8

UNIT V MASS TRANSFER

Syllabus

ysical origins, applications of mass transfer, Mixture Composition, Phase diagram, Fick's Law of Diffusion with
naumerical treatment, Restrictive Conditions, Mass diffusion coefficient, Conservation of species.

ne Mass Dfusion equation Cartesian coordinates derivation, cylindricai coordinates and spherical coordinates
(no derivation), Boundary and initial conditions.
This masstransfer is known as diffusion for which
8.1 Introduction the driving potential is the concentration difference. Itie
analogous to electrical system.
It is a matter of common experience that heat flows
from higher temperature body Definition of mass transfer The mas
to lower temperature
body when brought in contact in order to come in transfer refers to the diffusion of chemical species
thermal equilibrium. The components from a region of high concentrationt
driving force for heat transfer
is the temperature
gradient. that oflowerconcentration.
Similarly, when the system is not in equilibrium, the
8.2 Modes of Mass Transfer
physical quantities move from a region of higher level to
lower level until the equilibrium is achieved. It is
The process of mass transter can be classified
according to second law of thermodynanmics. Let us as
follows
considerthe following examples
i) The gases from higher pressure region moves into 1. Mass transfer by diffusion

the of lower pressure naturally. These gases 2. Mass transfer by convection

region
cannot be brought back to their original state 3. Mass transfer by change of phase
without expenditure of external energy
8.2.1 Mass Transfer by Diffusion
ii) Flow of mixture of gases in a pipe having slope.
In above cases, there is a bulk flow causing the mass Mass transfer by diffusion is also called as
and energy transfers at macroscopic level. Such molecular diffusion.
problems of mass, momentum and energy transfers are
The mass transfer by diffusion occurs due to
treated in the subject of fluid mechanics.
concentration gradient of chemical species
In this chapter, we are concerned with mass transfer
components in a system through a stagnant fluid.
at microscopic level i.e. on molecular level. e.g. consider
a system containing two or more species (components) To understand the above definition, consider a large
having variable concentration throughout the system. open beaker with little water at its bottom surface kept
There is a natural tendency for species to move from in a room. The concentration of water vapour near the
higher concentration region to the lower concentration water surface will correspond to saturation pressure of
region (like heat flow) till the chemical equilibrium is water at its room temperature while the concentration
reached. Thus, there is a transfer of mass caused by the of water vapour near the mouth of beaker will be lower
variation in concentrations of the various constituent and it will be corresponding to the concentration of
species. water vapour in the room itself.
 (SPPU) 8-2
Transfer Mass Transfer
and Mass
H e a t a n dM a s

t
centration difference of water vapour at the 8.3 Important Definitions Relevant to

surface across the stagnant column of

a n du p p e rs u r f a c e

the water vapour to diffuse and

Mass Transfer
t h eb e a k e ra l l o w

due
air
i nt surface at microscopic level towards Since the mass transfer by diffusion takes place
arater
to concentration gradient of chemical species, here
e f r o m

beaker e to
ore of
define the concentration and other terms relevant
ofmolecular diffusion are:
mouth

r
he examples
S o m eo f
ofthe mass transfer.
of tea.
sugar in cup
8.3.1 Concentrations
o f s

Dissolution

of N, a n d 0,.

2.
Mixing ofjars 1. Mass Concentration or Mass Density, P
of salt in
water
3 ion
Dissolution
number of species
A mixture may have
in tank.
Evaporation of petrol (components). Then,
from lake, sea or river to ass or
Definition: The m a s s concentration
of water
tion
i
5.
Evapor:

increase the humidityof passing

air stream.
density, p is defined as the m a s s of the species per
of fragrance
in surroundings.
unit volume ofthe mixture. It's unit are kglm'
Spread
6
of water from moist clothes while Accordingly
Evapor Mass density,
drying. Mass of species or components, i(m)
usion of carbon in steel for case hardening PI Volume,V
8
glass bulb. ...(8.3.1)
of helium from
a
Escaping
9
Mass
Transfer by Convection Mass density of mixture,
8.2.2
surface and a moving .(8.3.2)
transfer between the
The mass
mass transfer. It may also
as convective
fuid is referred
two immisible moving
between
fluids. Mass fraction, x,:
take place the ratio
convective defined as

Therefore, this
phenomenon is similar to Definition : Mass fraction is total of mixture,
mass
species, m; to the
heat transfer. of m a s s ofi
mass transfer are the m.
convective
Examples of be
clothes which can
of water from moist Accordingly.
evaporation fan or Mass of ith species, m
moving the air in
contact by using
enhanced by mn
Total mass of mixture
=

of water by moving air in desert Mass fraction, Xi

the evaporation
coolers. mm/V p
8.3.3)

8.2.3 Mass Transfer by Phase Change of mixture

m = total mass

fluid
where,
of phase of a
The mass transfer by change
occurs by combination of convective
and diffusion mass

Also,
x =1 (8.3.4)

transfers eg
Molar Density, G:
) the mass transfer of boiling water
into atmosphere. 2. Molar concentration o r
natural o r molar
transfer of hot flue gases by Definition: The molar concentration
i) the mass
moles of thel
chimney and then
its diffusion
into ofthe number
density, C; is defined
as
convection in
mixture.
atmospheric air.
species i per unit volume of the
mole / m.
It'sunits are kg mole / ma ork E TechKnowledya
Heat and Mass Transfer (SPPU) 8-3 Mass Transfer
Accordingly, Partial pressures, Pa+Pb p
Molar concentration,
Mass density, PatPo P
Number of moles of species i,
C n Mass fraction,
Xa +X = 1

Volume, V . 8.3.5)

By definition, (Refer Equation (8.3.4))

Number of ya+y 1
moles of i species, Mole fraction,
Mass of th
species, m (Refer Equation (8.3.10) .fiv
Molecular of wieght of ith species, M
Number ofmoles:
8.3.6) ma
Molar concentration of mixture, n,M, n M,
Total number of moles, n
C = .(8.3.7) n Mand n= n + n
Volume, V

where, n 2n mb
ma
M, M M
C -Z .(8.3.8)
m

Mole fraction:
But, m

Definition The mole fraction of i species is -(8.3.12)

defined as the number of moles of t speciesto the
From gas equation,pV = R°T
total number of moles in the mixture.
It is denoted as
y where, R° = Universal gas constant

