, it will not diffuse and the situation will
conform to diffusion of A through non-diffusing B.
• The liquid level in the vertical tube will drop very slowly and
pseudo-steady state assumption (i.e. A diffuses through the
tube virtually at steady-state at all time) is reasonable.
• This means that as the liquid level falls by a small amount, a
new steady-state rate of diffusion is established
simultaneously.
• The drop in the liquid level over a period of time is noted.
• Let, at any time t, the liquid level be at a distance Z from the
top of the vertical tube, PAl be the partial pressure of A at the
liquid surface and PA2 that at the top.
• The diffusional flux of A through this distance Z is given as
follows
DAB P
NA = (pA1 - pA2 )
RTz pB,LM
• If the fall in the liquid level is dz in a small time dt, the

number of moles of A that diffuse out is adz (ρAIMA). By a
material balance over the time dt,
a DAB P (p
(ρA/MA)adz = a NA dt = A1 - pA2 )
RTz pB,LM

where,
a is the inner cross-section of the vertical tube
ρA and MA are the density (of the liquid) and molecular weight
of A respectively.
If at time t = 0, the liquid level is at Z0 from the top, and at

time ( (i.e. at the end of the experiment) the liquid level is at
ZF, integration of the above equation and rearrangement
gives
ρA RT pB,LM (zF2 – z02)

DAB =
2 MA P tF (pA1 - pA2 )

Twin-bulb Method
• The apparatus used in this method consists of two
reasonably large bulbs or chambers of volumes VI and V2,
connected by a narrow tube fitted with a plug-type valve or a
stopcock.
• There should be a suitable arrangement for stirring the
contents of the bulbs in order to keep the concentrations in
them uniform (the bulbs are said to be ·well-mixed').

• The entire assembly should be maintained at a constant
temperature.
• Initially, the valve in the connecting tube is kept closed. The
two bulbs are evacuated.
• One of the bulbs is repeatedly flushed with pure A and the
other with pure B and then filled with the gases at the same
pressure, P.
• The valve is then opened to allow diffusion to start and
continue undisturbed for some time, at the end of which the
valve is closed.
• Samples of the gases from the bulbs are taken and analyzed
for their composition.

• Because the total pressures in the bulbs remain constant
and equal, equimolar counter diffusion through the
connecting tube occurs.
• The bulbs being large, the concentrations or partial
pressures of the components in the bulbs will change rather
slowly.
• Diffusion in the system can be made with the pseudo-steady
state approximation.
• This means that, at any instant, diffusion through the
connecting tube occurs at steady state.
• As the concentrations in the bulbs change a little, a new
steady state of diffusion is attained simultaneously.

• The working equation for the calculation of the diffusion
coefficient from the concentration changes in the bulbs is
given below.
a DAB
a NA= (pA1 - pA2 ) = - a NB
RTz
• If CA1 and CA2 are the instantaneous concentrations of A in
the bulbs, the rates of change of these concentrations are
given by the following equations:
dCA1 V1 dpA1
- V1 = a NA - = a NA
dt RT dt
dCA2 V2 dpA2
V2 = a NA = a NA
dt RT dt
• Here CA1 decreases with time but CA2 increases.

Combining the equations
d 1 1
- (pA1 - pA2 ) = a RT + NA = a DAB (p - p ) 1 + 1
dt V1 V2 z A1 A2
V1 V2
d (pA1 - pA2 ) a DAB 1 1

- (p - p ) = z + dt
A1 A2 V1 V2
We use the following conditions

At t =0, PA1 - PA2 = P – 0 =P
At t =tF, PA1 - PA2 = PAl,F - PA2,F
Integration of the above equation within the limits gives the

working equation for the calculation of DAB.
P a DAB 1 1
ln = + tF
(pA1,F - pA2,F ) z V1 V2
The mutual diffusion coefficient DAB can be directly

determined from the above equation.
The quantities to be measured in this experiment are the
initial pressure in the vessels and the partial pressures of
one of the components (say A) in the vessels at the end of
the experiment.

Prediction of Diffusivity
Although experimental diffusivity values for a large number of
binary gas mixtures are available we often come across
mixtures for which no experimental data have been reported.
Diffusivities for different systems could be estimated using the
empirical equations.
• Wilke-Lee correlation
• Chapman- Enskog correlation

• Fuller, Schettler and Giddings correlation
The gas-phase diffusivity generally varies with the absolute

temperature raised to the power 1.5 to 1.75, and inversely to
the total pressure up to about 10 -15 atm.
The diffusivity strongly depends upon the intermolecular forces
in a mixture and is also governed by collisions of the diffusing
molecules with others present in the mixture.
The rate of collision increases as the mean free path

decreases. This is favoured at a higher pressure, and hence
the diffusivity of a gas decreases with increasing pressure.

