Philippine Handbook Mass Transfer and Diffusion

in Chemical Engineering by Servillano Olaño, Jr.

I3. MASS TRANSFER AND DIFFUSION

I3.1. INTRODUCTION

The movement of one type of molecules through other types of molecules is influenced by
the concentration gradient, the physical and molecular properties of the participating species
and the external forces. These factors affect the rate of transfer of the molecules. This
molecular interaction is the basis of determining the rate of mass transfer, which is important
in the design of mass transfer equipment such as gas absorbers, humidifiers, distillation
columns, and others. To simplify the discussion, only binary system will be considered in this
presentation.

There are two types of diffusion that will be considered. One is molecular diffusion, which is
highly influenced by concentration gradient, and the other is eddy or turbulent diffusion,
which is influenced not only by concentration gradient but also by the movement or mixing
of the material due to some external applied force.

I3.2. MOLECULAR DIFFUSION

Consider a binary system where a certain species A is moving at an average velocity uA in a

bulk of material containing species B moving at an average velocity of uB. Let us assume that
the mixture is moving at a bulk velocity uo referred to a stationary observer. Then the molar
fluxes of A and B may be determined by the Fick’s Law of diffusion

dc A
I OA  c A u A  uO    DAB (I3 – 1)
dZ

dcB
I OB  cB uB  uO    DBA (I3 – 2)
dZ

where IoA is the molar flux of A through a plane moving at uO and cA and cB are the
concentrations of species A and B while DAB is the diffusivity of A relative to B and DBA is the
diffusivity of B relative to A. The diffusivities are transport properties which may be
determined experimentally or estimated from empirical equations in terms of the physical and
molecular properties of the diffusing components.

In design calculations, what is more important is the diffusion flux, not relative to the
movement of the bulk but relative to a stationary observer. These diffusion fluxes, N A and NB
are given by

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Philippine Handbook Mass Transfer and Diffusion
in Chemical Engineering by Servillano Olaño, Jr.

NA = cAuA (I3 – 3)

NB = cB uB (I3 – 4)

while the total flux of the entire bulk, N is given by

N = NA + NB = rm uo (I3 – 5)

If uA, uB and uo are eliminated from Eqs. (I3 – 1) and (I3 – 2), we get the equations

cA dc A
I OA  N A   ( N A  N B )   DAB (I3 – 6)
m dZ

cB dcB
I OB  N B  ( N A  N B )   DBA (I3 – 7)
m dz

If we add Eqs. (I3 – 6) and (I3 – 7), it can easily be seen that

IOA + IOB = 0 (I3 – 8)

and

DAB = DBA = Dv (I3 – 9)

That is, the sum of the molar fluxes relative to the movement of the bulk is zero and, for
binary system, the diffusivity of A relative to B is the same as the diffusivity of B relative to
A. Here, we will just refer to this as the volumetric or mass diffusivity, Dv with units of m2/s
or ft2/hr. It is important to note that the diffusivity is based on the movement of the entire
bulk and not on a stationary position. For gases, the diffusivity can also be expressed in terms
of molar units, Dm defined by

Dv PT
Dm  Dv  m  (I3 – 10)
RT

where the units of Dm is in moles/time-length and rm is in moles per unit volume.

Solving for the molar flux relative to a stationary observer, NA from Eq. (I3 – 6), we get

dc A c A
N A   Dv  (N A  NB ) (I3 – 11)
dz  m

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Philippine Handbook Mass Transfer and Diffusion
in Chemical Engineering by Servillano Olaño, Jr.

It is seen that the diffusion flux, N A is composed of two terms, the molecular diffusion flux as
given by Fick’s Law and another type of flux which we can consider here as convective flux
or phase drift.

The differential equation presented in Eq (I3 – 11) may be solved by considering two ideal
steady state diffusion models. These are Equimolar Counter Diffusion and Unicomponent
Diffusion. An example of the former is encountered in the rectification of volatile
components where both can co-exist in both phases such as ethanol-water system. An
example of the latter is in the absorption of a soluble component from an inert gas that is
insoluble in the solvent where the soluble component is able to penetrate the solid-liquid
interface while the inert gas becomes stagnant since it cannot diffuse to the liquid phase.

I3.3. EQUIMOLAR COUNTER DIFFUSION

When the molar flux of A and B are moving at equal rates and in opposite direction,

NA = - NB or NA + NB = 0 (I3 – 12)

Equation (I3 – 11) reduces to

dc A
N A   Dv (I3 – 13)
dz

This equation may be integrated for the total molar rate of diffusion, N TA, if the diffusion
area, A, perpendicular to the direction of motion is constant,

NTA  c c 
 Dv  A1 A 2  (I3 – 14)
A  z2  z1 

It is to be noted that for constant area, the concentration profile is linear across the direction
of diffusion. If the diffusion area is not a constant, it must be expressed in terms of z and the
differential equation solved applying the limits from z1 to z2..

