Diffusion
Diffusion
ﺍﻟﻤﺮﺣﻠﺔ ﺍﻟﺜﺎﻟﺜﺔ
ﺍﻧﺘﻘﺎﻝ ﻛﺘﻠﺔ
(+- \
= :b^B
R.t
Pr -L^
?-{PD
-
\- Pr,
(za)
@ >.LL r\=\ o.,n \\A C-^'..-. \ vesse \
rts \l
N\=)cxNl Qr Drs {^* cr'\-)\
r=:.s Zl 1
ez P. \
L
I
-hng_ Pr
i-,a-- R- lfr \
il-
T P.-Pq lz l*-Jt -*l
+
R.T- 5-P.-Ps $
Crtn) =:P\B
[z
( SJ v\ oJ * s cav\g[^.it , t,^ftvari4 s *r l\f, (Z) ,
. ^rt
w a \n avr- t- ! iJ o. rq.\ fft -.. tdli*r-. 1$r.r.^
t\^ qn
c" N r'''
s A R,.r p.-pn Iz
zL,_ lnr.
No\& = -Dne Pr (-' A?^-
zl N R'T d, P.-Pn
t^^ (9:\ r- :a
\'^
L_Z
7- Pn
o-' So trz -DAs'Fr APn
+ (4,* zx!t--z) ; R.t
\
e\
r-
5 fr- F+,
Po,
-o-1
^i.Ll t. a. - p \r*, o\ t; ,-;;, 3(vcn {r\;t
DtB : e.Lg € cnr/s , ^ff I ff* *J Zs'c.\". va.pe6
prrrsllLr+ .& *^l^t. of Z1'c i.S a. a j\3 ft^ ,f,aj**r\i. .
t-t.'.1
Zz ?o-
CJz -Dng' ato
\=
/N
7\ R,T I
Pn,
P--h
$r "...^Jt- 9t^A n"ff..,,,. tt--,-^ (.I)^J (z)
to^&- _
\ - \ c.^ r
\g L L-Z
o--L--\ft
. 2ctn
rT
I
l
I
A =Lr
)"+
= a- . Pr T [s- ztf E *z')]z
3 Ns Mn
l_-'
-l\\a,5
+- L- L Z'* z
., 3
3 Sn \^N t
sz -\F 3 Ja.S
o- +L
(=r)
D tIf \^si.,\ \-
1tsAS ^"^J .,^\o,.r-\e S
[si^]s 4 \]t*=irr..t^'
-l w a\...,** c-ara, t4 eavr^F.fr.l
e \< *. I.t[ r,,.s rv;\a tS\R) .
Pr f-^t/t *\)u"'I
D ss - )..a R\ *^=..r\ . '/ e< a.
r{__
b = C-sSLa-n\ :a.oo\J
Pr = :Ilt^, s5st* FH.ssw*^ (PJ , ( t..t / -')
1JN , tg = \^ ' \or y -\.r.'^-r. -S ( \ ,..^ I B) $ ,, -".^\
u.\',.11 F-i;\ ( c,3/5.-.\
Mo,\4,g = wr-\o-..^-\orr. t.^l 1a$\
O N* )r.^ESor^J *q*lfi-n
f\.
{,/ \g b.T
lc\.rctv\
tt+rlr{n*t\s )
P, (t n'/' + \)*t" ) .il F\-*M;
L
( sz)
O F*-\q,,. - r1.].--
Dq{R =
Pr ,lK (e!^','* Z1gu"')'
r^r\"Jur,.L. o,
- \
Ml* = , B- \ *t--?
\/r-
aon t.T \
R (\A.t/. *\)o"t ) ' N{A l'\B
-.\
(=z)
N\o*l t- c'.1et (b*) ov (g*-)s. I\Wr-^{
cor J..ft i. -,r s
.T
t F.g
2oo , (s .,,,tg)
Ztt,
l>A B =
L.
\''-*t--? ('7'3) t'}t
- f tq l.zs)t/t* (z-.t1\/r1z r+**i'
Dn*- 4'+3 *tJ6 -'/*-c-
(: {)
-T- v
I r-s.4 c
of ?r---c T
- 1 ( z 1s-1
L13
(.l';
Maxwell's Law of diffusion For Binary System
Maxwell's postulated that the pressure gradient (dP A) in the direction of diffusion for a
constituent of two components gaseous mixture was proportional to:
A) The relative velocity of the molecules in the direction of diffusion.
B) The product of the molar concentration of the component.
Thus;
-dp A α C A C B (ν A – ν B )dz
-dp A = α AB C A C B (ν A – ν B )dz
−𝑑𝑑𝑑𝑑 A 𝜌𝜌 A 𝜌𝜌 B
= α AB ( ) (𝑀𝑀 B) (νA – νB )
𝑑𝑑𝑑𝑑 𝑀𝑀A
𝜌𝜌 A 𝜌𝜌 B
NA=νA.CA → NA=νA.( ), NB=νB.(𝑀𝑀 B)
𝑀𝑀A
𝑀𝑀A 𝑀𝑀B
νA =NA . , νB =NB .
