Chapter ...

DIFFUSION

In a mixture consisting of two or more compont:•nt~, 1f the concentration s of the componen

vary from point to point then th ere is a n.1h. a al tench.•nev fur each component to migrat
transport from regions of high concentration to tl,o. · l f bw concentration. This process
transfer of mass as a result of the concentrc1t10u ci" ffr rPILl'P of th~ component in a mixture i
called as ma.§_§ transfer. (The transport of a romponP11. p E'~Pnt in a mixture from a rigion
higher concentration to a region of lower conce11tratio11 .vithi11 thP mixture is called as mas
transfer.)
The operations carried out for separating the comp nents of mixtures , involving th
transfer of material from one homogeneous pha:::ie to anothf•r, utilising differences in vapo
pressure, solubility or diffusivity, - in which the ctrivi l!, forct' for transfer is a concentratio
difference are called as mass transfer operations.
In case of evaporation of water from a pool ot "c1tE. t mto a stream of a ir flowing over th
water surface, molecules of water vapour di flus~ thr, ~rl those of the air at the surface into th
main portion of air stream, as a consequence of which they are carried away with air. In thi
case, mass transfer is a result of a concentl'aL n diff('renre, or gradient, the diffusin
substance (water) moving from a region of high toncPntrahon to one of low concentratio
Hence, the driving force for mass transfer is a conct•ntr,ttion difference Just as a temperatur
difference in heat transfer.
Fractional distillation (one of the meth ods of f,eparation) depends on the difference 1
vapour pressures of different components at the same temperature (volatility), whil~ g~
absorption depends on the difference in solubilit) of gai:;e-, in a t;elect ive solvent. Liquid-hqUl
extraction and leaching depend on the differenct• in solubility in a liquid solvent.
Mass transfer operations include sepa ration tc•cb.niques such as distillation, g~
absorption, liquid extraction, drying, crystalli E:.atiun. l tc
. . . In mass transfer operations, mass transfer ma) o ,cur :
(a) In one direction, e.g., gas absorption.
(b) In opposite directions, e.g., distillation.
(c) W~th sim~ltaneous heat tra~sfer, e.g., _drying and <>,y-,talhsation. ·ed bY
(d) With. a simul~aneous chemical react10n, e.g. , r.ts ctbsorption accompani
chemical reaction (absorption of CO 2 m an aqueou-; .mlutwn of KOH)
(e) With the exchange of one or more componf'Iits.
(f) Isothermally (at constant T) and non-iboth( rmaJly.

(7 1'
 II s\'IY 0~
0 era t·ons - 7 ·2 :v
1

h ~
~~
L..~ Dittus,
unit ti • ...it4\C
transfer opera ons, t e J.Ollowmg phenomena must eJdst: ~r-rECri
In.,...,.
At ]east tw> phases must come m contact with each other. • ::, 1..1e'RI'~{
. pO\.., r_
4- '£:,IP
M terials should flow from one phase to the other ~r.J)~- . ~
~
( a) Yl
h ~' O •
'·< _
(b) a . .
A part of the total flow. ofmatenal must occur by molecular diffusion. ·~'~*
-,,
BAJl~
( C)
ree states of aggrega n
t.10 f
° b . ·::----_
a su stance are gas, liquid and solid and_ th~s · ~IX
Th"]'fes
1 1 of the phase contact. Gas-gas (not practically realised), gas-hgu1d, gas-sol,~,
.
I1q u1d-
poss. b 1iq
' ~id ' liquid-solid and solid-solid (no industrial separation operation in ,s
) th
category . .
Mass transfer operations have been classified according to the phases in contact as given
in Table 7.1.
Table 7.1
Phases in contact
Mass transfer operation
Liquid-vapour (gas)
Distillation (Fractionation)
Liquid-gas Gas absorption
Stripping
Humidification
Dehumidification
iquid-solid
Crystallisation
Leaching
Adsorption
iquid-Iiquid
1 Extraction
~olid-vapour
Sublimation
~olid-gas
Adsorption
f et solid-gas (usually air) Drying
H~nce, distillation, gas absorption, stripping are gas-liquid operations, liquid extraction
tdhquid-liquid operation, crystallisation is a liquid-solid operation and drying is a gas-
0 1 operation.

meAssun·1
_the basic
1 ·t· mechanism is the same whether the phase is a gas, liquid or solid, there are
- ari 1es between the various mass transfer operations and these are :
(a) Equilibrium between the phases is attained after a sufficiently long time/period of
Phase contact.
(b) Materi~l transfer is caused by the combined effect of molecular diffusion and
turbulence.
(c) Th ·
1
of :re . ~ n? resistance to mass transfer at the phase interface (because of the existence
(d) quihbrmm at the interface).
aate of mass transfer is evaluated by deviation/departure from equilibrium
l. co~nt
. .
ration.
o'-;-..
s
~onen: hll ~on : Distillation is a gas-liquid operation. It is a method of separating the
~ffer'ent of a liquid mixture by use of thermal energy. The difference in vapour pressures
t~lactionat~~P?nents is responsible for such a separation. It is also called as fractionation
8~ aeI>arat· istillation. (The term fractionation is commonly used in petroleum refineries).
llation. ion of a crude petroleum into gasoline, kerosene, etc. is a typical example of
 • 0 "'
,,,ot1on s-''· J1 1S Cl
,1~it d 'fftlSJO
Unit O erations - 11 7.3 v I8 r i echn
Dittu . ectJ • the p1
Consider a binary liquid mixture. For this, we have . C = 2, P = 2. sion ~ttlsi?J'l :J11jr1M flo\~·c/
1
:. F = 2 (as F = C - P + 2). These are four variables; temperature, pressure, com . d jdS 1J1 fer is by e
A in the liquid and vapour phases. Ir tJ,n pressure is fixed, only one variable e g Pthositionor fl~ss trfl~: classified .08
' · ·, e 1· oJ•· t 1'- t 10
phase concentration can be varied and the temperature and vapour phase concentratio fi iqUid grt1die 11 :ed in sta
Here the equilibrium data are presented ir. temperature-composit10n diagram at n ollow Jlcotl!lte~ d in the case
. . . . 1· ·a h . consta e pteie . mus
pressure or b y plotting vapour phase composition agamst iqm p ase composition. Such nt eJJcotl ·ffasion 1n
is called the equilibrium curve. a plot JlOleof~ _. 011 111 ny occur
2. Gas absorption : Gas absorption is a gas-liquid operation. It is a method 1:if sep . D1flt1 ~\~tillntion, t
1 ~
one or more constituents . of a gas mixture
. by contactmg . i·t w1·th a smtable
. Th In ca~·e ob u,tween
arating
solvent. t 11c Pl1
necessary condition is the solubility of the constituents in a given solvent. Tho washin e jnterfacel l c The less
ammonia · f rom a ammoma-air · · mixture
· b y means o f wa t er 1s · a typ1ca · 1 example of g of vapot1r P ,as ·
. hasc to the
b · gas apou1 P .
a sorption. the" ·e to the 111t(~
1
Consider that a gas mixture contains two components and one component is transferred the gasp :~ween the pl
◄
We have C = 3 , P = 2 and :. F = 3. There are four variables; temperature pressure, and th~ iJJtezface_ e . to t.he cry
concentratio!l of A in liquid and gas. If the temperature and pressure are fixed, one ~ot~er hq~!O; isturc) (
concentration may be chosen as the remaining independent variable that may be varied and liquid _water mo '
the value of other concentration follows . A plot of equilibrium concentration in gas vis and di~fuse~
concentration in liquid phase gives an equilibrium relationship. extractwn, t O 1 qu ic f.
'flJ>O
n . \l . I
80
ar
. 'd ex t rac t·10n : L.iqm'd extract10n
3 . L 1qu1 · · a 1·iqu1"d -1·1qu1·d operation.
is · 1t 1s· a method of phase (solvent• p 1rnRc) • rot
separating the constituents of a liquid mixture by treating it with a suitable solvent that Molecular Diffusion:
preferentially dissolves one or more of the constituents of a mixture. It is also called as solvent Concentrations, vclo
extraction. It is used as a separation technique only when distillation 1s merfect1ve and Let us consider two
difficult. The separation of penicillin from fermentation mixtures is a typical example of separated by a impermcn
application of liquid extraction. thstth e species A ..viJJ dif
4. Crystallisation : It is liquid-solid operation and used to obtain materials in attractive 8
con 5t nntly dccrC' asi n
and uniform crystals of good purity. Crystallisation is the formation of solid particles within a ::c;~ration of its consti
homogeneous liquid phase. J•ir 1. used in one unoth
f 8 Ul US ,
5. Drying : Drying is gas-solid operation. In general, it means the remova I O _ion 1s governed by I
relatively small amounts of water from a solid material. :;i:~oncd term s baHed <
In case of drying, there are two phases and three components. C - 3, P = 2, :. F .= 3. If i.e ton We m('an a m ixt
The variables are : temperature, pressure, the concentration of water in sohd and g~s: g eo·• one Phase
ema1n1n ncen...... ti a gasc>ouA
t h e temperature an d pressure are fixed , one concentration may be taken as th e r be Th ~nt on:
independent variable and the other concentration follows. These two concentrations can "' ere are •
"'u1ticorn various
plotted as the equilibrium curve. ConcentratP_0 nent system/
DIFFUSION b' het ?.t ion
It is the movement of an individual component through a mixture from a region of 0ut It·18 ass con' mass fract .;f
concentration to one of lower concentration at fixed temperature and pressure with or Wl ;quivalen;entration
,

