Mass Transfer

GATE & ESE

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2
Contents
Chapter 1 Mass Transfer 05 - 28
Chapter 2 Mass Transfer Coefficient (KC) 29 - 40
Chapter 3 Distillation 41 - 73
Chapter 4 Extraction 75 - 96
Chapter 5 Absorption 97 - 106
Chapter 6 Humidification 107 - 111
Chapter 7 Drying 113 - 122
Chapter 8 Adsorption 123 - 127

3
4
 Mass Transfer

Chapter 1 – Mass Transfer

Unit Operation is of two types.
• Chemical Operation: Driving force is Chemical as well as Mechanical
• Mechanical Operation: Driving force is only Mechanical
Chemical Operation does not mean chemical reaction, the n is chemical because driving
force is not mechanical.
In chemical operation change takes place because of chemical driving force.

Chemical Driving Forces are

(i) Concentration difference
(ii) Mole fraction difference
(iii) Partial pressure difference
An operation can be Chemical Operation with or without presence of chemical driving
force.
Chemical driving force Results in Chemical Change.
An operation can be called a chemical operation if and only if it results in a chemical
change.

Chemical Changes are

(a) Change in concentration
(b) Change in mole fraction
(c) Change in partial pressure
Flow of fluid through a pipe having pressure difference between two ends is not a
Chemical Operation (No concentration change) but flow of fluid (let H2O) through a sugar
pipe is Chemical Operation (Concn change is there).
Driving forces present in a given system may be chemical or may be non-chemical. Both
results in the chemical change with different extents. If chemical driving force is present,
then extent of chemical change is more. But if it is not present, then extent of chemical
change decreases.
To sum up contribution of all driving forces, a word is introduced known as Potential
or Potential difference. As we are dealing with chemical operation, this word is named
as chemical potential difference. Hence, chemical Potential difference is defined as
summation of all driving forces.
If chemical potential difference is present, then also we are not sure whether chemical
change will happen or not. It means other than chemical potential difference there exist
some factors or parameters on which chemical change or chemical operation depends,
presence of these factors / parameters are required to bring the chemical change.
Collectively all those parameters or factors are named as chemical resistance.

5
 Mass Transfer

Finally, chemical operation can be written as Ratio of Chemical Potential difference to

chemical resistance.
• If chemical potential difference is zero and chemical resistance is non-zero, then
process is eligible for the chemical change and for chemical change to happen
process needs just the potential difference
• When chemical resistance is zero and chemical potential difference is not zero,
then process is even not eligible for chemical operation
• When both chemical resistance and chemical potential difference is zero. Then also
process is not even eligible, but no change is going to happen
So, from above case we can conclude that out of chemical resistance and chemical
potential difference, decision maker is chemical resistance, or we can say it is more
prominent out of two. If it is non-zero, then chemical change can happen but if it is zero
chemical change cannot happen.
Transfer of mass from one point to another point in a phase or from one phase to
another phase with help of a driving force is Mass Transfer.

Types of Mass Transfer

• Conductive mass transfer [motion is due to internal energy of molecules]
• Connective mass transfer [medium is moving]
For conductive heat transfer, there is no motion of molecules but for conductive mass
transfer there is motion of molecules, but medium remain, stationary.

Approach for heat transfer is particle based.

Approach for momentum is motion based.
Approach for mass transfer is medium based.

Conductive Mass Transfer

In this mode of mass transfer, mass transfer takes place in a stagnant medium,
molecules are moving by virtue of their thermal energy. Approach in mass transfer is
medium based. This is also known as Molecular Diffusion Mass Transfer.