For ideal gases, the diffusion equation may be expressed in terms of partial pressure, pA, that
is,

pA
cA  (I3 – 15)
RT
or
NTA D dp A
 v (I3 – 16)
A RT dz

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Philippine Handbook Mass Transfer and Diffusion
in Chemical Engineering by Servillano Olaño, Jr.

I3.4. UNICOMPONENT DIFFUSION

For unicomponent diffusion of A through a stagnant component B, then NB = 0. Equation (I3-

11) becomes,
dc c
N A   Dv A  A N A (I3 – 17)
dz  m

since cA + cB = rm, the above equation may be converted to

NTA  c  dc
  Dv 1  A  A (I3 – 18)
A  cB  dz

If this is expressed in terms of the mole fractions of A and B, that is xA and xB, the above
equation can be integrated in the form of

NTA Dv c A1  c A 2
  (I3 – 19)
A z2  z1 xB ln

where xBln is the logarithmic mean of the mole fraction of B at point 2 and point 1.

For ideal gases, Eq. (I3 – 18) may be expressed in terms of pA,, that is,

NTA D P dp A
 v T (I3 – 20)
A RTpB dz

if the diffusion area is constant, with pB = PT – pA, the above equation can be integrated to
give

NTA Dv PT P  pA2
 ln T (I3 – 21)
A RT z PT  p A1

It is noted that the concentration profile for this case is non-linear but logarithmic.

I3.5. EVALUATION OF DIFFUSIVITIES

The volumetric diffusivity, Dv for gases and liquids may be determined experimentally or
from empirical correlations based on the kinetic theory of gases. Some of the more important
equations are presented here.

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Philippine Handbook Mass Transfer and Diffusion
in Chemical Engineering by Servillano Olaño, Jr.

I3.5.1. From Empirical Equations

1. For gases, Chen and Othmer Equation. (McCabe and Smith, 1976)
0.5
 1 1 
0.01498T 1.81
  
 MA MB  (I3 – 22)
Dv 
pTCA TCB 
0.1405
V0.4
CA V CB 
0.4 2

2. For gases, Gilliland Equation. (Brown, et al., 1950))

3
0.0166T 2
1 1
DG  2
 (I3 – 23)
MA MB
PV A 3  V B 3 
1 1

3. For gases, Chapman and Engskog Equation (Geankoplis, 1997))

1/ 2
1.8583 x107 T 3/ 2  1 1 
DAB     (I3 – 24)
P AB  D , AB  M A M B 
2

4. For liquids, Stokes-Einstein Equation (Geankoplis, 1997))

9.96 x1016 T
DAB  (I3 – 25)
VA1/ 3

3. For Liquids, Wilke and Chang (Treybal, 1968)

D AB 

7.4 10 8 M B  T 0.5

(I3 – 26)
 'V A0.6

Other empirical equations maybe found from literature. The nomenclature used in
these equations is found in the Appendix.

I3.5.2. From Experimental Data

Sources of diffusivity data can be found in Perry and Green (1984), Green, et al. (1997),
McCabe, et al. (2001), Geankoplis (1995) and other textbooks.

If the diffusivity is given at a particular reference temperature, say 273K and 1 atm, it is
possible to estimate the diffusivity at a desired temperature and pressure by making use of the
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Philippine Handbook Mass Transfer and Diffusion
in Chemical Engineering by Servillano Olaño, Jr.

empirical equations as the basis. If the calculation is based on Chen and Othmer correlation,
the equation becomes

 T 1.81 
Dv  f   (I3 – 27)
 p 
or
1.81
 T  1
 Dv T P   Dv 273,1atm      (I3 – 28)
1
 273   p

I3.6. TURBULENT DIFFUSION

The equation for molecular diffusion may be modified and applied to turbulent diffusion by
introducing a correction eM referred to as the turbulent or eddy mass diffusivity. Thus, Eq. (I3
- 1) may now be written as

dc A
I oA    DAB   M  (I3 – 29)
dz

I3.7. MASS TRANSFER COEFFICIENTS

For equimolal counter diffusion, IoA = NA. The above equation can therefore be integrated
across a film thickness of (z2 – z1), to give

DAB   M
NA  (c A1  c A 2 ) (I3 – 30)
z2  z1

This equation is then simplified by expressing it in terms of a convective mass transfer

coefficient, kc’ based on the movement of the entire bulk phase.

N A  kc' (c A1  c A 2 ) (I3 – 31)

For mass transfer of A in a non-diffusing B, Equation (I3-19) may be modified to give

( DAB   M ) c A1  c A 2
NA   (I3 – 32)
z2  z1 xB ln

which may be simplified to

kc'
NA  (c A1  c A 2 )  kc (c A1  c A 2 ) (I3 – 33)
xB ln

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Philippine Handbook Mass Transfer and Diffusion
in Chemical Engineering by Servillano Olaño, Jr.