𝜌𝜌 A 𝜌𝜌 B
−𝑑𝑑𝑑𝑑 A 𝜌𝜌 B 𝜌𝜌 A
= αAB (NA .𝑀𝑀 B– NB )
𝑑𝑑𝑑𝑑 𝑀𝑀A
𝑃𝑃A 𝜌𝜌 A
For ideal gas law; P.V = n. R.T, CA = =
𝑅𝑅.𝑇𝑇 𝑀𝑀A
−𝑑𝑑𝑑𝑑 A 𝛼𝛼 AB
= (NA .PB – NB .PA )
𝑑𝑑𝑑𝑑 𝑅𝑅.𝑇𝑇
−𝑑𝑑𝑑𝑑 A 𝛼𝛼 AB
= (NA .(PT – PA) – NB .PA )
𝑑𝑑𝑑𝑑 𝑅𝑅.𝑇𝑇
𝑅𝑅2.𝑇𝑇2
Diffusivity coefficient (DAB) =𝛼𝛼 AB.𝑃𝑃T
−𝑑𝑑𝑑𝑑 A 𝑅𝑅.𝑇𝑇
= 𝐷𝐷AB 𝑃𝑃T(NA.PT– NA.PA – NB.PA )
𝑑𝑑𝑑𝑑
Now, applying the two cases that have been considered before, i.e. equimolardiffusion,
and diffusion through stagnant layer, then we can reach to the final equation.
NA = - NB
−𝑑𝑑𝑑𝑑 A 𝑅𝑅.𝑇𝑇
= 𝐷𝐷AB 𝑃𝑃T( NA.PT)
𝑑𝑑𝑑𝑑
b)For NB = 0
𝑅𝑅.𝑇𝑇
-dpA = 𝑁𝑁A(𝐷𝐷AB 𝑃𝑃T) (PT – PA )dz
−𝐷𝐷AB 𝑃𝑃T 𝑃𝑃T – 𝑃𝑃A2
NA= ( )( )ln( )
𝑅𝑅.𝑇𝑇 �𝑍𝑍2 – 𝑍𝑍1� 𝑃𝑃T – 𝑃𝑃A1
𝑃𝑃T
Where: ( ) = Drift factor.
𝑃𝑃BM
𝑃𝑃T
Drift factor ( ) = Represent the enhancement effect on mass transfer due to
𝑃𝑃BM
thenon diffusing component (B) and to total flow in the direction of diffusion.
Maxwell's Law for Multi-Component Mass Transfer
−𝑑𝑑𝑑𝑑 A
= αAB CA CB (νA – νB ) + αAC CA CC (νA – νC ) + αAD CA CD (νA – νD ) + ………….
𝑑𝑑𝑑𝑑
−𝑑𝑑𝑑𝑑 A
= [αAB CB + αAC CC+ αAD CD ].NA
𝑑𝑑𝑑𝑑
−𝑑𝑑𝑑𝑑 A 𝑁𝑁A
= (𝑅𝑅.𝑇𝑇 ) [αAB PB + αAC PC + αAD PD]
𝑑𝑑𝑑𝑑
𝑅𝑅2.𝑇𝑇2
When αAB = 𝐷𝐷AB.𝑃𝑃T, therefore:
−𝑃𝑃T 1 𝑑𝑑𝑑𝑑 A
NA = ( ) [ 𝑃𝑃 𝑃𝑃 C 𝑃𝑃 D ] 𝑑𝑑𝑑𝑑 …….(*)
𝑅𝑅.𝑇𝑇 B
+ +
𝐷𝐷 AB 𝐷𝐷 AC 𝐷𝐷 AD
−𝑃𝑃T - 𝑑𝑑𝑑𝑑 A
NA = ( ) D
𝑅𝑅.𝑇𝑇 𝑑𝑑𝑑𝑑
1 𝑃𝑃B 𝑃𝑃C 𝑃𝑃D
Put = + +
𝐷𝐷- 𝐷𝐷AB 𝐷𝐷AC 𝐷𝐷AD
(𝑃𝑃T – 𝑃𝑃A)
Divided equation (*) by
(𝑃𝑃T – 𝑃𝑃A)
:
−1 𝑃𝑃T 1 𝑑𝑑𝑑𝑑 A
NA = [ 𝑦𝑦 B- 𝑦𝑦 C- 𝑦𝑦 D-
]
𝑅𝑅.𝑇𝑇 (𝑃𝑃T – 𝑃𝑃A) 𝑑𝑑𝑑𝑑
𝐷𝐷 AB + +
𝐷𝐷 AC 𝐷𝐷 AD
1 𝑦𝑦 B- 𝑦𝑦 C- 𝑦𝑦 D-
Where =
𝐷𝐷- 𝐷𝐷AB
+ +
𝐷𝐷AC 𝐷𝐷AD
PA dp A 𝑅𝑅.𝑇𝑇 Z2
-∫P A = (D -.P )NA∫Z1 dZ
(P T – P A) T
Where:
PT = PA +PB +PC +PD [diffusing + nondiffusing]
Solution:
− 𝐷𝐷- 𝑃𝑃T 𝑃𝑃A2 – 𝑃𝑃A1
NA = ( 𝑅𝑅.𝑇𝑇 ) (𝑃𝑃 ) ( )
im 𝑍𝑍2 – 𝑍𝑍1
1
D- = 𝑦𝑦 B- 𝑦𝑦 C-
𝐷𝐷 AB +
𝐷𝐷 AC
2 1
𝑦𝑦B-=3 =0.667 ,𝑦𝑦C-= 3 =0.333
D- = 2.46*10-5 m2/s
NA = 3.91*10-5 kmol/m2.sec.