th e h e 1p .of an e xterna1.1orce.
c {'or th to the den
. . . . . . ixture is 1
e abov b.
A mixture non-umform m1tially will be ultimately brought to uniformity (a JI1 tratioO th e inary s
everywhere uniform in the concentration of its constituents) by diffusion as a con~ell uch a e~ Pis the
0
gradient which is the common cause of diffusion tends to move the component. in :.o tbB 1at- c mass densit
direction as to equalise concentrations and destroy the gradient. If we Jllain:e bigb oncentration
concentration gradient by constantly supplying the diffusing component to ~·ffusillS ~here
ay,._ ~ •
1
concentration end and removing it at low concentration end then the flow of
· · Th ,,s ~lli I\ is th
component 1s contmuous. is movement is utilised in mass transfer operations. . sJled "- Ii &re k e rnoJecuJ
15
When diffusion results from the random movement/motion of the molecules, it ~es, the6 "1 ence, for ma.o~in 3 •
mo ecuI ar d I.ffu s1on
I · ..A s th
. e mo1_ecu1ar diffusion
· · requires actual migrat~on · s W}le~ tb.
of .JllOJec b 1nary sys
rate of mass transfer 1s higher m gases than liquids and very slow 1n solid : I st~
movement of the molecules occurs with the help of an external force (e.g.; mech~~:joJJ·
and convective movement of the fluid) then it is called as eddy or turbulent di
 t
·ons - II 7.4 Diffusion
~ di•ffusion is a .slow process whereas eddy di'ffus10n . . a 1as
c t
,t
t1lar 1s proce ss . The molecular
0 tec_ ·s the mechanism of mass transfer in a st t· fl .d . fluid at rest and
510 n 1 . fl I f a 1onary u1 , 1. e., a . f
ff·lls in 1arr11nar ow. n ~ase _o mass transfer in fluids in turbulent flow, the mecharusin: o
lilld transfer is by eddy d1ffus10n. The transfer of material in the presence of a concentrat10n
a~ent is classified _as molecul~r transfer and eddy transfer. Molecular transfer of mass ~s
a tered in stat10nary fluids or fluids in laminar flow whereas eddy transfer is
coun red m • t h e case of fl u1· d s un d er turbulent conditions.
~~e t . .
diffusion in mass transfer :
!JnleOf . h . .
Diffusion 1:11ay. occur in one P ase_ or 1n both phases in all the mass transfer operat10ns.
. e of distillation, the more volatile component diffuses through the liquid phase to the
·Il cas face between th e Ph ases (1.iqui'd and vapour phases) and away from the interface into . th e
1

te\r phase. The less volatile component diffuses in the opposite direction and passes from
;::apour phase to t_he liquid phase. In case of gas absorption, the solute gas diffuses through
fhe gas phase to the interface and then through the liquid phase (liquid solvent phase) from the
f terface between the phases. In case of crystallisation, the solid solute diffuses through the
bother liquor to the crystals and deposit on the solid surfaces. In case of drying operation,
iquid water (moisture) diffuses through the solid towards the surface of the solid, evaporates
and diffuses as a vapour into the gas phase (drying medium). In case of liquid-liquid
~xtraction, the liquid solute diffuses through the raffinate phase and then into the extract
I
phase (solvent phase) from the interface between the phases.
Molecular Diffusion :
Concentrations, velocities and fluxes :
Let us consider two chemical species A and B are placed in two compartments that are
separated by a impermeable partition. Now, assume that the partition is suddenly removed so
that the species A will diffuse into B and the species B will diffuse in A and this will continue at
a constantly decreasing rate until the mixture becomes everywhere uniform in the
concentration of its constituents. The process is one of molecular diffusion in which the species
are diffused in one another solely as a result of the random motion of molecules. The rate of
diffusion is governed by Fick's law and before dealing with this law, we will define the abov·e
mentioned terms based on the combination of such species. We make it clear that by word
solution we mean a mixture of species of the same phase - gas in gas, liquid in liquid, etc.,
i.e., one phase - a gaseous, a liquid or a solid mixture.
Concentration :
I.
There are various ways to express the concentration of the various species in a
multicomponent system/mixture. We limit our discussion to mass concentration, molar
concentration, mass fraction and mole fraction.
. Mass concentration : It is the mass of species A per unit volume of the solution (mixture).
1tis equivalent to the density of A and designated as PA-
For the above binary system composed of A and B,
Wher . PA + PB = P ... (7.1)
e P 1s the mass density of the solution.
Molar concentration: It is the number of moles of species A per unit volume of the solution.
PA ... (7.2)
CA= M
Where
syst M A 1s · t h e molecular weight
· A
of component · of mo1ar concentration
A . Th e umts · · SI
1n
em are kmol/m 3
by llence, for a bin~y system of A and B, the total molar concentration of the mixture is given

C = CA+CB ... (7.3)

~U;:.;n.:.:.it=...:::.t:Op:.:::e.:..:ra::.:t~io:::..n~s_-....:.:.11_ _ _ _ _ _ _ _ _ _ _ _.:..7~.5:...__ _ _ _ _ _ _ _ _ _ _ _ _ _ _ ~n

'
Mass fraction : The mass fraction x;._ of a species A may be defined as the ratio of the mass
concentration of species A to the mass density of the solution.

XA = pPA .,,(7,1)
Mole fraction : The mole fraction (xA) of a species A can be defined as the ratio of the molar
concentration of A to the molar concentration of the solution.
CA
XA = C .. · (7.5)
For a binary system, we have :
I I

+~ = 1 XA

and xA + xB = 1
In the gas phase, concentrations are usually expressed in terms of partial pressures.
For the ideal gas A, PAV = nAR T
nA PA
= V = RT ... (7.6)
where PA is the partial pressure of species A in the mixture, nA is the number of moles of A in the
mixture, Vis the mplar volume of the mixture, Tis the temperatu...-e (absolute), and R is the
univeral gas constant.
xA in terms of PA is given as :
CA PAIRT PA
XA = C =p/RT =p ... (7.7)
where P is the total pressure exerted by the gas mixture.
C = CA+ ~ = RT PA PB p
Also, we have + RT = RT ... (7.8)
Velocities :
In a diffusing mixture, various chemical species are moving at different velocities a they
may have different mobilities. The •b ulk velocity of the mixture would be some sort )fan
average velocity. Let Ui be the velocity of the ith species with respect to the stationary coora.nate
system. Then, for a mixture of n species, the local mass average velocity u is defined by,
n
L Pi Ui
i=l
u = ... (7.9 1
n
2. Pi I
i =1
pu i~ the local rate at which mass passes through a unit cross-section when it is placed
perpendicular to u.
In a binary system of A and B components
u = pA UA + PB UB ••' (7.10)
p
The local molar average velocity of the mixture U, is defined by
n
2. Ci Ui
i=1
u =
n ... (7.11)
I c;
i=1
 . o era t.,ons ~;_-..---
- II --- __ / u u,ttus1on
,,..,;10~
~ •s- thhfe
r local rate at which mole$ pass through a unit cross-section which is placed
cul
dicular to U .
perpefl
Io a binary system,
U :_ CAuA + CB_ Us ·..:.._,'
C ... (7.12)

s define tvvo diffusion VPlocitiE.'s relative to/with respect to the two bulk velocities (mass
Let u average ve 1oc1·t ies · o f t 1lP nu xture ).
d IJlOIar
eJ1 Th mass diffusion velocity of a specie~ 1s the velocity of that species relative to the local
e erage velocity o f' t l w m1xturP.
.
!Ilass av . _ _ .
Mass diffus10n velocity of species 1 w.r.t. u = Ui - u
Mass diffusion velocity of speci"s A w.r.t. u = uA - u.
1
The molar diffusion ve 0C'ih of a f,pecie9 is the velocity of species with respect to/relative to
the local molar average velocity of the wixture
Molar diffusion velocity of ,-;ppcif>s I w.r.t. U = Ui - U ... (7.13)

Molar diffusion velocity of ::,peciE"'~, A\\ r.t. U = uA - U ... (7.14)

Mass flow rate: It is the quantity of material flow in mass units per unit time.
Molar flow rate : It i~ the qwu1t ity of material flow in molar units per uni) time.
Flux: The mass transfer flu'=' of a rriVl'n species (vector quantity) is defirl-e_d as the amount
of that species, in either maf.,d or. molar units, that crosses a unit area per unit t ~
We will define four types of fluM-.~, t ,J., ¼- 1th reference to fixed coordinates in space and tv. o
with respect to local maf.,s ,1veragf' vdocity and local molar average velocity (w.r.t.
coordinates moving with ma~~ avE:ragP velocity and molar average velocity).
-----tMass flux : The mas9 flux of a ~peciE•s 1 1s defined as the mass of the species i that passes
through a unit area per unit tim(;'.
The mass flux relative to the .;tnt ic,nary/f xf'd coordinates is given by,
ni - Pl lq .. . (7. 15)

The mass flux relativE' to thP mas~ average velocity u is given by,
ji - Pi (u 1 u) ... (7 .16)

t~olar flux: It is defined as the moles of species i that passes through a unit area per unit
e.
'I'he rn 0 1ar fl ux relative to the:• ~t atwnary coor d 1nates
· . given
1s . b Y,
... (7.17)
Ni - Ci Uj

The molar flux relativE' to thE' molar average velocity U is given by,
... (7.18)
II It . Ji ~ Ci ( Ui u )
~ffusi: true that any one of thP above mentioned notation used for the flux is adequate for all
iesfrabf Problems , but pach has certam advantages. In process calculations, it is usually
!llriti~e ~ to refer to a coordinate i,;ystNn fixed in an equipment so the flux Ni is llrttld ir
6t-inuta~· llg. The fluxes ji and Ji are the usual measures of rates of diffusion and are useful h
tng the equations of change for multicomponent systems.
 7.7
Unit O erations - 11
F b' ystemofAandB : ·ons - II 7.8
erat1 'ff . fi b'
or a mary s 1 tive to stationary coordinates are : ~it O ' laW of di u s1on or a mary mixture f, D!ttusi
The mass fluxes of A and B rea
F'ick s or steady state difT, . on
nA = PA UA so usion can be
••. (?,19) ,s JA = - DAB. dC
-...A llXJ>rea.aed
nB = PB UB . dz
1 t' to mass average velocity are : ., , (7,20)
The mass fluxes of A and B r e a ive }i molar flux of A in the z direction rel t ' ... (7.31)
J is t e . km 1/( 2 )] a ive to the m 1
jA = PA(u A- u) bere per unit time, o m .s . 0 ar average velocity I
11
P..
1•t area ino ea
.. · (7.21) r11r un oncentration of A [moles of A per unit vol 1
fa = PB(ua - u )
r- C is the c
__
ume, 11Ullol/m3]
~ is the concentration gradient in the z-direction.
... (7,22)
The molar fluxes of A and B Wl·th . ect to stationary coordinates are :
iesp
NA = CAuA dz . 1·t
... (7.23) . the proport10na 1 y constant, known as th
NB = ~ UB D 1s e mo1ecular diffu • .t
... (7,24) A? t for component A diffusing t hrough B, m2/s and z . th di s~vi Y or diffusion
The molar fluxes of A an d B relative t o molar average velocity U are : caeilic1en
· n Ill is e stance m the direction of
diffus!O ' . .
h = CA(uA- U) ... (7.25) The negative sign indicates/implies th at diffusion occurs · th di .
JB = CB (uB - U) ... (7.26) ncentration . in e rection of a drop in i
1,
J Aand JB are diffu s10n
. fl ux of components A and B. The various fluxes can be interrelated co o•ffusivity is defined as the ratio of the flux to the corresponding con t t· adi :.,
1 . f . . . cenraiongr ent.
as, h d·mensions of the d1f usiv1ty are L2/0 and its SI units are m2/s The di'ffu • •ty f I
Te 1 • • • • • • sivi o any
nA = PA UA component is a measur_e of its d1ffus1ve mobility and is a function of the temperature, pressure,
nature, and concentration of the other components·.
= PA (u+uA- u )
PAu+pA(uA-u ) Diffusive mobility i s a function of t he number of collisions. Therefore, diffusivity
PAu + jj increases with decrease in pressure because number of collisions are less at lower pressure.
... (7.27)
However, the effect of pressure is negligible in case of liquids. Also, as the random motion of
We have, PA
XA = p PA= ~p the molecules increases with increase in temperature, diffusivity increases with increase in
temperature.
I

nA = XA (pu) + jj For a binary syst em in the z direction, dropping the subscript z :