. Mole fraction of i species, 8.3143 kJ]/k mole K

(8.3.9) From Equation (vi)

Yinn/V C
Also, 8.3.10)
RT T andT-
:C a G y and C=ù*RT
.Vili
Note It is convenient to use massfraction in the study of
dliffusion in solids and liquids while the concept of mole
fraction is convenient in study of diffusion in gases
C C,+Cp ix)

3. Dalton's law of partial pressure: 8.3.2 Velocities

It states that the total pressure exerted by a mixture
In a mixture, the various species move at different
of gases is the algebraic sum of the partial pressures
velocities. Let, V, be the velocity of ith species.
exerted by the individual gases when they occupy
the same volume and temperature as the mixture of Here, we define bulk velocity of the mixture as the
average velocity of the mixture.
gases
We can define two types of average velocities as
(pT = (P. + P» t v r = (2 P Jv,T(8.3.11)
follows:
4. Concentration of binary gas mixture:
a) Mass average velocity, u.
Consider two gases A and B mixed in a vessel of
b) Molar average velocity, v.
volume, V and at temperature, T which exert a total

pressure, p.
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ublicatlans
 Transfer
(SPPUn 8-4 Mass Transfer
Mass
Heatand
, u:
M a s s a v e r a g ev e l o c i t y , i
1. Mass diffusion flux, J
a)
an be
defined based on the mass density as Definition: The mass flux of the species tS
It
defined as the mass of a species that passes
follows:

through a unit area per unit time relative to

u stationaryobserver.
..(8.3.17
Absolute mass flux = Pr

..(8.3.18)
2P-x p
8.3.13) Bulk motion flux

absolute
= Pu

flux of any species

seen by any
The
fraction,
Since,
the mass
stationary observer
P flux, J + Bulk motion flux
x (from Equation (8.3.3)) M a s s diffusion

average velocity,
v: m
(b) Molar the molar concentration
PU +Pu
be defined based
on
It can
as folows Mass diffusion flux,
or
molar density

2 ..(8.3.19)
V P (u -u)
flux, J, is the product
diffusion
Therefore, the mass

. 2C y .8.3.14) of the mass density and the m a s s

diffusion velocity.

8.3.2.1 Diffusion Velocity 2. Molar diffusion flux, N, A):

diffusion process, the motion of

various Definition: The molar flux defined a s the
is
During the
species passes through unit|
a
takes with respect to bulk o r average
place number of moles of a
species observer.
velocity of the mixture.
Based on this concept we can
areaper unit time relative to stationary
molar diffusion velocities
define as mass diffusion and
velocities as follows: the product of the molar
based on average is defined as

Mass diffusion velocity of ith species represents the and the molar
a) density or molar concentration, C
with respect to their mass
velocity of these species diffusion velocity.
average velocity.
Mass diffusion velocity ofPh species
=
u -

u8.3.15) N =G ( u - v ) + .(8.3.20)

b) Molar diffusion velocity of ith species represents where,

to their
the velocity of these species with respect .(8.3.21)
Absolute molar flux,
molar average velocity.
Molar diffusion velocity of th species = u - v ..(8.3.16) Bulk molar flux, n = C v 8.3.22)
Therefore the basic quantities of mass transfer
8.3.3 Fluxes be summarized
discussed above in section 8.3 can as

as the rate at
general, the diffusion flux is defined
In follows
of
which a species diffuse with respect to bulk motion
fuid. Based on this concept we can define various types

offluxes as follows

TechPuDtICatlons
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 Heat and Mass Transfer (SPPU) 8-5 Mass Transfer
Table 8.3.1 Summary of basic quantities in mass transter

Terms Mass quantities Molar quantities Importantrelationships

1. Densities
Species m
Py (kg/m?) C(moles/m) a) n M

P
b) C M
ii Fraction a) x y,=1
b) CM
c)M=2G M
d) G v o
RT

2. Velocities
)Species a) u=2x-u
b) v 2 u
V
ii) Bulk
iii) Diffusion (u-u) (u-v)

3. Fluxes
i) Absolute Pi Cu mi
A h

CGV
ii) Bulk
N
ii) Diffusion
J=P(-u)=A N, C (u-v)=A
in MN2 32 kg/ kg mole,
Ex. 8.3.1 A mixture of gas has N2 and CO2 kept a

of Mco2 44 kg/kgmole
container having pressure 200 kPa and temperature
find (i) Mole fraction
27 C. If the molar fraction of Na is 0.4,
i)Mole fraction of Co,i.e. Ycoz
Molecular weight of mixture (ii) Partial pressures
ofCO (i)
1
exerted by each gas (iv) Molar concentration of each gas (v) Mole fraction, yN2+ Yco2
of each gas and total density (vi) Mass Ans.
Mass density mass
Yco2 1-0.4 =0.6
fraction of each gas.
ii) Molecular weight of mixture, M
Soln.
M YN Mya + Yco2" Mcoz
P 200 kPa,
= 0.4x 28+ 0.6 x 44 37.6 .Ans.
T 27°C = 27+ 273 300 K,

N2 0.4

TechKaewledge
PubIcatiens
 (SPPU) Mass Transfer
Mass
Transfer 8-6
leat and
lpressures of gases 1.e. PNa and Pooa
898
3.015 0 . 2 9 7 9
.Ans.
XN2
) P a r t l a l

P
11 .Ans.
co2 3015 0.7021
YN2 P= 0.4 x 200
= 80 kPa Ans,
PN ot Ng 18
Ex. 8.3.2: If in Examplo 8.3.1, the moan volocity
= 0.6 X 200 = 120 kPa other things
Yco2 P Ans.
*

Pco2 0.1 m/s and tho gas CO, le stationary with all
C o n c e n t r a

of each gas| l.e. Cy2 and Gco2 romaining tho samo. Find:
Iv)
(0) Mass diffuolon volocity of oach gas.
n RT
p V () Molar diftusion volooity of oach ga.
200 (H) Mass flux of oach ga.
C 8.3143 x 300
RT (v) Molar flux of oach gas.
= 0.08018 kg mole/m3 Soln.

0.1 m/s and Ucoz

Cy yN2 C=0.4x 0.08018B UN2
)Mass diffusion velocity of N, and CO:
= 0.03207 kg mole/m3 Ans.