Molecular Diffusion in Liquid Phase
𝐶𝐶 – 𝐶𝐶
N A= - D L� 𝑍𝑍A2 – 𝑍𝑍A1�, Or
2 1
(𝑋𝑋 A2 – 𝑋𝑋 A1 )
NA= - D L . C av (𝑍𝑍2 – 𝑍𝑍1)
Where:-
D L: diffusivity of solute (A) in (B) (m2/s).
1 𝜌𝜌 1 𝜌𝜌 2
C av =2[ + ]
𝑀𝑀𝑀𝑀𝑀𝑀1 𝑀𝑀𝑀𝑀𝑀𝑀2
Where:-
Cav: average concentration of (A+B) in (kmol/ m3).
Mwt1 & Mwt2: average molecular weight of the solution at points 1 & 2
respectively(kg/kmol).
𝐶𝐶 (𝑋𝑋 A2 – 𝑋𝑋 A1 )
N A= - D L . ( 𝑋𝑋 av ) (𝑍𝑍2 – 𝑍𝑍1)
BLM
(𝑋𝑋B2 – 𝑋𝑋B1 )
Where 𝑋𝑋BLM = 𝑋𝑋B2
ln 𝑋𝑋
B1
𝐶𝐶A2 – 𝐶𝐶A1
N A = - D L( 𝑍𝑍2 – 𝑍𝑍1
)( Dilute solution only)
Diffusivities in Liquids:
Diffusion coefficient in liquids at 293 K is given in table (10.7) in volume (1) of
chemical engineering by( Coulson, J.M.; Richardson, J.F.,) fifth edition (page 506).
Where:
DAB = diffusivity of solute (A) in very dilute solution in solvent (B), (cm2/s).
MwtB= molecular weight of solvent (B).
T = temperature (K).
μ B = viscosity of solvent (B), (CP or gm/ cm.s).
𝜐𝜐A = Solute molar volume at its normal boiling point (cm3/mol).
- 1
Where:D = 𝑋𝑋 B 𝑋𝑋 C 𝑋𝑋 D
+ + 𝐷𝐷 AD
𝐷𝐷 AB 𝐷𝐷 AC
XRM(same as Pim)= remaining mole fraction log mean. ( all component except (A)).
Example:
Calculate the rate of diffusion of CH3COOH (A) across a film of non-diffusing water (B)
solution (1 mm) thick at 17oC when the concentration on opposite sides of the film are 9
and 3 wt% respectively. The DAB = 0.95*10-9 m2/s.
Give that:-
MA = 60, MB = 18.
ρ= 1012 kg/m3 (9% solution).
ρ= 1003 kg/m3 (3% solution).
Solution:
𝐶𝐶 (𝑋𝑋 A2 – 𝑋𝑋 A1 )
NA= - DL. ( 𝑋𝑋 av ) (𝑍𝑍2 – 𝑍𝑍1)
BLM
0.09
60
XA1 = 0.09 0.91 = 0.0288 at position (2).
+
60 18
0.03
60
XA2 = 0.03 0.97 = 0.0092 at position (1).
+
60 18
1
M1 =
0.09
60
+
0.91
18
→M1 = 19.8 kg/kmol
1
M2 =
0.03
60
+
0.97
18
→M2 = 18.4 kg/kmol
𝜌𝜌 1 𝜌𝜌 2 1012 1003
] →=2[
1 1
Cav=2[ + + ]
𝑀𝑀𝑀𝑀𝑀𝑀 1 𝑀𝑀𝑀𝑀𝑀𝑀 2 19.8 18.4
52.8 0.0092−0.0283
NA = -0.95*10-9 * *
0.98 0.001
NA = 0.977*10-6kmol/m2.sec
Molecular Diffusion in Solid Phase
Diffirsion in solids takes place by different mechanisms depending on the
diffusing atom, molecule, or ion; the nature of the solid structure, whether it be porous
or nonporous,,crystalline, or amorphous; and the type of solid material, whether it be
metallic, ceramic, polymeric, biological, or cellular. Diffusion in solid phase can be c
classified as:
1- Diffirsionwhich follows Fick's law and does not depend onthe structure of solid.
2- Diffrrsion in which the structure of solid are important.
s- "*3 lsrF) of A
cm3 solid. atm
To convert the solubility (S) of A to concentration (Co):
cA=s"rrIu*pn 1
Where:
.1 mol A ?,
1-A= TsrP) of A : A
,J = "*3 , PA atm, and 22.414 - "*3
cm' atm. cm3 (sottd) mol
In many cases the experimental data for diffusion of gases in solid are given as
permeability (PM) in cm' of solute gas (A) at STP {0oC, and I atm} per diffusing per
second per cm' cross-sectional ut"i through of solid of I cm thick under a pressure
difference of 1 atm.
