CHAPTER ONE

Principles of Mass Transfer

1
Mass Transfer

Mass Transfer

Molecular Diffusion Convective Mass Transfer

Chapter 6 Chapter 7

Gases Liquid Solid

2
Introduction
 Mass transfer occurs when a component in a mixture migrates in the same phase
or from phase to phase because of a different in concentration between two point.
 Somewhat similar to heat conduction, but in conduction the medium is stationary
and only energy in the form of heat is being transferred.
 Example of mass transfer
1. Evaporation of water in the open pail to the atmosphere
2. Coffee dissolve in water
3. Oxygen dissolved in the solution to the microorganism in the fermentation
process

 Possible driving force for mass transfer

1. Concentration different
2. Pressure different
3. Electrical gradient, etc

3
Type of Mass Transfer
1. Molecular diffusion
 Transfer of individual molecules through a fluid by random
movement from high concentration to low concentration
 E.g. coffee dissolve in water in making coffee

2. Convective mass transfer

 Using mechanical force or action to increase the rate of
molecular diffusion
 E,g stirred the water to dissolve coffee during coffee making

4
Molecular Diffusion
 Diffusion of molecules when the bulk fluid is stationary given by
Fick’s law
* dx A
J  cDAB
A
dz
c : total conc. of A and B (kgmol A+B/ m3)
xA : mole fraction of A
DAB :molecular diffusivity of A in B (m2/s)

 If total conc., c is constant and cA=xAc, then:

dc A
J   D AB
*
A
dz 5
Convection Mass Transfer
 When a fluid flowing outside a solid surface in forced convection motion, rate of
convective mass transfer is given by:

N A  k c (c L1  c Li )
kc : mass transfer coefficient (m/s)
cL1 : bulk fluid conc.
cLi : conc. of fluid near the solid surface

 kc depend on:
1. System geometry
2. Fluid properties
3. Flow velocity

6
Molecular Diffusion in Gases

Mass Transfer

Molecular Diffusion Convective Mass Transfer

Chapter 6 Chapter 7

Gases Liquid Solid

7
Contents:
1. Introduction

2. Equimolar counter diffusion

3. Diffusion of gases A and B plus convection

4. Gas A diffusing through stagnant, non-diffusing B

5. Diffusion through varying cross sectional area

6. Diffusion coefficient for gases

8
Fick’s Law for Gases

 Molecular diffusion from cA1 to cA2 from z1 to z2

D AB (c A1  c A 2 )
J * Az 
z 2  z1

 For ideal gas PV=nRT, where c=n/V=P/RT

D AB ( p A1  p A 2 )
J * Az 
RT ( z 2  z1 )

9
 Equimolar Counter Diffusion PA1 > PA2
PB2 > PB1
J *
AZ  J *
BZ

c  c A  cB
dc  dc A  dc B  0
dc A   dcB

* dcA * dc B
J A  D AB   J B  ()DBA
dz dz Fig. 6.2-1
DAB  DBA 10
 EXAMPLE 6.2-1.
Equimolar Counterdiffusion
Ammonia gas (A) is diffusing through a uniform tube 0.10 m long containing N 2 gas (B) at 1.0132 x
105 Pa pressure and 298 K. The diagram is similar to Fig. 6.2-1 in lecture. At point 1, p A1 = 1.013 x
104 Pa and at point 2, pA2 = 0.507 x 104 Pa. The diffusivity DAB = 0.230 x 10-4 m2/s. Calculate the
flux at steady state. Repeat for
Solution:
Equation (6.1-13) can be used, where P = 1.0132 x 105 Pa, z2 - z1 = 0.10 m, and T = 298 K.
Substituting into Eq. (6.1-13) for part (a),
 

Rewriting Eq. (6.1-13) for component B for part (b) and noting that p B1 = P - pA1 = 1.0132 x 105 -
1.013 x 104 = 9.119 x 104 Pa and pB2 = P - pA2 = 1.0132 x 105 - 0.507 x 104 = 9.625 x 104 Pa,
 

