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Instructor

Dr. Ahmed A. Abdala


 Office: Bu Hasa, Room. 2-214
Phone: 607-5584
e-mail: aabdala@pi.ac.ae
 Office Hours:
 Posted hours + Open Door Policy
Class Schedule
 Sunday/Tuesday/Thursday 13:00-14:00
 Bu Hasa, Room 2-123
Books
 Required Text:
Jaime Benitez, Principles and Modern Applications of Mass
Transfer Operations, John Wiley & Sons, Inc., New York
(2002).
 References:
 Seader, Henley, Separation Process Principles, 2nd Edition,
John Wiley & Sons, Inc., New York (2006).
 Frank P. Incropera and David P. DeWitt, Fundamentals
of Heat and Mass transfer, Separation Process Principles, 5th
Edition, John Wiley & Sons, Inc., New York (2006).
 Treybal, F. “Mass Transfer Operations,” 3rd ed., McGraw-
Hill, New York (1980).
Grading
3 One-hour exams 50 %
Final Exam 25 %
Homework and Quizzes 20 %
Class participation 5%
A ≥ 90
B 80-89
C 70-79
D 60-69
F < 60
Purpose of the Course
 Introduce the student to both, microscopic and
macroscopic approach to mass transfer.
 In the first part of the course, microscopic diffusional
processes and the prediction and use of transport
processes are discussed.
 The second part of the course primarily deals with the
design of mass transfer equipment both packed and tray
columns.
 The third part of the course deals with macroscopic
separation processes including absorption and stripping,
distillation, extraction, and membranes separation.
Course Outlines and Timeline
 Fundamentals of Mass Transfer (2 weeks)
 Diffusion of Gas in Porous Solid (1 week)
 Convective Mass Transfer (2 weeks)
 Interphase Mass Transfer (2 weeks)
 Equipment for Gas-Liquid Mass Transfer
Operations (2 weeks)
 Absorption and Stripping (2 weeks)
 Distillation (3 weeks)
 Liquid-Liquid Extraction (2 weeks)
Course Outlines and Timeline
Week (Dates) Topic Chapter
Fundamentals of Mass Transfer
1-3 Molecular Mass transfer
1
(Jan 27-Feb 14) Diffusion Coefficient
Steady State Molecular Diffusion
4 (Feb 16-Feb 21) Diffusion of Gases in Porous Solids Treybal
Exam 1 (Last week of February)
Convective Mass Transfer
Mass Transfer Coefficients
5-6 Mass and Heat Transfer Analogy
2
(Feb 24-Mar 6) Convective Mass Transfer Correlations
Multicomponent Mass Transfer
Coefficients
Interphase Mass Transfer
Equilibrium
7-8
Diffusing Between Phases 3
(Mar 9- 20
Material Balance
Equilibrium Stage Operations
9 (Mar 23- 27) Spring Break
Exam 2 (First Week of April)
Course Outlines and Timeline
Week (Dates) Topic Chapter
Equipment for Gas-Liquid Mass Transfer Operations
10-11
Liquid dispersed 4
(Mar 30-Apr 10)
Gas Dispersed
Absorption and Stripping
12-13 Countercurrent Multistage Equipment
5
(Apr 13- 24) Countercurrent Continuous-Contact Equipment
Thermal Effect during Absorption and Stripping
Exam 3 (Last week of April)
Distillation
Single Stage Operation-Flash Vaporization
Batch Distillation
14-15
Continuous Rectification 6
(Apr 27- May 8)
McCabe-Thiele Method
Binary Distillation in Packed Towers
Multicomponent Distillation
Liquid-Liquid Extraction
16 Liquid Equilibria
7
(May 11-18) Stage-Wise Liquid-Liquid Extraction
Equipment for Liquid-Liquid Extraction
Final Exam
10
Introduction to Mass Transfer
 Mass transfer refer to the movement of a
component in a mixture between regions of
different compositions
 In a system containing two or more
components (mixture) with whose
concentrations vary from point to point, there
is a natural tendency for mass to be transferred
 The direction of movement is from a region of
higher concentration to that of a lower
concentration
Mass Transfer in our Daily Life
 Scent of a delicate perfume
 Dissolution of Sugar or salt in tea
 Drying of laundry
 Evaporation of water to the atmosphere
 Diffusion of chemical impurities in lakes, ground,
etc
Mass transfer in Unit Operations:
 Unit operations based on mass transfer:
 Distillation
 Gas Absorption
 Adsorption
 Humidification and dehumidification
 Liquid extraction
 Membrane separation
Distillation
A liquid mixture of miscible
and volatile substances
separated into individual or
groups of components by
partial vaporization
 Crude petroleum
distillation into gasoline,
kerosene, fuel oil, and
lubricating stock
Gas Absorption
A soluble vapor (in a mixture of other inert
gases) absorbed by a liquid.
 Washing of ammonia from a mixture of
ammonia and air by means of liquid water
 Removal of acid gases from
natural gas using amine
Adsorption

A species (adsorbate) from a gas or a liquid


mixture is preferentially concentrated on a
solid (adsorbent) surface
 Removing objectionable odors and
impurities from industrial gases
 Removing objectionable taste and
odor from drinking water
Liquid Extraction
 Separation of the constituents of a liquid solution
by contact with another insoluble liquid
 The solution which is to be extracted is called the
Feed, and the liquid with which the feed is
contacted is called the Solvent
 The solvent-rich product of the operation is called
the Extract, and the residual liquid from which the
solute has been removed is called the Raffinate
Liquid-Liquid Extraction
Liquid-Liquid Extraction All of solvent exits
in the extract
Solvent Feed
S Extract
S, B
Liquid Feed
A, B Raffinate
A, B All of carrier exits
in the raffinate
Crystallization
 A non-volatile component is separated from
a liquid phase saturated with this
component
 Usually involves cooling
 The mixture components must have
different crystallization temperature
Humidification-dehumidification
 The liquid phase is a pure liquid containing but one component while
the gas phase contains two or more substances.
 Usually the inert or carrier gas is virtually insoluble in the liquid.
 Condensation of carbon tetrachloride out of a stream of nitrogen is
one example of humidification
 Removal of water from wet air is one example of dehumidification
 Humidification involve transfer from the liquid to the gas
 Dehumidification involves mass transfer from the gas to the liquid

 .

dehumidification
humidification
Membrane Separation
 Separation by selectively controlling the passage from one side
of the membrane to the other. The membrane serves to:
 Prevent intermingling of two miscible
phases
 Prevent ordinary hydrodynamic
flow, thus movement of substances
through it is by diffusion
 Dialysis is an example of membrane
separation
Mechanism of Mass Transfer
 Mass transfer occurs by two basic mechanisms:
 Molecular Mass Transfer
 Mass is transferred by the molecular in quiescent fluid
 Convection
 Mass is transferred from a surface of a moving fluid aided by the
dynamic characteristics of the flow
 Both mechanisms often act simultaneously
 Frequently, one mechanism can dominate
quantitatively so that approximate solutions
involving only the dominant mode can be used
Molecular Mass Transfer
Molecular Mass Transfer in Gases

 According to the kinetic theory of gases:


 Gas molecules move in space in random
motion with average velocity
 Gas molecules repeatedly undergoing
collisions with other moving gas
molecules which causes them to be
deflected into a new direction
(molecules move along a zigzag path)
Molecular Mass Transfer in Gases
 Across a hypothetical section normal to the concentration gradient,
there are more solute molecules in one side of the section than in the
other
 Accordingly, an overall net transfer from a region of higher
concentration to one of lower concentration will result
 The net flow of each molecular species occurs in the direction of a
negative concentration gradient.
Mixture Compositions

 Mass transfer always involves two or more


components (mixtures)
 Consequently, we must account for the
variation of physical properties which
normally exist in a given system
 Composition of multicomponent mixtures
can be expressed as:
 Mass concentration
 Molar concentration
Mass Concentration
 The mass concentration of component i is the mass of
component i per unit volume
m
ρi = i
Vol
 The total mass concentration or density
n
m
ρ =
=
Vol
∑ρ i
i

 The mass fraction of component i is the


mass fraction of species I divided
by the total mass
m i ρi
w= = Molecular
i
m ρ Symbol Component # moles
Weight

∑w i =1 A 11 16
B 4 30
C 6 2744
Molar Concentration
 The molar concentration of component i (ci) is
the number of moles of component i per unit
volume =c
ni
=
ρi
i
Vol M
i
molecualr weight of species i

 The total molar concentration, c


n
c = ∑ ci
i =1

 The mole fraction of liquids and solids mixtures, xi


ci
xi =
c
Molar Concentration, Ideal Gas

partial pressure of species i
 The molar concentration, ni Pi
=
ci =
Vol RT

 The total molar concentration, c


ntotal P
=c =
Vol RT
 The mole fraction of ideal gas mixtures, yi
ci ni Pi
y=
i = =
c ntotal P

 The sum of the mole fractions is 1


 The density of gas species i, ρi
mi n *M i
ρi
= = i = ci M i
V ol V ol
 The total density of a gas mixture, ρ
m total ntotal * M av
=ρ = = cM av
. V ol V ol
M av = ∑ y i M i
Mixture Composition, Example
 A flue gas consists of CO2, O2, H2O vapors, and
N2. The mole fraction of CO2 and O2 in the gas
stream is 12% and 6%, respectively. The weight
fraction of H2O in the gas is 6.17%. Calculate the
density of this gas at 500° K and 110 kPa.
 Solution Strategy:
n
=ρ c=
M av ; M av ∑M
i =1
i *yi

 Find yi to calculate Mav


 Calculate c assuming ideal gas, c=P/RT
Problem 1.4, Benitez
Solution: calculation of yi
Basis: 1 mole (ntotal=1)
=n iy=n y ; =
i ∑y 1
total i i (1 )
m i = ni M i (2 ) Species yi=ni wi Mi mi, g

CO2 0.12 - 44 5.28


=
m total ∑
= mi ∑ ni M i (3 ) O2 0.06 - 32 1.92
m H 2O
w H 2O = (4 ) H2O
N2
yH2O
yN2
0.0617 18
- 28
18 yH2O
28 yN2
m total
From equation 4:
18 y H 2O
=
m total = 291.7 y H 2O (5 )
0.0617
Solution: Calcualtion of yi, Contd.
 From 3
m total = 5.28 + 1.92 + 18 y H 2O + 28 y N 2 (6 )
Thus:
291.7 y H 1O =
7.2 + 18 y H 2O + 28 y N 2 (7 )
but
y N2 = (
1 − y H 2O + y CO 2 + y O 2 )
1 (y
=− H 2O + 0.12 + 0.06 ) (8 )

 Solving 7, 8 gives:
 yH2O= 0.1; yN2= 0.72
Solution: Calculation of Mav, c and ρ
g
 M av = ∑M i y i = 0.12 x0.44 + 0.06 x 32 + 0.1 x18 + 0.72 x 28 = 29.16 1
mol

110 x10 3
 =c =
P
= 26.5
mol
RT 8.314 x 500 m3

mol g g
=ρ c= x 29.16 = 0.772
 M av 0.0265
liter mol liter
Average Velocities: Mass Average
 In a multi-component system species normally have different velocities
 Evaluation of a characteristic velocity for the gas mixture requires the
averaging of the velocities of each species present
 Let vi denotes the absolute velocity of species i relative to stationary
coordinate axis
 The mass-average velocity for a multi-component mixture is defined in
terms of the mass densities n n

∑ ρ iv i ∑ ρ iv i n
=
=
vω v =
i 1=
n
=
i 1
ρ
∑ i i

∑ i ρ
i =1
i =1

 The molar-average velocity for a multi-component mixture is defined in


terms of the molar concentrations of all components by:
n n

∑c v
i i ∑c vi i n
==
Vi 1=
n
= i 1
= ∑x v i i

∑ci
c i =1

i =1

 Note that (upper-case) V is used for the molar average velocity,


whereas (lower-case) v is used for the mass average velocity
Flux
 Flux of a given species is a vector quantity represents the
amount of such species that passes per given unit time
through a unit area normal to that vector
 Mass flux of component i, ni ni = ρiv i

 Molar flux of component i, Ni N i = civ i

 Total mass flux, n n


=n ∑
=
1
n i ρv

n
 Total molar flux, N =N ∑
= N i cV
1
Diffusion versus Bulk Flow Flux
 The flux (molar or mass) is the sum of two
vectors quantities:
 Diffusion flux (concentration gradient)
 Mass diffusion flux, ji = j i ρi ( v i − v )
 Molar diffusion flux, Ji =
J i c i ( v i −V )
 The total mass or molar diffusion flux is zero
 Bulk flow flux (bulk motion)
 Mass ρiv = w i n
 Molar c iV = y i N
Mass and Molar Flux Units
 Mass flux
m  L  m
 Dimensions n ρ=
= v  3 =
 t 
x
L    L t
2

 Si Units kg m-2 s-1

 Molar flux
Dimensions  mol   L  mol
 = =  3
N cV  x  t=
 L    L t
2

 Si Units kmol m-2 s-1


Fick’s Law of Diffusion
 Equation describes the rate of mass diffusion
 For binary, isothermal, isobaric system:
J1 = −c D12 ∇x i

diffusivity

mole fraction of species i

J1 = − c D12 ∇
 xi
total concentartion
molar diffusion flux operator del

∂ ∂ ∂
Remember ∇
= + +
∂x ∂y ∂z

 D12 is the diffusivity or diffusion coefficient

Adolf Fick (1829-1901)


Diffusion Coefficient
 Dimensions
=
D12 =
−J 1 ( mol L −2
t −1 ) =
L2
 Units: c ∇x i ( mol L −3 )( ) L −1 t
 Common unit is cm2/s
 SI unit is m2/s
 Diffusion coefficient depends on pressure,
temperature, and composition of the system
 Typical value
 0.5x10-5-1.0x10-5 m2/s for Gases
 10-10-10-9 for liquids
Lennard-Jones (6-12) Potential
 The L-J potential describes the repulsion and
attraction forces between molecules
 σ 12  σ 6 
φ ( r ) ε   −   
=
 r   r  

 σ is the center to center distance


between molecules at zero potential

Interaction Energy
σ
energy
 ε is the minimum energy

ε
σ
D12 for Binary Ideal Gas Mixture
1. Based on the kinetic theory of gases, diffusion in binary
gas mixture can be described using Lennard-Jones
potentials 0.00266 T
3
2

D12 =
σ AB ΩD
1
2
P M AB
2

2. Wilke-Lee Equation
D12

=
( AB )(
 )
3.03 − 0.98 / M 12  10 −3 T 3 2
1
P M AB2
σ AB
2
ΩD
T ≡Temperatur e , °K
P ≡ Pressure ,bar
σ AB ≡ Collision diameter
M AB ≡ " Average" molecular weight
Ω D ≡ Diffusion Collision Int egral
D12 for Binary Ideal Gas Mixture
−1 D12 =
0.00266 T
3
2

D12 =
 ( AB )(
 )
3.03 − 0.98 / M 12  10 −3 T 3 2

 1 1  P M AB σ AB ΩD
1 1
2
2 P M AB σ AB
2 2
ΩD
= +
M AB 2  
M A M B  a 1.06036
b 0.15610
σA + σB
σ AB = c 0.19300
2
d 0.47635
a c e g
ΩD = + + + Diffusion Collision Int egral e 1.03587
(T ) *
b
exp dT * ( ) (
exp fT * ) (
exp hT * ) f 1.52996
T*
kT
= ; ε AB ε AεB g 1.76474
ε AB
h 3.89411
Experimental values of ε A and σ A can be obtaine from appendix B , page 439

It can also be estimated as follow :

εA
= 1.15 Tb ; Tb ≡ Normal boiling point
k
1

σ = 1.18V b ; 3
V b ≡ molar volume of species as liq uid at Tb
1

σ = 1.18V b ; 3
V b ≡ molar volume of species as liq uid at Tb
Estimation of Molar Volume
 Vb can be obtained from table 1.2, page18
 It can also be estimated based on the atomic volume
contributions of the elements forming the component
(table 1.3, page 18)
 It can also be estimated from critical volume:
V A = 0.285 V c1.048
Examples: Estimation of Vb
 Ethanol (C2H6O):

=
V b 2* 14.8 + 6 * 3.7 + 7.4
= 59.2 cm 3 / mol

 phenol : OH

=
V b 6 * 14.8 + 6 * 3.7 + 7.4 −=
15 103.4 cm 3 / mol
Estimation of Diffusion Coefficient for
Gas system
 Larson (1964) measured the diffusivity of
chloroform in air at 298°K and 1 atm and
reported its value as 0.093 cm2/s. Estimate
the diffusion coefficient by the Wilke-Lee
equation and compare it to that calculated
using the kinetic theory and to the
experimental value.