Connective Mass Transfer

In this mode of mass transfer, mass transfer takes place by virtual of motion of medium,
which means along with particle motion medium motion is also contributing towards
mass transfer and this is the reason that this case is also known as bulk motion mass
transfer.
Bulk motion: Only medium is moving
Bulk motion Transport: Along with moving medium mass transfer [chemical operation]
also takes place

6
 Mass Transfer

• Convective mass transfer: between two phases

• Bulk motion transport: between single phases

5mol/min

Conductive MT
Gain of Loss of
5mol/min 5mol/min

Liquid Bulk MT Gas Bulk MT

−d(Gy) = d(Lx)

Convection is represented by Rate of Mass Transfer

Convective mass transfer and bulk motion mass transfer remains same for single phase
but becomes different for multiphase.

Some Basic Terms in Mass Transfer

 kg 
• ρi → Mass concentration of ith species in the solution.  3 
m 
 kg 
• ρ → Total mass concentration of the solution.  3 
m 
• wi → Mass fraction of ith species in the solution.
 kg  th
Pi  3  i concentration
m 
• wi → = It is dimensionless. 
P kg
Solution
m3
 kmol 
• Ci → Molar concentration of ith species in the solution.  3 
 m 
 kmol 
• C → Total Molar concentration of the solution.  3 
 m 
• xi → Mole fraction of ith species in the solution. (Liquid phase mole fraction).
 KN 
• pi → Partial pressure exerted by ith species in the given mixture.  2 
m 
 KN 
• P → Total pressure exerted by the gaseous mixture.  2 
m 
• yi → Mole fraction of ith species in the given mixture.

Such that ∑wi = 1, ∑xi = 1, ∑yi = 1, ∑pi = P

ci pi
=xi = , yi
c p

7
 Mass Transfer

Question:
Why we are not using mass or molar and why we are using concentration?
• Mass and moles do not give us absolute idea about the mass present at a given
point in a given volume if a given mass is dispersed in more volume, then conc. of
that mass at a given point decreases or it becomes less dense and mass transfer
always takes place to a higher dense region to a lower dense region.

200 kg 100k
Direction of MT
1000 m 3
100 m3

C = 0.2kg/m3 C = 1kg/m3

Even if mass of Box 1 is more transfer of mass has taken place from 2 → 1 as 2 is denser.
→ Average Velocities

Σfi ui
=
Σfi

fi → Basis over average is calculated

(i) Mass Average Velocity (u)

Σpi ui
u =
Σpi

(ii) Molar Average Velocity (U)

ΣCi Ui
U =
ΣCi

• Whenever the things are defined, they are always defined in terms of Lagrangian
approach (particle-based approach) and whenever the things are calculated
they are always calculated on basis of Eulerian (bulk) approach. (or continuum
approach).

Flux
Rate of change of any quantity per unit area normal to the direction of transport.
Direction of area and transport are same.
(1) Mass Flux
kg
Rate of transfer of mass per unit area normal to direction of diffusion. 2
(Represented by small letters.) m .s

ni = (ρi)(ui − uo)

8
 Mass Transfer

• uo is defined as velocity of observer and to calculate that we need another

observer, to solve this issue velocity of observer is assumed to be same as
medium’s average velocities as they are already known
(1) When observer is moving with velocity same as mass avg. velocity of given
medium

ii = ρi (ui − u)

(2) When observer is moving with velocity same as molar avg. velocity of given
medium.

ji = ρi (ui − U)

(2) Molar Flux

kmol
Rate of transfer of moles per unit area normal to direction of diffusion.
(Represented by capital letters.) m2 .s

(i) Ii = (Ci)(ui − u)

(ii) Ji = (Ci)(ui − U)

(iii) Ni = (Ci)(ui − 0)

Total Fluxes
(i) Total mass flux w.r.t. a stationary observer

∑ni = ∑(ρi )(ui − 0)

= ∑(ρi ui)
∑Ni = ρu

(ii) ii = ρi (ui − u)

∑ii = ∑(ρi)(ui − u)

= ∑(ρi ui) − ∑(ρiu)

= ρu − ρu
∑ii = 0

(iii) Ji = ρi (ui − U)

∑Ji = ∑(ρi)(ui − U)

= ∑(ρi ui) − ∑(ρi U)

= ρu − ρU

∑Ji = ρ(u − U)