Since, L, nj L,pj Uj = pv JA = CA(uA - U) ... (7.32)
Equating equation s (7.31) and (7.32), we get
nA X~ L, nj + jj ... (7.28) I
Similarly, NA = CAUA
= CA (U + UA - U )
CA UA = - DAB dCA
~ + CU
A ... (7.33)
= CA U + CA (uA- U)
Now, U according to equation (7. 12) is given by
NA = CA u +JA ... (7.29)
NA = XA (CU) + J A U f, (CA uA+Ca ua)
I.Ni = LCi Uj = CU
... (7.301 CA U = ~A (CAuA+Ca ua)
NA = XA (I, Nj) + J A

~ of diffusion: . adieol
Substit t' CAU = xA (CAuA+Ca ua)
t
A relation between the flux of the diffusing substance and the concentr~tio;
responsible for molecular diffusion-mass transfer was first proposed by FICK 10 1 5 80
f di1
u ing CAD in equation (7.33), we ge
. D dCA + XA (CA uA +CB ua)
CA uA = - AB dz
therefore referred to as Fick's first law of diffusion. ,riixJU~ Dsing • becomes
The f7, equation (7.23), t h e above expression
u~ f i,,us_
0 d ' #. · . .
m g component A (diffusion . .
fl ux of A) in z direction •
in a binaTY
dCA +xA (NA + Na)
of A and B is proportional to the molar concentration gradient. N A = - DAB dz ... (7.34)
N - J + XA (NA+ Na) . flux and XA (NA+ NB) is
lh llere J . A - A tration gradient, diffusion
e bulk ' A ~s the contribution due to concen
lllot1on contribution, flux due to bulk flow .
t'" Unit O erations - II

Molecular Diffusion in Gases :

.
7.9

For the diffusion in the z direction and for NA and NB both constant (stead
. Y state)
• 0 eretlons:::-11

..,.. state diffusion of A through n o n ~

~s•n<>dY
2' h steady state diffusion of an ideal
for t e
7.10

Btaanant B:
gas A through
~
denve equations for the flux. 'We\1/iU a stagnant gas B
For an ideal gas, we have bY DAB p ' the tluz is liven
NA=
~
RTz . Pa, M (pAl - PA2)
~A = =YA
,,,(71,
'"ii)
iA the log mean partial pressure of g B ... (7.40)
where PA is the partial pressure of component A. where PB, M as ,
ve · NA - D dCA CA
and P is the total pressure. We ha . AB dz +c (NA+ Na)
1. Steady state equimolar counter diffusion: For .ffthe. steady state diffus IOn
· oftw ,
0 NA - DAB dpA PA
gases, where an equal number of moles the gases are d I using counter current t O 1det1 RT dz + p (NA+ Na)
(in opposite directions to each other), the flux is given by each other
or the steady state diffusion of A through nondiffu .
DAB F smg B, we have :
NA = RTz (PAI - PA2) "•(7.36, NA = constant and Na = 0
where NA is the molar flux of A in kmol/(m 2 .s), DAB is the diffusivity of A in B . 2 With this, the above equation reduces to
z (z2 - zI ) is the distance through which diffusion occurs in m and PAI and PA2 are thin m(1, NA = - DAB dpA PA
pressures. • of the component A (in Pa) at the beginning and end of the dI'ffu s10n ,e parti~
p 1,
RT dz +p · NA
respectively. a~ Rearranging, we get
We have : NA JA+xA(NA+NB) - DAB dpA
NA
dCA CA
- DAB dz +c (NA+ NB) R'T ~
IfDAB is constant, then the above equation can be integrated.
For an ideal gas : PA CART

'2:!tj CA
RT
_Tu_
NA
Z2

fdz
DAB . p
RT
- PA2
dpA
P-pA
I
dpA Z1 PA!
dCA RT
NA DAB p ln[P- PA2] , .. (7.41)
p RTz P-PAI
C
RT We have,
Putting values of CA, C, and dCA, we get PAI +PB1 =P P-PAI
PB1
NA = - DAB dpA + PA (NA + NB) ". (7.311 and PA2 + PB2 = p PB2 P-PA2
RT dz P PB2- PBl PAI - PA2
For equimolar counter diffusion,
DAB P In (PB2)
NA - Na=: constant and the above equation reduces to RTz PB1
NA DAB dpA ... (7.3! DAB p (ps2 - Psi) In (PatPB1l
- RT ~ NA = RTz (ps2- Psi)
IfDAB is constfmt, then the above equation can be integrated. Ps,M is the log mean partial pressure ofB.
z2 PA2 Pa2- Pai
NA f
ZI
dz DAB
RT
f dpA (Ps2-
Replaci
PB, M = In (paz/Pa1) the numerator and putting PB, M for

ng Pa2 - PBl by PAI - PA2 in

PAI Pni)/ln (PB21Pa 1 ), we get .. ,(U2)
-DAB ~ - p,u)
~ (pA2 - PAI) N =
DA!! p
~ aed in terms of parti'al
l-I A RTz · PB, M . difference expres th tagnant
= z Rearranging the above equation, we get ; Press;re, the flux is proportional to the conthcendit~a=~ • and the concentrationdol,r~re Bux
8
re of A and inversely
· propo rt·10nal to , t ce to di 11
DAB ,.,(1 8 JS\, · • crease• an '
gii 8 (p ..a1on in
NA RTz (pAl-PA2) )10~ B M) w ·th . .
decr 0 ' • I increase 1n z an Pa, M, d rests an
ases .
Here, the concentration difft:lrence is ex , . . ossure. It caJ1 '
expressed in terms of mol 0 f t' pressed m terms of partial pr
rac ion or molar concentration.
 7.11 rations - 11 ;-.12
II
~
Unit Operations ~ o l a r Counter Diffusion:
Molecular Diffusion in Liquids : ~YS:i.ffusion of two components in opp 81't .
'fb8 . f iJnportance in distillation of a b? e directions in e h
1 . Steady-state equimolar counter diffusion : t taI
iJlitture isperature
o
an
d th
e same o
mary syst
pressure th
I
em. f tbe tw
ac other in
a •tationary
We have: NA = - NB = constant
The flux equation for steady state equimolar counter diffusion is given by
,eJ!le te~ it will be simply the replacement of the ::to net movement
an co IJlponent.. Ind a' language
o~:::rn~nta are_ at the
1 take
lace er t· . of diffusion tw ecules
, o compo of one compo nent by the will
llllXture
DAB
NA = -
DAB
(CAl - CA2) = z
(_Q_)
M
(XA1 - XA2)
Pfo tb. the opposite irec ions m each other T .
0rate in tar counter diffusion .
nents diffuse at tb
. his overall transfer e same molar Oow
mo._
___ , 81

z avg. '•• (7.43)

eql'jnlD s1· der a case of two gases A and B at const t t process is called u
where xA - xA2 is the concentration difference in terms of mole fraction . con h an otal p
t us consider that t e two large chambers co t . . ressure p in two chambe
1
(p/M)avg. = Cavg. = [pi/M1 + p!IMzl/2 ~ such a way that molecular diffusion ~t st ~
ammg gases A and B are rs.
· f d B · km O1/ 3 .• · (?.44l tu~ JJl-'constant throughout. ea y state is occurtjng. The to:nnected by _a
Cavg. is the total average concentration o A an m m , P1 and p2 are th l)lljforJ.L11 pressure P 11
densities of the solut~on in kg/m 3 at !~cations 1 ~nd 2 respecti vely, ~nd M 1 and Me average
average molecular weights of the solution at locations 1 and 2 respectively in kg/kmot are the
A B
2. Steady state diffusion of A through nondiffusing B:
PAI
NA = constant, NB = 0 PA2
Psi Poz
J~ --
The flux is given by +-JB 2
... (7.45) ~x

(a)
where XB, M

Diffusion in Solids : P=p"+ ·pe

The operations like leaching, drying, etc. involve contact of flu ids with solids d ·
diffusion in the solid phase. an mvolve t PAI Paz
Fick's law for the steady state diffusion can be written as p orP
P1.2
dCA ... (7.46) Psi
N A = -DAdz
X

where NA is the_ rate of diffu_sion of A per unit cross-section of soli d. DA is the diffusivity of A
through the sohd, - dCA/dz 1s the concentration gradient in the direction of diffu sion. (b)
Fig. 7·1 : Equimolar counte1 diffusion of gases A and B; (a) system, (bl concentration profile
1 • Diffusion through a flat slab of thickness z :
Th Stir~ng provi ded in each chamber keeps the concentration in each chamber uniform.
Taking DA constant, integration of the above equation (7.46) yields
~ partial pressure PAl > PA2 and PB 2 > PBl- The molecules of A diffuse to the right, while tbe
DA [CA1 - CA2] ... (7.47) mo ecules of B diffuse to the left.
z tot~ t~e temperature and total pressure p is constant throughout, the ne~ ~oles of A diffusing
z ~- z1 = thickness of the slab nght must be equal to the net moles of B diffusing to the left. If this 1s not so, tbe total
pressure wo uld not remain constant throughout the system. This · li es1·mdicate s th at
· imp
CA1 and CA2 are concentrations of A at the opposite sides of the slab J _ J ... (7.49)
For other solid shapes ' the rate of diffu s1on
. 1s. given
. by · of ~on:-p:ne:t A in the x-direction due to molecular diffusion in
J .
1 th
W = NAAavg. = D Aavg• (CA1 - CA2) ... (7.48) 1uniA/
s e molar flux
(m 2 .s) .
Wn·rmg Fick's law for · C.
component B for constant molar concentration,
A avg. is
. th e average cross-section available
z
co ... (7.50)
. . , 11 r d I'ff USlOn.
.
8 dCB
F or t
length L : h e radial diffusion throu h . .
g a solid cylmder of inner and outer radii r1 and rz no JB = -DBA dx
liere th e fl ux 1s
N . m. the x-direction.
. . dB
Aavg. = 2n (r2 - r1) L ow as the total pressure is the sum of the partial pressures of A an , ••• ('1.51)
ln (r 2/r) , andz=r2 - r 1 ... (7.51)
For the radial diffusion through a h . 1 p = PA+PB
A _ sp encal shell of inner and outer radii r1 and rz, and p oc C [for gases]
avg. - 4n r 1 r 2 and z -_ r2- r1
Unit eratlons - II 7.13
66) und (7.67)
. f'or t h e gosoou 8 mixture is given by
The total ruolnr concontrotion )18 • aro tho equations fi ~-:---...Jllllllllll
or steady state 8Quimol
C = CA+ On oW thuL ar counter~
W0 ~fl dCA dC
Differentiating both t.ho sides of equation (7.53 ) wi th reHpoct to x, = - 8
dx dx
dCi.\ dC8
O = dx + dx ·ont of 13 iti equal but opposite in si,,n t th ... (7.88)
gro dl O at of A s·
Tho ust be molar flux of B, ll!i stated by equation (7.50). C in~e t~e gradient for B lli■te,
. b