Wilke-Lee correlation
Expressions for estimating D in the absence of experimental
data are based on considerations of the kinetic theory of gases.
The Wilke-Lee modification of the Hirschfelder-Bird-Spotz

method is recommended for mixtures of nonpolar gases or of a
polar with a nonpolar gas
10-4 (1.084-0.249V1/MA + 1/MB ) T1.5 V1/MA + 1/MB

DAB = m2/s
P (rAB)2 f(κT/εAB)

where
DAB = diffusivity, m2/s

T = absolute temperature, K
P = absolute pressure, N/m2
k = Boltzmann's constant
MA,MB = molecular weight of A and B, respectively, kg/kmol
rAB = molecular separation at collision, nm = (rA + rB)/2
εAB = energy of molecular attraction =Vε ε
A B
f(κT/ εAB) = collision function

D varying almost as T1.5 and inversely as the pressure, which
will serve for pressures up to about 1500 kN/m2.
The values of r and ε are listed in Table
Force constants of gases as determined from viscosity data

Collision function for diffusion

If necessary, they can
be estimated for each
component empirically
1/3
r = 1.18 V
ε
κ = 1.21 Tb
where,
v is the molal
volume of liquid at
normal boiling
point, m3/kmol
Tb is the normal
boiling point in
Kelvin
Diffusivities of gases at standard atmospheric pressure, 101.3 kN/m2.

Experimental diffusivity values for selected gas
pairs at 1.013 bar pressure

Chapman and Enskog correlation
Chapman and Enskog used the Lennard-Jones potential
function (Chapman and Cowling, 1970) given below to
calculate the interaction parameters.
DAB =
1.858 x10-7 T1.5 V1/MA + 1/MB
m2/s
P (σAB)2 ΩD)
where
T = absolute temperature, in K
MA , MB = molecular weights of the components A and B
P = total pressure, in atm
σAB =a characteristic length parameter of the binary, in A
ΩD =collision integral which is a function of kT/εAB
εAB is another characteristic binary parameter
k is the Boltzmann's constant
Lennard-Jones potential parameters for selected compounds

The values of (σ and ε for substances not listed in the above
table can be calculated from the following approximate
relations
1/3
σ = (5/6) Vc
ε
κ = 0.75 Tc
where,
Tc is the critical temperature (K)
Vc is the critical volume (cm3/gmol) of a component.

Numerical values of the collision integral, ΩD

Fuller, Schettler and Giddings correlation
An empirical equation suggested by Fuller, Schettler and
Giddings (1966) is reasonably accurate in predicting binary
gas-phase diffusivity up to moderate pressures.
DAB = 1.0133 x 10-7 T1.75 1/2

1/MA + 1/MB m2/s
2
1/3 1/3
P (ΣvA) + (ΣvB )
where,
T = Temperature, in K
MA and MB = molecular weights of A and B respectively
P = Total pressure, in bar.
(Σv) = Atomic diffusion volumes (Adding each of the
components atomic diffusion volumes)
Atomic and diffusion volumes (Fuller et aI., 1966)
Example: let us estimate the diffusivity of cyclo-hexane (A)

in nitrogen (B) at 15°C and 1 atm pressure.
Cyclo-hexane (C6H12) has one ring.
ΣVA = (6)(16.5) + (12)(2.31) - 20.1 = 106.5
ΣVB = 17.9
Correlation to find diffusivity coefficient in
gases
D AB =
( )
10−4 1.084 − 0.249 1/ M A + 1/ M B T 1.5 1 / M A + 1 / M B
Pt ( rAB ) f  κ T 
2
ε 
 AB 
where DAB = diffusivity, m2/s T = Absolute temperature, K
MA and MB = molecular weight of A and B, respectively, kg/kmol
Pt = abs pressure, N/m2 k = Boltzmann's constant
rAB = molecular separation at collision, nm = (rA + rB)/2
εAB = energy of molecular attraction = √ εAεB
f(kT/ εAB) = collision function for diffusion

Problems
• Estimate the diffusivity of ammonia vapor, NH3, (A), through
air (B) at 1 std atm pressure and at 0°C.
• Estimate the diffusivity of ammonia vapor, NH3, (A), through
air (B) at 2 std atm pressure and at 25°C.
• Estimate the diffusivity of ethanol vapor, C2H5OH, (A),
through air (B) at 1 std atm pressure and at 0°C.
• The diffusivity of carbon dioxide in helium is reported to be
5.31 X 10-5 m2/s at 1 std atm, 3.2°C. Estimate the diffusivity
at 1 std atm, 225°C.

