MASS TRANSFER OPERATIONS-I

UNIT I –Molecular Diffusion- Equations

Fick’s I Law (for diffusion in z direction):

For a constituent A in solution in B:
∂C A
Valid for steady state diffusion of component A: JA = - DAB ….(1.1)
∂z
Where JA= molar flux of component A in z direction in kmol/m2.s
DAB = diffusivity of A in B in 2/s
CA = concentration of A in Kmol/m3
Z = distance z2 – z1 in m
∂C A
= concentration gradient in kmol/m4
∂z
The negative sign indicates that diffusion occurs in the direction of drop in concentration.
Conditions: (i) steady state, molecular diffusion.
(ii) no bulk flow.
(iii) diffusivity is independent of concentration.
∂x A
JA = -cDAB ….(1.2)
∂z
where c = total concentration in Kmol/m3 xA = mole fraction of A

Types of Flux:
J : Flux of a constituent w.r.t. average molar velocity of all the constituents
N : Flux relative to a fixed location in space
Eg: Fish swimming upstream against the flowing current
Velocity of the fish w.r.t. a fisherman’s baited hook is analogous to N
Velocity of the fish relative to the stream is analogous to J

Relationship between N and J :

In a binary system comprising of A and B,
Total flux, N is the summation of flux of A and flux of B
NA + NB = N ….(1.3)
The movement of A is made up of two parts: (i) resulting from the bulk motion, N and
the fraction xA (ii) resulting from diffusion JA
NA = NxA + JA ……(1.4)
c ∂c
NA = (NA + NB ) A - DAB A …..(1.5)
c ∂z

cB ∂c
NB = (NA + NB ) - DBA B …..(1.6)
c ∂z
Adding these gives
∂c ∂c
- DAB A = DBA B or JA = - JB …..(1.7)
∂z ∂z
If cA + cB = constant, it follows that DAB = DBA at the prevailing concentration and temp.
Binary System:
Steady State Molecular Diffusion In Fluids At Rest And In Laminar Flow:
In eqn (1.5), separation of variables give
c A1 z
− dc A 1 2
∫c N A c − c A ( N A + N B ) cD AB z∫ dz …(1.8)
=
A2 1

where 1 indicates the beginning of diffusion path (cA high) and 2 the end of diffusion
path (cA low). Letting z2 –z1 = z, we get
1 N c − c A2 ( N A + N B ) z
ln A = ……….(1.9)
N A + N B N A c − c A1 ( N A + N B ) cD AB
or
NA c
− A2
NA D AB c (N A + N B ) c
NA = ln ……….(1.10)
NA + NB z NA c
− A1
(N A + N B ) c

Molecular diffusion in gases:

NA DAB pt NA/(NA+NB) -- yA2
NA = ------------ ------------- ln ----------------------------------- (1.11)
(NA+NB) RT z NA/(NA+NB) -- yA1

Molecular diffusion in liquids:

NA DAB ρ NA/(NA+NB) -- xA2

NA = ------------ ------------------ ln ----------------------------- (1.12)
(NA+NB) z x B,M M av NA/(NA+NB) -- xA1

GASES:
Steady State Molecular Diffusion In Gases In Laminar Flow:
Case 1: Diffusion of A through non diffusing B:
For gases (obeying ideal-gas law):
C = n/V = pt/RT
cA pA
= = yA (1.13)
c pt
Converting concentrationterms to pressure terms, equation (1.10) becomes

NA p A2
NA D AB p t (N A + N B ) − pt
NA = ln ……………(1.14)
(N A + N B ) RTz N A p
(N A + N B ) − pt
A1

Case 1: Diffusion of A through non diffusing B:

NA is finite, NB = 0 Hence
 NA
----------------- = 1
(NA+NB)

Equation (1.14) becomes

D p p − p A2 D AB pt p
NA = AB t ln t = ln B 2 ………………(1.15)
RTz p t − p A1 RTz p B1

pt − p A! = p B1
pt − p A 2 = p B 2
Subtracting one from the other,
p A1 − p A 2 = p B 2 − p B1 ……………………..(1.16)
Multiplying and dividing equation (1.15) by these equal terms,