dCA - dCB
or dx = - dx ··· (7,66) 1hore :od
(7.68) gives ombinat1on of equation■ (7.50),
(7,5 6) JA = - Ju
Therefore if a a-radiant exists in tho gas A, a gradient exists in tho gas B. The a.•act·
' o·
is equal but opposito in sign to thnt of A.
b' lent OfB . 11ows that the rates of diffusion arc equal but in . ... (7,69)
TJusts 8 in the binary mixtures, irrespective of what optpoh site direction■, Equation (7.69) ia
Fick's law for component A for constant totnl concentration is ays ru o er mechanism 8 fi
aIII' perating. Tho rates of transfer of the two species b or mu■ tran■far
DAB ~ Ymo1ecular transport (~:,r. __ . )
0y bo o . •t d' .
JA = - dx Ill I ye oqual but rn oppos1 o 1rect10ns. When molecular t . "'"UlllOn
... (7.56) re a wa . II d ransport 18 the only mecharusm, .
a
the overa II transfer process is ca o as an equimolar counter d'fl'. .
. i,, us ion.
Combining equations (7.49), (7.50) and (7.51), Transfer Coefficients:
MOSS r ·
JA = D dCA In ..most mass transier operat10ns, the turbulent flow is desi'red t • h
- AB dx , . o mcrease t e rate of
transfer per umt area . In such cases, the mass transfer rate is expressed in terms of maas
transfer coefficients. In turbule~t flow ~here are three regions of mass transfer but it is very
-Jn = -[- DBA d;:] 88
... (7.57) difficult to know the value of distance m turbulent region through which diffusion occurs it ia
wnsidered that the entire resistance to mass transfer lies in a l~nar sublayer ofthicim'eas z
D dCA
- AB dx = DBA dCB
dx ... (7.58)
(effective laminar film thickness). The resistance offered by the effective laminar film
lhickness is approximately the same as the combined resistance offered by three regions in
dCA dCB turbulent motion. The flux equations for such situations are of the type:
but
dx dt "' (7.59)
Flux = (Mass transfer coefficient) x (Concentration difference)
DAB = DBA "' (7.60) As the concentration can be expressed in number of ways, we have a variety of types of
This shows that for a binary mixture of A and B, the diffusivity coefficient DAB forA mass transfer coefficients.
diffusing in B is the same as DBA, for B diffusing in A.
Mass transfer coefficient is thus defined as the rate of mass transfer per unit area per unit
We have : JA = D dCA concentration difference.
- AB dx 761
·.. ( . ) The flux equation obtained for the steady state equimolar counter diffusion (components A
For ideal gases, molar concentration of A is related to the partial pressure of A by and Bdiffusing at the same molar rates in opposite directions) for turbulent motion becomes
C - NA _EA.
A - V RT ... (7.62) DAB ( ) ... (7.70)
NA = RTza PA1 -PA2
dCA _!_ dpA
dx = RT dx "' (7,63) For a given
· D is constant and it
situation the term _M_ · can be t ermed as the mass transfer
' RTza
JA = - DAB dpA
film coeffi1 1· ,
... (7.64) c ent for the gas, ~
Integrating, we get
RT dx
• I ,.,(7,71)

JA =
DAB (pA1- PA2) I 'I'h
"
A G
N
... (7.65) (atatio:a flux equation obtained for the ste~dy
= k (PAI - PA2)
st:~e
diff .on of A through non•
usi
diffu '
sing
RT (x2 - X1) ry) B for turbulent motion may be wntten a · ( 72)
DAB (pAl - PA2) )1 p .... 7
= = Xz -X1 ,.. (7.66 DAB (PAJ - PA2)
RT X , X
NA RTz PB,M
For species B, ... (7.73)
NA = ka (PAI -pA2)
JB = DBA CPB1 -PB2) ... (7.67) Where DAB P
RT X s·
I 1lllilarI ka = RTz PB,M
equations can be written for the 1·iqm'd phase ·
 Unit O erations - II 7.15
erafons
1 - 11 7 • 16
The flux equation for the equimolar counter diffusion for the liquid phase is 0
volt J{i, is. based .on the concentration
. <lifterence over . . _____olff,...,__
D '
NA = ___Al! (CA1 - CA2) = Kj_ (CA1 - CA2) where ncentration of solute Am liquid ph a11 driving force ti 1.1. :!!....__._.
• the co ase that w0 uld or 1.11.e liquid ph
ZL
• ' . . .. (7.111 Ci is fA in the bulk gas phase. be in equilib . Ille.
ure o nwn with
where zL is the effective laminar film thickness and \ is the mass transfer fibn press transfer (film) coefficients may also b PA> P8rtial
r,{ass e expressed .
for the liquid or the' liquid film mass transfer coefficient/individual coefncie~t bases as lil terms of dri .
oftbe p NA = k ( VI.Ilg forces in each
coefficient for the liquid phase. mass transfer * G PA - PAi) = kL (CAi - CA)

'--'"' Mass transfer film coefficient may be defined as the rate of mass transfer fr PA-PA = (pA- PAi)+(pAi- p*) ... (7.82)
+- . d . . +- om theb
one phase to an interface of unit area 1 or unit rwmg ,orce. Ulkot t te of equilibrium can be given by Hen , 1A ... (7.83)
The flux equations for transfer of A through non-transferring B (i.e. d"ff As a * rys aw
1 .
through non-diffusing B) in terms of the driving force expressed in terms ~f usion of A PA HCA, PAi = HCAi and PA=HC:
. concent . * A
and molefraction are : ratio0 PA - PA (PA - PAi) + H (CAi _ CA)
NA = ky (yAl - YA2) , NA = kc (CAl - C A2) for gases
. . .. (7.75) * NA N
for hquids •...
(7 76) ~-~ Kc'~-~=~.~-~-~
1 1 H kL
Similar equations for equimolecular counter diffusion are : -+-
' Kc ka kL ... (7.84)
NA k y (YAl -yA2)' NA kc (CA1 - CA2) for gases ... (7.77) 1
Here vnu_ is the total resistance, in both the phases , based On the overall gas phase driving
'
NA k X (xA1 - xA2), NA kc (CA1 - CA2) for liquids ... (7.?S) ,
force and is equal to the sum of the gas film resistance 1./ko and the liquid film resistance: .
In two film concepts, z is the effective thickness of the film .
The overall driving force for the liquid phase : L
Relation between film coefficients :

Gases:
'_f_
kc RT
' PBM '
= kc C = kc1fT = 1b p = ky = ~ = ku
I k
PB,M = kuYB,M · P
c: - CA (C: - CAi)+ (CAi -CA)
* PA - PAi
CA - CA - H - + (CAi-CA)
PB, M = (PBl - PB2)/ln (PBl / Pa2) , YB, M = (YBl - Ya2)/ln (YBl / Ya2),
1 1 1 ... (7.85)
t I I I
--+-
Liquids : kL C = 1\, p/M = ~ C = kx = kx Xa, M = kL xa, M C KL H ka kL
CAi is the concentration of A at an interface between the phases.
_....,.,Overall Mass Transfer Coefficient: Controlling Film Concept :
The mass transfer film coefficients are difficult to measure except for cases where the ... (7.86)
1
concentration difference across one of the phases is small and can thus be neglected. We have :
In such cases, the overall mass transfer coefficients are measured on the basis of the gas phase Kc H.
If H · . 1 bl ) the liquid film resistance -k 1a
or the liquid phase driving force . is very small, H =- O (a case with a highly sou e gas , L
The flux equation in terms of the overall mass transfer coefficient and the overall driviDI
ne ]' 'b 1 al th film resistance (i.e. gas film
force for diffusion of A through non-diffusion B is given as : g igi le compared to - and the total resistance equ s e gas
NA = Kc (pA - pA)* ... ~ offers . ko ~ rocess is called gas film (gas phase)
entire resistance to transfer). Such transier P
u_ · h
i"G 1s t e overall gas phase mass transfer coefficient and (PA _ p*) is the overal n
1d 'villi controlling as the resistance to transfer lies entirely in the gas film.
force for the gas phase in terms of partial pressure. A 1 1
*·
PA is t e partial pressure of solute A over a solution having the composition of bulk ruidti
h · iq h
Kc
= ko
or u _ - k th gas film coefficients
CA· (Parti_al press~re of A in the gas phase that would be in equilibrium with CA, t f The nu - ~ . such cases are based on e
10
concentration of A m the bulk liquid phase.) on] overall mass transfer coefficients f this kind.
The flux can also be written as: Y. Th b · an exainP1e 0
. wat er is
e a sorption of ammonia in
... (7-~
We have : ... (7.87)