Bulk velocity,
Alternately

PN2 80
Cw2 8.3143 x 300
RT = 0.2979x0.1 +0.7021 x0

= 0.03207 kg mole/m3 Ans. = 0.02979 m/s

X C = 0.6 x 0.08018 a) Mass diffuslon velocity of N,
Cco2 yco2
= 0.04811 kg mole/m3 Ans. = UN2 u = 0.2979 -0.02979

vMass concentration ofeach gas i.e. P and Pco

= 0.26811 m/s Ans.

P b) Mass diffusion velocity of CO,

C M i.e. P C M

PM2 0.03207 x 28 = 0.898 kg/m3 .Ans. Uco2- u =0- 0.02979

- 0.02979 m/s
Pcoz0.04811 x 44 2.117kg/m3 .Ans. Ans.

i) Molar diffusion velocity of Na and CO

Total mass density,
0.898+ 2.117 Molar bulk velocity, v = 2 y
P PN2+ Pco2 =

y N 2 uN2 + Yco2 UNz

= 3.015 kg/m* Ans.
= 0.4x0.2979 +0.6 x 0
Alternately
P M 1.1916 m/s
P P
P RT a) Molar diffusion velocity of N2
(R/M) T RT
= UN2 Vv = 0.2979 - 1.1916
200 x37.6
B.3143 x 300 3.015 kg/m* Ans.

= -
0.8937 m/s Ans.
vl) Mass fraction of each gas i.e.
XN and Xco b) Molar diffusion velocity of Co,

= Uco2- v = 0-1.1916

= -1.1916 m/s
Ans.

7Tech Kneuledya
 Heat and Mass 'Transfer (SPPU) 8-7 Mass Transfer
ii) Mass flux of N, and CO i.e. JN and Jcoz :

IN2 PNz (u-u) =0.898 (0.26811) = 0.24076 kg/ns

Ans
Jcoz Pco2 ( Uco2-u ) 2.117 (- 0.02979)
= =
- 0.06307 kg/m* s Ans.
iv) Molar fluxes of each gas i.e.
NN, and Nco,
Na Ca(uN-v) = 0.03207 (- 0.8937)= - 0.02866kg mole/m*s
Ans
co, Cco2 (Uco2- v ) = 0.04811 (-1.1916) = - 0.05733 kg mole/m* s
Ans
8.4 A Physical Law for Diffusion Fick's Law
Fick's law gives the relationship between the diffusion flux to its driving potential ie. the concentration gradlent
ased on experimental results. In order to understand the concept of mass diffusion of species, let us consider a
chamber having gases A and B separated by a partion wall as shown in Fig 8.4.1.
Partition
Chamber

o oo o o
Species,A o o o
o O
Species,B

o o oo o o o
A B X
X
C Concentratilon of species,A
C Concentration of species,B

Fig. 8.4.1: Fick's law of mass diffusion in binary mixture

Left side of chamber has the concentration of gas A A area through which mass is flowing (m2)
only represented by open circles while the right side of
chamber has the
concentration of gas B 0nly JAA rate ofmass flux per unit area of
represented by dark circles.
When the partition is removed, the gas A diffuses species A ( kg/s m2)
into gas B from left to right while the gas B diffuses into PA mass concentration ofspecies A per
gas A from right to left due to concentration gradient mA
which acts as driving potential. The diffusion of gases unitvolume, (kg/m)
continues until the equilibrium is established and the dpA
concentration of gases is uniform throughout. The rate d mass concentration gradient
(It acts as
ofdiffusion of gases
is related by Fick's law as follows: driving potential)
DAB proportionality or diffusion coefficient
Statement of Fick's law
(m/s)
The Fick's law of diffusion states that the rate of
mass flux of a constituent or species per unit area is
Note Negative sign indicates that the diffusion of
proportional to the mass concentration gradient.
species takes place from a region of higher
concentration to lower concentration
Mathematically, the diffusion of species A into
species B be is related by the equation, Similarly, the diffusion rate flux for species B into
species A can be written as
mA dpa
J DaB d .8.4.1)
mg dpB 8.4.2)
where, mA = mass flow rate of species A (kg/s)
JsA DaA dx

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PublIC JtTOns
 Transfer (SPPU) 8-8 Mass Transfer

t and Mass
rient of diffusivity, DAB DBA (say, D) since
=
Heat
Thus the units of DAR are identical to the units o
T h e

ent the relative difusivities of gas A w.r.t. thermal diffusivity, a.

B and
vice-versa. The magnitude of diffusion
vi Note that DAB = DBA = D
e f i c i e n td e p e n d snds on the pressure, temperature and the
species
in the Physical mechanism ofdiffusion:
the or
concentration
terms of molar concentration : ReferFig. 8.4.2. We observe that the is
's
law
in
species A (moles/unit volume) on left of partition
on the
than the of species A
of molar flux N molar = much greater concentration
terms
ick's law in molecules of
The
right side of the plane. Therefore, the more
(Number of moles / unit volume) and right than in
concentration
Ca A cross the plane per unit time from left to
frusivity DAB can be expressed as the net mass
efficient of the opposite direction. It results into
the region of high
transfer of species A from
nA dCa of lower concentration
till

NAA- DAB dx .(8.4.3) concentration to the region

the equilibrium is established.
Equation (8.4.1) can be used in terms of A
Therefore,

centration ( Pa ) and Equation (8.4.3) when

conce Partition
in terms of nolar concentration
mass

uantities a r e specified or plane

dCA
(Ca
that the Equations (8.4.1)
It should be further noted
w r i t t e n .for mass or molar concentration
are
to (8.4.3) X-direction. Similarly, the Fick's law
adient in
written for concentration gradient in Y
can be
equation
directions also. Concentration profile
and Z Fig. 8.4.2:
Equation (8.4.1) is analogous
The Fick's law diffusion Fick's law of diffusion:
Important aspects of
to:
conduction ie. These are:
Fourier's law of heat evidence. It
dT Fick's law is based on experimental
A = -k i)
x cannot be proved analytically.
matter i.e. in solid,
is: Fick's law is valid in all states of
i) Newton's
law ofviscosity o r viscous shear equation ii)
du liquid and gaseous states.
T d (where,dy velocity gradient) is applicable to mass diffusion of
y ii) Fick's law
concentration gradient. The
substances due to
conduction describes the
The Fourier's law of heat of diffusion depends
coefficient
the pressure, on

to temperature gradient,
the
transport of heat due temperature and nature of
the substances.
the transport of
viscous shear equation describes direction of
takes place in the
momentum across fluid layers due to velocity
the iv) Mass transport
diffusion law decreasing concentration.
gradient, and analogous to these, the Fick's
describes the transport of mass due to concentration Representation of Fick's law in
terms of partial
gradient. pressures of the gases
and assuming isothermal
Units of diffusion coefficient, DAB Using perfect gas equation
be written in terms of partial
reaction, the Fick's law can
From Equation (8.4.1),
pressures as follows
kg/s m
mA dx dx
DABAXdCA m2 (kg/m) p p R.T P PT
Tech KnewBadgë
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Heat and Mass Transfer (SPPU) 8-9 Mass Transfer
Hence the above equation derived ah
is same as