(c.Er-cAl
NA=-D.anl-H
Applying (Eq. 84), then
S.P n S'P,q.,
6ur: - . tnen:
= 22.4r4'
-^*&cA2
D,en.S ( P,q, - Plr ') P^(PA - P,qr)
^r
tVA:--:::-l
Where:
22.4141 22
.--
1): 22.4r4(Zz - Z)
t*3 lsrF) of A
Pm = Dtrg.S - 2
.s.ot*
" lcm
If series of solids zre presented in series l, 2, 3, .., etc of thickness of each Lr, Lz,
L2,..., etc respectively, then:
Nt=(P'et-P'qz)
22.414
Where:
(P,\ - P,E) is the overall partial pressure difference.
Diffusion in which the structure of solid are important:
Porous Solids
When solids are porous, predictions of the diffusivity of gaseous and liquid solute
species in the pores can be made. This type of diffusion is also of great importance in
the analysis and design of reactors using porous solid catalysts. It is sufficient to
mention here that any of the following four mass transfer mechanisms or combinations
thereof may take place:
1. Ordinary molecular diffusion through pores, which present tortuous paths and
hinder the movement of large molecules when their diameter is more than l0% of the
pore diameter.
2. Knudsen diffirsion, which involves collisions of diffirsing gaseous molecules with
the pore walls when the pore diameter and pressure are such that the molecular
mean free path is large compared to the pore diameter.
3. Surface diffusion involving the jumping of molecules, adsorbed on the pore walls,
from one adsorption site to another based on a surface concentration-driving force.
4. Bulk flow through or into the pores.
Ir Zz-Zt
Where s the fractional porosity (typically 0.5) of the solid and T is the pore-path
tortuosity (typically 2 to 3), which is the ratio of the pore length to the length if the
pore were straight in the direction of diffusion.
Example
A sintered solid of silica (2mm) thick is porous with void fraction of 0.3 and tortuosity
of 4. the pores are filled with water at 298 K. at one face the concentration of KCI is
held at 0.1 mol / liter and fresh water flow rapidly by other face. Neglecting any other
resistance but that in porous solid, calculate the diffirsion of KCI at steady state. Given
the diffusivity Das is equal to 1,i8*10'e m'ls.
Solution
Since neglecting any other resistance but that in porous solid, then ordinary diffusion
is occurred
( c,q, - crl ')
^
NA=-Dell-G)
And D"n,is calculated by equation 89
lcrnot KCt
NA = -1.4025,r.19-l0f*) = 7.01* tg-e
\o.oo2l *2*,
Convective Mass Transfer for Binary gas Mixture
In previous sections we have considered molecular diffrrsion in stagnant fluid (laminar
flow) where the rate of diffusion is slow. To increase the rate of mass transfer, the
fluid velocity is increased until turbulent mass transfer occurs. As given before in
equation (1):
Ni: Xi.N + moleculardiffusion flux of i + eddy diffusion flux of i -...(,)
The eddy diffusion flux term is given by:
J-,F
Az
r dca
--tr6 .....(z)
"'-'\:
dZ
Then
(qe)
The general form for the mass transfer is:
NA = K'c (Cl.r -cA) --"(,,)
All these individual mass transfer coefficients are related to each other.
For gases:
N A = K'c (C\ -cAz) = K'G (Par -PA,z): K'y (ve, -Y A) '{.)
So
--\' "c' ^Y
K'n =k'.Rl:
C7
Home work: find the relations for the liquid phase.
2-For uni - molecular mass transfer
A) For gases:
rr -(Dn +!e).+. (N,q+ Nr) . (q)
l'A- n-r +*
dz'P7
. _ .
(qr)
Methods to Determine the Mass transfer Coefficient
The mass transfer coefficient can be evaluated using empirical correlations involving
dimensionless numbers. These empirical equations were obtained from experimental
data using various types of fluids, different velocities, and different geometrics. The
most important groups (dimensionless nunbers) are:
1- Reynolds Number (Re No.):
Re. No indicate the degree of turbulence.
Pud irit^.Yie.l $orc,e
RoNo-
-p Visc oqs 9or.t
Where:
:
p density of flowing mixture fluid (solute A and solvent B).
:
p viscosity of flowing mixture fluid (solute A and solvent B).
:
d diameter of the pipe in which the fluid is flow.
Do May be used in Reynolds number equation instead of d when flow across a sphere,
also L may be used if the flow was above a flat plate.
LJ: mean average velocity in the pipe.
If the flow was across a packed bed, U will be substituted by:
TT
U=Y
€
Where
Uis the superficial velocity of empty cross- section of packed bed column.
t: void fraction.
ts")
Now after introducing the dimensionless groups, now we will present the correlations
used to calculate the mass transfer coefficient.