Problem 1.12, Benitez


Solution
( )( )
3.03 − 0.98 / M 12  10 −3 T 3 2
 Using Wilke-Lee 
=

AB
D12 1
P M AB2
σ AB
2
ΩD
a 1.06036
 Let A ≡Chloroform; B ≡Air b 0.15610
 From Appendix B, c 0.19300
d 0.47635
 σA= 5.389 ; σB=3.620 Å e 1.03587
 (ε /k)A=340.2; (ε/k)B =97.0 °K f 1.52996
g 1.76474
σA + σB 5.389 + 3.620 h 3.89411
σ AB
= = = 4.5045 Å
2 2

ε AB
= ε AεB
= 340.2 *=
97.0 181.66 °K
−1 −1
 1 1   1 1 
M AB = 2 +  = 2 +  = 46.9 g / mol
M A M B   119.4 29 
a c e g
ΩD = + + + kT T 298
(T )
*
b
(
exp dT *
) (
exp fT *
) (
exp hT *
) =
T* =
ε AB ( ε AB
= = 1.64
/ k ) 181.66
Solution cont’d
1.06036 0.193 1.03587 1.76474
ΩD = + + + =
1.157
0.15610
1.64 exp (0.47635 * 1.64 ) exp ( 1.52996 * 1.64 ) exp ( 3.89411* 1.64 )

D12

=
( AB
 )(
3.03 − 0.98 / M 12  10 −3 T 3 2 
 =
) (
3.03 − 0.98 / 46.9 1 / 2  x10 −3 x 298 3 / 2)
0.0928 cm 2 / s
1 1/ 2 2
PM σ Ω2 2
AB AB D
1 x46.9 x4.5045 x1.157

Using K TG based model:

3
0.00266 T 2 0.00266 x 298 3 / 2
=D12 = 1 1/ 2
= 2
0.100 cm 2 / s
P M AB
2
σ AB Ω D 1 x46.9 x4.5045 x1.157
2

D12 ,calculated − D12 , measured 0.0928 − 0.093


% Error (wilkee − lee / Experimental ) = x100 = x100 = −0.2%
D12 , measured 0.093

D12 , K TG − D12 , measured 0.100 − 0.093


=
% Error ( K TG / Experimetal ) = x100 = x100 8.3%
D12 , K TG 0.093

D12 ,W ilkee − Lee − D12 , K TG 0.0928 − 0.100


% Error (W ilkee − Lee / K TG ) = x100 = x100 = −7.8%
D12 , K TG 0.100
Diffusion in Liquids

Diffusion in Liquids
Diffusion Coefficient for liquids
 For Binary dilute liquid systems Stokes-Einstein
Equation can be used as the theoretical basis for
other correlation: D = 6 π r kT
0
AB
µ

A B
radius of solute viscosity of solvent

 This relation is valid for colloidal particles or large


round molecules through a solvent which behave
as a continuum relative to the diffusing species
 Semiempirical correlation has the general form:
0
D AB µB
= f (V A )
kT
Wilke and Chang Equation
 Widely used correlation for non-electrolytes in
an infinite dilute solution
D µB 7.4 x10 (Φ B M B )
1
0 −8 2

=
AB
T V A0.6
0
D AB = diffusivity of A invery dilute solution in solvent B ,cm 2 / s
M B = Molecular weight of solvent B
T =temperature , °K
µB = viscosity of solvent B ,cP
V A = solute molar volume at its normal boiling point ,cm 3 / mol
= 75.6 cm 3 / mol for water as solute
Φ B = association factor of solvent B , dimensionless
= 2.26 for water as solvent
= 1.9 for metahnol as solvent
= 1.5 for ethanol as solvent
= 1.0 for unassociated solvents, e.g. benzene, et her, heptane
Hayduk and Minhas Equation-Aqueous
 For aqueous solution
= 0
D AB (
1.25 x10 −8 V A−0.19 − 0.292 T 1.52 µBε )
9.58
ε
= − 1.12
VA

 For Non-aqueous (nonelectrolyte) solution


V B0.27 T 1.29 σ B0.125
−8
D 0
= 1.55 x10
V A0.42 µB0.92 σ A0.105
AB

σ = Surface tension at normal boiling point , dyne / cm 2


( ) (1 − T )
2 1 11

=σ Pc 3 Tc 3 0.132 αc − 0.278 br
9

Tb  T ln ( Pc / 1.013 ) 
=Tbr ; =αc 0.9076 1 + br 
Tc  1 − Tbr 
Pc = critical pressure , bar
Tc = critical temper ature , °K
Hayduk and Minhas Equation-Restrictions

1. The method should not be used in viscous solvent,


i.e. µB has to be less than 20 cP
2. For water as solute, the dimer volume should be
used, i.e. VA=37.4 cm3/mol
3. For organic acids in solvents other than water,
methanol, or butanol, the dimer volume should be
used i.e. VA=2VA(actual)
4. For nonpolar solutes diffusing into monohydroxy
alcohols, VB should be multiplied by a factor of
8µB
Example: Liquid Diffusivity
 Calculate the diffusivity of ethanol in dilute
solution in water at 288° K. Compare your
estimate with the experimental value
reported in Appendix A. the critical volume
for ethanol is 167.1 cm3/mol and the
viscosity of water at 288° K is 1.153 cP.
Solution: Using Wilke-Chang Correlation

D µB 7.4 x10 (Φ B M B ) 2
1
0 −8

=AB
T V A0.6

A is ethanol=V =
0.285 V 0.285 =
* 167.1
A c
1.048 1.048
60.9 cm 3 / mol

B is water =Φ 2.26 ,=M =


18 , µ 1.153 cP B

7.4 x10 −8 ( 2.26 x18 ) 2


1
0
D x1.153
AB
=
288 60.9 0.6
0
D AB = 1.002 x10 −5 cm 2 / s

(D )
0
AB measured
= 1.00 x10 −5 cm 2 / s ( App em dix A )

1.002 x10 −5 − 1.00 x10 −5


% Error = x 100 0.2%
1.00 x10 −5
Solution: Using Hayduk and Minhas
Correlation
A is ethanol
= V =
0.285 V A c
1.048
0.285 =
* 167.1 1.048 60.9 cm 3 / mol

B is water µ = 1.153 cP

Using the correlation for aqueous solution


= 0
D AB ( )
1.25 x10 −8 V A−0.19 − 0.292 T 1.52 µBε

9.58 9.58
ε = − 1.12 = − 1.12 = −0.963
VA 60.9
0
D AB ( )
1.25 x10 −8 60.9 −0.19 − 0.292 288 1.52 x1.153 −0.946
= 0.991 x10 −6 cm 2 / s

0.991 x10 −5 − 1.00 x10 −5


% Error = x 100 = −0.9%
1.00 x10 −5
Diffusion Coefficient for Multicomponent Mixtures

 Multicomponent systems can be handled by using an


effective diffusivity or pseudobinary approach

Ji =
−c D i ,eff ∇x i

D i ,eff is characteristic diffusion coefficient of component i in the mixture


n
N i − yi ∑N j
j =1
D i ,eff =
(y jN i − yiN )
n
1

j =1 D
j
ij
j ≠i
Example
 Ammonia is being cracked on a solid
catalyst according to the reaction Ammonia

NH 3 
→ N2 + H2
Nitrogen
1 3
2 2 Hydrogen

at one place on the apparatus where the


pressure is 1 bar and the temperature
is 300° K, the analysis of the gas is 40%
NH3, 20% N2 and 40% H2 by volume.
Estimate the diffusion coefficient of
ammonia in the gaseous mixture.
Example
 Rewrite the equation as
Ammonia (A)

A 
→ 12 B + 32 C Nitrogen (B)
n
N A − y A ∑N j Hydrogen (C)
j =1
D A ,eff =
∑ D (y N A − y AN j )
n
1
j
j =1 Aj
j ≠i

N A − y A (N A + N B + N C )
D A ,eff =
1 1
(y BN A − y AN B )+ (yC N A − y AN C )
D AB D AC
= =
y A 0.4; =
y B 0.2; y C 0.4

from the stoichiometric equation :


NB =
− 12 N A ; N C =
− 32 N A
Solution continued
σ, Å ε/k, °K M, g/mol
 DAB and DAC can be
calculated as discussed NH3 2.900 558.4 17

for binary gas mixture N2 3.798 71.4 28


using Wilke-Lee
H2 2.827 59.7 2
equation and the
following parameters

D12 = 
( )(
AB 

)
3.03 − 0.98 / M 12  10 −3 T 3 2
W ilke − Lee Equat ion
σ AB ΩD
1
2
P M AB
2

 DAB=0.237 cm2/s
 DAC=0.728 cm2/s
Solution Continued
N A +N B +NC =
N A − 12 N A − 32 N A =
−N A

N A − 0.4 ( −N A )
D A ,eff =
1
0.237
( 0.2N A − 0.4(− 12 N A ) +
1
0.728
( 0.4N A − 0.4 ( − 23 N A ) )

N A (1.4 )
=
 0.2 + 0.2   0.4 + 0.6 
NA   + N A  
 0.237   0.728 
1.4
=
0.4 1
+
0.237 0.728
= 0.457 cm 2 / s
Diffusion in Stagnant Gas Mixture
 For stagnant gas mixture, the flux of all
component except component A are zeros
 The effective diffusivity equation reduces to
N A − y AN A 1− y A
= =
D A ,eff
( ) (y j )
n n
1 1
=

j 1=D
y j N A ∑
j 1 D
Aj Aj
j ≠i j ≠i

1
=
( y 'j )
n
1

j =1 D Aj
j ≠i

yj
where y 'j =
1− y A
Diffusion of Dilute Solute through
Homogenous Solution of Mixed Solvents
n
D 0
1 ,eff µ 0.8
M = ∑ x j D10, j µ 0.8
j
( Perkins and Geankoplis )
j =2

D10 ,eff = effective diffusivity of a dilute solute A int o themixture ,cm 2 / s


µM = mixture viscosity, cP
µ j = viscosity of pure component j ,cP
D1j0 = Diffusivity of infinte dilution of component A into solvent j ,cm 2 / s
Steady State Molecular Diffusion in
Fluids
∂C i
 Continuity Equation ∇•Ni +
 ∂
− R
i =0
divergence  t chemical reaction
 If
accumulation

 no accumulation, i.e. ∂C i = 0
∂t
 no chemical reaction, i.e. RA=0
 Then the continuity equation reduces to:
∂N i ,x ∂N i ,y ∂N i ,z
∇=
•Ni + + = 0
∂x ∂y ∂z
 For diffusion only in z direction
∂N i ,z
=0 ⇒ N i =N i ,z =constant
∂z
n

.
∑N
i =1
i = constant
Steady State Diffusion in Gases
 For steady-state diffusion in z direction without
chemical reaction in a binary mixture
N=
A J A + y AN


dy A
NA =
−cD AB + y A (N A + N B )
dz
−dy A dz
=
 Separating the variables: N A − y A ( N A + N B ) cD AB

 At constant temperature and pressure, c and DAB


and NA, NA+NB=const
−dy A
y A2 z2
dz

y A1
N A − y A (N A + N B )
= ∫ cD AB
z1
Steady State Diffusion in Gases
−dy A
y A2 z 2
dz
∫ N A − y A ( N A + N B ) z∫ cD AB
y A1
=
1


1  N A − y A2 (N A + N B )  z 2 − z 1 z
ln  =  =
NA + NB  N A − y A1 ( N A + N B )  cD AB cD AB
NA
 Rearrange and let = ψ A we get
NA + NB

cD AB Ψ − y A 2 
NA =ψA ln  A 
z Ψ A − y A1 

 For ideal gas mixture, c =P/RT


D AB p Ψ A − y A 2 
NA =ψA ln  
RTz Ψ A − y A1 
Example:
Nickel Carbonyl (A) is produced by passing carbon
monoxide (B) at 323° K and 1 atm over nickel slab. The
following reaction takes place at the surface solid surface:
Ni ( s ) + 4CO ( g ) 
→ Ni ( CO )4 ( g )

The reaction is very rapid, so that the partial pressure of


Co at the metal surface is essentially zero. The gases diffuse
through a film of 0.625-mm thick. At steady-state, estimate
the rate of production of nickel carbonyl, in moles/m2.s.
The compsoition of the bulk gas phase is 50 mole% CO.
The binary gas diffusivity under these conditions is DAB =20
m2/s.
Graphical Representation of the
Problem

Bulk Gas Phase


50% CO, 50% Ni(CO)4
2

z=0.625 mm
Ni(CO)4
CO
NB

NA

Ni
Ni
Solution

 From the reaction stoichiometry


N B = -4N A ; N=N A +N B = -3N A
NA 1
ΨA = =−
N A +N B 3

 For binary gas at steady state conditions

D AB p Ψ A − y A 2 
NA =ψA ln  
RTz Ψ A − y A1 
Solution, contd.

 yB1=0
y A1 = 1 − y B1 = 1 − 0 = 1
y A2 = 0.5

 Substituting numerical values

 m2  1.0135 x10 5 Pa 
 20 mm / s x   1 atm x   − 1 − 0.5 
2

1  10 6 mm 2  atm   3 
NA = − ln  
3  2
x Pa     − 1 −1 
( )
3
 8.314 m m
323 K  0.623 mm x 3   3 
 mol K   10 mm 
 
= 0.189 mol / m 2 .s
Steady State Diffusion through Stagnant
Gas
 For diffusion of gas A through stagnant Gas B
 NB=0; ΨA=1
 Flux equation for binary ideal gas mixture at SS condition becomes

D AB p  1 − y A2 
NA = ln  
RTz  1 − y A1 

 It also can be written in terms of linear driving forces:

NA =
D AB p
RTp B ,M z
(
p A2 − p A1 ) z

Mole fraction, y
where p B ,M is the logerithmic mean partial pressur e of B ; yB

p B 2 − p B1
PB ,M =
 p B2 
.

yA
ln  
 PB
 1 
Distance, z
Steady State Equimolar Counter Diffusion

 For equimolar counter diffusion


 NB=-NA; ∑Ni=0
dy
−cD AB A + y A ( N A + N B )
NA =
dz

dy A
∴NA =
−cD AB
dz
z2 y A2

N A ∫ dz = −cD AB ∫ dy A
z
z1 y A1

=
N A
D AB P
RTz
( )
y A1 − y =
A2
D AB
RTz
(
p A1 − p A2 )
Steady State Diffusion in Liquids
 Unlike the case of gas mixtures, the
concentration and the binary diffusion
coefficient may vary considerably
 Nevertheless, we can estimate the molar flux
using an average concentration and best average
diffusion coefficient available
 We have:
D c Ψ − x 
0

N A =Ψ A
A A
AB
ln  2

z Ψ
 A − x 
A1 


0
D AB  ρ  Ψ A − x A2 
=Ψ A  
z  M av Ψ A − x A1
NA ln

Steady-State Diffusion in Liquids
 Diffusion of A through Stagnant B:
 NB=0, ΨA=1 then
 ρ 
0

( )
0
D AB  ρ  Ψ A − x A2  D AB
N A =Ψ A  =  ⇒ NA   x A1 − x A2
z  M av Ψ A − x A1 
ln
x BM z  M av
where x BM is the logarithmic mean mole fraction of B

x BM =
(x B2 − x B1 )
ln ( x B2 / x B1 )

 Equimolar Counterdiffusion
 NB=-NA, N=0 then
 ρ 
0

( )
D AB
=NA   x A1 − x A2
z  M av
Example:
A crystal of Chalcanthite (CuSO4•5H2O) dissolves in a large
tank of pure water at 273° K. Estimate the rate at which the
crystal dissolves by calculating the flux of CuSO4 from the
crystal surface to the bulk solution. Assume that the
molecular diffusion occurs through liquid film uniformly 0.01
mm thick surrounding the crystal. At the inner side of the film,
adjacent to the crystal surface, the solution is saturated with
CuSO4, while at the outer side of the film the solution is
virtually pure water, the solubility of chalcanthite in water at
273° K is 24.3 g of crystal/100 g of water and the density of
the corresponding saturated solution is 1140 kg/m3.
The diffusivity of CuSO4 in dilute aqueous solution
at 273 K can be estimated as 3.6x10-10 m2/s.
The density of pure liquid water at 273° K is
999.8 kg/m3.
CuSO 4 5 H 2 O ( s ) 
→CuSO 4 ( aq ) + 5 H 2 O ( liq )
CuSO 4 5 H 2 O ( s ) 
→ A( aq ) + 5 B( liq )

0
D AB  ρ  Ψ A − x A2 
N A =Ψ A   ln  
z  M av Ψ A − x A1 

Pure Water
D 0
AB =
z =
xA2 xB2

z=0.01 mm
ΨA =

CuSO4

H2O
NA
X A1 = Boundary Layer

NB
xA1 xB1
X A2 =
Crystal
 ρ 
M  =
 1

 ρ 
M  =
 2

 ρ 
M  =
 av

NA =
Graphical Representation of the
Problem
CuSO 4 5 H 2 O ( s ) 
→CuSO 4 ( aq ) + 5 H 2 O ( liq )
CuSO 4 5 H 2 O ( s ) 
→ A( aq ) + 5 B( liq )

Pure Water

xA2 xB2
z=0.01 mm
CuSO4

H2O
NA

Boundary Layer
NB

xA1 xB1

Crystal
Solution
 From the reaction equation
N B =5N A ; N=N A +N B =6N A
NA 1
Ψ A= = = 0.167
N A +N B 6

 Now we need to find the mole fractions at the


inner side of the film
 At the inner side of the film, the solution is
saturated (24.3 g CuSO4•5H2O /100 g water)
Solution, cont’d
 100 g of H2O as a basis
 Mass of CuSO4•5H2O= 24.3 g

M CuSO 4 159.63
=
Mass of CuSO 4 =24.3x =
24.3 x 15.53 g
(M CuSO 4 +5 M H 2O ) 159.63 + 5 * 18

5M H 2O 5 * 18
=
Mass of Hydration water=24.3x =
24.3 x 8.77 g
(M CuSO 4 +5 M H 2O ) 159.63 + 5 * 18
Total Mass of water =100 + 8.77 =118.77 g
=
Number of moles =
of CuSO 4 15.53 / 159.63 0.973 mol
=
Number of moles =
of H 2 O 118.77 / 18 6.043 mol
0.973
x A1 = = 0.0158
0.973 + 6.043
Solution, Cont’d
 Since the other end of the film is virtually pure
water, xB2=1, xA2=0
 The molar density of the film ( ρ/M) changes from
point 1 to point 2
 At the inner side of the film (near the crystal)
 Mav=159.63*0.0158+18*(1-0.0158)= 20.24
 ρ/M =1140/20.2=56.32 kmol/m3
 At the other end of the film (pure water)
 ρ/M =999.8/18=55.54 kmol/m3
 ( ρ/M )av=(56.32+55.54)/2=55.93 kmol/m3
Solution, Cont’d
 For SS binary liquid diffusion
0
D AB  ρ  Ψ A − x A2 
N A =Ψ A   ln  
z  M av Ψ A − x A1 

 Substitute numerical values:

( 3.6 x10 −10


m2 / s )
N A = 0.167
 m
( 55.93 kmol / m ) ln 0.167
3 0.167 − 0 
− 0.0158 
 0.01 mm x 3 
 10 mm 
= 3.342 kmol / m 2 ⋅ s

 3600 s 
=
Rate of dissolution of the crystal ( 3.342 kmol / m 2
)
⋅ s x ( 249.71 kg / kmol ) 
 h 

= 30 kg / m 2 ⋅ h
Analogies Among Molecular
Momentum and Mass Transfer
z
 Momentum equation

v elocity

shear stress
d u
τ = −  μ u
v iscosity
dz

momentum per unit volume

μ d (ρu ) d ( )

τ =
−   −ν
=
ρ
 dz dz
K inematic viscosity or

Shear stress is a viscous momentum flux


Momentum diffusivity

 Kinematic viscosity has same units as diffusion coefficient
 uρ is the volumetric momentum concentration
 This equation is analogous to Fick’s law
 Schmidt number is defined as the dimensionless ratio of
momentum and mass diffusivities (µ / ρ )
Sc =
D AB
Analogies Among Molecular Heat and
Mass Transfer
 Fourier’s Lawrate of heat Transfer T
 
t hermal conducitivity
dT
q = − k
dz

K inematic viscosity or
   
Momentum diffusivity thermal energy per unit volum

q =

 k  d ρ Tc p ( ) =

d Tc ρ
t hermal diffusivity

α
p ( )
 
 cρp  dz dz
z
 α has same units as mass and momentum diffusivity
 This equation is analogous to corresponding equations for momentum
and mass transfer
 Prandtl umber is defined as the dimensionless ratio of momentum and
mass diffusivities ν C µ
Pr= = P

α k
 Lewis number is defined as the dimensionless ratio of thermal and mass
diffusivities α S
=
Le = c

D AB Pr
Maxwell-Stefan Relations
 Momentum balance for binary ideal gas mixture:
∇p 1 =−f 12 y 1 y 2 (v 1 − v 2 )
∇p 1 y 1 y 2 (v 1 − v 2 )
=
d1 =
− Maxwell − Stefan Equation
P D12

P
=D12 Maxwell − Stefan diffusivity
f 12
Convective Mass Transfer
 In chapter 1, we discussed the transport of species via
molecular motion (diffusion/microscopic scale)
 The Diffusion flux, Ji=-Dijc ∇xi
 In addition to transport by molecular motion, mass may
also transported by the bulk motion of fluid
(convective/macroscopic scale)
 The convective flux = ci V
 Convective mass transfer involves
 Transport of species between boundary surface and a moving fluid
 Transport of species between two relatively immiscible moving
fluids
 This mode of transfer depends both on the transport
properties and on the dynamic characteristics of the
flowing fluid

2
Convective Mass Transfer
 When a fluid flows past a solid surface under turbulent flow
conditions:
 A laminar condition exists at a region close to the surface
 Stagnant layer of the fluid exists near the solid boundary
 Molecular diffusion is responsible for mass transfer through
the stagnant and laminar flowing fluid layers
 The controlling resistance to convective mass transfer is
often the result of this "film" of fluid.
 However, under most convective conditions, this film is
extremely thin and its thickness is virtually impossible to
measure or predict theoretically.
 Mass transfer rates cannot be calculated
based on the concepts of molecular diffusion turbulent
Fluid

laminar 3
Solid Surface
Flow past solid Surface

 With increasing distance from the surface,


the character of the flow gradually changes,
becoming increasingly turbulent, until in the
outermost region of the fluid fully turbulent
conditions prevail

u turbulent
laminar
stagnant
Solid surface

4
Flow past solid Surface
 In the turbulent region:
 Particles of fluid no longer flow in the orderly manner
found in the laminar sub-layer
 Instead, relatively large portions of the fluid, called
eddies, move rapidly from one position to another with an
appreciable component of their velocity in the direction
perpendicular to the surface past which the fluid is flowing
 These eddies contribute considerably to the mass-transfer process
 Because the eddy motion is rapid, mass transfer in the turbulent region is
much more rapid than it would be under laminar flow conditions
 This situation cannot be modeled in terms of Fick's law.
Instead, it is explained in terms of a mass-transfer
coefficient, an approximate engineering idea that simplifies
the analysis of a very complex problem

5
Convective versus Molecular Mass
Transfer
 As we learned, the mechanism of molecular diffusion, at
least for gases, is fairly well known
cD AB Ψ A − (c A 2 / c ) 
NA =ψA ln  
z Ψ A − (c A1 / c ) 

 On the other hand, the mechanism of the flow process


involving the movement of the eddies in the turbulent
region is not thoroughly understood
 Therefore, the rate of mass transfer through the various
regions from the surface to the turbulent zone is usually
estimated in the same manner found useful for molecular

diffusion
.