Pa PA MT .1 PA
PAMa (ii)
as Equation (8.4.4). Thus the equations of mass
R.T molar diffusions as Equations (8.4.1) and (8a
respectively are similar.
(8.4.4)
where, PA =
partial pressure of gas A (Pa or N/m2) Mass diffusion coefficient, D ( Dau or DaA) for binan
PA density of gas A(kg/m')
mixtures:
MA molecular weight of gas A ( kg/kg mole) From kinetic theory of gases, it can be shown tha
the mass difuslon coefficient DAB in the equation of
R universal gas constant
Fick's law for gases and vapours is proportional t
= 8314.3 Nm/kg mole K
ToM/p.
T temperature (K) Gilliland proposed a semi-emperical equation
for
mass diffusion coefficlent in a binary mixture of two
The Fick's law diffusion Equation (8.4.1) is,
follows
gasesAand B as
dpa
- DAB d x
T3/2
D4357P[VP-v1
PA M,
d 8.4.7)
- DAB RT Where, D DAB= DBA
A dx
= Diffusion coefficient in cm2/s
Ma dpA
m - DAB dx (8.4.4) T Temperature in Kelvin.
RT
p Total pressure ofsystem in N/m* or p,

- DMa
a Bdpa
mg = (Pa * Pa)
d 6.4.5)
Similarly,
RT VA and V3= Molecular volumes of gases A and B as
Using Equation (8.4.3) for molar diffusion, calculated at normal boiling point in cm
per gm mole [Refer Table 8.4.1]
dCA
.(8.4.6) Table 8.4.1:Molecular weight and molecular
volumes of gases at 1 atm. pressure and 25°C
mA
But, na and Ca =M, Molecular volume
M, Constituents Molecular

PA
weight (cm/gm mole)
mA Air 28.96 29 29.9
AA-M, -Das" dx
34.0
Carbon 44
Ma PA 1 dioxide (CO)
d RT M4 15.6
= - DAB
dx
Nitrogen (N)| 28

Oxygen (0) 32 7.4

mA 1 dpA
Hydrogen 2 28.6
A-M-DAB RT d (H)
Carbon 28 30.7
Ma aPA
D RT
(From Equation (8.44)) monoxide

(CO)
TechKnewledyë
PubICdllv*
 Mass Transder
MassTranaier (SPPU) 10

Molecular Molecular volume Collision integral, a dimensikonless

ent
and of
welght (cm /gm mole) function of the temperature
intermolecular potential
field for one
64 44
1 molecule
of B
molecule of A and
Aicaide( 5 0 )
and B
18 188 M, M, Molecular weiets ofspeciesA
W e rv a p o u r

respectively (gm mole)

17 258
Aracoornla
The value ofQis calculated as

(BA.10)

32 256 E
SApur

other and K Boltzman constant

efficdent at pressures where, =

fuston

e m p e r a t u r e s :
1.38101 ergs/K
interacting for
a

be calculated by using the following equation EAEEnerey of

molecular
t an ¬E, (ergs)
binary system AB =VE,
) 848)
can be calculated as
components
The value of pure
Diffusion
coefficdent
forliquids: follows:
ís much smaller as
of DA for Iiqulds
The value of DA for various 118,=0.841 V=244
the gases. The value
to
Compared avallable.
determined by eperiments is 84.11)
iqulds as increases
tis obrerved
that the value of DAa for liquids -(8.4.12)
And, E = 1.15 T, =0.77 Ta
increase in temperature
with the
where,
Diffusion
coefficlent forsolids: Volumes at boiling
and critical states
of solíds is extremely small. The V, and Va =

The diffusion in
case
respectively (cm?/gm mole)
diffusion in case of solids is not
enperimental data
on
and critical
Temperatures at boiling
T, and T
=
much available.

for non polar and non reacting state respectively (K)

Diffusion coefficient
mixture:
molecules ofa
gas
General Mass Diffusion Equation in
The gas misures having
polar, non reacting
non 8.5
3.5
in Stationary
Cartesian Co-ordinates
the diffusion coefficient given
ís as:
molecules,
T2 1 Medium
n..
D, 0.001858 (A
in stationary medium
8.4.9) The general diffusion equation in the
can be derived
for mass transfer of any species
of specles A through B as derived for
Fourier's law of heat
where, DAe = Mass diffusívity similar manner

conduction equation in chapter 1.

(cm/s) of species A and B
mixture
Let us consider a bínary
Since
T Temperature (K) in a homogeneous
medíum which is stationary.
it implies that the
P Total pressure (atmospheres)=PA+Pe the medium considered is stationary,
velocity, u or the molar average velocity,
v
mass average
OAE Collision diameter (Armstra -A) are zero. It also implies that the
mass transfer mnay

occur only by diffusion process.