The mass transfer coefficients kc’ and kc have a unit of m/s or ft/hr. It is possible to express
these coefficients in terms of other units depending on the driving forces used in the defining
mass transfer equation. Examples are

N A  kG ( p A1  p A 2 )  k y ( y A1  y A 2 )  k x ( x A1  x A 2 ) (I3 – 34)

I3.8. EVALUATION OF MASS TRANSFER COEFFICIENTS

I3.8.1. Dimensionless Numbers

The dimensionless numbers obtained by the usual procedure of dimensional analysis that are
important in mass transfer operations are the following:

Du  inertia forces
Reynolds Number, N Re   (I3 – 35)
 viscous forces

 momentum
Schmidt Number, N Sc   (I3 – 36)
 Dv mass diffusivity

kc' L turbulent diffusion

Sherwood Number, N Sh   (I3 – 37)
DAB molecular diffusion

The mass transfer coefficient is correlated as a dimensionless, JD factor given by

kc' k' P N Sh
JD  ( N Sc ) 2 / 3  c T  (I3 – 38)
v v  m N Re N Sc
1/ 3

I3.8.2. Mass, Heat and Momentum Transfer Analogies

The transport mechanism of mass, heat and momentum have similarities that could be used to
relate the three mechanisms especially in determining approximate values of the transfer
coefficients in the absence of a more reliable experimental data. The more common analogies
are presented here.

Reynolds Analogy (NSc = NPr = 1.0)

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Philippine Handbook Mass Transfer and Diffusion
in Chemical Engineering by Servillano Olaño, Jr.

f h kc'
  (I3 – 39)
2 c p G uav
Chilton-Colburn Analogy

f h k'
 JH  ( N Pr ) 2 / 3  J D  c ( N Sc ) 2 / 3 (I3 – 40)
2 c pG uav

I3.8.3. Mass Transfer Coefficients

A. For Flow Inside Pipes

For Laminar flow, refer to Fig. 7.3 –2 (Geankoplis, 1995)

For Turbulent Flow, for NSc of 0.6 to 3000

D
N Sh  kc'  0.023 N Re
0.83
N Sc0.33 (I3 – 41)
DAB

B. For Flow Outside Solid Surfaces

1 Parallel Flat Plates

L (I3 – 42)
N Sh  kc'  0.664 N Re,
0.5 1/ 3
L N Sc
DAB

2. Flow Past Single Spheres

For gases, NSc = 0.6 to 2.7 and NRe = 1 to 48,000

N Sh  2  0.552 N Re
0.53 1/ 3
N Sc (I3 – 43)

For liquids, NRe = 2 to 2000

N Sh  2  0.95 N Re
0.5 1/ 3
N Sc (I3 – 44)

NRe = 2000 to 17,000

N Sh  0.347 N Re
0.62 1/ 3
N Sc (I3 – 45)

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Philippine Handbook Mass Transfer and Diffusion
in Chemical Engineering by Servillano Olaño, Jr.

C. For Packed Beds

For Gases through spheres with NRe = 10 to 10,000

0.4545 0.4069
JD  JH  N Re (I3 – 46)


For Liquids with NRe = 0.0016 to 55 and NSc = 165 to 70,600

1.09 2 / 3
JD  N Re (I3 – 47)


For Liquids with NRe = 55 to 1500 and NSc=165 to 10,690

0.250 0.31
JD  N Re (I3 – 48)


The representative equations given above are obtained from Geankoplis(1995). Many more
correlations are available in Green, et al. (Perry’s Handbook, 1997) and other references.

D. Penetration Theory of Mass Transfer

For cases where surface renewal rather than film theory applies, for equimolal diffusion, the
individual mass transfer coefficient is given by

2 M Dv
k (I3 – 49)
 tL
where tL is the average time the fluid elements remain at the interface. This is dependent on
the fluid velocity, fluid properties and the geometry of the system.

THE WETTED WALL COLUMN

The wetted wall column is the most popular apparatus used in experimentally determining the
mass transfer coefficient of a system since the mass transfer area can be determined with
reasonable accuracy. Correlations on the behaviour of the dimensionless numbers such as the
Sherwood number, Reynolds number and Schmidt number under turbulent diffusion have
been derived using this apparatus.