Problems
Estimate the diffusivities of the following gas mixtures:
(a) Acetone-air, at STP. Ans.: 9.25 X 10- 6 m2/s.
(b) Nitrogen-carbon dioxide, I std atm, 25°C.
(c) Hydrogen chloride-air, 200 kN/m2, 25°C.
(d) Toluene-air, 1 std atm, 30°C.
(e) Aniline-air, STP.

Diffusivity in Liquids – Experimental methods
There are a number of methods for the determination of the
liquid-phase diffusion coefficient.
Here we describe a common method that uses a 'diaphragm
cell'
The diaphragm cell is a two-

compartment cell separated
by a porous diaphragm
usually of sintered glass.
Solutions of the species A in

the solvent B at two different
concentrations are taken in
the two compartments.
Diffusion is allowed to occur through the narrow passage
ways of the pores from the higher concentration cell to the
lower concentration cell for some time.
At the end of a run, samples of the solutions are taken from

the cells and analyzed for the Diaphragm concentrations of
A.
The contents of the compartments are always kept well-

stirred.
If the area of cross-section of the diaphragm is a and ε is its

porosity, then the effective area available for diffusion is aε.

The working equation for the calculation of the diffusion
coefficient from the data collected with a diaphragm cell can
be derived following the procedure adopted in the case of the
twin bulb method.
The above equation can be

integrated at steady state to give
where, l is the thickness of the diaphragm, and Iτ is the

effective length of the diffusion path.
V1 and V2 are the volumes of the solutions in the two cells and
CA1 and CA2 are the concentrations therein at time t,
Adding the above two equations and substituting NA
If CA1,0 and CA2,0 are the initial concentrations and CA1,f and
CA2,f are the final concentrations in the compartments at time
tf , integration and rearrangement of the above equation
yields
The above equation is used to calculate the diffusion
coefficient from the measured concentrations and time.

Diffusivity in Liquids (Wilke-Chang)
For smaller molecules (A) diffusing in a dilute liquid solution of
solvent (B):
117.3 x 10-18 (Φ MB)1/2 T
DAB =
μB VA0.6
DAB - diffusivity in m2/s
MB - molecular weight of solvent B
T - temperature in K
μ - viscosity of solvent B in kg/m s
VA - solute molar volume at its normal boiling point in m3/kmol
Φ - association parameter of the solvent, which 2.6 for water,
1.9 for methanol, 1.5 for ethanol, and so on
DAB is proportional to 1/μB and T
Diffusivity in Liquids
For very large spherical molecules (A) of 1000 molecular
weight or greater diffusing in a liquid solvent (B) of small
molecules:
9.96 x 10-16 T
DAB = applicable
μ VA1/3 for biological
DAB - diffusivity in m2/s
solutes such
T - temperature in K as proteins
μ - viscosity of solution in kg/m s
VA - solute molar volume at its normal boiling point
in m3/kmol
DAB is proportional to 1/μ and T

Diffusivity of Electrolytes in Liquids
For smaller molecules (A) diffusing in a dilute liquid solution of
solvent (B):
8.928 x 10-10 T (1/n+ + 1/n-)

DoAB =
(1/λ+ + 1/ λ-)
DoAB is diffusivity in cm2/s
n+ is the valence of cation
n- is the valence of anion
λ+ and λ- are the limiting ionic conductances in very dilute
solutions
T is absolute temperature
DAB is proportional to T
Liquid diffusivities

Correlation to find diffusivity coefficient in
liquids
D AB =
(117.3 ×10 ) (ϕ M )
−18
B
0.5
T
µ v A0.6
where DAB = diffusivity of A in very dilute solution in solvent B, m2Is
MB = molecular weight of solvent, kg/kmol
T = temperature, K μ = solution viscosity, kglm.s
VA = solute molal volume at normal boiling point, m3/kmol = 0.0756 for water
as solute
= 2.26 for water as solvent
φ = association factor for solvent = 1.9 for methanol as solvent
= 1.5 for ethanol as solvent
= 1.0 for unassociated solvents,
e.g., benzene and ethyl ether

Problems
1 . Estimate the following liquid diffusivities:
(a) Ethanol in dilute water solution, 10°C and at 1 atm..
(b) Carbon tetrachloride in dilute solution in methanol, 15°C
(observed value = 1.69 X 10-3 cm2/s). Ans: 1.49 X 10-9 m2/s.
2. The diffusivity of bromoform in dilute solution in acetone at
25°C is 2.90 X 10-5 cm2Is. Estimate the diffusivity of benzoic
acid in dilute solution in acetone at 25°C. Ans: 2.269 X 10-9
m2/s.
3. Calculate the rate of diffusion of Nacl at 18°C through a
stagnant film of water I mm thick when the concentrations
are 20 and 10%, respectively, on either side of the film. Ans:
3.059 X 10-6 kmol/m2s.