2 TecaKaauledgi
 Mass Transfer
Heat and Mass Transfer (SPPU)
8-11
mass accumulation
of species A alone
long
NAY+dy A2+d
Similarly the
directions can be written as:

theyand z
Iny-direction yNAy) dy
dx dz
=
..iv)
NAX+dxX
dx dy
In z-direction =(NA,)
dz
mA V)
accumulation in control volume will
Net rate of mass
accumulation in x, y and z direction
A
be the sum ofmass
N2 mass accumulation
in control volume of
Net rate of
species, A

(A )*NA)dk dy d
.(8.5.1)
diffusion equation of mass díffusion processes, the mass
Fig. 8.5.1: Control volume for mass In case
due to chemical reactions
may also
occur
dz shown in generation
Consider a control volume dx dy as
absorption of or
Therefore there may be generation
A diffusing
Fig. 8.5.1. The mass balance of species species A within the control volume. It would result into
medium B is
through the control volume in stagnant the rate of change of molar
concentration of species A
given as: in the control volume.
Along the x-direction: Let,
Mass influx at the left face =
NAX dy dz Mass generation rate,
unit time due to chemical reaction"Ag
ma
where.NA0 Then, net rat of mass generation of species A in
control volume
Mass efflux at the right face =
NA.x+ dx dy dz
But according to Taylor's series, mAg NA,g dx dy dz 8.5.2)
Total rate of change of
.
mass concentration in
NA,x+dz NAx+NA,x dx control volume of species A

Mass efflux at right face Rate of mass accumulation + Rate of Mass generation

Na dy dz+(NA dy dz)
dx
ddy d -aNay)*ad
x dx dy dz + dx dy dz NAg
-NM0N d dydz .i)
On dividing the above equation on both sides by dx
Accumulation of mass species A in control volume
dy dz we get,
due to its mass diffusion in X-direction will be equal to

the difference of mass influx and the mass efflux.

Accumulation mass species A due to diffusion

in control volume, ...(8.5.3)

Mass influx - Mass efflux
According to Fick's law for stationary medium (Refer
NA,x dy- dz-| Na X+ N a X) dx |dy dz Equation 8.4.3] we have

dCA aCA
=(NA dx dydz NA-DAB dx-DAB x
Tech O
Kaewledge
T c t i o n s
 Mass Transfer

Mass Transfer (SPPU) 8-12

Heat a n dMa.
PPAPe
law equatio (8.4.3) in equation (8.5.3)
Chambobr
UsingFickK's hE
Pa
w eg e t Passage

Ca DAB ABy PA2

..(8.5.4)
constants, the above equation
and C are
counter diffusion
If DAB Fig. 8.6.1: Equimolar
reduces to:
under steady state
Equations
0CA 0CA 0CA Using Fick's law, the molar diffusion

atPaBLàx7
ay2* ] * Nag (8.4.3) we have,

82CA NA .(8.5.5)
dCA .(8.6.1)
NA = - Dau dx
... (8.6.2)
1
Ca DAB dt ..(8.5.6) Ng -DaA
Under steady state conditions,
the governing equation fobr
Above equation represents ..)
equation in Cartesian
co-ordinates. NA+Ng =0 i.e. NA-NB
mass diffusion

This equation is analogues to Fourier's heat

-DABdx +DAB dx
dC
conduction equation.

Diffusion But, DAB DaA hence,

8.5.1 Specific Cases of Mass
Equation
dCa .ii)
dx

specified boundary
concentration at x =0 From Equation (8.4.5),
1. For

DAB ddCa
ie. CA CA0
at a surface
NA -
2. Specified m a s s flux
CA2
NA
-

DAB a t x= 0.
NA J dx = -

DAB "

J dCA
OCA 0 . 1 CA1
3. Without mass generation i.e.
NA 2 - X
=
- DAB (CA2-Ca)
reduce to: V2 CA = 0 .(8.5.7)
Equation (8.5.6) CA-CAl
NA -DAB (x2-X1) ...(8.6.3)
State Equimolar Counter
8.6 Steady
Diffusion and PA V= n RT
Ca

Definition: Equimolar counter diffusio of a i.e. PA

binary system is defined as an isothermal diffusion RT
process in which each molecule of species A are
by each molecule of species B and vice- PA
replaced CA .iii)
Dersa RT
A
Consider two large chambers having gas species
and B connected by a passage as shown in Fig. 8.6.1
in PA2 and CAL
PAL iv)
CAz
such a way the each molecule of speciesA are replaced RT RT
by each molecule of species B and vice-versa.

Tech Knemledye
PublIC atlons
 Heat and Mass Transfer (SPPU) 8-13 Mass Transfer
4. The concentration profile ot liquid vapour dae
On substituting the values from Equation (iv) in
does not
change due to diffuslon of vapour into stagnant
gas
Equation (8.6.1) we get Under steady state conditions, the upw
movement of liquid vapour A must be balanced
alanced by a
PA-Pa
N -Dan-X, 1 .. (8.6.4) downward diffusion of gas B so that the concentratia
RT at any distance from liquid surface remains ant.

The mass diffuston of gas B in downwards directie

Similarly, direction is
given by the Equation (B.4.6)
as:

N -Da (Pa-Po 1 .(8.6.5)

(-,) RT
m
A
-D
RT
dpp
dx
Equation (8.6.4) and (8.6.5) represent the equations
for equimolar counter diffusion under isothernmal and where, A = Cross-sectional area of vessel/tank
steady state conditions.
(ma) -D .A. P
or,
RT
dx 8.7.1)
8.7 Molecular Diffusion Through a
The liquid particles separated from its liquids
Stagnant Gas Film_ surface at point 1 move upwards and at the same time
the diffusion of gas from the top of the tank towards the
There are many practical situations where the
liquid surface occurs.
liquids vapour molecules diffuse through a stagnant air
At the interface of gas and liquid, the gas is neither
film eg. evaporation of pure liquids like water, gasoline,
produced nor it moves downwards. Therefore, there
benzene etc. in air.
must be some other mechanism to supply gas B to
Consider the isothermal evaporation of water or any
maintain its concentration of gas at the interface. Hence
other liquid A from a surface and the subsequent
there must be bulk mass movement of the mixture of
diffusion through a stagnant gas layer B as shown in
liquid vapour and the gas upwards with a sufficient
Fig.8.7.1. velocity, in order to compensate the mass diffusion of
the gas downwards
Stagnant
gas(6) Let, u = Velocity of gas B in upward direction.
Then the bulk mass transfer of gas upwards
Tank
mA
Liquid vapour p p m T) becomes,
- .
-LIQUID (A)-
(mgJup =
-Ps A u=- Pg A u
8.7.2)
RT
Total pressure,
P On equating Equation (8.7.1) and (8.7.2) we get,

Fig.8.7.1:Diffusion ofliquid vapour Ain stagnant gas B -D A . , dPa

dx Ps Mg. Au
RT RT
Assumptions:
1. The system is under steady state under isothermal
conditions.
u
padx (8.7.3)