Similarly, ... (7,81

Unit Operations - II
7.17
. . ~
I .,.ii
i,,;
~
-~o
· ns - 11
orpt10
bs
. .. 7.18

• n of a solute gas A m a liquid solvent fr

om a gas mixt
ccurs in t he gas phase from PA to P . ( t th . ure, as shown in v::. -•
. l H >1 (a case with a insoluble gas), the gas film res1stance 1 w 11
1
fer o Ai a e mterfa ) d. '"'"5• '"'•
When H is very arge, > . 1 ~ .
•1. k0 is .,s trfllls t th e interface) t o CA· As equilibrium exists at th . ce an m the liquid phue
. l the liquid film resistance r:- and th
Ill""
Jll CM
. (11
. tance t o mass t rans1er
c .
at the interface d e interface (b etween the phases)
negligible and the total res1stance equa s . KL . e trau sfer :ere is ~o re;:~ation ship : an PAi and CAi are related through~
. h . ·dered to be liquid film controlhng. The absorption of a
process in sue cases is cons1 . . d gas of I e11Ul
'\ibl'lUJll PAi = H CAi
· t · example of this kin . ow ... (7.88)
solubility such as CO 2 or 0 2 in wa er 1s an
1 1
.
e fl 1s the H enry's constant for the system under cons'd
1 erat·10n.
, qber
I gqlJl'l.:rbri1Jlll :
V transfer .
operations usually there are two phases wh' h b .
Jo !Ilass . . al( ) ic are rought m contact for
The overall mass transfer coefficients in such cases are based on liquid film coe ffi cients
. fer of constituent m aten s from one phase to another or in bOth th h
e trlill 8 f - -b • h e P ases If two
thbases co e to a state o eqm 1i rmm, . t e net
. transfer of material ceases. The eqmlibnum
.'. .
only . Ill
P . hip between the phases mvolved is of basic importance in all th
For absorption of a moderately soluble gas obeying H enry's law either Kc or KL can be relations . . . . . e mass transfer
. f l h d. . d . used calculations. The eqmhbnum r elationships can be expressed by an equation or can be shown
for mass transfer calculations. The absorption o su P ur 1ox1 e m water is an exa mp1e of
graphically•
this kind. For gas" absorption opera~i o~ , the relationship between the equilibrium concentrations of
✓ lnterpbase Mass Transfer : solute in 11 gas phase and a h qm d phase at constant temperature and pressure is the desired
In most important industrial app~ications of mass transfer, i~e _m aterial is transferred equilibrium relationship_ between the . two p~as~s. Now we will obtain the equilibrium
~cro_ss a phase bou_n dary (calle~ the int~rface_). For example, m distillation th e vapour and relationship for absorption of ammoma by hquid water from an ammonia-air mixture.
hqwd are brought mt~ c?ntact m a frac~1onatmg col um~ and the more volatile component is Consider that a definite amount of liquid water along with a gaseous mixture of ammonia and
transferred from the hqwd to vapour while th e less volatile component is transferred from th air is placed in a closed container which is maintained at constant temperature and pressure.
vapour to liquid. In gas absorption, the solute gas is transferred from the gas to t he liquid. 1: AB the ammonia is very soluble in w ater, some of the ammonia molecules will transfer from
both of these examples, one phase is liquid and the other is gas. the gas phase to the liquid phase, crossing the interface separating the two phases. Some of the
Phase: It is a homogeneous and physically distinct part of a system which is bounded bya ammonia molecules return back into the gas, at a rate proportional to the ammonia
surface an~, t~erefore, can be separated from the other parts of the system, e.g., water is one concentration in the liquid. As more and more ammonia enters the liquid, its concentration
phase, but ice 1s another phase. Phases may be liquid, solid or gaseous. in that phase increases and due to this the rate at which ammonia returns back to the gas phase
. Interphase mass transfer : It is the process of mass transfer from the bulk of one phase to the increases. This will continues and ultimately a stage will reach at which the rate with which
mterphase surface, and then from the interphase to the bulk of another phase. mmonia enters the liquid phase becomes exactly equal to the rate with which it leaves the
In. absorption of ammonia by water from an ammonia-air mixture, the solute ammonia hq~d phase and also at the sam e time ammonia concentration throughout each pha~e becom:es
:ay tff1:1se through the gas p~ase and then pass through the interface between the phases, and umfonn throu gh the mechan ism of diffusion. A dynamic equilibrium is now said to eXIS t
na1 Y diffuse through the adjacent immiscible water phase (liquid phase). between the phases . In a state of equilibrium, the net transfer of ammonia ceases even though
and Masst ttransfer
f occurs
Tb . in. each ph ase d ue t O th e concentration
· gradient
• • • m
existing · that Pha.se ~monia molecules continue to transfer back and forth from one ~base_ to another. ;;11e
as a e O eqw 1 num is assumed to exist .at the inteiface between the two fluid phases. oncentration s of ammonia w ithin each phase do not change with ti~e. Then t ese
concentrations of ammonia in these two phases are its equilibrium concentrat~ons. .
If we fu th . . . . h t . r equilibrium will be disturbed,
Interface the system r ·ner inJect additional ammorua. into
. . t e con
d fiaine
ally ' we get a new set of eqw·1·b
i n·um
concentr t·Wl try to at t ain the state of eqwlibnum an 1:1 e higher than the previous
Liquid obtaineda ions. These equilibrium values of concent,rati~n:. ar hip between the equilibrium
concentr:tlues .. In this way we can obtain the complete r; :~~ns ressure. If we express the
equiJibr· ions m both phases at constant temperatur . tprms of its mole fractions XA
1um c . . (A) • b th phases in e . )
and y . oncentrations of ammoma in ? d 1 t the values of YA (as ordinate
agains~ ~~:he liquid and the gas phase respec~ively : o~t:in a curve as shown in Fig. 7.3.
Such a corresponding values of XA (as abscissa)! Th's curve changes only by
CA eol\ditio c~rve is called an equilibrium distribution cdurve. el One should note here that
-i--;::::-:--.!....__ ___. at ns un ture an pressur • . • th
eq,,;l.b . posed on the system such as tempera b are not equal but it lB e
Distance--. ch .., i riUin · · the two P ases • al't
1 0f
helllical , the concentrations of ammoma lll . b th phases and it is this equ :Y
Fig. 7.2
~ elllica1 Potential of ammonia that is the ~ame i:ic~ causes the net transfer of solute
ainllloni Potentials and not of concentrations, w
a) to cease.
 r,S - II 7.20
7.19 ~o I . the bulk of gas --
Unit Oper atlons - II ~I entration of solute~ m h -- .
18
.
'file cone The concentration of solute A in th ~- ase YA molefract• '
1te interfapc~aaea to xA in t,he bulk liquid The b1qlukid phase falla frO::nx, and it fall, to 1AI
,t 1 the h . t,h I . . C u con t . Al at the int___ _
tween b cause ot erw1ae e so ute wJll not be diffi
t i,euiJibrill111 ea.ssurned that, the reaiatance to tranHfe O red cen rat1ona y and -•-
from the ga, to'\he l' x~are not in
eil W)!itr1lahn aide of the interface, in which the t r f.solute A lies in two h.,.,!21. ..... ~~·
c " [' rans er ia e t' J . . , . ~ film,
one on. 811 o rosiaiancc y, t~ana er acroaH the interface• nd n ire1Y by molecular diffi . '
88
~here 19 n re t,he equilibrium valuca. · a a reault the con"-t llt10D.
' d )(Al a r h """" ration,
M an dy ataic maHa tranH1er, t e rate oftranRfor (fA .
Y 11 r atea .
r 0 fch A 1a t,ranRicrrc
r d f' th . ' t() the mterfi
rom o interface to the b lk Of . . acemuatbeequaltothe
rstc st ~t:on or depletion of A at the interface. u liquid phue ao that there i, no
1 ccurn° fore we can write the maAH iranafor flux of A or ra•·· ft
'J'horo oefficien
' ia an d concon tra 1,·rnn ch angel! occurring • wth. o ranefer of A i f - -
h . n ..,,..,. ofma,1
iransfor c N _ k ( m e P ases involved.
Mole fraction of A In liquid _ . A y YA YA1J
(XA) kx (xA, xA)
... (7.89)
'fho diffcronceH in ~'a and x'a arc the driving forces for mass transfer.
Fig. 7.3 : Equilibrium-distribution curve at. constant temperature Rearranging equai1on (7.89), we get
Mechanism of Mnss Transfer : k x = YA YA;
Tho mechanism ... (7.90)
. . of mass irnm1for across a phaHo boundary (an iniorfaco) can be ox p1ainco
. ky xA, xA
by tho various theories such as : 1 YA YAi kl'
(i) Whitman's two-film t,heoryi I XA X11; ky ... (7.91)
(ii) Higbie's peneirnt.ien t.heory I Fig. 7.5 AhowH t,ypical values of tho concentrations of the bulk phasea (PJ and at the
(iii) Danckwert's surface renewal theory
(iv) Toor and Marchollo's film penel,raiion t,hoory. intcrfoco ( Q).
The Two-film Theory :
Salient features of Whitman's two film theory are :
(i) Resistance t,o t,ransfor in each phase is regarded as lying in a t,hin film close to lhi
interface (i.e., in two fict,itioua films one on each side close to t,he inierface). -Equilibrium curve YAJ =f(x.J
t
(ii) The transfer in these films is by a st.ondy siate process of molecu lar diffu~ion.
(fo) The conconiration gradient, is assumed to be linear in these films and it is zc~
outside the films, i.e., zero in the bulk fluid .
Slope
-k
y
=-r
Interface
Liquid
Gas x,. x,.,-
YA Liquid film Conccn1ration
of solute A in liquid

In Fig. 7.15 ~ f solute A it is possible to measure

O
on}cxpcriment1:1l deierminations of the rate of trans er th i~terface concentrations ia
Ord~ th~ bulk concentrations of the solute A and _to measurehow\ in Fig. 7.5 is unique at
fi
tnan! Y impossible.
• The equilibrium- d'18 t ri'bution curve s f Th refore the entire two
Distance
1Xed T a d ,. . . ood measure o XA· e ' .
18
n P, soyA in equilibri um with XA a g f
asc m d . t ms o an overa11 mass transfer coefficient
t' the
Fig. 7.4 Ph
0filll I{
tt
i ass transfer effects can be measure in er 1 to the overall coefficient •.,, imea
(iv) 1:11° th00ry assumes that the turbulence in the bulk fluid die out at the interface dY.' _-e., the rate of mass transfer can also be set equa . the gas phase which is in
films.
(v) The
. film ca ·t · . • . d'
paci Y 18 neg1igible 1.e. time taken for concentration gra ien t to e
816 biJ,
e
riving force ( *)
YA -yA ,whereyA 1s
* . the composition of solute in
.1s small compared to time of transfer. e ']'II& quilibrium. ·
w'th
... (7.9'2)
mus~~:s1der a catse o:
a solute gas (A) diffusing from a gas phase into a liquid phh::.1'hi'
a concen ration gradient in th d · t ·
11 '
I XA,

shown in Fig 7 4 h' . e irec ion of mass transfer wit h in

' each P
· · grap ica11y m terms of distance .through the phases.
 Unit O eratrons - II

1
7 .21

(yA - YA)+ (yAi - Y:) ufll! 0 e

l ~::;~:~~:~::7~_:22:::::::~:-------••1.
· ns -
ratio
entration grac:h_ent is transferred from the Ii ui .
Ky NA cone the interface mto the· vapour phase. The I q d ph~se to the lllterface aa4 .... _
froill . d t. d ess volatile com . .._
YAi -yA
* . the opposite irec ion an passes through the v . PGnent 1a f:nnatenu
1 YA-YAi + - - - in . olar counter diffusion takes place if the apour into the liquid. Here
NA NA equ1~ the same magnitude. 01 o1ar 1atent heats of the eomponenta