1- Using the analogy or similarity of momentum, heat, and mass
- Colburn Analogy:
transfer using Chilton
P.oo".,
iM = iH = iD =[-:ry-2q42t3
L \rm
Z-For flow inside pipe
t;
C=)"':_k;
For both gases and liquids, where Re > 2100
v'- o
n-, ) n
sh No = - 0.023(Re;o'8rr (sc;o'r3'
D,ln
Note:
Sc: 0.5 - 3 for gases
, Sc > 100 for liquids
Or
jM = jH = jD =0.023(Re)-o'2 - -' (+)
Forl0000<$e<1000000 \/a_\ tJ J
lt/t
=u;il 3- :i: (-; t (-,\R")(s.) '(5) (P.,l...,.i.,.j
3- For flow p?rallel to flat plate of length L
A- for gases
jM = iH = iD =o'664(Re)-o's
LUp
For Re < 15000 where Re =
And
jM = iH = iD =o'036(RQ-o'2
(r)
Lup
For 15000 < Re < 300000 whereRe =
B- for liquids
jM = iu = jD =o'99(Re)-o's (s)
LUp
For 600 < Re < 50000 where Re =
(sr)
4- For flow normal to a long circular cylinder of diameter D, where the
drag coefficient includes both form dtag and skin friction, but only the skin
friction contribution applies to the analogy:
Uu)rarfriction - jH - jD =0'1931ne;-0':az '-' (t)
Dcylind u P
For 4000 < Re < 40000 where Re =
lt
Uu)ranfriction - iH = iD =0'0266(Re;-0'1ls '-' (rt)
DcYlind U P
For 40000 < Re < 250000 where Re - p
5- For flow past a single sphere of diameter Do
(rz)
Uu)rarrriction -jH-jD=0'37*1Rs1-0'a
D ruP
For 20 < Re < 100000 where Re - -;
The above equation is used for both gur., and liquids. Another method is used to
calculate the mass transfer coefficient.
For very low Re No. (Re < 1) the Sh No. approach a value of 2, then:
Lcd
au' 7
shNo- -2
D,qn
shNo=le
t =2+(o.rrrRe0'53x5"0'333) (rn)
D,q.n
For liquids:
shNo=
*:-r-!--2+(onrRe0'5x5"0'333) (,E)
D
'En
For Re=2-2000
And also for liquids
jn = jD =1.17(Re)-o'4ts . (t+7
DpU p
For 10 < Re <2500 whereRe =
p
For other shapes of packing a colrection factor can be used such as:
*7p (sPhere)
7p (cylinder): 0.79
7p (cube)
:0.71 * io (sPhere)
7- For fluidized beds of packed with sphere, for both gases and liquids:
jD=o.ot+ ,-o=8u (rs)
Reo's8 - 0.483
(sz;
Methods for Mass transfer at Fluid - Fluid lnterface
(Phase Boundary)
In the previous sections, diffirsion and mass transfer within solids and fluids
were considered, where the interface wis a smooth solid surface. Of greater
interest in separation processes is mass transfer across an interface between
a gas and a liquid or between two liquid phases. Such interfaces exist in
absorption, distillation, extraction, and stripping. At fluid-fluid interfaces,
turbulence may persist to the interface. Mass transfer rate between two
fluid phases will dePend on:-
l-Physical properties of the two phases.
2- Concentration difference AC.
3-Interfacial area.
4-Degree of turbulence.
1'hefollowing theoretical models have been developed to describe mass
transfer from a fluid to such an interface.
FilmTheory
A simple thebretical model for turbulent mass transfer to or from a fluid-phase
boundary was suggested in 1904 by Nernst, who postulated that the entire
resistance to mass transfer in a given turbulent phase is in a thin, stagnant region
of that phase at the interface, called a film. This film is similar to the laminar
sub - layer that forms when a fluid flows in the turbulent regime
parallel to
a flat plate. This is shown schematically in Figure 4. For the case of a gas-liquid
interface, where the gas is pure component A, which diffuses into nonvolatile
liquid B. Thus, a process of absorption of A into liquid B takes place, without
desorption of B into gaseous A. Because the gas is pure A at total pressure
:
p pr,there is no resistance to mass transfer in the gas phase. At the gas-liquid
interface, equilibrium is assumed so the concentration of A, Ca1 is related to
the partial pressure of A, P e,, by some form of Henry's law, for
( srt)
example, Cni: HePt. In the thiq 'stagnant liquid film of thickness 6, molecular
diffi.rsion only occurs with a driving force of (C 1 - C An ). Since the film is assumed
to be very thin, the entire diffusing A passes through the film and into the bulk liquid.
If, in addition, bulk flow of A is neglected, the concentration gradient is linear as in
Figure . Accordingly, Fick's first law, for the diffusion flux integrates to:
,
JA=
DAB(^ t1 \_ff?(*u,_xAb) _ _(r)
VAi-tAo):-6
6 \ 1rr ,'
Bulk Iiquid
sAlt
Figure I Film theory for mass transfer from a fluid - fluid interface into a liquid.