6
Flux of Convective Mass Transfer
 For convective mass transfer the cDAB/z term of the
general flux equation that characterize molecular diffusion,
is replaced by F, a mass-transfer coefficient:
Ψ A − c A2 /c 
A =F ln
NΨ  
Ψ − c /c
A
 A A1 
 Since the surface through which the transfer takes place
may not be plane, so that the diffusion path in the fluid may
be of variable cross section, NA is defined as the flux at the
phase interface or boundary where substance A enters or
leaves the phase for which F has been defined

7
Convective Mass transfer: Diffusion of
A through Stagnant B
 For diffusion of A through stagnant B in a binary
system: (NB=0; ΨA=1)
 1 − c A2 /c 
N A = F ln  
 1 − c /c 
For Gases:
A1

 y B 2 − y B1
y b ,M =
=NA
FG
y B ,M
(y A1 − y A2 )  yB
ln  2
 yB


 1 

NA=
FG
y B ,M
(y A1 )
− y A2 = k y (y A1 ) (
− y A2 = k G p A1 − p A2 = k c c A1 − c A2 ) ( )

 For Liquids
 1 − x A2 
N= FL ln   ⇒ N=
FL
(x − x A= kx ) (x − x A2 )
 1 − x A1 
A A A1 A1
x B ,M 2

x B 2 − x B1
x b ,M =
 xB 
ln  2 
 xB
 1 

8
Example:
 A gas absorber is used to remove benzene (C6H6) vapors
from air by scrubbing the gas mixture with a nonvolatile
oil at 300° K and 1 atm. At a certain point in the absorber,
the benzene mole fraction in the bulk of the gas phase is
0.02, while the corresponding interfacial benzene gas-
phase concentration is 0.00158. The benzene flux at that
point is measured as 0.62 g/m2/s.
a) Calculate the mass transfer coefficient in the gas phase at that
point in the equipment, expressing the driving force in terms of i)
mole fractions, ii) molar concentrations, kmol/m3.
b) If the benzene fraction in the bulk of the liquid phase is 0.125,
while the corresponding interfacial benzene liquid-phase
concentration is 0.158. Calculate the mass-transfer coefficient in
the liquid phase, expressing the driving force in terms of mole
fractions.

9
Solution part a: Gas Absorber
 T=300° K, P= 1 atm Air

 This is a diffusion of A (benzene) in stagnant B (Air) Non-Volatile Oil

 yA1=0.02; yA2=0.0156
 nA=0.62 g/m2.s
 a)  g 
0.62  2 
n
N A= A =  m ⋅ s  =7.94x10 -3 mol
MA  g  m2 ⋅s Air-Benzene
78.1  
 mol 
Oil-Benzen

=NA ky (y A1 − y A2 ) interface
Oil
 mol 
7.94x10 -3  2 
ky =
NA
=  m ⋅ s  = 1.89 mol Benzene

(y A1 − y A2 ) (0.02 − 0.0156 ) m2 ⋅s 2 1

Air + benzene
10
Solution Part b: Gas Absorption

 b)=
N A (
k c c A1 − c A2 )
pA y AP
=
cA =
RT RT

p A1 y A1 P 0.02 x1 ( atm )
=
cA 1 = = = 0.81 mol / m 3
RT RT  atm ⋅ m  3
0.0825 x10 −3   x 300 ( K )
 mol ⋅ K 
p A2 y A2 P 0.0158 x1
c=
A2 = = −3
= 0.64 mol / m 3
RT RT 0.0825 x10 x 300

 mol 
7.94x10 -3  2 
NA  m ⋅ s  46.8 x10 −3 m
kc = = =
(c A1 − c A2 )  mol 
(0.81 − 0.64 )  3 
s
m 

11
Solution Part c: Gas Absorption

 c) In the liquid side of the interface


 xA1=0.158, xA2=0.125; xB1=0.842, xB2=0.875
interface
Oil
N=
A
FL
x B ,M
(x A1 )
− x A2= k x (x A1 − x A2 )
x B1 − x B 2 0.842 − 0.875
=
x B ,M = = 0.858 Benzene
 x B1   0.842  2 1
ln  ln  
 x B   0.875 
 2 
 mol 
7.94x10 -3  2  x0.858 Air + benzene
FL =
N A x B ,M
=  m ⋅s  mol
= 0.206 2
(
xA − xA
1 2
)
(0.158 − 0.125 ) m ⋅s

 mol 
7.94x10 -3  2 
kx=
NA
=  m ⋅ s  = 0.24 mol
(x A1 − x A2 ) (0.158 − 0.125 ) m2 ⋅s

12
Convective Mass transfer: Equimolar
Counterdiffusion
 For equimolar counter diffusion (N =-N , Ψ =undefined)
A B A

 For Gases:
( ) ( ) ( ) (
N A= FG y A1 − y A2 = k y′ y A1 − y A2 = k G′ p A1 − p A2 =k c′ c A1 − c A2 )
P
= P k c′ = k 'y
FG k= '
G
RT
 For Liquids
NA =
= ( )
k x′ x A1 − x A2 =
FL x A1 − x A2 = ( )
k L′ c A1 − c A2 ( )
=
FL k=
'
Lc k x′

13
Example:
 A packed bed distillation column is used to adiabatically
separate a mixture of methanol and water at a total
pressure of 1 atm. Methanol, the more volatile of the two
components, diffuses from liquid toward the vapor phase,
while water diffuses in the opposite direction. Assuming
that the molar latent heat of vaporization of both
components are similar, this process is usually modeled as
one of the equimolar counterdiffusion . At point a in the
column, the mass transfer coefficient is estimated as
1.62x10-5 kmol/m2-s-kPa. The gas phase methanol mole
fraction at the interface is 0.707, while at the bulk gas it is
0.656. Estimate the methanol flux at that point.

14
Solution
Methanol

 Equimolar counterdiffusion
 Let A is methanol; B is water
 Gas side of the interface V L

N = F (y − y =
A G ) k ′ ( y − y =) k ′ ( p
A1 A2 y A1 A2 G A1 ) (
− p A2 =k c′ c A1 − c A2 ) Water-Methanol

 k’G= 1.62x10-5 kmol/m2-s-kPa; P=1 atm


 yA1=0.707; yA2=0.656 Water

vapor

pA = y AP 2 1
M
= =
p A1 0.707 atm ; p A2 0.656 atm W
 kmol   101.325 kPa 
( )
N A= k G′ p A1 − p A2 = 1.62 x10 −5  2  (0.707 − 0.656 )( atm ) 
 m ⋅ s ⋅ kPa   atm 

kmol
= 8.37 x10 −5 2 Liquid
m ⋅s

15
Analogy Between Heat and Mass
Transfer
 There are similarities between mass and heat transfer
governing equations when expressing the driving force in
terms of dimensionless variables
 There are more experimental data available for heat
transfer than for mass transfer
 There are also many similar dimensionless groups that
contain the heat and mass transfer coefficient
 These dimensionless groups can be used to convert
equations or correlation of data on heat transfer to
correlation on mass transfer by replacing the
corresponding groups of heat transfer with groups of mass
transfer

16
Analogy between Heat and Mass
Transfer
Mass transfer Heat transfer
 These analogies should be used Reynolds number
when the flow conditions and Re =
v ρ
µ
geometry are the same Schmidt number Prandtl number
 If the heat transfer data is based Sc =
µ
ρ D AB
Pr =
CPµ
k

on situation where no mass Sherwood number Nusselt number


h
transfer is involved, the analogy Sh =
F
cD AB
Nu =
k

would produce mass-transfer Grashoff number


g  3 ρ ∆ρ
Grashoff number
g  3 ρ 2 ∆T
coefficients corresponding to no Gr D =
µ 2 Gr H =
µ2

net mass (equimolar counter Peclet number


v
Peclet number
C P v ρ
flow) and the mass transfer = =
Pe D Re Sc = =
Pe H Re Pr
D AB k

coefficient would be k’G, k’C, k’y Stanton number


Sh Sh F
Stanton number
=
St H
Nu
= =
Nu h
=
St D = = Re Pr Pe H C P v ρ
Re Sc Pe D cv

Chilton-Colburn j- Chilton-Colburn j- 2

factor j = St Sc factor j = St pr
2
3
3
D H
D D

17
Heat transfer Mass transfer

Reynolds number Reynolds number


v ρ v ρ
Re = Re =
µ µ
Prandtl number Schmidt number
C µ µ
Pr = P Sc =
k ρ D AB
Nusselt number Sherwood number
h F
Nu = Sh =
k cD AB
Grashof number Grashof number
g  3 ρ 2 ∆T g  3 ρ ∆ρ
Gr H = Gr D =
µ 2
µ2
Peclet number Peclet number
C P v ρ v
= =
Pe H Re Pr = =
Pe D Re Sc
k D AB
Stanton number Stanton number
Nu Nu h Sh Sh F
=
St H = = =
St D = =
Re Sc Pe H C P v ρ Re Sc Pe D cv
Chilton-Colburn j-factor Chilton-Colburn j-factor
2

j D = St H pr 3
j D = St D Sc
2
3
Example: Flow Normal to Cylinder
 For flow normal to a cylinder, the average heat-transfer coefficient-
averaged around the periphery of the cylinder- is given by
Nu av = 0.43 + 0.532 Re 0.5 Pr 0.31 ; 1 ≤ Re ≤ 4000

where Nuav and Re are computed using the cylinder diameter as the
characteristic length, and the fluid properties are evaluated at the
average conditions of the stagnant fluid film surrounding the solid
(average temperature and average concentration). Estimate the rate of
sublimation of a cylinder of UF6 (M= 352), 1.0 cm diameter and 10 cm
long exposed to an air stream that flows normal to the cylinder axis at
a velocity of 1.0 m/s. The surface temperature of the solid is 303° K, at
which temperature the vapor pressure of UF6 is 27 kPa. The bulk air is
at 1 atm and 325 K.

19
Phase Diagram for UF6
UF6 is a solid below a temperature of 134°F (57°C)
and a gas at temperatures above 134°F.

20
Solution
 For heat transfer we have:
Nu av = 0.43 + 0.532 Re 0.5 Pr 0.31 ; 1 ≤ Re ≤ 4000

 Replacing Nuav with Shav and Pr with Sc we get:


Shav = 0.43 + 0.532 Re 0.5 Sc 0.31 ; 1 ≤ Re ≤ 4000

Or F  v ρ 
0.5
 µ 
0.31

=
0.43 + 0.532   + 
cD AB  µ   ρ D AB 

Air
The properties are calculate at average Solid
Air

temperature and average concentration UF6


1 2 UF6
27 + 0
T=
303 + 325
= 314 °K ( p=
av )UF = 13.5 kPa
av 6
2
2
( p av )UF13.5
( y=
A )av = 6
= 0.133 ;
P 101.3

=
M av ∑ y=
M i i 0.133 x 352 + ( 1 − 0.133 )=
x 29 71.96
i

21
Solution: average Properties
PM av 101.325 x71.96
ρav
= = = 2.8 kg / m 3
RT av 8.314 x 314

Air
Air
Solid
µav can be estimated using Lucas Corresponding states method UF6
1 2 UF6

µrM = 0.807T rM0.618 − 0.357 exp ( −0.449T rM ) + 0.340 exp ( −4.058T rM ) + 0.018
ξM µ =

 T
1
 6 ∑y Zi ci
T O2 N2 UF6
ξM 0.176  3cM=  ;TcM ∑
= y T ;P RTcM i
= ;T
∑y V
4 i ci cM rM
 M av PcM  i i ci TcM
Yi 0.182 0.685 0.133
i

Tc , K 154.6 126.2 5005.8

µav = 22.9 x10 −3 cP Pc, abr 50.4 33.9 46.6


M, g/mol 32 28 352
Vc, cm3/mol 73.4 89.9 250
Zc 0.288 0.290 0.272

22
Solution Continue: DUF6-air
( )(
P 1.013 bar
3.03 − 0.98 / M 12  10 −3 T 3 2
 AB  )
D12 =  W ilke − Lee Equat ion
σ AB ΩD
1
2
P M AB
2

T 314 K

σA +σB T* 2.07
σ AB = ;
2
a c e g
ΩD = + + + a 1.06 e 1.04
( )
T*
b
(
exp dT * ) (
exp fT * ) (
exp hT * )
b 0.156 f 1.53

ε AB = ε A ε B c 0.193 g 1.76

d 0.476 h 3.89

Specie Mi si ei/k DAB


WD
g/mol Å K cm2/s
A UF6 352.00 5.97 236.8
B Air 29.00 3.62 97

AB 53.59 4.79 151.6 1.062 0.09

23
Solution continued: Dimensionless
Numbers
  kg  
 m   kg    2.29 x10 −5  

 dv ρ  
0.01 ( m ) x1   x 2.8  3    µ    m ⋅ s   0.905
=
Re =
 s  m  = =Sc =   =
 1223 
µ  ρ D AB    kg  −4  m 
2
    kg  
2.29 x10 −5 


 m ⋅s 
 

  2.8  m 3  x0.09 x10  s  
  

Fav
=
Shav = 0.43 + 0.532 Re 0.5 Sc 0.31
cD Ab
Fav cD Ab 0.43 + 0.532 x ( 1223 ) x (0.905 ) 
0.5 0.31
=
 
P 101.3
= = 0.09 x10 −4 x18.4 x0.09 x10 −4 x18.4
RT av 8.314 x 314
kmol
= 6.52 x10 −4
m2 ⋅s

To calculate the flux of A through B (stagnant)


 
 1 −0  −4 kmol
=N A F=
av ln   2.021 x10
 1 − 27  m2 ⋅s
 101.3 

2 πd 2
The flux is based on the surface area of the cylinder; S= + π dl= 3.3 x10 −3 m 2
4

24
Solution continued: Dimensionless
Numbers
 To calculate the flux of A through stagnant B
 
 1 −0  −4 kmol
=N A F=
av ln   2.021 x10
 1 − 27  m2 ⋅s
 101.3 

The flux is based on the surface area of the


cylinder, S S=
2 πd
4
2
+ π dl= 3.3 x10 m −3 2

The sublimation rate of the solid cylinder, WA


kg
=W A N=
AS M A 2.021 x10 −4 x 3.3 x10=
−3
x 352 2.35 x10 −4
s

25
Convective Mass Transfer Correlations

 Mass transfer coefficients can be estimated based on


correlation deduced from analogy with heat transfer
 Mass transfer coefficients can also be estimated based on
correlation developed from experimental data
 These experimental data are usually obtained by blowing
gases over various wet with evaporating liquids, or causing
liquids to flow past solids which dissolve
 The situations produces average coefficients rather than
local
 For very dilute concentration, the k-type coefficients can be
obtained from F coefficient by assuming pBM/P, xBM=1

26
Mass Transfer Coefficient for Flat
Plates
 Examples
 Evaporation from a free liquid surface
 Sublimation of a flat solid surface
 The following correlation can be used:
1

ShL = 0.664 Re 0.5


L Sc 3
L Re L < 3 x10 5 ( Laminar )
1 0.6 < Sc < 2500
ShL = 0.036 Re 0.8
L Sc 3
L Re L ≥ 3 x10 5
(Tur bulent )
Air

 or
J D = 0.664 Re L−0.5 Re L < 3 x10 5 ( Laminar ) L
J D = 0.036 Re −0.2
L Re L ≥ 3 x10 5
(Turbulent )

27
Example
Liquid Benzene flows in a thin film down the outside surface
of a vertical plate, 1.5 m wide and 3 m long. The liquid
temperature is 300° K. Benzene-free nitrogen at 300° K and 1
bar flows across the width of the plate parallel to the surface
at a speed 5 m/s. Calculate the rate at which the liquid should
be supplied at the top so that the evaporation will just prevent
it from reaching the bottom of the plate. The density of liquid
benzene at 300° K is 0.88 g/cm3. The vapor pressure of
benzene at 300° K is 106 mmHg, the diffusion coefficient
Dbenzene-Nitrogen=0.0986 cm2/s and the viscosity benzene-
Nitrogen mixture is 161 µP.

28
Solution

 To prevent benzene from reaching the bottom of


the plate, the rate of benzene supply should equal
the rate of evaporation
 Rate of evaporation of Benzene (A)=NAMAS
 Since nitrogen (B) does not react with benzene
 NB=0
 This is a flow of A in stagnant B

3m
 1 − y A2 
N A = Fav ln  
 1 − y A1  N2

1.5 m

29
 yA2= 0
 Nitrogen is free from benzene
 yA1 corresponds to the vapor pressure of benzene
at 300°K (106 mmHg)
 yA1=106/760=0.139
 Average properties at the interface Wall
can be estimated benzene
 F can be estimated based on Interface

flat-plate correlations
 . Re
= =
ρvL 1.26 x 5 x1.5
L
µ 1.61 x10
= 5.87 x10
−5
5
( Turbulent )
Bulk Nitrogen
µ1.61 x10 −5
=
Sc = = 1.29
ρ D AB 1.26 x0.099 x10 −4
[0.6 < Sc < 2500 ]

30
Solution Cont’d
1

 For turbulent Flow: ShL = 0.036 Re L0.8 Sc 3


L
1

( 5.59 x10 ) (1.29 ) 1610


0.8
−5
Sh =
0.036
L
3

F
ShL =
c D AB

ShL cD AB ShL ρ D AB 1617x1.26x0.099x10 -4 kmol


=Fav = = = 4.23 x10 −4 2
L M av L 1.5 x 31.4 m ⋅s

 1 − y A2  −4  1 −0  kmol
=N A F= ln   4.25 x10 = ln   6.34 x10 −5 2
 1 − y A1   1 − 0.139  m ⋅s
av

kg
=
Total mass vaporation ,W A N=
A SM A 6.37 x10 −5 x ( 3 x1.5
= ) x78 0.022
= 1.34 kg / min
s

31
Mass Transfer Coefficient for a Single
Sphere: No natural convection
 General equation contains terms for molecular diffusion
and forced convection 1

=
Sh Sh0 + C Re m Sc 3
 For low Re, Sh approaches theoretical value of 2
1

Sh= 2 + C Re Sc m 3

 For transfer into liquid stream (Brian and Hales)


(4 + 1.21 Pe )
1
2
= Pe D < 10000
3 2
Sh D ;
1
Sh = 1.01 Pe D 3 ; Pe D > 10000

 For transfer into gases (Froessling and Evnochides and Thodos)


1
1
= 2.0 + 0.552 Re Sc
Sh 2 3
; for 2 < Re < 12000 and 0.6 < Sc < 2.7

32
Mass Transfer Coefficient for a Single
Sphere: with natural convection
 Natural convection is negligible only when
1 −1
R e ≥ 0.4Gr D 2 Sc 6

 For significant natural convection, the following


correlations are used
( )
1 0.62
=
Sh Shnc + 0.347 R e Sc 2
1 ≤ Re ≤ 30000 and 0.6 ≤ Sc ≤ 3200

Shnc = 2.0 + 0.569 (Gr D Sc )


0.25
; Gr D Sc < 10 8

Shnc = 2.0 + 0.0254 (Gr D Sc )


1
3
Sc 0.25 ; Gr D Sc > 10 8

33
Mass Transfer Coefficient for Single
Cylinders
 Sublimation from solid cylinder into air flowing
normal to its axis
 Dissolution of solid cylinders into turbulent water
(other liquids) stream
 Bedingfield and Drew Correlation
k G PSc
= 0.281 Re −0.4 400 < Re < 2500 and 0.6 < Sc < 2.6
GM

G M is the molar mass velocity of the gas


G M = vc

34
Example:

Estimate the mass transfer coefficient (F) for


sublimation of a cylinder of UF6 (M= 352), 1.0
cm diameter and 10 cm long exposed to an air
stream that flows normal to the cylinder axis
at a velocity of 1.0 m/s. The surface
temperature of the solid is 303 K, at which
temperature the vapor pressure
of UF6 is 27 kPa. The bulk air is
at 1 atm and 325 K

Air
Air
Solid
UF6
1 2 UF6

35
Solution
The properties are calculate at average temperature and average
concentration inside the stagnant film:
This image cannot currently be displayed.