* ::s~rption in packed column : In this case, a solute as to , •

1 YAi -yA
1 - + -,----,----~ (ii) es up against the downward flow of a liquid ( / t) geThtber WJth a earner gu
Ky ky kx (xAi - xA)
1 1 m
mov
through the gas p h ase t o th e mterface
. so ven
where it dissolves d. th .. ~
e solute gas di~----
-+- bulk of the liquid. an is en transferred ID1i8'
Ky ky kx the . tr t· . k
,., (7~ (iii) Liquid-liqm~ ehx al~ i~nd m pach eel/spray column : In this case, both the streams are
where, m = slope = (YAi - Y:) I (xAi - xA) liquid . The hg ter 1~m nses t rough the denser one. The solute diftuses from the
raffinate phase to the mterface and away from the interface into the extract phase.
1/Ky is the overall resista~ce to m~ss transfer and llky and mlkx are the resistances in thii ,ExaJllples ofCocurrent
liquid and gas films . The resistances m two phases are added to get an overall resistance
170w: d 1· "d .
The cocurrent flo.,v o ?as an 1qm_ streau_is usually m the downwarq direction through a
hence it is also called as two resistance theory. 8~ eked column is used for - catalytic chemical reaction between components of fluids,
On a similar line, x: is a measure ofyA and it can be readily shown that rffusional operation when a gas to be dissolved in a liquid is a pure substance and for
1 1 1 diJTusional operation accompanying a chemical reaction, e.g., in absorption of hydrogen
-K X = --k-+ -k ... (7~ sulfide in sodium hydroxide sol ution. The cocurrent flow produces a separation effect
m y X
The Penetration Theory: equivalent to that obtained with only one theoretical stage so used for such cases only, With
cocurrent flow there is no flooding and there is no upper limit for permissible phase flow rates.
The penetration theory was proposed by Higbie. The main features of this theory are· The cocurrent flow is rarely used in the absence of a chemical reaction.
1. As the time of exposure of fluid for mass transfer generally being shon Analogies among Heat, Mass and Momentum Transfer:
development/establishment of the concentration gradient of film theory (ch11 ·act.eri51r Depending upon the fluid flow conditions, the mechanism of the transfer ?rocess can be
classified as molecul ar transport (characteristic of stream line flow) ~n~ co~bm~d molec~ar
of steady state) is not possible.
2. The transfer is largly because of fresh material brought to the interface by the ddie,. and eddy transfer (characteristic of total flow regime). There are s1mdantiea m goverrung
3. A process of unsteady state transfer occurs for a fixed period at the freshly expo.,.,: equations for molecul ar transport as well as for turbulent transport and we can say th_at we
surface.
~ave analogies among these transport processes. A great deal of effort has been devoted m tbe
4
- Each fluid element _(eddy) resides for the same length of time period at the surfs~ tliterature rans,er. ~ in dev e 1oping
, ana Iog1es
. among these three transport processes for turbulent
According to this theory, the mass transfer coefficient is proportional to the squarel\,\1 Genera1 M:0Iecu1 Trans .
of the diffusivity.
v Surface Renewal Theory : '111_
genera1 1ar port Equation : . h t · d by the same
iue eq t · ar transport of momentum, h ea t an d mass 1s c arac ense
lilol ecu
ua ion of the type :
According to this theory proposed by Danckw rt
Rate of a tr ans fier process -=:-::---:.~'---
Driving force ... (7.95)
~- ~h\~d~es _of the fluid at the surface are :xp:sed to varying lengths of time. tsi,
e as1s of exposure-time histories ' an age distribution for the surface eleroen
. canl culated. ~ 1 Resistance tum beat and mau
~"llSfer
t,.._ -~ ecuiar
• transport or molecular diffusion equations for momen '
3. The mass transfer ffi . . h diffusi11,
rt · characteristic
regardless f th coe 1c1ent is proportional to the square root of t e inese• e quations . . flow as molecular transpo is a
a:d
'111_
of lalll.· are applicable to lammar
Counter current Ce nature of the surface renewal rate. illar/str . , . f
M OCUrrent Mass Transfer.• Ne\Vto11 ' 8 eam hne flow . wt 's equation for molecular diffusion o
ass transfer processes th t . I carriedI~o/1 ltlolllent law for momentum transport, i.e., Ne on
continuously by passing th fl "d a involve two fluid streams are frequent y t fasbio~ Ull::I for constant density is
st
a column device The e UI reams either in a counter current or a cocurren r in . 1
Illaller ~
t . average drivi r rce for a given situation wi·11 b e large _ µ d (ux p) ... (.7.98)
coun ercurrent operation +h
equi Pment 1s
. ng 10
· needed for an. 1n the co current operation . f
and because o w hich s tioO·
p
'tzx = dz
counter current flow is mo; given set of flow conditions for countercurrent opera d (Ux p)
The e common
(') exa.mp1es of counter current . ..r '1,r, t t,. = -v-.,;- 'I ,... wheN . .
I Distillation in Packed lmass transfer processes are : allY creBII'.:;
co urnn ·· I n thi s case, a vapour stream (therilltate, a _ts''J
movi n~ up against the <low
liiiit t~ is th e
8
Of U Of (It momentum transferred per
unit time per uni ,
t
llltJtllicl, v ~-ll:1)/s . [It is also called as the mome:i~~
w
' --.t ..,,ill
flux) µ. is VtltOBit)' 8811 r ·
the ditfuaivit)' otmomd
• of tn,2;8s. th e kinematic viscosity and also c
5 88
dYnam1c equilibrium is set :ward flow of a liquid reflux. At steady \he action
p. The more volatile component under
 7.23
Unit eratlons - II Oifluai t1ons - II 7.24
0 era
.
J,'ourwr's l aw for heat tranKpor t , i ·O·, Fourier's equation for molecular difTu 810n
. of h
Or,
unll properties, v' a and DAB) all in m2/e and d . .
for constant p and Cp is ~at trao8r n11rt 'th respect to th e d.1s t ance on the right' ha da 'denvat1ve of the COllceQtration of
81
9.1 ~ie._9PT2 Pr0pert~ W1 1 to the driving force. All three of th e.l In all the above eaaee the ,1
• - o: d·, (7 rt1ona . I Th e mo ecular tr ' 8111 II
A ~ .. . 981 ProPoellla t'1c ally identica . us, we state we have a I anaport equation, •-
. h . n ana ogy or 81, • . -•
tllatb h there 1s a mat ematical analogy among th h m11anty among them
whore q, is t he heat transferred per unit time per unit area and is called afi heat flux hat,,j thoug
£van . can be totally different. • em ' t e actual P ya1ca mechaniatba•
h · I
. . o f h oat 1n oecurt1ng . . . D h . . .
A
units of W/m2 [J/(m2.s)]. o: is the thermal diffusivity or d'ff
1 us1v1ty ·
m2/s . ng
rnass diffus1v1ty AB, t e kinematic viscosity, v and th . . .
The 8 seen from the above equations. erma1 diffua1vity, u are
Fick's law of molecular mass transport_ o~ Fick's equation for molecular diffusion of analogous a . .
mass for constant total concentration in a fluid 18 'roilanty m nature of transfer of these three processes ~
The s1 . . b . are re1erred to 88 analo
dCA . at similant1es etween govermng equations of heat mass a d IIY,
JAz = - DAB dz Lo?king be expected that the correlations for heat transfer 'coefficie:t momdentum transfer,
·t 1s to b · ·1 V · . s an maaa transfer
I f!icients would also e su~u ar. anous quan~1tative relations are available to describe the
d(pA/MA) coeal ogi•cal behaviour. The simplest and oldest 1s due to Reynolds.
- DAB dz .. ,(7.ll'!J an
'l'be Reynolds Analogy :
where J Az is t he molar fl ux of component A in the z direction d~e to molecular diffusion
10 Reynolds was first to note similarities in transport processes and relates turbulent
kmol A/(m 2.s), D AB is th e molecular diffusivity o; molecule A m B or mass diffusivity in momentum and heat transfer.
m 2/ 8. CA is th e molar concentration of A in kmol/m .
The basic assumption of the Reynolds analogy is that the ratio of two molecular
These equations state, respectively, that (a) momentum transport occurs because of 8 diffusivities equals to that of two eddy diffusivities.
gradient in momentum concentr ation, (b) energy transport occurs because of ~ gra~ent 10
energy concentration, and (c) t h e mass transport occurs because of a gradient 10 ma15 -V EM
= Np,=- ... (7.104)
CX EH
concen t r ation.
For turbulent flow conditions, the Reynolds analogy equations are :
Turbulent diffusion equations for momentum, heat and mass transfer :
The statement of Reynolds analogy between heat and momentum transfer is :
For combined molecular and eddy transfer, the relations for momentum, heat and mass
are : _ h_ _ _h_ = Na =f ...(7.105)
CP up - CP G 2 . .
For turbulent momentum transfer for constant density, -·t util.' tr'an8fer 18 ··
The statement of Reynolds analogy between mass an d momen
d(ux p) ... (7.100)
'tzx = - (µ/ p + EM ) dz k
C f ... (7,106)
-
d (p Ux) u = 2
... (7.101 1

'tzx = - (V + EM ) dz
Therefore, the complete Reynolds analogy is
For turbulent heat transfer for constant p and Cp,
... (7,107)
q. ( ) d(p C0 T) ... (7.lfll'
A = - ex+ EH dz
... (7.108)
f
For t urbulent mass transfer for constant total molar concentration,• N - Nst == -2 · f
St - m. . . . th average velOClty o
dCA ... (7.1031 \Vh f skin friction), u 18 e
JAz = - (DAB+ En) -d ere f is the Fanniµg friction factor (measure o
z ~ nUid k, 1. . t , h 18 t e convective heat transfer
£ coeffic1en
. h
. rn2/s, Ea ' c s the convective mass trans er
In the above equations, Em is the turbulent or eddy diffusivity of momentUIIl ind £ is ~1
the t urbulent or eddy diffusivity of heat or eddy thermal diffusivity in rn 2/s _an ~ ;uar C f
oe ficient
E . . ntal data (corre a
1 tes data) for gases in
th skin friction is
.

turbulent or eddy diffusivity of mass in m2/s. Again, these equations are qUlte s tUrbJuation (7 .107) a grees well with expe=eare about unity and onl~el:te the data for
analogous to each other. ·iniJa!~ Prese en~ flow if the Schmidt and Pr~dtl_numi . The equations ~o 00
liquja°t 1ll a flow past a flat plate or inside _P rauunar flow, i.e., JJl SU
!i:~
the analogy is
Equations (7.97), (7. 98) and (7.99) for momentum heat and mass transfer ar_e s1 have I 8 10
005 llot in turbulent flow n or for any fluids
each oth er an d to th e general molecular t r ansport equation
' (7.95). All these equ ati t or )l)S::J Valid.
flux on t h e left hand side having the units of a quantity of momentum, bea f!SS (i-1
transferred per unit time per unit ar ea; a diffusivi mom ntum heat and rn
O
 111111111111111
Unit erations - II