If the liquid phase is dilute in A, the bulk-flow effect can be neglected and (Eq. I
applies to the total flux:
Where:
Irr, - J,qr,
{1 -"rn}rx :
* ftrm]mr
lnf(t *xgnllfi.*sn,)J
In practice, the ratios Des/6 in (Eq. L) and Das/6*(1- XJr* in (Eq. 3 ) are
replaced by mass transfer coefficients and K| and Kr, respectively, because the film
thickness, 6, which depends on the flow conditions, is not known.
(ss)
The film theory, which is easy to understand and apply, is often criticized because it
appears to predict that the rate of mass transfer is directly proportional to the
molecular diffusivity. This dependency is at odds with experimental data, which
indicate a dependency of D', where n ranges. from about 0.5 to 0.75. However, if
D^B/6 is replaced withK' which is then'bstimated from the Chilton-Colburn analogy,
Prl.r.tl | - - ?,'3 which
r. r
(Eq.'f-),-*. obtain Kc proportional toD"n'rt, is in better agreement with
experimental data. In effect, 5 depends on Das (Sc NoJ. Regardless of whether the
criiicism of the film theory is valid, the theory has been and continues to be widely
used in the design of mass transfer separation equipment.
(Er)
Example
A wetted wall column of inside diameter (2 in) contains air and CO2 flowing at 3 fVs.
at a certain point in the column, the COz concentration in the air is 0.1 mol fraction, at
the same point in the column, the concentration of CO2 in the water at the water - air
oC.
interface is 0.005 mole fraction. The column operates at l0 atm and25 Calculate
the mass transfer coefficient and the mass flux at the point of consideration, given the
following data:
oC
The diffusivity of coz in air at25 and I atm:0.164 cm2ls
The density oi air atSTP : 0.0808 lb/ft3
oC
The viscosity of air at25 and 10 atm:0.018 cP
Hepnery constant : 1640 atm lmol fraction
Solution
Since we are dealing with a case of fluid flow inside a pipe, then to calculate the mass
transfer coefficient use the following equation:
t K'.d
ShNo- v - 0.023(Re;o'83r (sc; o'r:3
D,,qA
But we are dealing with mass transfer through stagnant layer (transfer of COz from
air
to water only), then
P7
KC = K,C
PB,,
Or
Kc*P"r* *d o'333
ShNo-
Pr * D.en
- 0.023(Re;o'8:r (,s")
And
Pr D4B=**
Krv : prr, * d 0.023(Re;0'83r (sc;0'r33
properties
To calculate the dimensionless groups we must first correct the physical
oC), also we must
from their conditions to the opelation condition (10 atm and 25
convert all the units of all the quantities to the SI system.
t* , = 0.9 $Y
u =3L*
.s 3.28ft .s
( 57)
p* mwt
p=
R*T
Then
10
\Pz )zggx,roatm e) = 298I
=eJ
b)srp
273
-rks .1t'zsrt13
pt =0.080s4 = 0.0808
ft' +.
ft' 2'2tb I l* '
-t.2s6g
mt
:. p2 = r.2s6
+.to ;rTrt = lr.en +
(ndilz=l.a).(!t\"
(o,qn\ lpz) \.4 /
) ) t - r2 --2
(D,Eilr - 0. !64cm :0.1 64"-' .( .!! l- = 7'64*to-s U-
,s ,s \toocm) 's
Pnz - Pat
n
'BL*=M)
[Pa' J
PAr = yt* Pf = 0.1* 10 - latm
PBI=10-l =9atm
Ptr2 canbe estimated from Henery law
PA=xA*H
PAz = 0.005 *L640:8.2
PBz =10 -8'2 -I'8atm
1.8-9 4.473612
, .,
.'. PBru =;F -
(5 E)
Kcv = ': " * 0.023(Re)o'833
Pt"*d'lt
----\---l (,sc;o'3r
Kr- = h
* D.an * p* u* d)o't"f r
0.023*( )0'333
Ptrr*d t p ) [p*D,En)
l0 * r.64 * l0-6 * 0.023
-( n.en* 0.915 * o.oror)o't" ( 0.018 * r0-3 )0'333
t
4.473612 0.0508 (. 0.018 * r0-3 ) * r.g. rr-u
[r r.rr, )
KC =o.oo8s68A
.S
NA=Kr(P4-P,Ez)
Kr
fs =
#r= o'0088 ut:
,nnnn.nffi_ I
otTil=-. -t-*looomol *zgBK
o.otz
mol* K 1000/ lcmol
Ks:3.62642*10-4 -hnol
mo * r* ot*
N A = 3.62642* l0-4 * (8.2
- l) = Z.6tt* t0-3 ry
*2*i
(;l>
Rate equation Units of coefficient
(EMD) Non-diffusing (B)
N A = K- G . ΔP A N A = K G . ΔP A
Moles transferred
(time) (area)(press. )
N A = K- y .Δy A N A = K y .Δy A
For Gas Moles transferred
mole
(time) (area) � �
fraction
N A = K- C . ΔC A N A = K C . ΔC A
Moles transferred
mole
(time) (area) � �
vol .
conversions P BM P BM PT
F = K G . P BM =K y = KC. = K- G . P T = K- y = K- C = K- C .G T
PT R. T R. T
N A = K- L . ΔC A N A = K L . ΔC A
Moles transferred
mole
(time) (area) � �
vol .