303 + 325 27 + 0
T=
av = 314 °K ( p=
av )UF = 13.5 kPa
2 6
2

( p av )UF 13.5
( y=
A )av = 6
= 0.133 ;
P 101.3

0.133 x 352 + ( 1 − 0.133 )=


PM av 101.325 x71.96
=
M av ∑ y=
M i i x 29 71.96 ρav
= = = 2.8 kg / m 3
i
RT av 8.314 x 314
µrM = 0.807T rM0.618 − 0.357 exp ( −0.449T rM ) + 0.340 exp ( −4.058T rM ) + 0.018
ξM µ =

 T  6
1
∑y Zi ci
T
O2 N2 UF6
=ξ M 0.176  3cM= 4 
;TcM ∑
= y i Tci ; PcM RTcM i
= ;T
∑y V
rM
 M av PcM  i i ci TcM Yi 0.182 0.685 0.133
i

Tc, K 154.6 126.2 5005.8

µav = 22.9 x10 −3


cP Pc, abr 50.4 33.9 46.6

M, g/mol 32 28 352

Vc, cm3/mol 73.4 89.9 250

Zc 0.288 0.290 0.272

36
  kg  
 m   kg    2.29 x10 −5  

 dv ρ  
0.01 ( m ) x1   x 2.8  3    µ    m ⋅ s   0.905
=
Re =
 s  m  = =Sc =   =
 1223 
µ  ρ D AB    kg  −4  m 
2
    kg  
2.29 x10 −5 


 m ⋅s 
 

  2.8  m 3  x0.09 x10  s  
  
400 < Re < 2500 0.6 < Sc < 2.6
k G PSc
= 0.281 Re −0.4
GM
ρ  m  2.8  kmol  kmol
G M= vc
= v av= 1   x  3 
= 0.039 2
M Av  s  71.96  m  m ⋅s

G 0.039
kG P =
0.281 xRe −0.4 x M 0.281 x1223
= −0.4
x 0.56
6.75 x10 −4 kmol / m 2 ⋅ s
Sc 0.905
1 − ( 1 − 0.266 )
=F k=
y y B ,M ( k G P=
) y B .M 6.75 x10 −4 x = 5.81x10 -04 kmol / m 2 ⋅ s
 1 
ln  
 1 − 0.266 
 Compared to 6.52x10-4 kmol/m2.s using analogy between
mass and heat transfer

37
Turbulent Flow in Pipes
 Mass transfer from the inner wall of a tube to a moving
fluid (wetted wall towers)
 Gilland and Sherwood correlation
 Different fluids in air
 2000 < R e < 35000 
Sh = 0.023 Re 0.83 Sc 0.44  0.6 < Sc < 2.5 
 
 The characteristic length is the tube diameter
 The properties are evaluated at the bulk conditions
of the flowing gas stream
 Best for gases only
 Linton and Sherwood Correlation Gas

1 4000 < Re < 70000 


Sh = 0.023 Re 0.83 Sc 3
 0.6 < Sc < 3000 
 
 Best for liquids and gases

38
Mass Transfer in Packed and Fluidized
beds
 Packed and fluidized beds offer a dramatic increase
in surface area
 Used in industrial mass transfer operations
 Adsorption, ion exchange, chromatography, drying,
humidification, distillation, and catalytic reaction
 For mass transfer of a species from the solid surface
of a packed bed to a flowing gas, or vise versa, use
the Sherwood et. al. correlation:
J D = 1.17 Re −0.415 [10 < Re < 25000 ]
d pG y
Re =
. µ
d p is the diamter of the sphere with the same surface area as the particle
G y is the gas mass velocity based on total cross section area

39
Mass Transfer in Packed and Fluidized
beds
 For mass transfer in both gas and liquid and fixed
and fluidized beds of spherical particles, use Gupta
and Thodos correlation:
0.863
ε J D 0.010 +
= [1 < Re < 2100 ]
Re 0.58 − 0.483
d dP
ε =
0.406 + 0.571 P for ≤ 0.14 ε is the void fraction of t he b ed
D D
Sh F
= =
j D St D Sc
2/3
= Sc 2/3 Sc 2/3
ReSc cv
 The surface are for packed and fluidized bed are expressed
6 (1 − ε )
in terms of a a=
d P

 The pressure drop across a packed bed, use Ergun


equation below ΔP=  (1ε)(G
− )   150(1-ε)
× + 1.75

2
y
  
(SI units, Z is the bed height )
Z  ε 3 dρP Re 
 

40
Mass Transfer in Hollow-Fiber
Membrane Modules
 Hollow-fiber membrane modules are the mass
transfer equivalent to tube and shell heat
exchangers
 One fluid flows through the lumen (inside the fiber
bundle) the other flows through the shell. Mass is
transferred from one stream to the other across
the fiber wall
 Mass transfer may involve both diffusion and
convection, depending on the
membrane type

41
Mass Transfer in Hollow-Fiber
Membrane Modules

Fiber bundle

42
Mass Transfer Coefficient for Hollow
Fiber Membrane
 Bao et. al. Correlation (Liquid through Shell Side)
−0.47
1 − φ   1 −φ  
Sh 0.53 ( 1 − 1.10 φ ) 
=  Re 0.53 Sc 0.33 [ 30 < 100 φ < 75 ] and  20 < Re   < 350 
 φ    φ  
2 Rk L
Sh = ; R ≡ Fiber Radius ; φ ≡ Fiber packing fraction
D AB
2 Rv 0 ρ
=Re ; v 0 ≡ superficial velocity based on empty shell
µ
 Flow through lumen corresponds to laminar flow inside a circular pipe
 Constant wall concentration
1
d  3
( Pe D )  i  1.62 (G z ) [ R e < 2100 ]
1 1
= =
Sh 1.62 3 3

L 

di kL d iv ρ
=Sh = ; Re ; v ≡ average fluid velocity
D AB µ
d 
G z ≡ Graetz number =
Pe D  i 
L 
 Constant wall flux concentration

43
Packed-Bed: Mass transfer from solid
surface to the gas stream
 Wilke and Hougan reported the mass transfer in beds of granular
solids. Air was blown through a bed of porous celite pellets wetted
with water, and by evaporating this water under adiabatic conditions,
they reported gas-film coefficients for packed beds. In one run, the
following data were reported:
 Effective particle diameter 5.71 mm
 Gas stream velocity 0.816 kg/m2-s
 Temperature at the surface 311 K
 Pressure 97.7 kPa
 kG = 4.415x10-3 kmol/m2-s-atm
With the assumption that the properties of the gas mixture are the
same as those of air, calculate the gas film mass transfer coefficient and
compare the result with the value reported by Wilke and Hougan.
Assume the film viscosity, µ =1.91x10-5 kg/m.s.

44
Solution
This image cannot currently be displayed.

 For packed bed and mass transfer particle

from solid surface to the gas water

j D = 1.17 R e −0.415 [10 < Re < 2500 ]


d pG y
Re =
µ
d p is the diamter of the sphere with the same surface area as the particle
Air
G y is the gas velocity based on total cross section area
d pG y
=
Re = 244
µ
= =
j D 1.17 Re −0.415 0.120
2 Sh jD
j D = St D Sc 3 =
St D = 2
Re Sc Sc 3
 µ 
Sc =   ( Dwater − Air )311 K = 2.52 x10 −5 m 2 / s
 ρ D AB 

Air 45
Solution Continued
P 97.7 x10 3
ρair cM
= = air M = 28.8 = 28.8 (0.0378
= ) 1.09 kg / m 3
RT 8.314 x 311

 µ  1.91 x10 −5
=Sc =  = 0.697
 ρ D AB  1.09 x 2.52 x10 −5

Sh jD 0.120
=
St D = = 2
= 2
0.152
Re Sc Sc 3 0.697 3

Fd P
=
Sh = St D Re= = 25.84
Sc 0.152 x 244 x0.696
D AB

cD AB 0.0378 x 2.52 x10 −5


= = 25.84
F Sh = −3
4.31 x10 −3 kmol / m 2 .s
dp 5.71 x10

F 25.84 kmol
=
kG = = 4.47 x10 −3 2
Py b ,M ( 97.7/101.3 ) x1 m ⋅ s ⋅ atn

4.47x10 -3 − 4.415 x10 −3


%error == x100 = +1.24%
4.415 x10 −3

46
yA, G

xA,i

yA,i xA,G

Interface
Bulk NH3-Air Water
Equilibrium Relation

 There are equations that describes the equilibrium


relation between the concentration of certain
component in the liquid and gas phase at certain
temperature and pressure
 Raoult’s Law    partial pressure Total pressure vapor pressure

=
p A y=
AP γ A x A PA =
pA y=
A P xA γ
A PA
activity coefficient

 Henry’s Law (dilute solution)


p A = y A P = Hx A

 Distribution-law (liquid-liquid)
c A, liquid 1 = Kc A, liquid 2
Diffusion Between Phases
 Consider the absorption of ammonia from a Water

mixture with air using liquid water, in a wetted


wall column
 The ammonia-air mixture enters the column
from the bottom and flow upward and water
flow downward on the inner wall of the column
 The concentration of the ammonia in the gas mixture
decreases as it flows upward
 the concentration of the ammonia in water increases
as it flows downward NH3-H2O
 under steady state conditions, the concentration at
NH3-Air
any point of the column does not change with time
Two-Resistance Theory
 The ammonia (solute) diffuses from the gas
phase to the liquid through an interface
 There is a concentration gradient in the
direction of mass transfer in each phase
 On concentrations on the interface (yA,I
and xA,i, are assumed to be in equilibrium)
y
This simply means the mass transfer
A, G

resistance is only in the fluid phase xA,i

and no resistance across the interface


yA,i xA,L

Interface
Bulk NH3-Air Water
Phase Transfer Coefficients
yA, G
 NNH3 can be expressed in terms of
xA,i
k-type coefficients:
N A= k y ( y A ,G − y A ,i )= k x ( x A ,i − x A ,L )
yA,i xA,G

Interface
k ( y A ,G − y A ,i )
− x =
Bulk NH3-Air Water

ky ( x A ,L − x A ,i ) yA,G
W her e :
y A ,i is the interface concentration in the gas phase side
x A ,i is the interface concentration in the liquid phase side
k y is the gas − phase mass transfer coefficient
k x is the liquid − phase mass transfer coefficient

 yA,i= f(xA,i)
xA,L xA,i

5
Overall-Mass Transfer Coefficient
x*A
 The interface concentration is yA, G

hard to accurately measure xA,i

 The flux can be estimated in terms


yA,i xA,L

Interface
of overall mass transfer coefficient
as follow
Bulk NH3-Air y*A Water

yA,G
N=
A ( )
K y y A ,G − y = K x x − x A ,L
*
A ( *
A )
W here :
y *A is in equilibrium with x A ,L yA,i

x *A is in equilibrium with y A ,G
yA*

xA,L xA,i xA*


Overall and individual Phase Coefficient

 If the equilibrium relation is linear ( y A ,i = m x A ,i )


 Dilute solution where Henry’s Law applies
=y *A m=
x A ,L ; y A ,G m x *A

= (
N A K y y A ,G − y *A )
1 y A ,G − y *A y A ,G − y A ,i y A ,i − y *A y A ,G − y A ,i m ( x A ,i − x A ,L )
= = + = +
Ky NA NA NA NA NA

1 1 m 1 1 1
= + Similarly = +
Ky ky kx K x mk y k x


1 1
Resistance in gas phase ky Resistance in liquid phase k
= = x
Total Resistance in both phases 1 Total Resistance in both phases 1
Ky KX
Effect of the Gas Solubility in the Mass
Transfer Coefficients
 For highly soluble gas (the slope of the equilibrium
line, m, is small)
 The major resistance is in the gas phase
1 1 m 1
= + ≈
Ky ky kx ky

 For low solubility gas (the slope of


the equilibrium line, m, is large)
 The major resistance is in the liquid yA

phase
1 1 1 1
= + ≈
K x mk y k x k x
XA
Example
In an experimental study of the absorption of NH3 by water in
a wetted-wall column, the value of KG was found to be
2.75×10-6 kmol/(m2-s-kPa). At one point in the column, the
composition of the gas and liquid phases were 8.0 and 0.115
mol% NH3, respectively. The temperature was 300° K and the
total pressure was 1 atm. 85% of the total resistance to mass
transfer was found to be in the gas phase. At 300° K, NH3-
water solution follows Henry’s law up to 5 mol% NH3 in the
liquid with m = 1.64 when the total pressure is 1 atm.
Calculate:
1. Flux of NH3
2. Individual film coefficients
3. Interfacial Compositions (yA,i and xA,i)
Solution
 Given
 T=300 K; P=1 atm
 KG= 2.75x10-6 kmol/m2-s-kPa
 yA,G=0.080; xA,L=0.00115
 .k1 = 0.85 K1
y y

(
 .N A K y y A ,G − y *A
= )
K y =K G P = 2.75x10 -6 x 101.3 = 2.786x10 -4 kmol/m 2 -s

= =
y *A mx A ,L = 1.886 x10 −3
1.65 * 0.00115

= (
N A K y y A ,G − y=
*
A )
2.786 x10 −4 (0.08 − 0.001886
= ) 2.18 x10 −5 kmol / m 2 ⋅ s

10
Solution
1 0.85
 ky.=
Ky
Ky 2.786 x10 −4
=ky = = 3.28 x10 −4 kmol / m 2 .s
0.85 0.85
 . 1
=
Ky
1
+
ky kx
m

 .
m 1 1 1 0.85 0.15
= − = − =
kx K y ky Ky Ky Ky
mK y 1.64 x 2.75 x10 −6
=
kx = = 3.05 x10 −3 kmol / m 2 .s
0.15 0.15

 N. A k y ( y A ,G − y A ,i
= )
NA 2.18 x10 −5
y A ,i = y A ,G − = 0.08 − = 0.01362
ky 3.28 x10 −4

y A ,i 0.01362
x A ,i =
= = 8.305 x10 −3
m 1.64
Local Mass Transfer Coefficients

 For general case


 Diffusion of more than one species
 No equimolar counterdiffusion
 The mass transfer rates are large
 k-type or k′-type diffusion coefficients cannot be
used
 F-type diffusion coefficient has to be used
 Ψ A ,G − y A ,i  Ψ A ,L − x A ,L 
=N A Ψ= F ln   Ψ F ln  
Ψ A ,G − y A ,G  Ψ A ,L − x A ,i
A ,G G A ,L L


Ψ A ,L FL
Ψ A ,G − y A ,i Ψ A ,L − x A ,L  Ψ A ,G FG
= 
Ψ A ,G − y A ,G Ψ A ,L − x A ,i 
Example
A wetted-wall absorption tower is fed with water as the wall
liquid and an ammonia air mixture as the central-core gas. At
a particular point in the tower, The ammonia concentration
in the bulk gas is 0.60 mole fraction and that in the bulk
liquid is 0.12 mole fraction. The temperature is 300° K and
the pressure is 1 atm. Ignoring the vaporization of water,
calculate the local ammonia mass-transfer flux. The rates of
flow are such that FL = 0.0035 kmol/m2-s. and FG = 0.0020
kmol/m2-s. The equilibrium-distribution data for the system
at 300° K and 1 atm is:
yA = 0.156 + 0.622 x A ( 5.765 x A − 1 ) ;
10.51 γ A x A ; γ A = x A ≤ 0.3
Solution
 Given
 T=300 K; P=1 atm
 yA,G=0.60; xA,L=0.12
 FL = 0.0035 kmol/m2-s; . FG = 0.0020 kmol/m2-s
 y. =
A 0.156 + 0.622 x ( 5.765 x − 1 ) ;
10.51 γ x ; γ =A A A x ≤ 0.3 A A A

 Although this is a diffusion or A through stagnant B, the


ammonia concentration is too high to use k-type mass
transfer coefficient, F-type coefficient must be used
 Ψ A ,G − y A ,i  Ψ A ,L − x A ,L  Ψ= Ψ= 1
 NA Ψ= F ln   Ψ F ln   A ,G A ,L

Ψ A ,G − y A ,G  Ψ A ,L − x A ,i 
A ,G G A ,L L

FL
 1 − y A ,i   1 − x A ,L   1 − x A ,L  FG
=N A F=
G ln   FL ln  ⇒ y A ,i =1 − ( 1 − y A ,G )1 − x 
 1 − y A ,G   1 − x A ,i   A ,i 
Solution
FL
1.75
1 − x   0.88 
y A ,i =1 − ( 1 − y A ,G )  1 − xA ,L 
FG
⇒ y A ,i =0.6  
 A ,i 
  1 − x A ,i 

yA = 0.156 + 0.622 x A ( 5.765 x A − 1 ) ;


10.51 γ A x A ; γ A = x A ≤ 0.3

yA =10.51 x A 0.156 + 0.622 x A ( 5.765 x A − 1 )  ; x A ≤ 0.3

 Graphically or numerically
 yA,i=0.49; xAi=0.23

 1 − y A ,i 
N A = FG ln  
 1 − y A ,G 
 1 − 0.49 
= 2 x10 −3 ln  
 1 − 0.6 
= 0.4.7 x10 −4 kmol / m 2 ⋅ s
Material Balance
 Consider steady state mass transfer L2, x2, X2 V2, y2, Y2

operation involving countercurrent


contact of two immiscible phases Z=z 2

 V is total moles of phase V


 Vs is moles of A-free V L, x, X V, y, Y
 L is total moles of phase L
 L is moles of A-free L
Z=z 1
 y is mole fraction of component A in V
 x is mole fraction of component A in L L1, x1, X1 V1, y1, Y1
 Y is the moles of A per mole A-free V
 X is mole of component A per mole A-
free L y x
Y = X =
1−y 1−x
Material Balance: Counter Flow