Applying the material balance and the rate of mass transfer of component A around
the differential area dA yields

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Philippine Handbook Mass Transfer and Diffusion
in Chemical Engineering by Servillano Olaño, Jr.

dNA = V’dY = ky(Yi - Y) dA (I3 – 50)

Since, V’ = V(1-y) and

1 dy
Y and dY 
1 y 1  y 2
Substituting in Equation (I3 – 50)), we get
dy
V 1  y   k  y  y dA
1  y 2 y i
A y2 (I3 – 51)
k y dA dy

o
V
 
y1
1  y  yi  y 

Under adiabatic conditions, the temperature of the liquid remains constant, thus the interfacial
concentration, yi may be taken also as constant. Integrating Equation (I3 - 51), we get

ky A

1
ln
1  y1  yi  y2  ........
(I3 – 52)
V yi  1 1  y2  yi  y1 

With the temperature, flow rate and concentrations measured experimentally, together with
the surface area of contact between the gas and the liquid, the mass transfer coefficient of the
diffusing component maybe determined.

Several correlations have been derived for wetted-wall columns. An example is the Gilliland-
Sherwood Equation (McCabe and Smith, 1976) given by

N Sh  0.023 N Re
0.81 0.44
N Sc (I3 – 53)

which is very similar to Eq. (I3 – 41). The equation applies for N Re between 2,000 to 35,000;
NSc from 0.6 to 2.5; and over a pressure range of 0.1 to 3 atm.

A second correlation for wetted-wall columns, which shows the general analogy for
momentum, heat and mass transfer, although less precise than the above equation, can be
written as

f  0.2
jM  j H   0.023N Re (I3 – 54)
2

where f is the Fanning friction factor for flow in smooth pipes. The above equation is not
applicable if form drag exists.

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Philippine Handbook Mass Transfer and Diffusion
in Chemical Engineering by Servillano Olaño, Jr.

NOMENCLATURE

Symbol Description Units

2
A Area perpendicular to the moving species m
cA Concentration of species A kg-mole/m3
cp heat capacity J/kg-K
DAB Diffusivity of A relative to B m2/s
Dm molal diffusivity kg-mole/s-m
Dv volumetric diffusivity m2/s
f Fanning friction factor [-]
G mass velocity kg/m2-s
h heat transfer coefficient W/m2-K
IoA Molar flux of A relative to bulk motion kg-mole/s-m2
kc mass transfer coefficient for unicomponent m/s
diffusion
kc’ mass transfer coefficient for equimolar m/s
diffusion
M molecular weight kg/kg-mols
NA Molar flux of A kg-mol/m2-s
NTA Total moles of A diffusing kg-mol/m2-s
NRe Reynolds Number
NSc Schmidt Number
NSh Sherwood Number
P, PT total pressure atm or Pa
pA partial pressure of A mm Hg or Pa
R universal gas constant=8314.34 J/kg-mol-K
T temperature K
Tc critical temperature K
u linear velocity m/s
VA solute molar volume at normal boiling point m3/kg-mol
Vc critical volume m3
xA Mole fraction of species A in liquid phase [-]
y mole fraction in the gas phase [-]
z Distance in the direction of moving species m
e porosity of bed [-]
m viscosity Pa-s
f association parameter of the solvent [-]
sAB average collision diameter m
WD collision integral [-]
rm Molal density of mixture kg-mols/s-m
eM eddy or turbulent mass diffusivity m2/s

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Philippine Handbook Mass Transfer and Diffusion
in Chemical Engineering by Servillano Olaño, Jr.

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Philippine Handbook Mass Transfer and Diffusion
in Chemical Engineering by Servillano Olaño, Jr.

References:

Brown, George G., D. Katz, A.L. Foust and R. Schneidewind. (1950). "Unit Operations",
John Wiley and Sons, New York
Foust, A.S., L.A. Wenzel, C.W. Clump, L. Maus and L.B. Andersen. (1960) "Principles of
Unit Operations", John Wiley and Sons, New York.
Geankoplis, Christie J. (1995) “Transport Processes and Unit Operations”, 3rd edition.
Printice-Hall International ed.,
Green, Don W.(ed) and James O. Maloney (asoc. ed), (1997) “Perry's Chemical Engineers'
Handbook, 7th edition", McGraw-Hill Book, New York
McCabe, Warren L., Julian C. Smith and Peter Harriott,(2001) Unit Operations of Chemical
Engineering, 6th edition, McGraw-Hill International.
Perry, Robert H. and D. Green. (1984). "Perry's Chemical Engineers' Handbook, 6th edition",
McGraw-Hill Book, New York.
Treybal, Robert E., (1968), “Mass Transfer Operations”, 2nd edition, McGraw-Hill
Kogakusha, Ltd., Tokyo

TABLES NEEDED:

Diffusion Coefficients of Combination of Gases at 1 atm

Diffusion Coefficients of a Gas in Air at 1 atm and 273K
Atomic Diffusion Volumes
Diffusion coefficients for Dilute Liquid Solutions
Atomic and Molar Volumes at Normal Boiling Point
Diffusion Coefficients for Dilute Solutions of Gases in Water at 20oC

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