For
Liquid N A = K- X . ΔX A N A = K X . ΔX A
Moles transferred
mole
(time) (area) � �
fraction
conversions ρ
F = K X . X BM = K L . X BM .C T = K- L . C T = K- L = K- X
M
Conversions
( NB = 0 ) ( NA = - NB )
K C = K G . R. T 𝑅𝑅.𝑇𝑇
K- C = K- y .
𝑃𝑃T
Ky = KG. PT K C = K- G . R. T
𝜌𝜌
K x = K L. ( ) avg. K- X = K- L . C avg..
𝑀𝑀WT
𝜌𝜌
= K- L .( ) avg.
𝑀𝑀WT
Film - Penetration theory
Toor andMarchello, in 1958, combined features of the film, penetration, and surface
renewal theories to develop a film-penetration model, which predicts a dependency of
the mass transfer coefficient Kc on the diffusivity, that varies from
"|DAB to Das.
Their theory assumes that the entire resistance to mass transfer resides in a film of
fixed thickness 6. Eddies move to and from the bulk fluid and this film. Age
distributions for time spent in the film are of the Higbie or Danckwerts type.
Fick's second law, (Eq. 100), still applies, but the boun dury conditions are now
At t:0 0<Z(oo Ce:Ceu
t>0 Z:0 Ce : Cai (Cei : initial concentration)
t>0 2:6 Ce : Ceu
Infinite-series solutions are obtained by the method of Laplace transforms. The rate of
mass transfer is then obtained in the usual manner by applying Fick's first law at the
fluid-fluid interface.
AC.I ,
NA =-D,qn?l : K"(g,
oZ lz=o L \ t -coo)
NA=- t- - \
(D,qn)c (^ _(Deilr \
^r - r" \C.qt-CAi)c=T\C.q,-cet)r ...-.(q)
We can express the rate of mass transfer in terms of mass transfer coefficients that
can
be determined from any suitable theory, with the concentration gradients visualized
more realistically as in Figure 1'b. In addition, we can use any number of
different
(1)
mass transfer coefficients, depending on the selection of the driving force for mass
transfer.
{al h)
Figure I Concentration gradients for two - resistance theory: (a) film theory; @) more
realistic gradients.
For gas phase, under dilute or equimolar counter diffusion (EMD) conditions, we write
the mass transfer rate in terms of partial pressure:
tl\
NA=Ks\Pet-PAi) - -(s)
Or for stagnant layer mass transfer (non - volatile liquid), the rate of mass transfer can
be written as:
NA=KrVnu-PAi) ---. (<>
where (')
refers to the equimolar counter diffusion case.
The above equations can be written in terms of mole fractions as:
Ko /
Na :';A nu - t Ai): K'r 0 nu - ! Ai) ^ (+)
And
--
N1 =?6uu - !Ai): *r bnu - vu,) -{BJ
( rr)
t
NA =
*6^, - xAb): x'*6u, - *.qr) - - - (tt) for equi - molar mass transfer
And
NA = ui - x Ab)= x, 6 n, -''en) (t9 for uni - molar mass transfer
rrLG
(ez1
-4,-V;:q
K',
-Uu-vt,) .-*- .4-.(z-)
Assume a column where a gas and a liquid are contacted. At any point (P) in the
column, the gas phase has a mole fraction of A (certain composition of A) that ir yo.
And the liquid has a mole fraction of A (certain composition of A) that is xa. Then at
that point an equilibrium between the gas phase and the liquid phase exist at ! At and
x1, at point (m)
c,
o e{\r\.\ wr.
CE
F
CL 0.8 C.yv{
o
(E
ct
ra-
E
o 0.6
ger gL5a
[!:ref]-
o 3\-F /
{J
(, 0.4
lvtviwr
trJ
, ki- ,/
|E ts'r c< :*/
t-
rF
c,
bA -L i,T
o 0.2
E l* _f
I
I
xAs' XerF
0 0.2 0.4 0.6 ^0.9 1
In the above figure plot the equilibrium data and also and point (p). Draw a straight
line from point (P) to intersect the equilibrium curve at point (l), lei it be q.
The slop of this straight line (pq) is:
yA-yAi Kx
Slop - xA - xAr I
Kv
Then, to estimate the interface composition, we must know the mass transfer
coefficient for both gas phase and liquid phase also the equilibrium data must be
known.
The equilibrium data are presented by a curve for concentrated solution, and by a
straight line for dilute solution.
(r:;
Case 2:
For uni-molecular difftrsion (mass transfer of A through stagnant layer of B)
Let ye : yau
and XA: XAb
NA= KrVu- rAi)= K*Ve, -*l - - (et)
Ori
NA=K'u /Vn-!t,)-+V,e,
\ K'- / \
-*1) - (z{
! Atru Arru x
Then
Kx _Vu - ve,)
-.r-F;=A
But the slop of the drawn between points (P) & (m) is
(,r^-_ YA-yAi
DioP =
K|
xA - xAi Ky
Therefore substitute K, and (by there equivalents as
Ky- =
-K.,,
| Atru
t -l
I
K* = 'tlr
x
__i
Ait*t
Cr*1
(r-*) -(1 -*n,)
xA.