'
7.25
Although the Reynolds analogy is of limited utility, significant conclusion

If the measure of the skin friction-fanning friction factor is known , the analo ·
Diflus~
that, at NPr = N5c = 1 O the mechanisms for momentum, heat and mass are ide Illt_ay he dr.

used to find the heat transfer coefficient from the mass transfer coefficient and . gy lllay 1.
0 lCa} ~~
"'
I

I
-11
ial pressure of A =
7.26

Molefraction of Ax
PA1 = XA1 p = 0.20 X 1013
PA2 = X p - 0
T~;-::::--....,.""""~~--
'otaI presaure-
· = 2O.26kP
a
.10 x 101.3 = 10.13 kPa
SOLVED EXAMPLES VJ.ce-ve
rsa. ue I We have,
p =
A2
PA1
-
+ PB1
Ex. 7.1: A large tank filled with a mixture of gases A and Bat 101 kPa and 298 PB1 = 101.3 - 20.26 = 81.04 kPa
connected to another large tank filled with a mixture of A and B of differ ent com I{ (~~ °C)ia I PB2 = 101.3·-10.13 = 91.17 kPa
A and B at 101 kPa and 298 K (25 °C). The t anks are connected by a tube of inner P?s1t10ns of
50 mm and is 150 mm long. Calculate the steady state rate of transport of A thr diallleter of PB,M (~2 - PB1) / 1n (PB2 / P1n)
~hen conc~~tra~ion of A in one tank is 90 mole % and other, 5 mole % a ssumi:ugh ~he tube = (91~17 - 81.04) /In (91.17 / 81.04) = 86 kPa
m composition m each tank and transfer t akes by molecular diffusion. The diri' ~~1forinity z =
in B is 4.3 x lo-3 m2/s. USJVJty of A 2 mm = 2 X 10-3 m, DAB = 1.81 X 10-G m2/s
R = 8.31451 m3.kPa/(kmol.K), T = 298K
Solution : Mole fraction of A in tank- I = xA1 = : = 0.90 5
1.81 X 10- [20.26 -10.13) X 101.3
NA =
5 8,31451 X 298 X 2 X 10..j X 86
Mole fraction of A in tank-2 = = 100 = 0.05
= 4.356 x 10-5 kmol/(m2.s)
DAB = 4.3 x 10-3 m2/s •.• An,.
z = 150 mm = 0.15 m = length of diffusion path 2. The flux for equimolar counter diffusion is given by :
7t 2 7t 2 DAB
Area =4 D = 4 x (0.05) = 1.963 x 10-a m2 NA = RTz (PA1 - PA2)
PA1 = XA1 . P = 0.9 x 101 = 90.9 kPa 1~81 X 10-5 X (20.26 - 10.13)
PA2 = xA2 . P = 0.05 x 101 = 5.05 kPa = 8.31451 X 298 X 2 X 10-3
R = 8.31451 m 3. kPa/(kmol.K)
= 3.7 x 10- 5 kmol/(m 2.s) ... Ana.
Rate of transport of A = NA. A = DAB (PA1 - PA2) A
Ex. 7.3 : Methane diffuses at steady state through the tube containing helium. At point 1, the
RTz x
= 4. 3 X 10-3
X (90.9 - 5.05) X 1.963 X 10- 3
partial pressure of m ethane is 55 kPa and at point 2 it is 15 kPa. The points 1 and 2 are 30 mm
8.31451 X 298 X 0.15 apart, The total pressure is 101.3 kPa and temperature is 298 K (25 °C). Calculate the flux of
, / = 1.95 x lQ-6 kmol/s ... Ans, ~H• at steady state for equimolar counter diffusion. Take the value of diffusivity as
~x. 7.2: In an oxygen - nitro . . 6.75 X 10-6 m2/s.
of oxygen at two phases 2 gen gas mix t r~at 101.3 kPa and 298 K, the concentrations
of diffusion of oxygen for tmhm apart ahre JO
an ~ by vol time respectively. Calculate the fllll
e cases w ere : · · - - .
Solution : The flux for equimolar counter diffusion
· · 1s · given
· bY
W the, nitrogen is n~on~-diffu"sing
(ii) there is equimolar counter d1"ff . 15.
NA = ~;z (PAl -pA2)
1.81 x l0-5 m2/s. u sw n of the two gases. Diffusivity of 0 2 in Ni where, DAB = 6.75 x 10-5 m2/s, R = 8.31451 m3,kPa/(kmol.K)

Solution : 1. For diffusion of A throu h . . T = 298K , z=30mm=0.03m

g non-d1ffusmg B, the flux is given by
PAl = 55 kPa, PA2 = 15 kPa
NA = DAB p
RTz PB, M (PA1 - J?A2) 6.75 X 10-5 (55 - l 5)
Total pressure, p = 101.3 kPa NA == 8.31451 x 298 x 0.03 ... ADI.
2
For ideal gas, volume % A - 3 63 X 10-5 )anol / (m ,s) clitiODI
= mole % A tl<. 7 4 lY - · • as (B) under ■tead1•tt •
With nit · : Ammonia gas (A) diffuses through ruttfnt 1ocation 1 ii U x 10' P•~ ~t ~t
=
2t)
100 = 0.20 location r2o~en non-diffusing. The partial p~essure o d 2aare 0.15 m apart, Tbe total pnllUN..:
10
l,103 )( 1: 5 x 10s Pa (Pascal). The locations 1 an th flux of ditfuaion of ammonit alto
c~lc\JJ.atelO Pa and temperature is 298 K. Calculat~in:aion aaeuminl th~ ni~n
= 100 = 0.10 d1fl'u.ein the flux of diffusion for equimolar co~ter ndition• as 9,80 x 10 m 11.
+, g, Take the value of diffusivity at prevailini co
 - - - -------........-- - -- -------111111111111111
7.27 . 5 -11
ration . 7.28
Unit rations - II
. for diffusion of A through non-diffusing B is
Solution : 1. The flux equation unit Of HCl - water mixture, there are 12 kg of lICl
JJl 100 kg t location-1, HCl concentration is 12 Wei""-t %)and lOO -12 • 88 q ofR'-O at
. -1 (as a 5u . . -...,
DAB p (PAl - PA2) oefltioll 12 87 km 1 88
NA = RTzpB, M
I toOies of ac1 o
== - ~ = 0.32
36.5
0 'moles ofll2O
18 4·= =- =
!loon l -
lYllol
where, DAB = 2.30 X 10-5 m2/s
rooles of mixture ofHCl == 0.3287 + 4.8888 = 5.2 lanol
p = 1.103 x 106 Pa 175
Total Moles of HCl 0.3287
PA1 1.5 x 104 Pa
XAi = Total moles = 5.2175 = 0.063
3
PA2 = 5 x 10 Pa
6 4
M1 = kg of mixture / kmol of mixture
PB1 P-pAl = 1.103 x 10 - 1.5 x 10 == 8.63 x 104 Pa 100
PB2 P-pA2 = 1.103 x 10
5
-
3
5 x 10 = 9.63 x 104 Pa == 5.2175 = 19.166 kg/km 0 I

PB2- PBl . n-2 ' the molefraction of HCI is

At locat 10
PB,M
= ln (PB2 I Pai)
4/36.5
4
(9.63 X 10 - 8.63 X 10 4 ) (4/36.5) + (100 - 4)/18
ln (9.63 X 10 4/8.63 X 104 ) 0.1096
= 9.121 x 104 Pa 0.1096 + 5.3333 = 0-0201
T 298K, z = 0.15m XB2 == 1--0.0201
3 0.9799
R = 8.31451 m . kPa/(kmol.K) == 8314.51 m 3 .Pa / (kmol.K) Average molecular weight at location-2 is
6
2.30 X 10- X 1.103 X 10 6 (1.5 X 104 - 5 X 10 3) 100
NA 8314.51 X 298 X 0.15 X 9.121 X 104 Mz == 4/36.5 + 96/18
7
7.484 x 10- kmol/(m 2.s) ... Ans. == 18.3728 kg/kmol
2. The flux equation for equimolar counter-diffusion is
DAB p1IM1 + p2IM2
Cavg == 2
NA = RTz (PA1 - PA2)
2.30 X
6
10- (1.5 X 104 - 5 X 103 )
_1; • (1060.7/19.166) + (1020.15/18.3728)
2
8314.51 X 298 X 0.15
7 = 55.4336 kmol/m 8
= 6.19 x 10- kmol/(m 2.s) ... Am,
EL 7~, Hyd,oohlorio ao;d (A) at 283 K d;ffuae, th,ough a th;n film of wato, (Bl 4 ~: I
xB, M == (xB2 - XB1) / In (XB2 / XB1)
thick. The = (0.9799 - 0.937) / In (0.9799/0.937)
1 106 concentration of A at location 1 on one boundary of the film is 1~2 _Eeight % (densi , '
p • -~ n •7 k gm d on ot h er boundary,
/ 3 3) an· · ' · at location 2, ·, is w •g h t-,_.%
, (dens1, xof
1
0.958
4
P2 = 102!U,5 kg/m ). The diffusivity of HCl in water is 2.5 x 10- 9 m2/s . Calculate e flu
th Th z == 4mm = 0.004 m
diffusion of A assuming water to be stagnant (i.e. non-diffusing). .
e diffusional flux for HCl with non-di·trusmg
· w ater is given by
Solution: Molecular weight of HCl = 36.5, Molecular weight of H 0 = 18 - DAB Cnvg (XA1 - XA2)
At location 1 : Mole fraction of HCl (A) 2
NA - XB M. z 01)
2 5 ' X 10- 9 X 55 ·4336 (0.063 - 0.02
XAl = - ~ - --'1-=-
2/..::.
3.::..:
6·..::.
5 _ __
. 0.958 X 0.004 '" Am,
12/36.5 + (100 - 12)/18 6 2

XB1
= 0.063
= 1- 0.063
~)( ~ - 1 55 x 10- kmol/(m .s)
-
Water (87).6 : Calculate the rate of d1ffus1on
·. .
t f acetic acid (A) across a
film of non-diftulin,
ite lidea of the
t"ons of acetic acid on, the op~Ol2 q1ma and
1
ftlin 1 tnm thick at 290 K if the conce~ _ra f % and 3% solutions are_. ,
= 0.937 2 9o/,° an d 3% respective . 1y. Th 0 dens1t1es •o 9 "d in water 1s , o•9 u11 x 10 m1,a.
1003 ate
Average molecular weight at location-l is . kg/rn3 respectively. The diffusivity of acetic aci ....s •
Sohttion
.\t l . : D A.B -
- 0 •
95 x 10-9 m2/s '
z = 1 mm = 1 x 10 m
M1 = 100
121 P ocation 1, on one side of film :
~~
36.5 + (100 - 12)/18 1012 2
0 kg/m , Acetic acid= 9% by weight Wt. of water (H2O) • 18
= 19.166 kg/kmol
• Wt. of ncetic acid (CH COOH) = SO, Mo. 1
3
 . , , . . . - _ , -11 730
•U!!!!! ~!!!!-~~L_________..!.7.:::..2~9___________
.:: nit2 perat,ons - II D
I tt ope
ration ;;_-- - - - - - - -...!.._·:._;j(
~ un JcPa (2 atm) hydrogen pressure th
9160 6 1
XA1 = 9/60 + (100 - 9)/18 p.t 202. 2 ' e so ubiJity is
0-:15 = 0.053 x 1 = 0.106 cm3 (NTP)/crn3