NA = AB t A1
(
D p p − p A2 p ) D
ln B 2 = AB
pt
( )
p A1 − p A2 -------(1.17)
(
RTz p B 2 − p B1 )
p A1 RTz p BM

where p B.M =
(p B2 − p B1 ) = log mean partial pressure of B
pB2
ln
p B1
Case 2: Equimolar Counterdiffusion:
Here, NA = -NB
NA + NB = N =0
NA
----------------- = ∞
(NA+NB)
Hence use the equation NA = NyA + JA or NA = N(cA /c) + JA
But N = 0
Hence NA = JA
NA = - DAB (dcA / dz) ………………………………..(1.18)
 c 
Applying equation (1.13), dcA =  d p A
 pt 
Substituting this into equation (1.18) ,
− D AB pt  d p A 
NA =   ………………………………..(1.19)
p t RT  dz 
integrating,

NA =
D AB
RTz
(
p A1 − p A2 ) …………………………….(1.20)
LIQUIDS:
Steady State Molecular Diffusion In Liquids At Rest And In Laminar Flow:
Case 1: Diffusion of A through non diffusing B:
Here, the total concentration varies w.r.t. position significantly. ie c ≠ constant.
As c = n / V = ρ /M,
Where ρ = density of the liquid solution and M = Molecular weight of the same,
Equation (1.10) becomes,
NA
NA D AB  ρ  (N A + N B ) − x A2
NA =   …(1.21)
N A + N B z  M  Av N A
(N A + N B ) − x A1
where (ρ /M)Av is average of concentrations at the start and end of diffusion path.
Case 1: Diffusion of A through non diffusing B:
NA / (NA + NB ) = 1
NA D AB  ρ  ( x A1 − x A 2 )
NA =   …………(1.22)
N A + N B z  M  Av x B,M

Where x B,M = Log average of mole fraction of xB =

(x B 2 − x B1 )
ln 
xB2
 x B1 
Case 2: Equimolar Counterdiffusion:
N= 0
NA D AB  ρ 
NA =   ( x A1 − x A 2 ) …………(1.23)
N A + N B z  M  Av

Steady state molecular diffusion of fluids:

A through nondiffusing B Equimolar counterdiffusion of A & B
Gases
NA =
(
D AB p A1 − p A 2 ) NA =
D AB
(
p A1 − p A2 )
RTz p B ,M RTz
Liquids
NA D AB  ρ  ( x A1 − x A 2 ) NA D AB  ρ 
NA =   NA =   ( x A1 − x A 2 )
N A + N B z  M  Av x B,M N A + N B z  M  Av
Multicomponent diffusion under steady state: For gas mixtures:

n
N A − yA ∑ Ni
i= A
Effective diffusivity, DA,m = n
………(1.24)
1
∑ ( yi N A − y A N i )
i = A D A,i

DA,I are binary diffusivities.

If this varies linearly with diffusion path distance,

1− yA 1
DA,m = n
= …………….(1.25)
yi n
y i'
∑
i = B D A,i
∑
i = B D A,i

Relationship between N & C:

c v + cB vB N A + N B N
Average velocity = v = A A = =
c A + cB c c
N = vc or v = N/c
NA = JA + c A v = JA + c A N/c
But c A / c = yA for gases = xA for liquids
NA = JA + NyA for gases = JA + NxA for liquids

Estimation of Diffusivity:

Diffusivity of vapour through Air:

Pseudosteady state Diffusion:
Stefan’s Equation:
Consider a volatile liquid A(eg. Acetone or CCl4 ), kept in a tube is evaporating into air
stream (B) at constant temperature and constant total pressure. The level of liquid in the
tube in the beginning ( at t=0) measured from the open end of the tube is z 0 and this level
decreases to z t at time t due to evaporation. Here, A diffuses through non diffusing B.

Hence the flux of A is

D
NA = AB
pt
RTz p BM
(
p A1 − p A 2 ) …………………(1.26)

As the level of liquid in the tube keeps decreasing, z, which is z 0 – z t , is varying w.r.t.
time. Thus it is unsteady state diffusion. However, dz / dt is very slow making NA almost
constant w.r.t. time. Hence, it is called pseudo-steady state diffusion.
ρ A dz ρ L dz
NA = L = …………………..(1.27)
M A A dt M A dt
where ρ L = density of the liquid A = kg/m3 & MA = molecular weight of A = kg / kmole
A = area of inner cross section of tube, m2.
Combining equations (1.26) & (1.27),
dz D AB M A p t
=
dt RTz ρ L p BM
(
p A1 − p A 2 )

∫z0
zt
zdz =
D AB M A p t
RT ρ L p BM
(
p A1 − p A 2 )∫ dt
t

0
…………..(1.28)

Integrating and rearranging,

RTρ L p BM (
z t2 − z 02 )
DAB =
(
M A p t 2t p A1 − p A 2 ) ……………(1.29)

Point 1 is at the liquid-vapor interface.