The negative value for means the flux goes from point 2 to point 1 11
Diffusion of Gases A and B Plus Convection1/2
vA
vA = velocity of A relative to stationary point
vAd =vdiffusion
Ad ofvA
m relative to moving fluid

vm = molar average velocity of whole fluid

or convective velocity
vA = vAd + vm
Multiply by cA
cAvA= cAvAd + cAvm
cAvA = NA = total flux of A relative to stationary point
cAvAd= JA*= diffusion flux relative to moving fluid
cAvm = convective flux of A relative to stationary point
N A= JA* + cAv m

12
Diffusion of Gases A and B Plus Convection2/2

 Let N is total convective flux of the whole stream relative to

stationary point;
N=NA + NB = cvm or vm = (NA + NB) / c
General equation become:
c dx A cA
N A  J A *  A (N A  N B ) or N A  cD AB dz
*
c
(N A  N B )
c

cB dx B c
NB  JB * (N A  N B ) or N B  cD AB *  B (N A  N B )
c dz c

If counter diffusion, the convective term become zero; NA = JA*

13
Gas A Diffusing Through Stagnant, Nondiffusing B1/2
 One boundary at the end of the diffusion path is impermeable to component B ( NB=0)
 Evaporation of pure liquid such as benzene (A) at the bottom of narrow tube , where a large amount of air (B)
passed over the top
 Benzene vapor (A) diffuse through the air (B) in the tube
 But at point 1, air (B) is insoluble in liquid benzene (NB=0)
 Also at point 2, pA2=0 since a large volume of air is passing through

 Absorption of NH3 (A) by water, which NH3 contain in air (B)

 Water surface is impermeable to air (B) (NB=0) but NH3 can dissolve in water

14
Gas A Diffusing Through Stagnant, Non-diffusing B 2/2
 General equation
D AB P P  p A2
NA  ln
RT ( z 2  z1 ) P  p A1

 Another form to write the eq is using pBM; also we know that

P = pA1 + pB1= pA2 + pB2

p B 2  p B1 p A1  p A 2
p BM  
ln ( p B 2 p B1 ) ln ( P  p A1 P  p A2 )
D AB P
NA  ( p A1  p A 2 )
RT ( z 2  z1 ) p BM

Time for evaporation

 A RTpBM zF2  zo2 
tF  15

2M A DAB P( pA1  pA 2 )
EXAMPLE 6.2-2. 1/2
Diffusion of Water Through Stagnant, Nondiffusing Air

Water in the bottom of a narrow metal tube is held at a constant temperature of 293 K. The
total pressure of air (assumed dry) is 1.01325 x 10 5 Pa (1.0 atm) and the temperature is
293 K (20°C). Water evaporates and diffuses through the air in the tube, and the diffusion
path z2 - z1 is 0.1524 m (0.5 ft) long. The diagram is similar to Fig. 6.2-2a. Calculate the
rate of evaporation at steady state in lb mol/h · ft 2 and kg mol/s · m2. The diffusivity of
water vapor at 293 K and 1 atm pressure is 0.250 x 10 -4 m2/s. Assume that the system is
isothermal. Use SI and English units.
Solution: The diffusivity is converted to ft 2/h by using the conversion factor from
Appendix A.1:

From Appendix A.2 the vapor pressure of water at 20°C is 17.54 mm Hg ,

or pA1 = 17.54/760 = 0.0231 atm
= 0.0231(1.01325 x 105) = 2.341 x 103 Pa
pA2 = 0 (pure air).
16
EXAMPLE 6.2-2. 2/2
Since the temperature is 20°C (68°F), T = 460 + 68 = 528°R = 293 K.
From Appendix A.1, R = 0.730 ft3 · atm/lb · mol·°R.
To calculate the value of pBM from Eq. (6.2-21),

Since pB1 is close to pB2, the linear mean (pB1 + pB2)/2 could be used and would be
very close to pBM. Substituting into Eq. (6.2-22) with z2 - z1 = 0.5 ft (0.1524 m),

17
 Diffusion Through Varying Cross Sectional Area
Diffusion from a sphere
 Example
 Evaporation of a drop of liquid
 Evaporation of ball of naphthalene
N NA DAB P ( pA1  pA 2 )
Diffusion rate
NA  A  N 
4 r12
A1
(kgmol/s)
A RTr1 pBM

 Simplified eq. if (pA1<<P; pBM≈P; 2r1=D1; cA1=pA1/RT)


2 D AB
N A1  (c A1  c A 2 )
D1

 Time for evaporation

 A r1 2 RTp BM
tF 
2 M A D AB P ( p A1  p A 2 ) 18
Diffusion Coefficient for Gases1/2
Empirical equation for DAB

1. Chapman& Enskog

1
 1 1 
-7 3 2
1.8583 x 10 T 2

D AB    
P AB
2
 D , AB MA MB 
P = absolute pressure in atm
σAB = average collision diameter
ΩD,AB = collision integral based on Lennard-Jones potential; is a ratio giving the
deviation of a gas with interaction as compared to a gas rigid, elastic spheres.