= 0.15 + 5.05 = 0.106 ma (NTP )/ma

0 15
= - = 0.0288
5.2
· ur£ f · 0.106 x 1 - 4 73
C at the inner s ace o pipe = -
100 Al 22.4 - . x lo-,'l krnol H2ftn3
M1 = Average molecular weight of solution = 5.2 = 19.21 kg/kmol At the outer surface, CA2 = 0
XB1 = 1 - 0.0288 = 0.9712 , Rate ofloss of hydrogen =
•' w =NA· Aavg. DA. Aavg. [CAI - CA2l/z
At location-2, on other / opposite side offil m :
3 1.8 X 10-10 X 0.1133 (4 73 1"-'
Weight % of acetic acid = 3%, p2 = 100.3 kg/m · x v V 0.V0.0125
-
2
3/60 7.72 x 10- kmol H:/s, per 1 m length of pipe
T-portant Definitions : ... Ana,
XA2 = 3/60 + (100 - 3)/18 = 0.0092
~ meJJ.U .
XB2 1 - 0.0092 = 0.9908 1.toGram mole : It 1s defined as the mass in grams of bt .
its molecular weight. a su 8 ance that is numerically
100 equa I .
18
3/60 + (100 - 3)/18 = .4° In this ,book, gram. mole and . mole are. specified as mol and km o1 res pect'1ve1y.
. kilogram
p1IM1 + p2IM2 2, Weight fraction : It 1s the ratio of the weight of the individual component to the total
Cavg· 2 weight of the system. It is denoted by x'. For two component system : \ + ~ = 10
(1012/19.21) + (1003.2/18.40) Weight % of A = Weight fraction of Ax 100
2
3, Mole fraction : It is the ratio of the moles of individual component to the total moles of
53.6 kmol/m 3 the system. It is denoted by x.
XB, M = (xB2 - XB1)/ ln (xB2 /xB1) For a binary system of A and B : xA + x8 = 1.0.
= (0.9908 - 0.9712)/ ln (0.9908/0.9712) Mole % of A = mole fraction of A x 100.
0.980 4. More volatile component : It is the component with lower boiling point or with higher
The flux of acetic acid is given by : uapour pressure at a given temperature (in a binary system). It is also called as tile lighter
component.
NA = DAB . Cavg (XAl -XA2 ) In case of distillation, compositions of vapour and liquid phases ere expressed in terms of
Z.XB,M
mole fraction of the more volatile component. . ..
0.95 X 10-9 5. Less volatile component : In a binary system, it is the component with higherhboil~g
l X lQ-3 X _ (0.0288- 0.0092) Pom. t · · t It is also called as the eaV1er
0 98 or with lower vapour pressure at a given tempera ure.
1.018 x 10-6 kmol/(m2.s) ,,. An!, component.
6 1· "d · defined as the absolute prt88Uf'e at
/ Ex. 7.7: Hydrogen gas at 202.6 kPa (2 atm) and 298 K (250C) flows through a pipe ~~de~
. · Vapour pressure: The vapour pressure ofe iqw_ JS
Which the liquid and its vapour are in equilibrium at a gwen temperature.
unvulcanised neoprene rubber with i.d. and o. d. 25 and 50 mm respectivelv. The diffusivit~ P 5 kP at 373 15 K (l00oC).
• \1 • d'ffus1on ure water exerts a vapour pressure of 101. 32 a · th tis present in a mixture
hyctrogen through rubber is 1.8 x lQ-6 cm 2/s. Calculate the rate of loss of hydrogen by 1
7. p t· ·a1 of a component gas a . th
per meter length of pipe. of ar 1al pressure · The parti pressure t ·r it alone were present m e
s gases in the pressure th~t would be exerted by that componen I
The solubility of hydrogen is 0.053 cm3 (NTP )/cm3·atm. ame Vol
ume and at the same pressure. . • as .
Solution : 1 m length of pipe, 8 Id 'd I as law JS given .
· eat gas law : Mathematically, an I ea g
o.d . - i. d . 50-25 ifp · PV = nRT . fR 'llbemS·kPa/(Ianol·K).
=- - = 12.5 mm = 0.0125 m is in kP T . K then umts o w1
2 2 a, Vin m3, n in kmol and m /(k l·K)
31451 m3. kPa mo
1.8 x 10-6 cm2/s = 1.8 x 10-10 m 2/s (R (gas constant) = B. , Jaw is given as
9•
lm Dalton's law : Mathematically, Dalton s .
+ PB + Pc+ ··· are the partial
Where p . p = PA seous mixture and PA, P11> Pc ...
Aavg. = 2nL (r 2 - r 1) 2n (1) (0.0125)
Pressure is the total pressure exerted by th e ga
ln Cr2/r1 ) = ln (0.025/0.0125) 8
of the component gases A, B, C, ····
= 0.1133 m2
 Unit rations - II 7.31
,
10. Raoult's law: It states that the eqm'l'b . f
1 rrnm pressure O component A •
Dittu8/1Jli
product of the vapour pressure and the mole fraction of A in the liquid phase. is equaJ to tL
o Qe
PA = PA . XA
PA is also related to YA by equation
PA= YA·P ~
YA is the mole fraction of A in gas phase.
11. Henry's Jaw : Mathematically Henry's law is given as,
DISTILLATION
PA = HxA
where H is the Henry's law constant. o 8
Henry's law expresses the relationship between the concentration of a gas d' 0 1 tvcUncu.~
liquid and the equilibrium partial pressure of the gas above the liquid surface. issolved in a
12. Gibb's phase rule : It is the relationship that governs all heterogeneous e Tb . I ~
given as qm I na, Itis ; ~istillation is a unit op eration in which the constituents of al" uid m' .
F = C- p + 2 : / ~mal energy. Basically, the clifference in vapo iq ixture (solution) are
separa . h . ur pressure, (volaiffittea} of
where C = number of components d erent constituents at t e same temperature 1s responsible for such a Jti Thia .
P = number of phases d
eration is also terme as racf t'100al d' 'II ·
isti ation or fractionation. Wrth separa on.
thi •__1._, IIIUt,.
op h I' 'd . t . . s -.wuqn11t11
and Fis the number of degrees of freedom or number of intensive variables (te possible to separate t e iqm mix ure mto its components in almost pure form and thiafacthaa
pressure, composition) that must be specified so that remaining variables wi~Pra~ure, made distillation perhaps t he most important of all the mass transfer operations.
automatically and the system will be defined completely. e IXed In distillation, the phases involved are : liquid and vapour or gas (the vapour phue ii
/ EXERCISES / created by supplying heat to th e liquid) and mass is transferred from both the phases t.o one
another, by vaporisation from the liquid phase and by condensation from the vapour phaae.
1. Give mathematical statement of Fick's law of diffusion and give the meaning of h The net effect is an increase in composition of the more volatile component in the vapour
· 1ve d 1n
t erms mvo · equat10n.
. eac (phase) and that of the less volatile component in the liquid. The basic requiremedt for a
1
2. Define with formula of each: separation of components by distillation is that the composition of the vapour be different from
(i) Mass fraction, the composition of the liquid with which it is in equilibrium - the vapour is always richei: ~ ~
(ii) Mole fraction, more volatile component than the liquid from which it is formed. If the vapour ~mpos1tion 11
(iii) Molar concentration the same as the liquid composition, distillation technique will not effect a separation.
(iv) Mass average veloci;y, and Distillation is commonly encountered in chemical and petroleum industries fiianda means
of separat mg · . . mixture
the hqmd . .
mto . componen t Parts. Separation of ethanol
its tiwater
( v) Molar average velocity. .1
mixt 95%O th I using benzene aepara on v1
3 · Defi~e : Mass flux and Molar flux and give the expressions for Mass and Molar fluxes ure, production of absolute alcohol from e ano . 188 0 'tctiatillatidll.
relative t? th~ mass average velocity and molar average velocity.
petroleum crude into gasoline kerosene, fuel oils etc. are the typical examp :t 11,..,
' · taining a non-vola!!.: N' ~...
4. Define Diffus10n, Molecular diffusion, Eddy/turbulent diffusion and explain brienr and Evapor~tion is concerned with the s~pai:ation of a solu:nu:nseparation of solution__.
the role of diffusion in mass transfer.
5. Expl~n bri_efly analogy between heat, ~ass and momentum.
6. Explam briefly Reynolds analogy.
is
a
th
e components ar~ appreciably volatile. Thus, th e
~,ev,aporation whereas the separation of a mixture of c
s:r:~::
all a volatile solvent whereas distillation 1s concerned WI . f brine into salt and water
0
:ater into its components ii

istillation.
7. Show that for equimolar counter diffusion D = DBA· Bolling Point :
B. State the Fick's law of diffusion ' AB 1 ~ . at a ~rtain single
F' d ·11 boil or vaponse . ~,..1.
9. Give the mathem t· 1

10. D fi
t ~
ransport ior lammar and turb l t fl
·.
. a ica expressrnn for analogy between heat mass and morn
. '
u en ow. Give the meaning of each terms.
e ne mass transfer coefficient. Give its ·t
entu~ or any ·
t te111Perat given pressure, a Eure ~gw I' ·d when heate Wl
Ii uid. It is the wmpenr~
the"va ure ~own as the boiling point of tbe ;ailing pressure. The ~iling
increa Pour Pressure of a hqmd equals the ~re sa The normal both1_1~
0
•
r. .r-..,..
t of a iiqwd iifW..-
. t of 8 1iquicl
~d it the
11
11. What do you me b · t
12 St te aii t ~ an y m erphase mass transfer ?
um · terupe::t
With increase in pressure and v;~e:e: p~ssure of 1 _a~- B ~ ia 8111 K
. a s en ieatures of two-film theo Pressure ute at which its boiling take~ pl~ce For exaJX1ple, the boihn_g po ~K.(M-,70-1)), -
13. Explain the controlling film concept. ry. (looo C) vary greatly for different liquids. d that of methanol 18 337•
c,oO th
atnios h' at of toluene is 383.6 K (110- C) an 6 °
p ere (101.325 kPa).
(8.1)