Partial pressure of A at pt.1 = vapor pressure of A at the given temperature,T = pA
Partial pressure of A at pt.2 = 0

Prediction of DAB :

Gases: Wilke-Lee Equation:

  3/ 2
10 − 4 1.084 − 0.249 1 + 1 T 1 + 1
 M A M B  MA MB
DAB = …..(1.30)
p t (rAB ) f (kT ε AB )
2

Where DAB = diffusivity, m2/s

T = absolute temperature,K
MA, MB = molecular weight of a & B respectively, kg/kmol
Pt = absolute pressure, N/m2
rAB = molecular separation at collision, nm = ( rA + rB )/2
ε AB = energy of molecular attraction = ε Aε B
k = Boltzmann’s constant
f (kT/ ε AB) = collision function

r = 1.18 v 1/3
ε /k = 1.21 Tb where v is the molal volume in m3/kmol of the liquid
at normal boiling point, Tb Kelvin.
Liquids :

For dilute solutions of non-electrolytes: Wilke-Chang Equation

(1.173 x 10 -18 ) (φ MB)0.5 T

0
DAB = ---------------------------------------- ………….(1.31)
µv A 0.6

Where DAB 0 = diffusivity of a in a very dilute solution in solvent B, m2 /s

MB = molecular weight of solvent, kg/kmol
T = temperature, K
µ = solution viscosity, kg/ m.s
vA = solute molal volume at normal boiling point, m3 / kmol
= 0.0756 for water as solute
φ = association factor for solvent
= 2.26 for water as solvent
= 1.9 for methanol as solvent
= 1.5 for ethanol as solvent
= 1.0 for unassociated solvents, e.g., benzene and ethyl ether.

For concentrated solutions:

Changes in viscosity with concentrations

 d log γ A 
0
(
DA µ = DBA µA ) (D
xA 0
AB µ B ) 1 +
xB
 ………………(1.32)……
d log γ B 

where

D0 AB is the diffusivity of A at infinite dilution in B and D0 BA is the

diffusivity of B at infinite dilution in A.
γ is the activity coefficient (obtained from vapor-liquid equilibrium)
pA y p
γA = = A t where pA is the vapor pressure of A at the given temperature
xA pA xA pA
 Diffusion in Solids

Steady state diffusion in solids:

Fick’s I Law (for diffusion in z direction) for solids:
∂C A
Valid for steady state diffusion of component A which is a fluid: JA = - DA
∂z

For diffusion through a flat slab of thickness z,

D (c − c A 2 )
JA = A A1 …………(1.33)
z
Where JA= molar flux of component A in z direction in kmol/m2.s
DA = diffusivity of A through solid in m2/s which is constant
cA1 & cA2 = concentrations of A on the opposite sides of the slab in Kmol/m3
z = distance z2 – z1 in m
(cA1 -cA2)/z = concentration gradient in kmol/m4

For other solid shapes,

D A S Av (c A1 − c A 2 )
W = NASav = …………..(1.34)
z

Where Sav = average cross-section for diffusion

= 2 Π (a2 –a1) …….. for radial diffusion through a solid cylinder of inner &
ln (a2/a1) outer radii a 1 & a2 and a2 –a1 = z

= 4 Π a1a2 ……. for radial diffusion through a spherical shell of inner &
outer radii a 1 & a2 and a2 –a1 = z

Conditions: (i) steady state, molecular diffusion.

(ii) no bulk flow.
(iii) diffusivity is independent of concentration.

Unsteady state diffusion in solids:

Fick’s II Law:
∂C A ∂ 2C A ∂ 2C A ∂ 2C A
= D AB + + ……………(1.35)
∂θ ∂x 2 ∂y 2 ∂z 2
where θ = time, x,y & z are directions of diffusion

Conditions: (i) Unsteady state, molecular diffusion. (ii) no bulk flow.