19
 Diffusion Coefficient for Gases2/2
2. Fuller et al.

1
 1 
2

 M  1M 
-7 1.75
1.00 x 10 T Equation 6.2-45
D AB   A B 


P   vA 
1
3    vB 
1
3  2

T, in K, P in atm,  in m3

Use atomic diffusion volume () from Table 6.2-2.

20
21
Table 6.2-2

22
 EXAMPLE 6.2-5.
Estimation of Diffusivity of a Gas Mixture
Normal butanol (A) is diffusing through air (B) at 1 atm abs. Using the Fuller et al. method,
estimate the diffusivity DAB for the following temperatures and compare with the experimental
data: a) For 0°C. b)For 25.9°C. c) For 0°C and 2.0 atm abs.
Solution: For part (a), P = 1.00 atm,T = 273 + 0 = 273 K, M A(butanol) = 74.1, MB(air) = 29.
From Table 6.2-2,

Substituting into Eq. (6.2-45),

 

This value deviates by +10% from the experimental value of 7.03 x 10 -6 m2/s from Table 6.2-1.
For part (b), T = 273 + 25.9 = 298.9. Substituting into Eq. (6.2-45), D AB = 9.05 x 10-6 m2/s.
This value deviates by +4% from the experimental value of 8.70 x 10 -6 m2/s.
For part (c), the total pressure P = 2.0 atm. Using the value predicted in part (a) and correcting
for pressure,
23
Molecular Diffusion in Liquids

Mass Transfer

Molecular Diffusion Convective Mass Transfer

Chapter 6 Chapter 7

Gases Liquid Solid

24
Introduction
 Typical phenomena of molecular diffusion in liquids
 Liquid-liquid extraction
 Gas absorption
 Diffusion of salts in blood
 Oxygenation of river, and etc

 Molecular diffusion in liquid is smaller than molecular diffusion in gases

 Reason: molecules in liquid are close together compared to molecules in
gases; molecules of diffusing solute will collide more frequently with
liquid molecules

 Diffusivity in liquid dependent on the concentration of diffusing solute.

25
Equimolar Counter Diffusion

DAB (c A1  cA 2 ) D ABc av(x A 1  x A 2 )

NA  
z2  z1 z 2  z1
 Concentration is not constant, take average concentration, cav

 1 2 
  
    M1 M 2 
c av   
 M  av 2
1 and 2 represent a position/point
M – average molecular weight
26
Average Molecular Weight
Recall for average molecular weight:

M ave   y i M i

yi – mole fraction
1 xi

M ave Mi
xi – mass fraction

Don’t confuse about the symbol use for determine ave Mw.
Using above eq. xA is for mass fraction and yA is for mole fraction. However,
for previous molecular diffusion, xA is stand for mole fraction.
27
 Diffusion of A through Nondiffusing B
 Example:
 Dilute solution of propionic acid (A) in a water (B) solution being
contact with toluene
 Only propionic acid (A) diffuses through the water phase, to the
boundary and then into the toluene phase
 Water (B) cannot diffuse in toluene-water interface
DAB cav
NA  (x A1  x A 2 )
(z 2  z1 )x BM

x B2  x B1
x BM 
ln (xB 2 xB 1 )
28
 EXAMPLE 6.3-1. Diffusion of Ethanol (A)
Through Water (B) 1/2
An ethanol (A)–water (B) solution in the form of a stagnant film 2.0 mm
thick at 293 K is in contact at one surface with an organic solvent in
which ethanol is soluble and water is insoluble. Hence, NB = 0. At point
1 the concentration of ethanol is 16.8 wt % and the solution density is
ρ1 = 972.8 kg/m3. At point 2 the concentration of ethanol is 6.8 wt % and
ρ2 = 988.1 kg/m3. The diffusivity of ethanol is 0.740 x 10-9 m2/s .
Calculate the steady-state flux NA.
Solution: The diffusivity is DAB = 0.740 x 10-9 m2/s. The molecular
weights of A and B are MA = 46.05 and MB = 18.02. For a wt % of 6.8,
the mole fraction of ethanol (A) is as follows when using 100 kg of
solution:

Then xB2 = 1 - 0.0277 = 0.9723. Calculating xA1 in a similar manner, xA1

= 0.0732 and xB1 = 1 - 0.0732 = 0.9268. To calculate the molecular
weight M2 at point 2,
29
EXAMPLE 6.3-12/2

 Similarly, M1 = 20.07.
 From Eq. (6.3-2),

 To calculate xBM from Eq. (6.3-4), we can use the linear mean since
xB1 and xB2 are close to each other:

 Substituting into Eq. (6.3-3) and solving,

30
Diffusivity in Liquids

1. Experimental determination of diffusivity

2. Experimental liquid diffusivity data (Table 6.3-1)

3. Predictian of diffusivity in liquids

a) Stokes- Einstein equation
B) Wilke-Chang equation
31
Table 6.3-1. Diffusion Coefficients for Dilute
Liquid Solutions


32
Stokes- Einstein Equation

9.96x1016 T This equation holds for:

DAB 
V 1/
A
3 -molecule with MW >1000
-molar vol ~ 0.5m3/kg mol

T- temperature in Kelvin
VA- solute molar volume at normal boiling point (m3/kgmol) Table 6.3-2
- viscosity of solution in Pa · s or kg/m · s
DAB- Diffusion Coefficient in m2/s

33
Table 6.3-2

34
 Wilke-Chang Equation
 Solute A is dilute in the solvent B
 Limited to VA (solute molar volume ) < 0.5 m3/kgmol
 If solute A is water, multiply the equation by (1/2.3)
T
D AB  1.173x10 16
(M B )
1
2

 BV A0.6
where  is in Pa.s, T in K, DAB in m2/s

 Value for association parameter, Φ

Water = 2.6 MeOH = 1.9 EtOH = 1.5

Benzene = 1.0 Ether = 1.0 Heptane = 1.0

35
 EXAMPLE 6.3-2. Prediction of Liquid Diffusivity
Predict the diffusion coefficient of acetone (CH3COCH3) in water at 25° and 50°C using
the Wilke–Chang equation. The experimental value is 1.28 x 10-9 m2/s at 25°C (298 K).
Solution: From Appendix A.2 the viscosity of water at 25.0°C is μB = 0.8937 x 10-3 Pas
and at 50°C, 0.5494 x 10-3. From Table 6.3-2 for CH3COCH3 with 3 carbons + 6
hydrogens + 1 oxygen,

For water the association parameter φ = 2.6 and MB = 18.02 kg mass/kg mol. For 25°C,
T = 298 K. Substituting into Eq. (6.3-9),

For 50°C or T = 323 K,

36
Molecular Diffusion in Solids

Mass Transfer

Molecular Diffusion Convective Mass Transfer

Chapter 6 Chapter 7

Gases Liquid Solid

37
 Introduction
 Diffusion of solute in solid is slower than diffusion of solute in liquid and gases

 Example application:
 Leaching of food
 Drying of timber, salt, food, etc.
 Catalytic reaction in solid catalyst
 Separation of fluid by membrane

 Diffusion solute in solids can be categorized into two group

1. Diffusion which follow Fick’s law and does not depend on the actual structure of
the solid
2. Diffusion in porous solids which is depend on the actual structure and void
structure of the solid

38
Diffusion in Solids which Follow Fick’s Law and
Does Not Depend on The Structure of Solids1/4
 Diffusion occur when the fluid or solute diffusing dissolve in the solid to form a
more or less homogeneous solution

Diffusion in Solid General Equation Neglect convective

term and assume
DAB ≠ DBA dc A
N A   D AB constant
dz concentration

Slab Solid Cylinder Wall

(c A1  c A 2 ) 2L
N A  D AB N A  D AB (c A1  c A 2 )
( z 2  z1 ) In(r2 / r1 )
r1: inner radius r2: outer radius