Mass diffusion of liquid vapour in upward direction

2. The liquid vapour and the gas both behave like an
is,
ideal gas.
3. The total pressure in the system remains constant. mA =
D A MA dpa
dx
RT
Tech Kneuledge
Publicsgn
 Mass Transfer
Transfer (SPPU) 8-14
ndMass

of liquid vapour
carried along with
ma Jlotal (x -X,)= D-A. pnpp .(8.7.5)
eion of
Bulkditfusion
g a sin
: upward direction, RT
movementof
bulk
PA
*A
u = j MA.A u
RT
.(i)
(ma)total D.A.T n (8.7.6)
RT
(maJoulk
and
mA +
mA +(ma
( m Jbulk The distribution of partial pressures of gas
is shoWn in
Jhotal quid vapour with distance x in the medium
: (ma D-A.
-
D.A
OPA4
dx PA A.
Fig. 8.7.2.
Jtotal RT RT
(mA
PPA PB
value of 'u' from Equation (8.7.3)
substituting the
On

(maJunal-D.A.,dPA * AA, D.dpo

w e g e t

D. A. dx PA"
RT RT

.(iii) Llquid vapour

Distance, x
Dalton's
law of partial pressure,
From : Distribution of partial
8.7.2
PA+ PB P{Aconstant) .iv Fig.
B
pressure of liquid vapour A and gas
On differentiating,
partial
Introducing the concept of log
mean

dpA pressures of gas (L M P) w e have, {where for gas,

dx
PB2PB1
putting the value of dx from Equation (v) in LMP In (Pe/Ps
On

P2 P-Pa1P-Pa)-(p- Pa)
MPs
InPag
get
Equation (ili)
we

PB LMPg
P aA DPa (dea)
(m,Je-D A RT
RT dx =PBPs1 _PAPA) .(8.7.7)
LMP LMP
- D . A . . dPa be modified in
(ma tal RT Accordingly the Equation (8.7.6) can

terms ofL M P
= -

D A.A aPa
Pa t Pa) Notes
dx PB
RT
1. The diffusion of liquid vapour in stationary gas in
P terms of concentrations can be written as
ma Jtotal -D A dx (p-P)
RT
C- C
...(8.7.8)
[Using Equation (iv)] (8.7.4)

Equation (8.7.4) is known as Stefan's law for 2. In case the change in pressure of liquid vapour is
diffusion of an ideal gas component through a stagnant negligible compared to total pressure in the system,
and ideal constituent of the binary system. then the rate of mass transfer of liquid vapour can be

On integrating Equation (8.7.4) between x and xz we calculated by using instead ofL M P,

have

X2 PA2
(mAeoradx = -D - A p J (dPa
-D
X1 RT
PA1
TechKnomiadye
PuDIICtlgn
Heat and Mass Transfer (SPPU) 8-15 Mass Transfer
8.8
Comparison Between Fick's Law of Diffusion and Fourier's Law of Heat Condtes
duction
Sr Fick's Law Fourier's Law
No.

1. Molecular diffusion is governed by the empirical Fourier's law for unidirectional heat conduction
is
relation givenas

-D or -D
represents rate of mass flux a) (Q/A) represents the rate of heat flux

b) dp represents the b)d represents the temperature gradient.

mass density gradient dx
DAB represents the diffusion coefficient for binary ) k represents the thermal conductivityof matert
mixture
erial.
2. Negative sign indicates that diffusion takes place in Negative sign indicates thatheatflows in the
the direction of direction of decreasing temperature.
decreasing concentration.
3. It describes the transport of mass by difusion. It describes the transport of heat energy.
4. Mass transfer ceases when concentration gradient is Heat transfer ceases when temperature gradient is
zero. zero.

8.8.1 Dimensionless Parameters As Applied

Sc Momentum diffusivity ()
to Convective Mass Transfer Mass diffusivity (DAB) -[88.2)
Role of Sc is similar to Prandtl number, Pr in
We have defined the following terms:
convective heat transfer.
a) Momentum diffusivity, (m/s)
v=
w/p ii) Lewis number, Le
b)Thermal diffusivity, a =k/pC (m?/s) Thermal diffusivity (od)
Le
c) Mass Diffrusivity, DAs (m?/s) Mass diffusivity (DAB) p C DA
Since the units of all the above diffusivities are in .(8.8.3)
m/s, thus the ratio of any two quantities given above Table 8.8.1: List of formulae to be used
will be dimensionless, we define :
1. Refer Table 8.3.1 for mass and molar
densities
i) Sherwood number, Sh: It is defined as the ratio of velocities and fluxes.
concentration gradient at the surface to overall
concentration gradient. i.e. 2. Fick'slaw:

Sh Concentration Gradient JA -Dau -Da ddx

Overall concentration gradient
RT
Molecular mass transport resístance
Convective mass transfer resistance
ADAB dx e
DAB M8.8.1) Diffusion coefficient, D
It is similar to Nusselt number in convective heat D DAB=DBA
transfer.
T3/2
ii) Schmidt number, Sc: It is defined as the ratio of 435.7 x MM
momentum diffusivity to mass difusivity i.e. PVA
TechKaeuledge
 (sPPU) 8-16 Mass Transfer
Transfer
andMass
in O
HeatI na b o v e

on are
e q u a t l o r
EX. 8.8.1: Determine the diffusion coefficlent for CO,

TK), p
(N/m), V (cm /gm mole) at 127°C and 1.1 bar prossuro. Given
D(ems) T Molecular volume of CO = 34 cmgm mole
with pand
Varlatlo. of D
Molecular volume of O,- 7.4 cmIgm mole
D Soln.
ar
n o n - p o l a r a
and non-reae gas molecules Glven:
for Mo, = 32,
6.
Du m i x t u r e
ofgas
MA Mco, = 44, M
T3/2
0.001858 xp(OAL)0M M VA Vco, 34 cm°/gm
= mole

mole,
above
equation
are: V= Vo, 7.4 cm'/gm
=

Units in (atmospheres
(cm/s),
T(K), P p 1.1 bar 1.1x 105 N/m2,
Pan
diameter in armstro-A) =A*O 400 K
127oC= 127+ 273
=