 Mole balance around the column


L2, x2, X2 V2, y2, Y2
moles of A entering  moles of A leaving 
 = 
 the column   the column  Z=z 2
V 1 y 1 + L 2 x 2 =V 2 y 2 + L 1 x 1

 Using solute free basis L, x, X z V, y, Y


V S Y 1 + L S X 2 =V S Y 2 + L S X 1

 Mole balance around plane z Z=z 1

V 1 y 1 + Lx =Vy + L 1 x 1
L1, x1, X1 V1, y1, Y1

 Using solute free basis


V S Y 1 + L S X =V S Y + L S X 1
Material Balance: Counter Flow
L2, x2, X2 V 2, y2, Y2

 The mole balance in terms of solute free basis Z=z 2

can be expressed as: L, x, X z V, y, Y

LS
VS
Y −Y 2
= 1
X1 − X2
or LS
VS
Y −Y
= 1
X1 − X
Z=z 1

L1, x1, X1 V 1, y1, Y1


Transfer from phase V to Transfer from phase L to
phase L (Absorption) phase V (Stripping)
Material Balance: Cocurrent Flow

 Mole balance around the column


L2, x2, X2 V2, y2, Y2
moles of A entering  moles of A leaving 
 = 
 the column   the column  Z=z 2
V 1 y 1 + L 1 x 1 =Vy + Lx =V 2 y 2 + L 2 x 2

 Using solute free basis: L, x, X z V, y, Y


V S Y 1 + L s X 1 =V S Y + L S X =V S Y 2 + L S X 2

 Using the operating line approach: Z=z 1

Y 1 −Y 2 L Y −Y L1, x1, X1 V1, y1, Y1


=
− S =1
X1 − X2 VS X1 − X
Material Balance: Cocurrent Flow
L2, x2, X2 V 2, y2, Y2

 The mole balance in terms of solute free basis Z=z 2

can be expressed as:


L, x, X z V, y, Y
Y 1 −Y 2 L Y −Y
=
− S =1
X1 − X2 VS X1 − X
Z=z 1

Transfer from phase V to Transfer from phase L to L1, x1, X1 V 1, y1, Y1


phase L (Absorption) phase V (Stripping)

20
Material Balance
 Masses, mass fraction, and mass ratio can be substitute
consistently for moles, mole fractions, and mole ratios in
the mass balance equations
 Cocurrent flow
'
LS '
Y 1 −Y 2
'
=
V S' X 1' − X '2
 Counter Flow
L'S Y 1' − Y 2'
− ' =
VS X 1' − X '2

Where the prime (´) indicates mass based property


Example: Adsorption of NO2 on Silica
Gel
 NO2 produced by thermal process for fixation of nitrogen, is to be
removed from dilute mixture with air by adsorption on silica gel in a
continuous adsorber. The mass flow rate of the gas entering the
adsorber is 0.5 kg/s. It contains 1.5% NO2, by volume, and 85% of NO2
is to be removed. Operation to be isothermal at 298° K and 1 atm. The
entering gel will be free of NO2. the equilibrium adsorption data at this
temperature are:
pNO2, mmHg 0 2 4 6 8 10 12

Solid conc. (m),


0 0.4 0.9 1.65 2.60 3.65 4.85
kg NO2/ 100 kg gel

If twice the minimum gel rate is to be used, calculate the gel mass flow
rate and the composition of the gel leaving the process for:
i. Counter flow operation
ii. Cocurrent flow operation
Solution:
Countercurrent
1. Plot the equilibrium data Gel Air/NO2

 Since the equilibrium data is given in


terms of mass ratios, it is easier to use mass
based equation in this case
 The partial pressure data have to be converted Air/NO2 Gel/NO2

to mass ratio data (Y´)


yi pi
=
Yi =
1 − yi P − pi Cocurrent
M NO 2 pi 46 kg NO 2
=Y i' Y= x Gel+NO2 Air/NO2
760 − p i 29
i
M A ir kg A ir

 Now the equilibrium data become:


Xi’, kg NO2/ 100 kg gel 0 0.4 0.9 1.65 2.60 3.65 4.85

Yi’, kgNO2/ 100 kg Air 0 2 4 6 8 10 12


Air/NO2 Gel
M NO 2 y1 46 0.015 46 kg NO 2
=Y 1' Y= = x = * 0.0242
1 − y 1 29 1 − 0.015 29
1
M Air kg Air

kg NO 2
( 1 − 0.85 ) xY 1' =
Y 2' = 0.15 * 2.42 =
0.0036
kg Air
kg NO 2
X '2 = 0.00
kg gel

 Minimum gel rate


 When the operating line touches
(reaches) the equilibrium line
 X1´=0.037 (From graph)
Y 1' − Y 2'
'
LS
= '
'
V S' X 1 − X '2
Y 1' − Y 2' 0.0242 − 0.0036
= =
'
L S min xV S' xV S'
X1 − X2
' '
0.037 − 0

1 1
= 1 ωB 1
V s' V= 0.5 x = = 0.488 kgAir / s
'
0.5
1 +Y 1
'
1 + 0.0242
L'S (min) = 0.268 kg gel / s

=L'S 2=
x0.268 0.536 kg gel / s

X= X +V
' ' '
(Y '
1 )
− Y 2'
= 0.00 + 0.488 x
0.024 − 0.0036
= 0.0186 kg NO 2 / kg gel
1 2 S '
LS 0.536
Cocurrent Flow
Cocurrent
Gel+NO2 Air/NO2

 Y1’=0.024
 Y2’=0.036
 X1’=0.00
 For (LS)min, (X2’)max can be
Air/NO2 Gel

found by drawing the


operating line reaching
the equilibrium line
 (X2’)max=0.0034
Solution, continued
Y 1' − Y 2'
'
LS
− =
V S'
'
X 1' − X '2
Y 1' − Y 2' 0.0242 − 0.0036
= = =
' '
L S min xV x0.488 2.957 kg gel / s
X 2 ,max − X 1 −
' ' S
0.0034 0
=L'S 2=
x 2.957 5.92 kg gel / s

X=
'
X '
+ V '
(Y '
1 − Y 2' )
2 1 S
L'S
0.024 − 0.0036
=
0 + 0.488 x =
0.00168 kg NO 2 / kg gel
5.92
• To reach the same degree of removal of NO2, countercurrent flow is
much more effect compared to cocurrent
• The amount of gel needed for cocurrent flow (5.92 kg/s) is about 11
times of that needed if countercurrent flow is used (0.536 kg/s)
Equilibrium-Stage Operation
 In many instances mass transfer devices are assembled by
interconnecting individual units (stages)
 The material passes through each one of these stages
 Two material streams moves countercurrently (cascades)
 In each stage the two streams are contacted, mixed, and then
separated
 As the stream moves between stage they come close to equilibrium
conditions
 If the leaving streams from a certain stage is in equilibrium, this
stage is an ideal stage
 If the stage are connected cocurrently they represent a single stage
 Batch mass-transfer operations are also a single stage
Stage-Operations
V1 V2 VN VN+1
VS VS VS VS
Y1 Y2 YN YN+1
Stage Stage n Stage Stage
1 2 N-1 N
L0 L1 LN-1 LN
LS LS LS LS
X0 X1 XN-1 XN

 The flow rate and composition of each stream are


numbered corresponding to the effluent from a stage
 X2 is the mole ratio in stream leaving stage 2
 YN is the mole ratio of stream leaving
 For ideal stages, the effluents from each stage are in equilibrium
 Y2 is in equilibrium with X2 and so on
 The cascade has the characteristics of the countercurrent process with

operating line goes through points (X0, Y1) and (XN, YN+1)
Th e c a s
Number of Ideal Stages

 Number of ideal stages can be determined graphically


(for two component systems)
Number of Stages

 For linear equilibrium line (Yi=mXi), analytical


solution is possible (Kremser):
 Define Absorption factor (ratio of the slope of the
operating line to the slope of the equilibrium line):
LS
A=
mV S

For transfer from L to V (Stripping) For transfer from V to L (Absorption)

 X − Y N +1 / m  Y − mX 0  1  1
ln  0 (1 − A ) + A  ln  N +1  1 − + 
 X N − Y N +1 / m   Y 1 − mX 0  A  A
N = A ≠1 A ≠1
ln ( 1 / A )
N
ln A

X0 − X N Y N +1 − Y 1
N = =A 1 N = A 1
X N − Y N +1 Y 1 − mX 0
1
Equipment for Gas Liquid Mass Transfer Operations

 Intimate contact between immiscible phase is required to


permit interphase diffusion

 The rate of mass transfer is dependent on the interfacial area


exposed between the phases

 Many operations require contact between a gas and a liquid


phase
 Distillation, humidification, dehumidification, absorption, desorption

 The equipment for gas liquid contact disperse either the gas or
the liquid in the other phase

CHEG351: Mass Transfer Chapter 4


Gas-Liquid Operations: Liquid Dispersed

 Liquid is dispersed into thin film or drops


 Wetted-wall columns
 Liquid flow downward inside a vertical pipe
 Gas flow countercurrently, upward,
 Spray and spray towers
 Nozzle disperses the liquid into fine spray of drops
 Can be used with countercurrent (vertical towers) or parallel
(horizontal spray chambers)
 Packed towers
 Vertical columns filled with packing materials
 Provide continuous contact between liquid and gas

CHEG351: Mass Transfer Chapter 4


Packed Towers

 Provide continuous contact between liquid


and gas for countercurrent or cocurrent
flow Mist eliminator
Gas outlet

 The liquid is distributed over, and trickle Liquid

down through the packed bed exposing distribution

a large surface to contact the gas phase


Packing

 Tower fill (packing) should;


Packing support
 Provide a large interfacial surface to contact
the liquid and gas
 Ensure high void fraction, ε, to permit
passage of gas and liquid at relatively high Gas inlet
velocity with low pressure drop

CHEG351: Mass Transfer Chapter 4


Tower Packing

 Tower fill or packing should:


1. Provide a large interfacial surface for contact between
liquid and gas per unit volume of packed space
2. Ensure high void fraction, ε, to permit passage of gas
and liquid at relatively high velocity with low pressure
drop
3. Be chemically inert to the fluids being processed
4. Posses structural strength to permit easy handling and
installation
 Material of Construction
 Packed towers shall be constructed from wood, metals,
chemical stonewares, acidproof bricks, plastic- or glass
lined materials

CHEG351: Mass Transfer Chapter 4


Tower Packing: 1. Random Packing

 Dumped into the tower during installation and


allowed to fall at random
 Made of metals, ceramics, or plastics
 Types of Packings
 Coke and broken glass and pottery
 First generation
 Raschig rings (d=6-100 mm)
 Second generation
 Pal rings
 Third generation
 Exotic shapes, saddles

CHEG351: Mass Transfer Chapter 4


Tower Packing: 2. Regular (Structured)
Packing
 Advantage:
 Structured packings provide low pressure drop for the
gas and greater possible flow rates
 Disadvantage:
 More costly to install
 Examples
 Intalox high performance
Intalox
 Flexigrid
 Wood grids

Flexigrid

CHEG351: Mass Transfer Chapter 4


Liquid Distribution

 Initial distribution of liquid at the top of the packing is


very important
 Part of the packing remains dry if liquid distribution
was Insufficient
 For random packing, the packing density (number of
packing pieces per unit volume) varies across the
radial direction of the column
 Leads to liquid segregation and gas channeling
 The effect is less pronounced for 1.0

dP < 1/8D, (dP < 1/15D is recommended) 0.8

0.6
 Liquid redistribution every 3-10 D ε
or at least every 6-7 m is provided
0.4

0.2
0
0 1 2 3 4 5 6
Distance from wall, r*=r/dp

CHEG351: Mass Transfer Chapter 4


Liquid Holdup
 For random packings, the gas pressure drop is dependent on the gas and the
liquid flow rates
 At fixed gas velocity, the pressure drop increases with the liquid flow rate
 The free cross sectional area decreases
 Loading point:
 The maximum gas velocity at which the liquid holdup is reasonably
independent of the gas velocity
 Preloading region
 Below the loading gas velocity, the gas is the continuous phase
 Above the loading point, the liquid accumulate in the column causing a
sharp increase in the gas pressure drop
 The flooding point
 The liquid becomes the continuous phase and the pressure drops increases
infinitely with the gas velocity

CHEG351: Mass Transfer Chapter 4


Liquid Holdup
 The specific liquid holdup, hL in the preloading zone can be estimated using
Billet and Scuhltes for different random and structured packing materials:
1 2
 Fr  3
 aH  3
hL = 12 L   a 
 Where  Re L   
 hL = specific liquid holdup, m3 holdup/ m3 packed bed
 ReL = liquid Reynolds number = vLρL/a µL
 vL = superficial liquid velocity, m/s
 a = specific surface area of packing, m2/m3
 FrL = liquid Froude number = vL2 a/g
a
g = acceleration of gravity, m2/s = C Re Fr Re < 5
h 0.5 0.1
 a
h L L L

 ah = hydraulic or effective, specific area


= of packing a
a
0.85 C Re Fr Re ≥ 5
h
h
0.25
L
0.1
L L

 a and Ch are characteristic of the particular Type of Packings vL, min, mm/s
packing type and size
Ceramics 0.15
 The superficial liquid velocity must exceeds
the following values to ensure complete Oxidized/etched 0.3
metals
wetting of the packing:
Bright metals 0.9
Plastics 1.2
CHEG351: Mass Transfer Chapter 4
Liquid holdup: Example
A tower packed with 25-mm ceramic Raschig rings is to be used
for absorbing benzene vapor from a dilute mixture with inert
gas using wash oil at 300° K. the viscosity of the oil is 2.0 cP
and its density is 840 kg/m3. the liquid mass velocity is Gx=2.71
kg/m2.s. Estimate the liquid holdup, the void fraction and the
hydraulic specific area of the packing.
 Given Data:
 T=300 K
 ρL=840 kg/m3; µL=2.0 cP
 Gx=2.71 kg/m2.s
 dP=25 mm
 Required:
 hL, ε, and ah

CHEG351: Mass Transfer Chapter 4


Solution
Gx 2.71 This image cannot currently be displayed.

 v = = =3.226 x10 -3 m / s
L
ρL 840
 From table 4.1, for 25 mm ceramic Raschig rings:
 a =190 m2/m3; Ch=0.577; ε =0.680
 v L ρ L 3.226 x10 -3 x840
Re L = = = 7.13
a µL 190 x 2 x10 −3

 v L2 a 3.226 x10 −3 x190


Fr L = = 0.202 x10 −3
g 9.81

ah
C h Re L0.25 Fr L0.1 =0.85 x 0.577 (7.13 )( )
0.1
0.202 x10 −3
0.25
=
0.85 0.342
 a
ah =
0.342 x190 65 m 2 / m 3
1 2 1/ 3
 Fr L  3  ah  3  0.202 x10 −3 
[ ]
2/ 3
 hL =
12    12 =  0.342 0.034 m 3 holdup / m 3 packed bed
 Re L   a   7.13 

 ε = ε dry - hL = 0.680 - 0.034=0.646

CHEG351: Mass Transfer Chapter 4


Pressure Drop at flooding

 Sherwood correlated the


1

flooding data for counter-


current packed columns
based on the flow
400
Floading
0.1
parameter, X 200

0.1
− 3.5021 + 1.028 ln X + 0.11093 ( ln X ) 

) ( µL )
2
lnY flooding =
  50

2
where :

Y =FP (C S

packing Factor 1
 ρG  2
Y flooding =
FP C S2 µL0.1 ; C S vG  
 ρ L − ρG  0.01 Gas Pressure Drop
0.5 Pa/m packing
 L'   ρ 
X =   G 
V '   ρ L 

 Pressure drop at flooding:


∆Pflooding =
93.9 FP0.7 0.001 0.5
ρ 
0.01 0.1 X=  L'   G  1 10
 V '   ρL 

CHEG351: Mass Transfer Chapter 4


Pressure Drop

 Pressure drop at 1

conditions other than


flooding can be estimated
using Generalized 400
Floading

Pressure Drop Equation


0.1

200

0.1
) ( µL )
50

2
Y =FP (C S
0.01 Gas Pressure Drop
Pa/m packing

0.001 0.5

0.01 0.1 X=  L'   ρG  1 10


V '   ρ L 

CHEG351: Mass Transfer Chapter 4


Packed Column Sizing

 Packed columns can be sized according to either


1. Fractional approach to flooding
0.5 D = diameter of the column
 4Q G 
D=   Q G = volumetric flow rate of the gas
 f v GF π  v GF = the gas velocity at flooding

2. Maximum allowable gas-pressure drop


 Gas pressure drop through the packed bed
 Absorber and strippers ∆P~200-400 Pa/m of packed depth
 Atmospheric fractionator ∆P~400-600 Pa/m of packed depth
 Vacuum stills ∆P~80-40 Pa/m of packed depth

CHEG351: Mass Transfer Chapter 4


Pressure drop

 The pressure drop can be predicted based on follow:


 For dry column
1 2  1 dP
= 1+ 
3  1 − ε  D
; W all Factor;
KW
∆P0 a ρ v2 1 1 −ε 
=Ψ 0 3 G G dP = 6   Effective particle diameter
Z ε 2 KW  a 
 64 1.8 
=Ψ0 C p  + 1.8  Dry packing resistance coefficient
 ReG ReG0.08 
v G d p ρG K W
ReG =
( 1 − ε ) µG
 For wet column

1.5
∆P  ε   Re  v L ρL
=  exp  L  Re L =
∆P0  ε − hL   200  a µL

CHEG351: Mass Transfer Chapter 4


Mass Transfer Coefficient

 For mass transfer resistance mainly in the liquid phase:


0.5
 D av 
k L = 0.757 C L  L L 
 ε hL 

 For mass transfer resistance mainly in the gas phase:


3 4
D P a  ReG  2
k y = 0.1304C V G   ScG 3
RT ε ( ε − hL )   K W 

 CL and CV are empirical constants (Table 4.2)

v d ρ K
 ReG = 1 − ε µ
G p G W

( ) G

CHEG351: Mass Transfer Chapter 4


Gas-Liquid Operations: Gas Dispersed

 Gas phase is dispersed into bubbles or foams


 Sparged Vessels
 Can be used for single stage and cocurrent
arrangement
 May involve chemical reaction between the gas and
the liquid
 Examples: bio-reactors, hydrogenation of vegetable
oils, fermentation,
 Tray Towers
 Liquid and gas are contacted in stepwise fashion on
trays or plates

CHEG351: Mass Transfer Chapter 4


Sparged Vessels (Bubble Column)

A sparger is used to introduce stream of gas in the


form of small bubbles into a liquid
 Can be an open tube (small-diameter columns) or
several orifices (large- diameter columns)
 Size of the bubbles depends on:
 Rate of gas flow through the orifices
 The orifice diameter
 The fluid properties
 The extent of turbulence in the liquid

CHEG351: Mass Transfer Chapter 4


Sparged Columns: Bubble diameter

 For air-water system, the bubble size, dP, can be


estimated as follow
1 1
d P = 0.0287 d o 2 Reo 3 for Reo ≤ 2100
d P = 0.0071 Reo−0.05 for 10000 ≤ Reo ≤ 50000
d o = orifice diameter
4 mG
Reo =
π d o µG

 Gas Hold Up, ϕG (volume of gas/volume of column):


 Gas superficial velocity, vG
 Slip velocity, vS (relative velocity of gas and liquid)
vG vL
v= − cocurrent
S
ϕG 1 − ϕG
vG vL
v= + countercurrent
S
ϕG 1 − ϕG