(diffusion radially through a cylinder wall39of

inner radius r1 and outer r2 and length L,)
Diffusion in Solids which Follow Fick’s Law and
Does Not Depend on The Structure of Solids2/4
 Sometimes flux can be expressed in term of solubility (S)
S= m3 (STP) /m3 solid. atm SI units
S= cm3 (STP) /cm3 solid. atm cgs units

 Relation between solubility and concentration

SI unit cgs unit

Sp A kgmol A Sp A gmol A
cA  cA 
22.414 m 3 solid 22414 cm 3 solid
Equation for flux: (SI unit), (PA in atm)

D AB S ( p A1  p A 2 )
NA 
22.414( z 2  z1 ) 40
Diffusion in Solids which Follow Fick’s Law and
Does Not Depend on The Structure of Solids3/4
 Many data in literature do not determine NA in term of the value of DAB and S ,
but more often in term of permeability, PM
 Then the flux is expressed as:

PM ( p A1  p A 2 )
NA 
22.414( z 2  z1 )

 Several unit for PM in literature

PM = DABS PM=m3(STP)/(s.m2.atm/m) SI unit

PM=10-4 P’M P’M= cm3(STP)/(s.cm2.atm/cm) cgs unit
PM=7.60 x 10-4 P’’M P”M= cm3(STP)/(s.cm2.cmHg/mm)
41
Diffusion in Solids which Follow Fick’s Law and
Does Not Depend on The Structure of Solids4/4
 When several layer solid 1,2,3…..in series and L1,L2,L3…represent
thickness, flux for diffusion in solid is:

( p A1  p A 2 ) 1
NA 
22.414  L1 L2 L3 
    ... 
 PM 1 PM 2 PM 3 

42
EXAMPLE 6.5-1. Diffusion of H2 Through
Neoprene Membrane
The gas hydrogen at 17°C and 0.010 atm partial pressure is diffusing through a
membrane of vulcanized neoprene rubber 0.5 mm thick. The pressure of H 2 on the
other side of the neoprene is zero. Calculate the steady-state flux, assuming that the
only resistance to diffusion is in the membrane. The solubility S of H 2 gas in
neoprene at 17°C is 0.051 m3 (at STP of 0°C and 1 atm)/m3 solid · atm and the
diffusivity DAB is 1.03 x 10-10 m2/s at 17°C.
Solution: A sketch showing the concentration is shown in Fig. 6.5-1. The
equilibrium concentration cA1 at the inside surface of the rubber is, from Eq. (6.5-5),

Figure 6.5-1. Concentrations for Example 6.5-1.

Since pA2 at the other side is 0, cA2 = 0. Substituting into Eq. (6.5-2) and solving,

43
 EXAMPLE 6.5-2. Diffusion Through a
Packaging Film Using Permeability
A polyethylene film 0.00015 m (0.15 mm) thick is being considered for
use in packaging a pharmaceutical product at 30°C. If the partial pressure
of O2 outside the package is 0.21 atm and inside it is 0.01 atm, calculate
the diffusion flux of O2 at steady state. Use permeability data from Table
6.5-1. Assume that the resistances to diffusion outside the film and inside
are negligible compared to the resistance of the film.
Solution: From Table 6.5-1, PM=4.17(10-12) m3 solute(STP)/(s·m2· atm/m).
Substituting into Eq. (6.5-8),

Note that a film made of nylon has a much smaller value of permeability
PM for O2 and would make a more suitable barrier. 44
Table 6.5-1

45
Diffusion in Porous Solids that Depend on the
Structure
 Concerned about the porous solid that have pores or interconnected void in
solid which will affect the diffusion

Diffusion in Porous Solids

Diffusion of Liquid Diffusion of Gases

D AB (c A1  c A 2 ) D AB (c A1  c A 2 ) D AB ( p A1  p A 2 )
NA  NA  
(z 2  z1 )  ( z 2  z1 ) RT ( z 2  z1 )

ε –void fraction;; DA,eff=(ε DAB/ τ)=effective diffusivity

τ –tortuosity (a factor which corrects for the path longer than (z 2 - z1) )
46