(collision T

and
K.T EAB =VEA ¬p in ergs. From Gillland equation;
where, S2 EAB T3/2
D=435.7 x LMco2 Mo2
(ergs/K) called
K 1.38x 10-1
Boltzmann constant
435.7x (400)/2
T/3 1.1x10 [(34)3+(7.4)"]*
1 . 1 8 V1/3
= 0.841 (V
=
2.44
D
.Ans.
= 0.2735 cm-/s
1.15Th = 0.77 Ter
EAB coefficient of water vapour
the diffusion
represent the
values at the Ex. 8.8.2: Calculate
27C. Asume,
where suffix
'b' and 'cr into air at atmospheric
pressure
and
states.
and critical
point of boiling molecular volumes a s :
mole and
29.9 cm/gm
cm/gm mole, Vair
=

18.8
VH2o =

18, Mair = 29.

molecular weights: MH,0
=

RT
vapour A in
stagnant gas B
Diffusion of liquid Soln.
7.
d DJStefan'slaw] Given:
(mDhoai
-

D.A RT p 1 atm. pressure = 1.01325x 105 N/m2;

273 300 K
D.A - p T 270C =27 +
RT Using Gilliland equation
T3/2 /2
where P Pat PB D 435.7x PVv, (M *M
P»2 and (p -

Pai)= PB1
e.(p PA2)
=

respectively,
we have and air as A and B
n terms of log
mean pressure ofgas (LMP,) Using water
(300)3/2
Pa2 rial
In P32- P2 Pei _Pa1 D 435.7 X
(1.01325 x 105) (18.81/3 + 29.91/3)
nDR LMPg LMPs

N XnC-C = 0.202 cm2/s

Ans.

E Tech Knowledye
PuDICtGn
 Heat and Mass Transfer
(SPPU) 8-17 ass Transfer
Ex. 8.8.3: A cylindrical jar of 100 mm diameter has Soln. Let water and air be represented as
benzene of molecular weight 78 at its bottom. The
stagnant and B respectively.
specles A
air column in the jar is 200 mm above the
liquid surface Given
There is sufficient air movement at the
top to remove the
diffused benzene vapour so that the partial pressure of T 27°C= 300 K, d 30 mm =
0.03m,
vapour at the top is zero. The partial pressure of benzene
X2-X 50 mm =0.05 m,

vapour at the interface of liquid benzene and air is 0.103 bar D DAB 0.25 x 10-' m?/s
and the coefficient of difusion, D = 9.5 x 10*° m/s.
Calculate the diffusion rate of vapour. Assume, p 1.013 A d M A = Muzo = 18 kg/kg mole
bar and T= 27°c.
The partial pressure of water vapour at the
Soln.:Given: of thetest tube corresponds to the saturation
bottom
Let benzene and air are represented at constituents ressure
ofsteam at T= T, 27C. =

A and B
respectively. From steam tables we get,
Diameter of jar, d = 100 mm = 0.1 m.
PAI= 0.03531 bar
Therefore, A dx0.1 m The vapour pressure of water vapour at the top of
test tube may be taken as zero i.e. PAz = 0.
D 9.5 x 10-6 m2/s,
Rate of diffusion of water vapour in air:
MA 78,
MA
T 27°C=27+273 =300 K, mA D.A.
xin-
p 1.103 bar
= 18
(0.25 x 10-) *x0.03) *8314.3x
Height of jar, (x -x) = 200 mm 300
= 0.2 m, pAs = 0.103 bar 1.013x 10 1.013-0
0.05 n1.013 0.03531)
PAz 0 (at top surface),
= 9x 10-°kg/s = 9 *
10-6gm/s mAns.
P 1.013 bar =1.013x10 N/m2
Ex. 8.8.5 : A 40 mm deep cylindrical vessel is filed with
Universal gas constant, R = 8314.3 J/kg mole K water upto a level of 20 mm. It is exposed to dry air having
The diffusion rate of liquid vapour A in stagnant gas pressure of 1 bar and temperature of 35°c. The mass
(air) B is given by the equation: diffusivity of water is 0.25 x 10 m/s. Calculate the time
required for all the water to evaporate.

(m,) DA A,
=

RT
Soln.: Let A represent the water and B as air
Given:p 1 bar, T= 35°C = 308 K,
78x(1.013 x 105)
=

(9.5x106)x|G(0.1)]* 8314.3x 300 DAB 0.25 x 10-*m-/s

1.013-0 The partial pressure ofwater vapour at T= T, = 35°C
xn 1.013-0.103/
using steam tables, we get
= 2.5344 x 10-*kg/s = 0.25344 gm/s Ans.
PAI 0.05622 bar
Ex. 8.8.4: The water at 27°C is kept at the bottom of a test
Assume partial pressure of water vapour at the top
tube 30 mm in dlameter and 50 mm long into dry air 27 C.
as zero i.e. PA2 = 0
Find the rate of diffusion of water vapour in air if the
diffusion coefficient of water in air is 0.25 x 10 m/s. 18 Assume, A 1 m:.
MA M2o = =

Assume, atmosphere pressure, p = 1.013 bar.

TechKneuledge
YPud1caga
 Heat
a n dM a s s
fass Transfer (SPPU) 8-18 Mass Transfer

ReferF i g8 7 . 1
mA 2 kgin time, t=5 hrs
= 0.02 m, Area of tube,
Y= 20 mm
10% m*
0.04
d x (0.012)
m 113.097 x
40 mm
=
A =

2
= 0.02 m
(o.04 0.02)
m
- X 1 ) = (0.04
= 5 x 3600 = 0.000111 kg/s
mA
(x2-x) n -D
mA RT But, mA
DAnXA Ma n-PA
(0.25x10-),1x188 RT
308
DanX[(113.097 x 10-x781x105
8314.3

0.000111 = 0.15
8314.3x 290
1-0.05622
= 5.084x 10-5 kg/s/m2 of area In01 Ans.
DAB 0.43193 m /s
amount
of water to be evaporated per m2 of
Total
vehicle has surface area of
of cylindrical
vessel, Ex. 8.8.7: The tyre tube of a a

filled with air

area
2.4 and wall thickness of 20 mm. The tyre is
=Volume of water
in vessel x density of water m bar. The
mA 3 bar and after 15 the pressure drops to 2.9
days
airl of rubber at m
solubility of air in rubber is 0.08m of
0.02x1x100o
= XXAx PA = K.
0.18 m° at 300
1 bar. The volume of air in tyre is
= 20 kg/m? a r e a Calculate the diffusivity of air in rubber.

.. The time required, Soln.