.^ILM =
And
(t-ru,)-tt -ve)
rAiru
M
'"6j5
From the slop equation we can conclude that there is a difficulty in calculating the
interface composition (y 4 andx 1. ), because they are already exist in the left hand
side of the slop, equation. This problem will be solved by trail and error by following
these steps:
l- Assume avalue for (!lrrrandxAiru ) and let itbe equal to (l).
2- Calculate the slop.
3- Plot the line (pq).
4- From the intersection point read xai and /a1 .
5- Calculate (!Ar,uandxArru ), then recalculate the slop of the line (pq) and let it be
if
the value of the two slops are equal then the assumed values of
(slop)2
Q4mandxArru ) is correct. If not, then use the value of (slop)2 to estimate a new
values of xal and y6 by repeating steps (3-5) until you will reach not more the l1Yo
change in the value of the slop.
Note:
niLM )' are equal to (l)
For dilute solutions (y,t,_-.andx1,-,-
'- "tLM
(es)
from point (p) to intercept the equilibrium curve at point (3) at this point y: 1la and x
*
: xA.
O ,e - y)) itcalled the overall driving force for the gas phase, and
t*l - x 1) iscalled the overall diving force for the liquid phase.
The slope of the equilibrium curve at point ( 1) is z1 :
YA-YAi
ml-
xA-xAr
The slope of the equilibrium curve at point (2) rs m2:
*
yAi - yA
m2=
xA - xAr
The slope of thq equilibrium curve at point (3) is z3:
yA-yAi
t7l3 =
-xA - xAr
The slops of the equilibrium curve at points 1,2, and 3 are equivalent if the solution is
a dilute solution. that is
1lll:1112:fIl3
o
o
(E
CL 0.8
o
(E
E'
rF
o 0.6
c,
o
iH
- rril
C' 0.4
K+
(tr
l-
rts )ni
q,
o 0.2
E rd
0
0 0.2
lii
Ab
0.4
xAi
0.6
xAn
0.8
(x) mole fraction of liquid phase
(et1
Now, the rate of mass transfer which will be calculated based on overall driving force
can be written as follow:
A) For EMD
NA=K'oy(yt-fi) (zr)
B) For UMp
NA=Koy(vt-fi)
Where
Ko, Ko, are the overall mass transfer coefficients with units (kmol/m2. s.mol
and
fract), which are based on the overall driving force in the gas phase.
y) , is the value of the mole fraction of A in the gas phase that would be in
equilibrium with xa.
The relationship between the overall mass transfer coefficient and the
individual mass transfer coeffi cient
A)Case I EMD
We can write the overall driving force as follow by adding and subtractingyAi, that is:
:f*
YA- Y A=0d - l,l,) + (1,1, - y A)
But
*
rti2
!,q, -lA
- xA-xAr
Then
:1.
Kx
Equation 174 canbe explained as follow:
The total resistance for mass transfer is equal to the summation of individual resistance
for each phase 9the gas phase & the liquid phase).
The same procedure could be made to find the relationship between the over all mass
transfer coeffrcient for the liquid phase and the individual mass transfer coefficients,
the relation is:
lll
, =-----l-*
Ko*
t
m3Ky,Kx
For the dilute solutions:
lTlI : l7l2 : ll13: lft
Then:
llm I
t-t---
Koy Ky Kx
111 ,\
J =- ,T--; (31)
Ko, *Ky Kx
B) Case I UMD
In this case only solute A is transferred through the interface and no B is transferred.
As shown in above:
K,,,
Kv- =
! Airu
And
I
r. Kx
l\-r - x Aitu
Then
NA :;l-K'u V/ n - y Ai ):;-
\ K. /
V,e, -
\
*n)
lAitu. '' xAiru
For the over all driving force, and by using the over all mass transfer coefficient, the
mass transfer rate is calculated by:
(<e)
NA=-y(r^-fi)=+(fi-.^) ( rs)
! Aru
'Au,r
Where:
*
XALM =
And
:f
|Aru =
Using the same procedure done in the EMD, we can find the relationship between the
overall mass transfer coefficient and the individual mass transfer coefficients, as
shown:
For the gas phase:
* 1)t
/ AtU _, ^iLM mzx Airu
r -----=
l/ rl
,
( sr)
noy ny K,*
For the liquid phase:
*
*AL^
r
Ko* m3K,
_,utr,r-=---;-
**ntw
Kx
( rr)
Again for diluie solution when:
lftI : l7l2 : l7l3: l7l
Then
**
*Aru: lAru: *4ut: YArrM: I
Question:
Is there an overall mass transfer coefficient base on partial pressure for
the gas phase, and other one based on concentration for the'liquid phase?
Answer:
Yes, these are presented as Iqs, and IQr.
Question:
Find the relationships between these overall mass transfer coefficients
and the individual mass transfer coefficient?
( L1)