CHEG351: Mass Transfer Chapter 4


Tray Towers
 Vertical cylinders in which liquid and gas are contacted
in stepwise fashion on trays or plates
 Liquid flows downward by gravity. On the way, it
flows across each tray and through a downcomer to
the tray below
 The gas passes upward through openings of one sort
or another in the tray, bubbles through the liquid
forming a froth, disengages, and passes on to the next
tray above
 The overall effect is a multiple countercurrent contact
of gas and liquid.
 Each tray of the tower is a stage
 Fluids are brought into intimate contact
 Interphase diffusion occurs
 Fluids are then separated

CHEG351: Mass Transfer Chapter 4


Tray Towers

 The number of equilibrium stages (theoretical trays)


depends on the difficulty of separation and is
determined by material balances and equilibrium
 The stage efficiency, and therefore the number of
real trays, is determined by the mechanical design
used and the conditions of operation
 Stage efficiency depend on the contact time between
the gas and the liquid
 Deep liquid pool on each tray (long contact time)
and high gas velocity (large interfacial area and
mass transfer coefficients) are required for high
efficiency
 However these conditions lead to some difficulties

CHEG351: Mass Transfer Chapter 4


Tray Stability

 Deep liquid contact increases pressure drop which


may cause flooding
 High gas velocity
 Low liquid velocity: entrainment
 Foaming systems: Priming
 High liquid velocity: flooding
 Low gas velocity weeping

 Low liquid velocity: Dumping

Liquid rate
 High liquid velocity: Weeping Satisfactory
Operation

 Low liquid velocity:


 Coning
Gas rate

CHEG351: Mass Transfer Chapter 4


Tray Type

 Sieve tray

Sieve tray
 Perforated tray deck with uniform hole
diameter of less than 1 mm to 25 mm
 Most economical in terms of cost and
maintenance

Fixed
 Valve trays

Valve trays
 Offers more flexibility over sieve trays
 More expensive

Caged
 Can be fixed or floating
 Bubble cap trays

Bubble Cap tray


 Provides the most flexibility
 However, the most expensive tray
CHEG351: Mass Transfer Chapter 4
Vapor Flow Through Tray

Sieve Tray Valve Tray Bubble Cap Tray

CHEG351: Mass Transfer Chapter 4


Vapor Flow Through Tray

Bubble Cap Tray

CHEG351: Mass Transfer Chapter 4


Vapor Flow Through Tray

Valve Tray

CHEG351: Mass Transfer Chapter 4


Vapor Flow Through Tray

Sieve Tray

CHEG351: Mass Transfer Chapter 4


Vapor Flow Through Tray

Sieve Tray Valve Tray Bubble Cap Tray

CHEG351: Mass Transfer Chapter 4


Satisfactory Operation of Tray Towers

 In order to have stable operation, the vapor and liquid


flows must be managed such that:
 vapor should flow only through the open regions of the
tray between the downcomers
 vapor should not be carried down the column in the
liquid
 liquid should flow only through the downcomers
 liquid should not weep through tray perforations
 liquid should not be carried up the column entrained in the
vapor
 vapor should not bubble up through the downcomers

CHEG351: Mass Transfer Chapter 4


Tray column Design

 Column internals
 Tray layout
 Downcomer area Tray above

 Column diameter
 Column height
clear
liquid

Froth

 Number of trays Froth

 Tray efficiency
Tray spacing
Gas Flow
 clear
liquid

 Vapor pressure drop Tray below

CHEG351: Mass Transfer Chapter 4


Column Internals

Weir Froth

Plate

Vapor streams (shown in red) bubble up through froth.


Liquid stream flows through froth and over weir.

CHEG351: Mass Transfer Chapter 4


Sieve Tray Layout
 The holes are usually placed in the corners of Ad
equilateral triangle at distances between the rw
Lw

θ
centers (p`=2.5-5 do)
Downcomer area

Lw weir
hW
rw

p` p`

p`

2
Ah π d o  d o 
= 0.907
Aa 4 sin (60 )  p' 
  p' 
=
inlet Downcomer  

CHEG351: Mass Transfer Chapter 4


Flooding Velocity
 Flooding occurs when the liquid flow rates inside the downcomer exceeds the downcomer
capacity due to small downcomer area (Ad ~ 10-20% of Aa is sufficient) or Excessive entrainment
of liquid droplets by the vapor
 The flooding gas velocity (vGF=QG/An) is related to the fluid densities by: drag

buoyancy

1/ 2
Q  ρ − ρG 
vGF = G = C  L 
An  ρG 
gravity

σ 
0.2

FST =Surface tension factor=  


 20 
FF = Foaming factor =1 for nonfoaming systems
Ah
FHA =1.0 for ≥ 0.10
Aa
W here:
= 5  h  + 0.5
A Ah
C = Empirical constant depends on the tray design  for 0.06 ≤ ≤ 0.10
 Aa  Aa
C = FST FF FHAC F Ah
=ratio of vapor hole area on t ray active ar ea
Aa

1 
=C F α log   + β
X 
=α 0.0744t + 0.01173
(t = tray spacing )
= β 0.0304t + 0.015
0.5
 L'   ρG 
= =
X flow param eter   ρ  (Use 0.1 for 0.01<X <0.1 )
G'  L 

CHEG351: Mass Transfer Chapter 4


Tray Diameter
 The column diameter D is based on a specified fraction approach to
flooding, f
Ad
0.5
 
Lw
4Q G
D=   rw

 f v GF ( 1- Ad At ) π  θ

Where
Ad At is chosen based on the value of X ½ r2θ ½ r2sinθ
 0.1 X ≤ 0.1
Ad  X − 0.1 Ad
=  0.1 + 0.1<X ≤ 1 r θ r θ
Ar  9 = - rw
 0.2 X ≥1

1 2
r (θ − sin θ )
Ad 2 θ − sin θ
= =
At πr 2 2π

θ  1 θ 
Lw = D sin  ; rW = cos  
2  2 2 

CHEG351: Mass Transfer Chapter 4


Tray Gas Pressure Drop

 Vapor pressure drop in sieve tray is due to:


 Friction for vapor flow through perforation (hd)
 Holdup of the liquid on the tray (hl)
 Surface tension (hσ)
 Interms of head loss, the tray pressure drop, ht is given
by: h = h + h + hσ
t d l

 where
hd = dry tray head loss
do
hl = equivalent head for liquid in tray plate 
hσ = head loss due to surface tension

vapor

CHEG351: Mass Transfer Chapter 4


Dry Tray Head Loss

 Dry tray pressure drop can be estimated using modified


orifice equation:

do
plate 
 ρW    Ah  
2 2
vo 
=hd 0.0051   ρG   1 −   
 
C o  ρ L   Aa  

v o is hole velocity

ρW is water density at the liquid temperature


2
 
 do 
C o is the orifice coefficent, C o =
0.85032 − 0.04231   for d o ≥ 

 tray thickness 
 

CHEG351: Mass Transfer Chapter 4


Clear Liquid Holdup Head Loss

 The equivalent height of clear liquid holdup depends on


weir height (hW), liquid and vapor densities and rates,
and downcomer length:
 2

  q  3

=hl φe hW + C   L
 
 φ
  W e 
L

plate 

φe effective relative froth density (height of clear liquid/froth height) =exp ( -12.55 K s0.91 )
1
 ρG 2
K s ≡ (capacity parameter , m / s ) =
va  
 ρ L − ρG 
v a ≡ sperficial gas velocity based on tray active area
50.12 + 43.89 exp ( −1.378 hw
Cl = )

CHEG351: Mass Transfer Chapter 4


Tray Gas Pressure Drop

 Head loss due to surface tension is given by the


difference between the pressure inside the bubble and
that of the liquid according to the theoretical relation:

hσ =
g ρL d o

 Here we assume that the maximum bubble size is taken


as the perforation diameter
 Typical vapor pressure drop for sieve tray is 0.3-1.0
kPa/tray

CHEG351: Mass Transfer Chapter 4


Weeping and Entrainment

 Weeping and liquid entrainment degrade the tray


efficiency
 Weeping ( the drain of liquid through the tray
perforation) must be very low compared To the liquid
flow over the weir and into the downcomer
 Weeping is caused by low vapor velocity and/or high
liquid rates
 Weeping is significant (substantially reduce tray
efficiency) if :
0.5
 ρG v o2 
=Fro   ≤ 0.5
 g ρ L hl 

CHEG351: Mass Transfer Chapter 4


Weeping and Entrainment

 Entrainment of liquid is due to carry up of suspended


liquid droplets by rising vapor or throw up of liquid
particles by vapor jets formed at tray perforation
 Athigh vapor rates entrainment becomes significant and
decreases tray efficiency
k
 hl 
1.1 0.5
Liquid entrainment mass flow rate  h2 φ   ρL 
E = =0 .00335      
Upward gas mass flow rate  t   ρG   h2 φ 

t = tray spacing
h2 φ = height of two-phase region on the tray

hl   do  
1.85
k s2
= + 7.79 1 + 6.9   
φe   hl   A 
φe g  h 
 Aa 
  h  
ks =
0.5 1 − tanh  1.3 ln  l  − 0.15  
   do   

CHEG351: Mass Transfer Chapter 4


Weeping and Entrainment

 Weeping and liquid entrainment degrade the tray


efficiency
 Weeping ( the drain of liquid through the tray
perforation) must be very low compared To the liquid
flow over the weir and into the downcomer
 Weeping is caused by low vapor velocity and/or high
liquid rates
 Weeping is significant (substantially reduce tray
efficiency) if :
0.5
 ρG v o2 
=Fro   ≤ 0.5
 g ρ L hl 

CHEG351: Mass Transfer Chapter 4


Weeping and Entrainment

 Entrainment of liquid is due to carry up of suspended


liquid droplets by rising vapor or throw up of liquid
particles by vapor jets formed at tray perforation
 Athigh vapor rates entrainment becomes significant and
decreases tray efficiency
k
 hl 
1.1 0.5
Liquid entrainment mass flow rate  h2 φ   ρL 
E = =0 .00335      
Upward gas mass flow rate  t   ρG   h2 φ 

t = tray spacing
h2 φ = height of two-phase region on the tray

hl   do   K2
1.85

= + 7.79 1 + 6.9    s

φe   hl   A 
φe g  h 
 Aa 
  h  
k =
0.5 1 − tanh  1.3 ln  l  − 0.15  
   do   

CHEG351: Mass Transfer Chapter 4


Tray Efficiency

 Number of theoretical stages can be calculated based on mass


transfer and equilibrium data
 This number of stages carry the assumption that streams reach
equilibrium
 This assumption is rarely justified
 Number of stages must be adjusted with a stage efficiency to
correct for not reaching equilibrium on the tray or stage
 Tray Efficiency is a fractional approach to an equilibrium attained
by the real tray
 efficiency require measuring the approach to equilibrium of all the
vapor and the liquid from the tray

number of theoretical stages (trays )


Efficiency =
 .

number of actual stages (trays )

CHEG351: Mass Transfer Chapter 4


Point Efficiency
 The composition of the vapor and liquid stream
across the tray varies. Therefore, the approach
to equilibrium varies across the tray as well
The local (point) efficiency can is calculated
Tray above
 (n-1)

based on the composition of the liquid and yn, local

vapor stream at certain point on the tray


xn-1
 The liquid flow in downcomer from tray n-1 (xn-
1) to tray n xn, local
 Consider a vapor coming pencil coming from
Tray n
tray n+1 (yn+1, local) to try n exchange mass with
liquid on tray n (xn, local) and leave with
concentration yn, local
yn+1, local
 The point efficiency EOG can be estimated as xn

follow: Tray below


(n+1)
y n .local − y n +1 , local
EOG =
y *local − y n +1 , local
y *loacl is the concentration in equilibrium with x local
 .

CHEG351: Mass Transfer Chapter 4


Point Efficiency

 For a gas molar flow rate is GM and interfacial surface between


the gas and the liquid a (area/volume of liquid-gas froth)
 As the gas rises a differential height dhl, the area of contact is adhl
per unit active area of the tray and the gas concentration changes
by dy
 The rate of solute transfer can be given by:
y n ,local
K ya
( )
dy
=
G M dy K y adhl y *
local − y n +1 , local ⇒ ∫
y n + 1 ,local y *local − y n +1 , local G M ∫
= dhl

y *local − y n , local K y ahl  y n ,local − y n +1 , local  K y ahl


− ln = − ln  1 − * =− ln ( 1 − EOG ) =
y *local − y n +1 , local GM  y local − y n +1 ,local  GM
 

 And therefore the point efficiency can be estimated based on the


mass transfer coefficient:
 K y ahl 
EOG =
1 − exp  − 
 .
 GM 

CHEG351: Mass Transfer Chapter 4


Point Efficiency

 The point efficiency can also be estimated based on


correlation:
 
 
 
 a2 a3 
a1  hl   Ah  
1 − exp  −
0.0029
EOG = Re Fe    
 DG ( 1 − φe )  d o   Aa  
 1 +m cG 
 cL  Ah  
 DL   
  Aa  

 where Re Fe =
ρG v o hl
µG φe
a1 = 0.4136
a 2 = 0.6074
a3 = −0.3195
m = local slope of the equilibrium curve
cG ,c L = molar concentration of gas and liquid, respectively
DG , D L = diffusivity of gas and liquid , respectively
1
 ρG 
φe =exp ( -12.55 K s0.91 ) ; K s = v a 
2

 ρ L − ρG 

CHEG351: Mass Transfer Chapter 4


Tray Murphee Efficiency

 The efficiency of the entire tray (Murphee Efficiency)


can be estimated based on the bulk average
concentration of the gas:
y n − y n +1
E MG =
y * − y n +1
y * is in equilibrium with the concentration of the liquid leaving the tray , x n

 The relation between EMG and EOG can be derived by


integrating the local EOG over the surface of the tray

CHEG351: Mass Transfer Chapter 4


EMG versus EOG

 Based on the degree of mixing of the vapor and the


liquid phases, the relations between EMG and EOG are
given by:
1. Liquid is completely backmixed and the vapors
entering the tray is perfectly mixed
E MG = EOG

2. Liquid is in plug flow (no mixing) but vapors entering


the tray is perfectly mixed
1
=E MG exp ( λ EOG ) − 1 
λ
mV
λ=
L

CHEG351: Mass Transfer Chapter 4


EMG versus EOG

3. Vapor is well mixed but liquid is partially mixed


E MG 1 − exp  − (η + Pe L )  exp (η ) − 1
= +
EOG   (η + Pe L )   η 1 + η 
 η + Pe L 1 +   

 η   η + Pe L 

 1

Pe L  4 EOG  2 
η=  1 +  − 1
2   Pe L  
 

for λ<3.0 the previous equation can be approximated as:

λ EOG 
N

1 + N  − 1
E MG = 
λ
Pe L + 2
N =
2

4 q L rw2
Pe L =
Aa hl D E ,L
0.5
D E ,L = 0.1  gh23φ  liquid eddy diffusivity

CHEG351: Mass Transfer Chapter 4


EMG versus EOG

4. Both Vapor and Liquid are only partially mixed


λ EOG 
N

1 + N  − 1
 
=E MG x 1 − 0.0335 λ 1.073 E OG
2.518
Pe L0.175 
λ
Pe L + 2
N =
2

The degree of vapor mixing can be estimated based on PeG:

the vapor is considered unmixed if


PeG >50 or h2 /h>=0.1

CHEG351: Mass Transfer Chapter 4


Effect of Entrainment on EMG

 Effectof entrainment on tray efficiency can be


estimated as follow:

 0.8 EOG λ 1.543 E 


=
E MGE E MG 1 − 
 m 

CHEG351: Mass Transfer Chapter 4


Example:
 A dilute aqueous solution of methanol is to be stripped with steam in a sieve-
tray tower. The conditions chosen for design are in the following table:
The equilibrium data at this Liquid Vapor
concentration indicate that m=2.5. T, °K 368
 Design as suitable cross-flow sieve tray P, kPa 101.3
Rate, kmol/s 0.25 0.1
for such a tower. Take do=6.0 mm on composition 15 mass% 18 mole%
equilateral-triangle pitch 12 mm between Density, kg/m3 961 -
hole centers, punched in stainless steel σ, dyne/cm 40 -
sheet 2 mm thick. Use a weir height of 0.213
Diffusivity, cm2/s 5.70x10-5
50 mm. Design for 80% approach to the cm2/s
Viscosity, cP 0.3 125x10-4
flooding velocity. Foaming Factor 1 -
 Report details respecting tower diameter, tray spacing, weir length, gas
pressure drop, and entrainment in the gas. Check for excessive weeping.
 Estimate the tray efficiency corrected for entrainment for that design.

CHEG351: Mass Transfer Chapter 4


Solution: 1. Flooding velocity
1/ 2
Q  ρ − ρG  Steam + methanol
vGF = G = C  L  H2O+ Methanol (rich)
An  ρG 
PM G ,av 1
ρG =
RT 2
=
M G ,av yM methanol + ( 1 − y ) M steam
= 0.18 x 32.04 + ( ( 1 − 0.18=
) x18 20.53
101.3 x 20.53
ρG = 0.68 kg / m 3 x=0.15 (mass) N–1 y=0.18 (mol)
8.314 x 368
N
C = FST FF FHAC F
H2O /methanol (lean) Steam
 σ 
0.2 0.2
 40 
=
FST =  =  1.15
 20   20 

Liquid Vapor
To get FHA we need Ah/Aa T, °K 368
Ah d o 
2
6 
2 P, kPa 101.3
=
0.907  p'  =
0.907  12  0.23 Rate, kmol/s 0.25 0.1
Aa    
Ah composition 15 mass% 18 mole%
> 0.1 ⇒ FHA =
1
Aa Density, kg/m3 961 -
σ, dyne/cm 40 -
Diffusivity, cm2/s 5.70x10-5 0.213 cm2/s
Viscosity, cP 0.3 125x10-4
Foaming Factor 1 -
CHEG351: Mass Transfer Chapter 4
Flood Velocity

 CF depends on the flow parameter (X) and tray


spacing (t)
 The tray spacing depends on the tray diameter
 At this stage we assume tray spacing of 0.5 and we
recheck once the tower diameter is calculated
1 
CF α log   + β ; assume tray spacing , t=0.5 m
X 
α = 0.0744t + 0.01173 = 0.0744 x0.5 + 0.01173 = 0.049
β = 0.0304t + 0.015 = 0.0304 x0.5 + 0.015 = 0.030
0.5 0.5
 L'   ρG   LM L   ρG 
0.5
 0.25 x19.27   0.68 
X=  
ρ
  = 
ρ
  0.1 x 20.53   961  = 0.066
 G '  L   GM G  L    
 1 
=C F 0.049 log  =+ 0.030 0.079
 0.1 

=
C= =
FST FF FHAC F 1.15 x1 x1 x0.09 0.091
1/ 2
 ρ − ρG 
0.5
Q  961 − 0.68 
v GF = G==C  L  =
0.103  0.68  3.42 m / s
An  ρG   

CHEG351: Mass Transfer Chapter 4


Column Diameter

 The column diameter is estimated based on a fractional


approach to flooding as follow: D =  f v (1-4QA A ) π 
0.5
G

 GF d t 

based on the value of X (0.062), Ad At =0.1


0.5
  G'   
0.5
 0.1 x 20.53  
 4    4 x  0.68  
  ρG     
D == = 1.25 m
 f v GF ( 1- Ad At ) π   0.8 x 3.42 x ( 1 − 0.1 ) π 
   
   