(iii) diffusivity independent of concentreation (iv) no chemical reaction.

c A,θ − c A  Dθ 
Diffusion from a slab with sealed edges: E= = f  2  …(1.36)
c A, 0 − c A a 
where E is the fraction of A remaining unremoved in the solid at time θ.
Diffusion through:
Polymers
Crystalline solids
Porous solids

I. Diffusion through a polymers:

Two bodies of gas, say H2 at different pressuresseparated by a polumeric membrane
(eg. Polyethylene): First the gas dissolves in the solid (dissolution obeys Henry’s law,
ie c ∝ p), then diffuses from the high- to low pressure side.
D is in the order of 10-10 m2 /s.
(
D s p − p A2
VA = A A A1
) …………(1.37)
z
Where VA = diffusional flux, cm3 gas (STP)/ cm2.s
DA = diffusivity of A, cm2 /s
p A = partial pressure of diffusing gas, cm Hg
sA = solubility coefficient or Henry’s law constant,
cm3 gas (STP) / (cm3 solid)cm Hg
z = thickness of polymeric membrane, cm

Permeability: P = DAsA ………..(1.38)

P is in cm3 gas (STP)/cm2.s.(cm Hg / cm)
Commercial example: Separating hydrogen from waste refinery gases in a shell and tube
device using polymeric fibre tubes of 30µm OD in a 0.4 m dia shell.

II. Diffusion through acrystalline solid:

The mechanism of diffusion:
1. Interstitial mechanism, 2. vacancy mechanism, 3.interstitialcy mechanism, 4. crowd-
ion mechanism and 5. diffusion along grain boundaries.

III. Diffusion of a gas through a porous solid:

A porous barrier or membrane separating 2 bodies of fluids:.
(i) If the absolute pressure is constant is constant across the porous solid : diffusion
(ii) If it varies, hydrodynamic flow.

(i)Total pressure constant across the porous solid:

Knudsen’s law:
If pore dia,d and gas pressure are such that the molecular mean free path,λ is relatively
large, d / λ < about 0.2 , the rate of diffusion is governed by the collisions of gas
molecules with the pore walls and follow Knudsen’s law.
In a straight circular pore of dia d & length l,
duA
NA = ------( pA1 –pA2 )
3RTl 8gc RT
where uA = mean molecular velocity of A = ------------ ……(1.39)
π MA
 DK,A (pA,1 –pA,2)
NA = ------------------------
RTl d 8gc RT
Where DK,A = Knudsen diffusion coefficient = ---- ------------ …(1.40)
3 π MA
NKn = Knudsen No. = λ / d where λ = mean free path and d is average pore dia.
d/λ
d/λ Diffusivity
Knudsen diffusion < 0.2 1 2
D K,A ∝ T
Knudsen + Molecular diffusion 0.2 to 20 DK,A & DAB
Molecular diffusion >20 D ∝T 2
3
AB

Generally the pore will not have a constant diameter along the diffusion path and the true
length,l of diffusion path is also not known. Hence, l is replaced by z, the membrane
thickness and DK,A is replaced by effective Knudsen diffusivity, DK,A,eff which is
determined experimentally.

DK,A,eff is independent of pressure and varies as (T/M)1/2.

Molecular diffusion: d / λ > 20

NA − y A2
NA =
NA D ABeff pt
ln
( NA + NB )
……….(1.41)
N A + N B RTz N A / ( N A + N B ) − y A1

Transition range: 0.2 < d / λ < 20

NA  D 
1 + AB ,eff  − y A2
D ABeff pt NA + NB D 
NA =
NA
ln  K , A,eff  …(1.42)
N A + N B RTz N A  D AB ,eff 
1+  − y A1
N A + N B  DK , A,eff 


Knudsen diffusion: d / λ < 0.2:

NA =
DK , A
RTl
(
p A1 − p A2 =)D K , A,eff
RTz
(
p A1 − p A 2 ) ……………(1.43)

(ii) Total pressure varying across porous solid:

Hydrodynamic flow of gases:
k
NA = pt ,av ( p t1 − pt 2 ) ……(1.44)
RTz
Where pt,av =( pt1 – pt2 ) /2
K = d2 gc / 32 µ l …….(1.45)