A and rubber as B.
mA 20 393391 seconds
Let air be represented as

t
5.084 x 10-5 Given
mA
V 0.18 m3
393391 A 2.4 m2,
109.275 hrs Ans.
3600 Ax = 20 mm = 0.02 m p1 =3bar,

A tube of 12 mm diameter contains benzenee 300 K

Ex. 8.8.6 P2 2.9 bar, T
at the bottom. The length of the tube above liquid
(M 78)
surface is 150 mm. The pressure and temperature of air at Time,t= 15 days; Solubility, S
= 0.08 m3 of air/ m3 of
Vapour pressure of benzene at rubber at 1 bar
1 bar, 17°C respectively.
The initial mass air in tyre,
17C is 0.1 bar.
Estimate the coefficient of diffusivity of benzene in air if 2 kg

mA1
PR Ti
V _3x103]X18
287x 300
0.6272 kg
of benzene is evaporated in 5 hours.
Soln.:
Final mass of air tyre,
Let benzene be represented as species A and air as

species B.
mAz
p,-V
R T2
2.9x 10) x 0.18 _
0.6063 kg
287 x 300
Given d = 12 mm = 0.012 m, 3600
Mass of air escaped in 15 days (1 day = 24 x

0.15
MA =
78, (x2- X) = 150 mm = m
seconds)
Am = mA1 - mA2 = 0.6272 0.6063
p 1bar, T = 17°C =290 K,
= 0.0209 kg
PA1 = 0.1 bar

Assume, PA2 = 0 at the top surface.

E TechKmowledy
 Heat and Mass Transfer (SPPU) 8-19 Mas Transfer
Mass flux of air
escaped, Tube diameter, d 20 mm = 0.02 m

i.e. A - x(0.02)
A A* 15x 24x 3600 24
(x2 X ) = 4 cm = 0.04 m,
6 x 10- kg/s. m2
Mean pressure of air in the T 27 C = 300 K
tyre tube,
D 0.26 x 10% m2/s
p ,"-295 bar
DxAxM xPInPP
Mean solubility of air in rubber tube at inner surface,
mA
RT (- p- PA
C'Sis given at 1bar)
S 0.075 x 2.95
(0.26x10-)x\4x0.02x 18
8314.3x 300
0.22125 m2 of air /m2 of tube 1.013x 10 1.013-0
Solubility, S =
V1 at mean pressure
0.04 1.013 0.03521
V 0.22125 m3/m' of rubber 5x109 kg/s Ans.
V2 = 0.075 m'/m* of rubber
Summary
Cair escapes at 1 bar pressure to atmosphere)
Mass transfer refers to the diffusion of
Mass concentrations of air at the inner and outer chemical
tube can be calculated as follow:
species components from a
region
of high
concentration to that of lower concentration.
PAL 2.19x105x0.0022125 Modes ofmass transfer are:
287 x 300
1. By diffusion

0.5628 kg/m3 2. By convection

PAZ =
21x105x 0.075 3. By change of phase
RT 287 x 300
Mass transfer by diffusion
called molecular
0.0871 kg/ m3 diffusion occurs due to concentration gradient of
chemical species components in a system through a
stagnant fluid.
DARX(PAL -PAz)
3-X)=i DABX(0.5628-0.0871)
The mass transfer between the surface and a
fluid is referred as convective mass transfer.
moving
6x 10-9=
0.02 Mass transfer by change of phase of a fluid occurs
by combination of convective and diffusion mass
DAB 2.5226x 10 m2/s .Ans.
transfers e-g. transfer of mass of boiling water into
Ex. 8.8.8 Estimate the diffusion rate of water at 27°C from atmosphere
the bottom of a test tube 20 mm in diameter and 4 cm long Definitions
into dry air at 27 C. Take the diftusion coefficient of water in
mass, mn
airas 0.26x 10m/s. a) Mass density, P volume, V
Soln.
b) Molar concentration, C, No. of moles
Volume
=

From steam tables the partial pressure of water

vapour at 27 C, c)Bulk velocity of the mixture is defined as the
average velocity of the mixture.
PA1 0.03531 bar and Pa2 = 0 at top surface

Tech Kneuledye
 Mass Transfer (SPPU) 8-20
Mass Transfer
iffusion velo ity of a species in a mixture difase
d Mass
difñusion

with respect through a stagnant air film. eg, evaporation

i s t h e
ity
velocity
of species to their of water, gasoline, benzene etc.
averagevelocity.

m, -PAz
e M a s sd i f f u s i o n

s p e c i e st h a t
diffusion
flux,
passes
J is fined
the mass of a
as

rough a unit area per unit

=

DART ( -P
to a ationary observer.
time
relative Exercise
UNote: For answers please refer the section numbe
AP(-u)
sion states that the rate of mass
indicatedin bracket.)
diffusi
of of mass
law Define mass transfer. State the modes
F i c k ' s I

species
per unit area per unit time is
of a transfer. (Sections 8.1, 8.2)
Mux
to the mass
concentration gradient,
ortional
with the
2. Explain mass transfer by molecular diffusion
p r o p o

dpA
Ja - DAa dx help of examples. (Section 8.2.1)

3. Define
concentration is
Fick's law
in terms
of molar (a) Mass transfer by molecular diffusion.
written as Section 8.2.1)
dCA (6) Mass transfer by convection. (Section 8.2.2)
N -DaBd (c) Mass transfer by change of phase. (Section 8.2.3)

pressures: diffusion and

Fick'slaw in
terms
ofpartial 4. State and explain the Fick's law of
law of heat conduction.
compare it with Fourier's

ma-
A DAs ,Ma
RT
dpa dx (Sections 8.4, 8.8)
isothermal
counter diffusion and
. Explain equimolar
counter diffusion of a binary system is evaporation of water. (Section 8.6)
-Equimolar
isothermal diffusion process in which
defined as an State at least five examples of
mass transfer.
A are replaced by each 6.
each molecule of species
(Section 8.2.1)
molecule of B.
short notes on "isothermal evaporation of
7. Write

NA - DAB (x2-*1)
C-Cal D water. (Section 8.7)

Write short note on : "Fick's law of diffusion".

8.
= -
PA2-Pa1),1
DAB (x2-X1) (Section 8.4)
RT
Cartesian
Derive the general mass transfer equation in
9.
Molecular diffusion through a stagnant gas film co-ordinates. (Section 8.5)
molecules
occurs due to diffusion of liquid vapour