 1< D < 3; recommended tray spacing is 0.6 m


 Now assume t = 0.6 D, m t, m
1 or less 0.50
 Recalculate α (0.056) and β (0.033) 1-3 0.60
 Recalculate CF (0.09) and C (0.103) 3-4 0.75

 Recalculate vGF (3.87 m/s) 4-8 0.9

 D =1.17 m (t=0.6 m is valid assumption)


CHEG351: Mass Transfer Chapter 4
Pressure Drop
 ρW    Ah  
2 2
vo 
1. Dry pressure drop =hd 0.0051   ρG 
C o 
 1 − 
 ρ L  
 
 Aa  

QG 3.02
=
vo = = 15.36 m / s
Ah 0.2
2 2
d  6 
Co =
0.85032 − 0.04231  o  =0.85032 − 0.04231   =0.74
   2 

2
 15.36   961 
=hd 0.0051   =
0.68   1 − 0.23 2  1.48 cm liquid
 0.74   1000 

 2

2. Clear Liquid head presure drop =  
hl φe hW + C t 

q L

φ
 W e 
L
 3
 

1 1 1
 
 ρG  2 Q G  ρG  2 3.02  0.68 2
K s ≡va   =   = = 0.09
 ρ L − ρG  Aa  ρ L − ρG  0.87  961 − 0.68 

φe =exp ( -12.55 K s0.91 ) = 0.24


50.12 + 43.89 exp ( −1.378 hw ) =
Cl = 50.12 + 43.89 exp ( −1.378 x 5 ) =
50.16

 2
  2

    (0.2 x19.27 ) / 961  3 
φe hW + C t  L   =
q 3
hl = 0.24 5 + 50.16    =2.19 cm liquid
 LW φe  
     0.85 x0.24  

CHEG351: Mass Transfer Chapter 4


Tray Gas Pressure Drop

3. Head loss due to surface tension


6σ 6 x40
=hσ = = 0.004
= m 0.4 cm liquid
g ρL d o 6
9.8 x 961 x
1000 6σ
hσ =
g ρL d o

 Total Tray gas Pressure drop

ht = hd + hl + h ρ = 1.48 + 2.19 + 0.4 = 4.09


4.09
∆ Pt h=
= t ρL g * 961*=
9.81 386 Pa / tray
100

CHEG351: Mass Transfer Chapter 4


Entrainment and Weeping

 Entrainment:
k
 hl 
1.1 0.5
 h2 φ   ρL 
E = 0.00335      
 t   ρG   h2 φ 

hl   do 
1.85
 K2 0.0409   6  
1.85

h2 φ =+ 7.79 1 + 6.9    s
= + 7.79 1 + 6.9   = 0.3 m
φe   hl    Ah  0.24   40.9  
φe g  
 a 
A
  h      40.9  
k =0.5 1 − tanh  1.3 ln  l  − 0.15   =0.5 1 − tanh  1.3 x ln   − .015   =0.044
   do       6  

k
 hl 
1.1 0.5
 h2 φ   ρL 
1.1 0.5 0.007
 0.3   961   0.0409 
=
E 0.00335       =0.00335      = 0.06= 6%
 t   ρG   h2 φ   0.6   0.68   0.3 

 Weeping: 0.5
 
 0.68x15.36 
0.5
 ρG v o2 
Fro =   =  = 0.61 >0.5
 g ρ L hl   9.8x961x 4.61 
 100 

weeping will not degrade tray efficiency significantly

CHEG351: Mass Transfer Chapter 4


1
Absorption and Stripping

Absorption (Scrubbing) Stripping (Desorption)


 Separation processes in which a gas  Separation processes in which a liquid
mixture is contacted with a liquid mixture is contacted with a gas (stripper)
(absorbent or solvent) to selectively to selectively dissolve one or more
dissolve one or more component component (adsorbate) by mass transfer
(absorbate) by mass transfer from the from the liquid to the gas
gas to the liquid  It is used to separate liquid mixtures,
 It is used to separate gas mixtures, remove impurities, pollutants, or catalyst
remove impurities, pollutants, or catalyst poisons from a liquid, or recover valuable
poisons from a gas, or recover valuable chemicals
chemicals

CHEG351: Mass Transfer Chapter 4


Equipment for Absorption and Stripping

 Packed Column Liquid in Vapor out

 Column diameter < 60 cm

Packed Column
 Low pressure drop (vacuum service)
 Corrosion concerns
 Low liquid holdup Liquid in Vapor out

Tray columns
1

Tray Towers
Liquid out Vapor in 2

 Low liquid/gas ratio


N–1
 Frequent cleaning is required N

Other equipment
Liquid out Vapor in

Bubble column Spray column Centrifugal Contactor
 Spray towers
 Sparged (bubble) columns
 Centrifuge contactors

CHEG351: Mass Transfer Chapter 4


Countercurrent Multistage Equipment
 Tray towers provide stepwise
contact of the liquid and the gas
 They are counter current
multistage cascades
 Number of theoretical (ideal)
stages can be estimated graphically
on an XY diagram by plotting the
operating and the equilibrium
Y1
equilibrium curve X0, Y 1
curves (lines) Y
Y2

 The nearer the operating line is to


the equilibrium curve, the more
Y3

stages will be required YN+1


XN, Y N+1

 Should the two curves touch at any


time corresponds to minimum X3
X X1 X0

LS/VS
CHEG351: Mass Transfer Chapter 4
Tray Efficiency and Actual (Real) Number of Trays

 Actual number of trays can be estimated based on the


theoretical number of trays and the Murphee tray
efficiency
 The actual number of trays can also be estimated
graphically
 By drawing a line (dashed line)
A
where: AB 3
=E MGE B
AC 2 C
y
 The dashed line represent the
1
real effluent from the trays
 The number of stages is the
actual number of trays x

CHEG351: Mass Transfer Chapter 4


Analytical Determination of Number of Ideal Stages

 Dilutesolution (the equilibrium curve is straight line) and


the operating line straight
 Number of ideal stages can be estimated based on
absorption factor, A = mVL
 Absorption factor, A, may vary from one end to the other end
of the Colum
 Geometric average absorption factor (A=(A1A2)0.5) maybe
used
Modified Kremser equations
Stripping Absorption
 x − y N +1 / m  y − mx 0  1  1
ln  0 (1 − A ) + A  ln  N +1  1 − + 
 x N − y N +1 / m   y 1 − mx 0  A  A
N = A ≠1 A ≠1
ln ( 1 / A )
N
ln A

x0 − x N y N +1 − y 1
N = =
A 1 N = A 1
x N − y N +1 y 1 − mx 0

CHEG351: Mass Transfer Chapter 4


Ideal Number of Stages

 Thetheoretical number of trays can be estimated using


“Modified Kremser Equations”
Stripping Absorption
 x − y N +1 / m  y − mx 0  1  1
ln  0 (1 − A ) + A  ln  N +1  1 − + 
 x N − y N +1 / m   y 1 − mx 0  A  A
N = A ≠1 A ≠1
ln ( 1 / A )
N
ln A

x0 − x N y N +1 − y 1
N = =
A 1 N = A 1
x N − y N +1 y 1 − mx 0

 IFEMGE is constant for all trays, an overall tray efficiency


(EO) can be estimated:
 1 
 1 + E MGE  − 1  
=EO
Equilibrium trays
= ln  A 
Actual trays  1  
 ln A 
   

CHEG351: Mass Transfer Chapter 4


Example (Problem 5.3)

A tray tower with six equilibrium stages is used for


stripping ammonia from a wastewater stream by
means of countercurrent air at 1 atm and 300° K.
Calculate the concentration of ammonia in the exit
water if the inlet liquid concentration is 0.1 mole%
ammonia, and 1.873 standard cubic meter of air are
fed to the tower per kilogram of wastewater. The
equilibrium data for this system, in this range of
concentrations and 300° K, can be represented by
yA,i=1.414xA,i

CHEG351: Mass Transfer Chapter 4


Solution

 P=1atm; T=300° K
 x0=0.1
Stripping
 yN+1=0 L0 (H2O+NH3) V1 (air+NH3)

 (ML,av)0=0.1*17+0.9*18=17.9
1
 V/L=(1.873x100/22.4)/(1/17.9) 2

= 1.5 mol Air/mol Liquid


5
 m =1.414 6

 A =L/mV=1/1.5/1.414=0.472 LN (H2O) VN+1 (air)

 x − y N +1 / m 
ln  0 (1 − A ) + A 
 x N − y N +1 / m 
N A ≠1
ln ( 1 / A )

 Substitute A, x0, yN+1, N you get xN=0.00059 by mole

CHEG351: Mass Transfer Chapter 4


Countercurrent Continuous Contact Equipment

 Packed column operates in a continuous manner, unlike


tray towers (cascades)
 Design equation for packed column can be developed
using differential mass balance
 For unimolecular transfer of component A ( ψ A,G, ψ A,L=1)
d(Vy)  1-y i 
=FG ah ln  
Sdz  1-y 
S=cross-section area of the tower
ah =effective specific area of the packing

 Both V and y varies along the column z+dz


 VS is constant V, y
z
V y  V S dy VS dy Vdy
d (Vy ) =d  S 
= = =
1 − y  ( 1-y ) ( 1-y ) ( 1-y ) (1 − y )
2

Gas
CHEG351: Mass Transfer Chapter 4
Countercurrent Continuous Contact Equipment
d (Vy ) Vdy G My dy
dz= = =
1 − y i  1 − y i  1 − y i 
SFG ah ln   SFG ah ( 1 − y ) ln   FG ah ( 1 − y ) ln  
1−y  1−y  1−y 

G My ( 1 − y
)i ,M dy
y1
G My dy

y1
Z=
y2 1 − y i 
FG ah ( 1 − y ) ln 
⇒ Z= ∫ FG ah (1 − y )( y − y i )
 y
1−y 
2

y1
 G My  ( 1 − y ) i ,M dy y1
( 1 − y )i ,M dy
Z= ∫  =  tG ∫
H= H tG N tG
y2  G h  (
F a 1 − y )( y − y i ) y2 (
1 − y )( y − y i )  
  height of gas phase number of gas phase
transfer unit transfer unit
constant
H tG

 Where
(1 − y ) − (1 − y i )
( 1-y )i.,M = logarithmic mean average of ( 1 − y ) , ( 1 − y i )
 (1 − y ) 
ln  
 (1 − y i ) 
 If arithmetic mean average is used
1 − y2 
y1
dy
=
N tG ∫
y2
y − yi
+ 12 ln  
1 − y1 
approximate value

CHEG351: Mass Transfer Chapter 4


Countercurrent Continuous Contact Equipment

Based on Gas Phase Based on Liquid Phase

Z= H tG N tG Z= = H tL N tL
   
height of gas phase number of gas phase height of liquid number of liquid
transfer unit transfer unit transfer unit transfer unit

G My G Mx
H tG = H tL =
FG ah FL ah

y1
( 1 − y )i ,M dy x1
( 1 − x )i ,M dx
N tG = ∫ N tL = ∫ 1 − x )( x i − x )
x (
y (
2
1 − y )( y − y i ) 2

1 − y2   1 − x2 
y1 x2
dy dx
=
N tG ∫ + 12 ln   approximate value N tL = ∫ + 12 ln  
y2
y − yi 1 − y1  x1
xi − x  1 − x1 

CHEG351: Mass Transfer Chapter 4


Dilute Solutions: Henry’s Law

 Fordilute solution when Henry’s law applies, the


equilibrium curve and operating line are straight lines
 It is convenient to use overall mass transfer coefficient
 Height of the packed column can be estimated by:
Absorption Stripping
Z = H tOG N toG Z = H tOL N tOL
   
Overall height of gas overall number of gas Overall height of liquid overall number of Liquid
phase transfer unit phase transfer unit phase transfer unit phase transfer unit

G My H
H=
tOG = H tG + tL
K y ah A G Mx
H tOL =
y1
dy 1 −y2 K x ah
=
N tOG ∫ y −y* + 1
2 ln
1 − y1  y1 
 x2 − m
y2

 y − mx 2 
ln  1
1 1
1 − + 
ln  ( 1 − A) + A

y 2 − mx 2  A  A x − y1 
=   1 m 
1 N toL =
1− 1−A
A

CHEG351: Mass Transfer Chapter 4


Thermal Effects during Absorption and Stripping

 For dilute gas mixtures and liquid solution mixtures it


is safe to assume isothermal operation
 When large quantity of solute gas are absorbed from
concentrated solution, absorption processes are
usually exothermic
 The equilibrium solubility of the solute may be reduced
due to increase of the temperature
 Stripping is usually an endothermic process
 Energy balance is required to account for the thermal
effects during absorption or stripping

CHEG351: Mass Transfer Chapter 4


Example
 Carbon Disulfide (CS2), used as a solvent in a chemical plant, is
evaporated from the product in a dryer into an inert gas (N2) in order
to avoid explosion hazard. The CS2-N2 mixture is to be scrubbed with
an absorbent hydrocarbon oil (C18H38). The gas will flow at the rate
of 0.4 m3/s at 297° K and 1 atm. The partial pressure of CS2 in the
original gas is 50 mm Hg, and the CS2 concentration in the outlet gas
is not to exceed 0.5%. The oil enters the absorber essentially pure at
1.5 times the minimum, and solution of oil and CS2 follow Raoult’s
law. Design a column packed with 50-mm ceramic Hiflow rings
(Ch=1.0). Assume isothermal operation. The gas pressure drop do not
exceed 175 Pa/m of packing. Calculate the tower diameter, packed
bed height and total gas pressure drop.
 The liquid and vapor properties are:
 Moil=254
 Density =810 kg/m3 CS2 vapor pressure = 346 mm Hg
 µL = 4 cP µV = 1.75x10-5 kg/m-s
 DL= 0.765x10-5 cm2/s DV= 0.114 cm2/s

CHEG351: Mass Transfer Chapter 4


Adiabatic Operation of a Tray Absorber

 For adiabatic operation of a countercurrent tray


absorber, the temperature of the streams leaving the
column will generally be higher the entering
temperatures Absorber

 The design of such absorber requires L0 V1

by calculating tray by tray from the 1


bottom of the column Ln n
Vn+1

 For ideal tray equilibrium with respect


to both temperature and composition N
LN
is assumed
VN+1

CHEG351: Mass Transfer Chapter 4


Adiabatic Operation of a Tray Absorber
 Solute balance around an envelope from the bottom of
the absorber up to tray n are:
 Overall Molar Balance Absorber

L n +V N +1 =L N +V n +1 L0 V1

 Individual (solute) molar balance 1


Ln n
L n x n +V N + 1 y N + 1 =
L N x N +V n + 1 y n + 1 Vn+1

 Energy Balance
L n H L ,n +V N +1 HV ,N +1 =
L N H L ,N +V n +1 HV ,n +1 N
LN
 Energy balance around the entire column VN+1

L0 H L ,0 +V N +1 HV ,N +1 =
L N H L ,N +V 1 H V ,1

 To get TN the temperature of the gas leaving tray 1 is


initially assumed and checked when the calculations reach
the top tray
CHEG351: Mass Transfer Chapter 4
Example:

 One kmole/s of a gas consisting of 75% methane and 25%


n-pentane at 300 K and 1 atm is t be scrubbed with 2
kmole/s of a non-volatile paraffin oil entering the absorber
free of pentane at 308 K. Estimate the number of ideal
trays for adiabatic absorption of 98.6% of the pentane.
Neglect the solubility of methane in oil, and assume
operation to be at constant pressure. The pentane forms
ideal solutions with the paraffin oil. The average
molecular weigh of the oil is 200, heat capacity is 1.844
kJ/kg. The heat capacity of methane over the range of
temperatures to be encountered is 35.6 kJ/kmole-K; for
liquid pentane is 177.5 kJ/kmole-K; for pentane vapor is
119.8 kJ/kmole-K. the latent heat of vaporization of n-
pentane at 273 K is 27.82 MJ/kmol.

CHEG351: Mass Transfer Chapter 4


Solution

1. Enthanlpy
 Take a reference temperature of 273 K
HL =( 1 − x ) c p ,oil M oil (T L − 273 ) + xc p ,C 5 (T L − 273 ) + ∆ H solution Oil Methane
L0 V1
=( 1 − x )( 1.884 )( 200 )(T L − 273 ) + x ( 177.5 )(T L − 273 )
(T L − 273 )( 376.8 − 199.3 x )
= kJ / kmole
1
HV =( 1 − y ) c p ,C 2 (TG − 273 ) + y c p ,C 5 (TG − 273 ) + ∆ H vap  2
=( 1 − y )( 35.6 ) (TG − 273 ) + y ( 177.5 ) (TG − 273 ) + 278200 
(TG − 273 ) ( 35.6 + 84.2 y ) + 27820
= kJ / kmole

2. Equilibrium LN
N
VN+1
 
Raoult’s law =
 i
y
PA x i
= mx i 
Oil+C4 C1+C4
 P 
 2477.07 
=PA exp 13.8183 − from Antoine equation
 T − 40 
 2477.07 
exp 13.8183 −
 T − 40 
m (T ) =
101.3
CHEG351: Mass Transfer Chapter 4
Solution Continued

3. Flow rates:
 Calculate required liquid flow to achieve 98.6%
removal of pentane
 Pentane entering with the incoming gas  kmol
=1 
 s
 kmol
 x 0.25=0.25 s

 kmol 
 Pentane absorbed =0.25 
 s
kmol
 x 0.986=0.2465 s

 Methane in the outgoing=methane in the incoming gas


kmol
V S =1 -0.25=0.75
s

kmol pentane in V 1 stream 0.25-0.2465


V 1 =V N+1 - Penatne absorbed=1-0.24651=0.7535 y1= = =0.0046
s V1 0.7535

kmol Penatne absorbed 0.24651


L N =L0 + Penatne absorbed=2+0.24651=2.24651 xN = = =0.1097
s LN 2.24651

CHEG351: Mass Transfer Chapter 4


Solution

 Enthalpy of the two streams entering the column (VN+1


and L0 )
(T0 − 273 )( 376.8 − 199.3 x0 ) =
H L ,0 = ( 308 − 273 ) ( 376.8 − 199.3 x0 ) =
13190 kJ / kmole

(T N +1 − 273 )( 35.6 + 84.2 y N +1 ) + 27820 =


HV ,N +1 = ( 300 − 273 )( 35.6 + 84.2 x .25 ) + 27820 =
8480 kJ / kmole

 To estimate the enthalpy of the other two streams,


assume T1 =308.5
(T1 − 273 )( 35.6 + 84.2 y 1 ) + 27820 =
HV ,1 = ( 308.5 − 273 )( 35.6 + 84.2 x0.0046 ) + 27820 =
81405 kJ / kmole

 To get the enthalpy of the liquid leaving the column


L0 H L ,0 +V N +1 HV ,N +1 =
L N H L ,N +V 1 H V ,1

2 x13190 + 1 x8480
= 2.2465 H L ,N + 0.7535 x1405
H L ,N = 15050 kJ / kmole

(T L ,N − 273 ) ( 376.8 − 199.3 x N ) =


H L ,N = (T L − 273 )( 376.8 − 199.3 x0.1097 ) =
15050 kJ / kmole
T N = 315.4 K

CHEG351: Mass Transfer Chapter 4


Solution

 The flow rate and composition of streams VN and LN-1


 2477.07   2477.07  Oil Methane
yN =
mx N =
exp 13.8183 −  xN =
xp 13.8183 −  0.1097 =
0.135 L V1
 T N − 40   315.4 − 40  0

VS 0.75
=
VN = = 0.867 kmole / s 1
1 − y N 1 − 0.135
2
L N = V N + L N −V N +1 = 0.867 + 2.2465 − 1 = 2.144 kmole / s