Module – 1 completed
Thank you

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BCHE207L Mass Transfer I

Instructor: Dr. Monash P.

Total Lecture hours - 45 hours

Dr. Monash Purushothaman BCHE207L Mass Transfer I 4

Dr. Monash Purushothaman BCHE207L Mass Transfer I 5

Digital Assignment 24/06/2023 10 10 Question and rubrics will be

Continuous 30/06/2023 50 15 As per the circular by Dean

Final Assessment 17/07/2023 100 40 Schedule will be announced by

Dr. Monash Purushothaman BCHE207L Mass Transfer I 6

Dr. Monash Purushothaman BCHE207L Mass Transfer I 7

Dr. Monash Purushothaman BCHE207L Mass Transfer I 8

• Diffusion is the macroscopic result of random thermal motion

Dr. Monash Purushothaman BCHE207L Mass Transfer I 9

Dr. Monash Purushothaman BCHE207L Mass Transfer I 10

Dr. Monash Purushothaman BCHE207L Mass Transfer I 11

• Liquids A and B are separated from

Dr. Monash Purushothaman BCHE207L Mass Transfer I 13

• Molar average velocity

Dr. Monash Purushothaman BCHE207L Mass Transfer I 14

Dr. Monash Purushothaman BCHE207L Mass Transfer I 15

Dr. Monash Purushothaman BCHE207L Mass Transfer I 16

Dr. Monash Purushothaman BCHE207L Mass Transfer I 17

where, DAB is the proportionality constant called the 'diffusion

The diffusional flux JA is a positive quantity by convention, Since diffusion occurs

• If the concentration gradient is expressed as the gradient of

Dr. Monash Purushothaman BCHE207L Mass Transfer I 19

Dr. Monash Purushothaman BCHE207L Mass Transfer I 20

• Molar diffusive flux of B in A: (2)

Dr. Monash Purushothaman BCHE207L Mass Transfer I 21

• For an ideal gas mixture at constant pressure

• Substituting (3) and (4) in (1) and (2), we get

Dr. Monash Purushothaman BCHE207L Mass Transfer I 23

stagnant and laminar flow conditions

Dr. Monash Purushothaman BCHE207L Mass Transfer I 24

Let us use NA to denote the total flux by convection (which is diffusion

The velocity of the above diffusive flux of A in B can be given by

The velocity of the net flux of A in B can be given by

The velocity of the bulk motion can be given by

(NA + NB) (mol/m2.s)

Multiplying the above by CA, we get

CA vA,convection = CA vA,diffusion + CA vbulk

Using equations (2) to (4) in the above, we get

NA = JA + CA (NA + NB) (5)

Substituting JA from equation (1) in (5), we get

NA = -DAB dCA (NA + NB)

Dr. Monash Purushothaman BCHE207L Mass Transfer I 27

Using (7a) and (7b), equation (6) can be written as

Dr. Monash Purushothaman BCHE207L Mass Transfer I 28

Using (16), equation (13) can be written as

NA = -CT DAB dxA + xA (NA + NB) (10)

Dr. Monash Purushothaman BCHE207L Mass Transfer I 29

In terms of partial pressures (using pA = CART and P = CTRT):

In terms of molar fraction of A (using xA = CA /CT):

NA = -CT DAB dxA + xA (NA + NB)

Dr. Monash Purushothaman BCHE207L Mass Transfer I 30

Equation (1) is therefore written as follows:

The above equation is most widely used form to find the

NA = DAB CT ln 1 - xA2 (3)

Introduce the log mean value of inert B as follows:

Dr. Monash Purushothaman BCHE207L Mass Transfer I 35

Dr. Monash Purushothaman BCHE207L Mass Transfer I 36

Dr. Monash Purushothaman BCHE207L Mass Transfer I 37

Dr. Monash Purushothaman BCHE207L Mass Transfer I 38