LN-1 n VN
 Repeat the same steps for the next tray N

and so on till you reach yn =< 0.0046


LN VN+1

where n is the number of trays Tn,


Tray # xn yn
K
N=4 315.3 0.1091 0.1340
N-1=3 312.0 0.0521 0.0568
N-2=2 309.8 0.0184 0.0187
N-3=4 308.5 0.0046 0.0045

CHEG351: Mass Transfer Chapter 4


Adiabatic Operation of a Packed-bed Absorber

 The release of energy due to latent heat and heat of solution


during absorption process leads to
 Increases the interface temperature above the bulk liquid
 Change the physical properties
 Change the mass transfer coefficient
 Change the equilibrium concentration
 This also may lead to solvent evaporation in the warm parts of
the tower (three components (A, B, and C) maybe present in
the gas phase)
 Design of packed column under these conditions require
simultaneous mass and energy transfer calculation and
balances

CHEG351: Mass Transfer Chapter 4


Design of Packed Column: Mass Transfer
 Mass transfer
 NA = molar flux of component A
 NB = 0 (component B does not transfer)
Solvent
 NC = rate of evaporation/condensation of solvent C
 The molar flux ratio A+ B
NA NC
ψA= ; ψC = ; ψ A +ψ C =1
N A +N C N A +N C

 The molar flux of A and C are


N A = ψ A FG, A ln
(ψ A - y A ,i ) mole
(ψ A - y A ) m2 ⋅s
dz
N C = ψ C FG, C ln
(ψ C - y C ,i ) mole
(ψ C - y C ) m2 ⋅s

 Molar flux in terms of Mass velocity of component B (GM, B)


-G M,B dY A =N A ah dz = ψ A FG, A ah ln
(ψ A - y A ,i ) dz mole
C+B
(ψ A - y A ) s
V V Gas

-G M,B dY C =N C ah dz = ψ C FG, C ah ln
(ψ C - y C ,i ) dz mole
Y A= A ;
VB
YC = C
VB
A+B
. (ψ C - yC ) s

CHEG351: Mass Transfer Chapter 4


Design of Packed Column: Energy Transfer

 .q G ah dz =hG,c ah (TG − T L ) dz
 qG is heat flux kJ/m2-s
 hG,c is gas phase convective heat transfer coefficient corrected for
mass transfer
 At Steady State
 dL=dV
 V=VB+VA+VC=(VB+YAVB+YCVB)=VB(1+YA+YC)
 dL=dV=VB(dYA+dYC)

 The temperature profile as well as the concentration


of the solvent inside the column as function of column
height can be estimated

CHEG351: Mass Transfer Chapter 4


Change of Temperature and yc

Mole
T, K Fraction

Height of Packing
CHEG351: Mass Transfer Chapter 4
1
V
y1 m Lm Vm+1
xm ym+1
m+1
1 L1 V2 L0
x1 y2
D
2 x0=xD xD VN
yN
N
Vn LN VN+1 B
yn xN yN+1 yW
n
Ln Vn+1 W
xn Yn+1
xW

1 1
Subcooled liquid
Saturated liquid
0.9 0.9

0.8 0.8 1
0.7
Partial vaporized
0.7 2
0.6 0.6 3
y0.5 Saturated vapor
y0.5
4
0.4 0.4

0.3 Superheated vapor 0.3 5


0.2 0.2
6
0.1 0.1
xW xF xD xW xF xD
0 0

CHEG351: Massx Transfer


0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
x
Distillation

 Method to separate the components of solution


depending on the distribution of substances between a
liquid and a gas phase
 All components will be present in both phases
 Unlike absorption, desorption or extraction no need for
external components to create
a second phase Condenser

 Energy requirement is usually Overhead


higher vapor Reflux
drum

 Carried out in tray columns Rectifying section


1
Reflux Distillate
(packed columns can also be used 2

for cases where pressure drop Feed Feed Stage

and/or corrosion are major


considerations) Stripping section
N Boilup

Bottoms
Reboiler
CHEG351: Mass Transfer Chapter 6
Flash Vaporization

 Single-Stage Operation
 Liquid mixture is partially vaporized
 Vapor is allowed to equilibrate with liquid
 The residual liquid and the resulting vapor are
separated and removed from the apparatus
 The product D is richer in the volatile components
Vapor
 The bottom W is richer in the least Heat
volatile components

Flash Drum
Exchanger
Feed
Valve

Q kW
Liquid

CHEG351: Mass Transfer Chapter 6


Flash Vaporization
D moles/s
yD
 Material balance HD

F= D + W

Flash Drum
F moles/s
F=z F D y D + W xW zF
 Energy balance HF

F H F +=
Q D H D +W HW Q kW W moles/s
xW
HW
 Solving the energy and material Balance
 equations

 Q 
HD −HF + 
W yD −zF  F
−= =
D xW −zF  Q 
HW −  H F + 
 F

CHEG351: Mass Transfer Chapter 6


Example
 A liquid mixture containing 50 mole% n-heptane (A), 50
mole% n-octane (B) at 303° K is to be continuously flash-
vaporized at a pressure of 1 atm to vaporize 60 mole% of
the feed. What will the composition of the vapor and
liquid and the temperature in the separator, if it behaves
as an ideal stage?
 The VLE relationship that applies under Raoult’s law. The
vapor pressure of the two components is related to
temperature through Wagner’s equation:
 Pj  A j χ j + B j χ 1.5 + C j χ j3 + D j χ 6j T
= χ j= 1 −
j
ln  ;
 Pc , j 1 − χ Tc , j
  j

 The parameters in this equation are:


Component Tc , K Pc, bar A B C D
N-heptane
 . 540.3 27.4 -7.675 1.371 -3.536 -3.202
N-octane 568.8 24.9 -7.912 1.380 -3.804 -4.501
CHEG351: Mass Transfer Chapter 6
Solution

xF 0.5  Pj
ln 
 A j χ j + B j χ 1.5
=
j + C j χ j3 + D j χ 6j
; χ j= 1 −
T
 Pc , j 1 − χj Tc , j
 
P 101325 Pa P j = Pc , j
 A j χ j + B j χ 1.5
exp 
j + C j χ j3 + D j χ 6j 

 1 − χj
D/F 0.6  
W/F 0.4
Component Tc, K Pc, bar A B C D
N-heptane 540.3 2.74E+06 -7.675 1.371 -3.536 -3.202
W/D 0.667 N-octane 568.8 2.49E+06 -7.912 1.38 -3.804 -4.501

Pheptane POctane POctane


=yD xW ; =
y octane = x octane ( 1 − xW )
P P P
 Pheptane − Poctane  Poctane
( )
Pheptane P
y D + y octane
= xW + Octane 1 − x heptane= xW   + = 1
P P  P P
 

 P  P  Pheptane
xW=  1 − octane 
 P  yD = xW
 P   heptane − Poctane  P

W yD −zF
− =
D xW − z F

CHEG351: Mass Transfer Chapter 6


Solution

 Assume T
 Calculate χhepatne, χoctane, Poctane, Poctane
 Calculate xW T 385.89

 Calculate yD χhep 0.286


χoct 0.322
 Calculate –W/D Phep 1.514 Pa
Poct 0.699 Pa
 Using Goal Seek function in excel the value of T that
give –W/D of 0.667 can be estimated x
y
0.39
0.58
w

d
-(W/D)estimate -0.67
 Q 
HD −HF + 
W yD −zF  F
−= =
D xW − z F  Q 
HW −HF + 
 F

CHEG351: Mass Transfer Chapter 6


Batch Distillation

 Continuous distillation is the most efficient distillation


method
condenser

 Batch distillation is preferred for: dD, y*

vapor
 Small capacity
 Separation is to be done only
L, x
occasionally QB Distillate

 Separation is preparative to produce a new product


 Upstream operations are batchwise or feedstocks vary
with time or from batch to batch
 Feed materials are not appropriate for a continuous flow
system

CHEG351: Mass Transfer Chapter 6


Batch Distillation

 Material balance
condenser

dD, y*

dL = −dD

vapor
d ( Lx ) =
0 − y * dD = Ldx + xdL
y *=
dL Ldx + xdL QB W, xw Distillate
Rearranging and intergrating D(t), y=yD=xD
F xF
dL F dx
∫L
W
= =
ln
W ∫
xW
y * −x
Rayleigh Equation

w here
F is the moles of charge of composition x F
W is the moles of residual liquid of composition xW

 The composited distillate composition, yD,av can be


estimated as follow:
Fx F −W xW
y D ,av =
D
CHEG351: Mass Transfer Chapter 6
Example

A liquid mixture containing 50 mole% n-heptane (A),


50 mole% n-octane (B) were subjected to batch
distillation at atmospheric pressure, with 60 mole% of
the liquid distilled. Compute the composition of the
composited distillate and the residue
 The VLE relationship that applies under Raoult’s law.
The vapor pressure of the two components is related
to temperature through Wagner’s equation:
 Pj  A j χ j + B j χ 1.5 + C j χ j3 + C j χ 6j T
= χ j= 1 −
j
ln  ;
 Pc , j 1 − χj Tc , j
 

 The parameters in this equation are:


Component Tc , K Pc, bar A B C D
n-heptane 540.3 27.4 -7.675 1.371 -3.536 -3.202
 .
n-octane 568.8 24.9 -7.912 1.380 -3.804 -4.501

CHEG351: Mass Transfer Chapter 6


Solution:
 D/F = 0.60
 W /F= 1-0.6 = 40
 xF = 0.5
 1 
xF 0.5
F dx dx
ln
W
= ∫ y * −x
ln  =
 0.40 
=
 0.916 ∫
xW
y * −x
xW

 Start with y* = zf
 Find xW by using goal seek function in excel and adjusting T to yield y*
 Change y* and repeat the last step
 Make a table for y*, xw
 Plot 1/(y*-xw) versus xw
 Curve fit the plot using polynomial fit
 Integrate the equation
 Evaluate the integration at x=zF and another lower value
 Estimate the difference of the integration at zf and the other x value
 Adjust the difference to be ln(F/W) i.e. 0.916 by changing x
 This is the final xw
 Find yD,ave=(FzF-WxW)/D

CHEG351: Mass Transfer Chapter 6


Solution Continued
Component Tc, K Pc, bar A B C D
N-heptane 540.3 2.74E+01 -7.675 1.371 -3.536 -3.202
N-octane 568.8 2.49E+01 -7.912 1.38 -3.804 -4.501

xF 0.5
P 1.0132739
D/F 0.6
W/F 0.4
Use Goal Seek Function to adjust y* by changing T
W/D 0.667

T 387.89334 386.593 385.2 383.831 383 382 380.8

χhep 0.282 0.284 0.287 0.290 0.292 0.292 0.295


χoct 0.318 0.320 0.323 0.325 0.327 0.328 0.331
Phep 1.597 1.543 1.488 1.432 1.392 1.375 1.318
Poct 0.742 0.714 0.685 0.657 0.636 0.628 0.598

xw 0.317 0.361 0.409 0.460 0.499 0.516 0.58


y* 0.50 0.55 0.60 0.65 0.69 0.70 0.75

CHEG351: Mass Transfer Chapter 6


Solution, Continued

 From the plot


1
= 22.54 x 2 − 18.96 x + 9.214
y * −x

0.5 0.5 0.5


dx
y * −x
( )
=0.916 =∫ 22.54 x 2 − 18.96 x + 9.214 dx =
22.54 3 18.96 2
3
x −
2
x + 9.214 x
xW xW xw

5.9

22.54 3 18.96 2 5.8


3.18 − xW − xW + 9.214 xW =
0.916
3 2
5.7

5.6 y = 22.544x2 - 18.968x + 9.214


R² = 0.9996

(y*-xw)-1
 Using Goal-Seek
5.5

5.4

 xW=0.327 5.3

5.2
F z F −W xW 1 x0.5 − 0.4 x0.327
=y D ,av = = 0.615
D 0.6 5.1
0.250 0.300 0.350 0.400 0.450 0.500 0.550 0.600
xW

CHEG351: Mass Transfer Chapter 6


Continuous Rectification-Binary Systems
 Continuous distillation (fractionation) is a multistage,
countercurrent distillation operation
 For binary solutions, it is possible to separate the solution into
its components
Total Condenser
 Distillation system components
Reflux Drum
 Column, total condenser, partial
reboiler, and reflux drum Reflux
 Sections Top stage 1 Distillate x

Rectifying Section
D

 Rectifying section (tray f to tray 1)


 Stripping section (tray N to tray f)
Feed z Feed stage
 Streams F f

Stripping
Section
 Feed (F, zF)
Bottom stage N
 Distillate (D, xD) Boilup

 Bottoms (W, xW) Partial reboiler


 Internal streams (reflux & boilup)
Bottom xW

CHEG351: Mass Transfer Chapter 6


McCabe-Thiele Method for Tray Towers

 Approximate graphical method to estimate the


number of equilibrium stages and the amount of
reflux required to a desired degree of separation
 The operating lines on the xy diagram can be
considered straight for each section of a fractionator
 This is true only if the total molar flow rates of liquids
and vapors do not vary from stage to stage
 Component A and B have equal constant molar latent heats of
vaporization
 Enthalpy changes and heat mixing are negligible compared to
latent heat of vaporization
 Heat losses are negligible
 Pressure is uniform throughout the column

CHEG351: Mass Transfer Chapter 6


Rectifying Section
V

 Material Balance: y1

V n +=
1 D + Ln
V n +1 =
y n +1 D x D + L n x n 1 L1 V2 L0
x1 y2
D
Ln D 2 x0=xD xD
=
y n +1 xn + xD
V n +1 V n +1

 For constant molar overflow: Vn


yn
n
= = V and
V n +1 constant =L n constant =L Ln Vn+1
xn yn+1
L D
=
y n +1 xn + xD
V V

L0 L
Reflux Ratio, =
R =
D D
L D L/ D D/ D
y n +1 = xn + xD = xn + xD
L +D L +D L/ D +D/ D L/ D +D/ D

R 1
=
y n +1 xn + xD Operating line for rectifying section
R +1 R +1

CHEG351: Mass Transfer Chapter 6


Rectifying Section-Number of Stages
V
y1

2 1 L1 V2 L0
x1 y2
D
2 x0=xD xD
3
5 4
Vn
yn
n
Ln Vn+1
xn Yn+1

CHEG351: Mass Transfer Chapter 6


Stripping Section

 Material Balance: m Lm
xm
Vm+1
ym+1
L= W +V m + 1 m+1
m

L=
m xm W xW +V m +1 y m +1
Lm W VN
=
y m +1 xm − xW yN
V m +1 V n +1 N
LN VN+1 B
 For constant molar overflow: xN yN+1 yW

= = V st and
V m +1 constant = L m constant =L st W
L st W xW
=
y m +1 xm − xW
V st V st

V st L st −W
Boilup Ratio, V=
B =
W W
V st + W W V st / W + W / W W /W
y m=
+1 xm − x=
W xm + xW
V st V st V st / W V st / W

VB + 1 1
=
y m +1 xm + xD Operating line for Stripping section
VB VB

CHEG351: Mass Transfer Chapter 6


Stripping Section

CHEG351: Mass Transfer Chapter 6


Feed Stage

 Material Balance around the feed stage f-1


F + L +V St = V + L st L
xf-1
V
yf

 Energy Balance F
f
Lst Vst
zF
FH F + LH L ,f −1 +V st H G ,f +1 =
VH G ,f + L st H L ,f xf yf+1
f+1

 Assuming that the enthalpy of all vapor


streams are identical and the enthalpy of all liquid
streams are identical
= (H =
H and H H )
G ,f + 1 G ,f L ,f L ,f −1

( L st − L ) H L ,f =
(V st −V ) H G ,f + FH F
L st − L H G ,f − H F
= = q ( the energy required to convert 1 mol of the feed to saturated vapor )
F H G ,f − H L ,f

CHEG351: Mass Transfer Chapter 6


Feed Stage and q-line
Feed Condition q-Value
1
Subcooled Liquid >1 Subcooled liquid
Saturated liquid

Saturated liquid 1 0.9

Partially vaporized 0<q<1 0.8

Partial vaporized
Saturated Vapor 0 0.7

Superheated vapor <0 0.6


y
Saturated vapor

q-line equation
0.5

0.4

q z
= x− F
Superheated vapor
y 0.3

1 −1 q −1
0.2

0.1

xD
The intersection of the operating 0
0
xW

0.1 0.2 0.3 0.4 0.5


xF
0.6 0.7 0.8 0.9 1

lines locates the feed stage x

CHEG351: Mass Transfer Chapter 6


Limiting Conditions

 Fora given specification, a reflux ratio can be selected


anywhere from Rmin to an infinite value (total reflux)
 As the reflux ratio increases the operating line of both
sections of the tower moves towards the 45° line until
they coincide
 Because the operating line is located as far as possible
from the equilibrium curve, a minimum number of
stages is required

CHEG351: Mass Transfer Chapter 6


Minimum Number of Stages

1
0.9

0.9 1
0.8
1
0.8 2
0.7

0.7
0.6 3
2
0.6 y
y 0.5
4
0.5
0.4

0.4 3 5
0.3

0.3
0.2 6
0.2 4
0.1

0.1 5 xW xF xD
0
xW xF xD 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
x
x

CHEG351: Mass Transfer Chapter 6


Minimum Reflux Ratio

 As the reflux ratio decreases from the limiting case of


total reflux ratio, the intersection of the two
operating lines and the q-line moves to from the 45°
line towards the equilibrium curve
 The number of ideal stages increases because the
operating line moves closer to the equilibrium curve
 A limiting condition is reached when the point of
intersection is on the equilibrium curve
 To reach the feed stage either from the rectifying or
the stripping section requires infinite number of ideal
stages
 The point of intersection (P) is called the pinch point

CHEG351: Mass Transfer Chapter 6


Minimum Reflux Ratio
1

0.9

0.8

0.7

0.6

y 0.5

0.4

0.3

0.2

0.1

0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
x

CHEG351: Mass Transfer Chapter 6


Optimum Reflux Ratio
 To reach a specific separation
any reflux ratio between
minimum and infinity can be
used
 The corresponding number of
theoretical stages will vary
from infinity to a minimum

Annual Costs, $/year


number
 The total cost of the operation
(the sum of the fixed and the
operating cost) will be
minimum at Ropt
 Ropt is usually 1.2-1.5 Rmin Rmin Ropt

Reflux ratio, R

CHEG351: Mass Transfer Chapter 6


Use of Open Steam

 For distillation of aqueous solution, steam can be used


to provide the heat required instead of using reboiler
 Using steam would result in increasing number of
stages F +V st =D + W
=
Fz F Dx D + W xw

D
1
xD

F
f
zF

Lst=W Vst
xW y=0

CHEG351: Mass Transfer Chapter 6


Tray Efficiencies

 Overall efficiencies EO can be estimated if the


Murphee efficiency of all trays are the same and the
operating and equilibrium lines are both straight over
the concentration range 
ln 1 + E

1 
 − 1 
A 
MGE

EO =
1
ln  
A 

 Alternatively,empirical correlation such as O’Connel


correlation can be used to estimate the overall
efficiency EO: E =0.5782 − 0.27511 log (αµ ) + 0.044923  loh (αµ ) 
O
 10
 L 10 L
2

where : 0.1 cP ≤ αµL ≤ 10 cP


µL = viscosity of the feed as liquid at the average temperature of the tower, cP
α = avaerage relative volatility, the ratio of the equilibrium concentration ratio
of A and B in one phase to that in the other
y * (1 − x )
α=
x (1 − y * )

CHEG351: Mass Transfer Chapter 6

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