9
 Mass Transfer

(iv) Ni = Ci (ui − 0)
∑Ni = ∑(Ci)(ui)
= ∑(Ci ui)
∑Ni = CU

(v) Ii = Ci (ui − u)
∑Ii = ∑(Ci)(ui − u)
= ∑(Ci ui) − ∑(Ci u)
= CU − Cu
∑Ii = C(U − u)

(vi) Ji = Ci (Ui − U)
∑Ji = ∑(Ci)(Ui − U)
= ∑(Ci Ui) − ∑(Ci U)
= CU − CU
∑Ji = 0

For binary Mixture u≠U

nA + nB ≠ 0 NA + NB ≠ 0

iA + iB ≠ 0 IA + IB ≠ 0

jA + jB = 0 JA + JB = 0

When u = U

nA + nB ≠ 0 NA + NB ≠ 0

iA + iB ≠ 0 IA + IB ≠ 0

jA + jB = 0 JA + JB = 0

Fundamental Equation of Mass Transfer

Take 1kg each of H2O and ethanol separated by a compartment. Now remove the
compartment and give them enough time to settle. So now check weight of each
compartment as density of H2O is higher. Mass Transfer will take place from H2O to
ethanol.
Mass transfer is always taking place because of two contribution molecular diffusion and
bulk motion transport
JA = CA (uA − U)

10
 Mass Transfer

= CAuA − CAU

JA = NA − CAU, as (NA = CAuA)

N 
JA = NA − CA total  Ntotal = CU
 C 

CA
= xA
C

JA = NA − xANtotal

NA = JA + xANtotal → Fundamental Equation of Mass Transfer

NA = Mass flux of A
JA = Molecular diffusion
xANtotal = Bulk Motion
Similarly, NB = JB + xANtotal
NA + NB = JA + JB + (xA + xB)Ntotal
NA + NB = Ntotal
So, JA + JB = 0

Fick’s Law for Molecular Diffusion

Molar flux of species A in a given direction with respect to an observer moving with a
velocity same as molar average of the medium is proportional to concentration gradient
of same species in same direction.

dCA
JAZ ∝
dz

dCA
JAZ = − DAB
dz

 Kmol 
 2 
 mS 

−) negative sign is because concentration gradient is -Ve.

(−
dz = m
dCA = Kmol/m3
DAB = Diffusivity / Molecular diffusivity / Molar diffusivity (m2/s)
DAB tells us the ease of Transport from A → B (How easily component A can diffuse into
component B.)

11
 Mass Transfer

Diffusivity is a name given to all those factors or parameters that support mass transfer
flux other than concentration gradient in case of molecular diffusion or stagnant
medium.

Reciprocal of Diffusivity is Chemical Resistance (s/m2)

dCA
JAZ = − DAB
dz

We know JA + JB = 0

dCA dCB
− DAB
0 = − DBA
dz dz

dCA dCB
−DAB + DBA
=
dz dz

Hence DAB ≠ DBA

Diffusivities are directional dependent terms which means it matters whether we are
mixing A in B or B in A
So, DAB = DBA is not possible only valid for special cases.
When CA + CB = Constant

dCA dCB
+ =
0
dz dz

dCA dC
= − B
dz dz

Hence DBA = DAB

Mass avg. and Molar avg. velocities are only defined when volume of mixing = 0 (only for
ideal solution).

ΣV
∅ = ∑Σ Vi Ci ui
∅ = Volumetric Avg Velocity

ΣV
Σ Vi = Partial Molar Volume
Ci = Concentration of ith species
ui = Avg Velocity of ith species

Mass Transfer is Totally Based on “IDEALITY”

In case of ideal solution diffusivities become “direction independent” i.e., DAB = DBA
(Magnitude)

12
 Mass Transfer

Diffusion of ‘A’ in Non-Diffusing ‘B’

For Gases
NA = JA + yA (Ntotal)
NA = JA + yA (NA + NB)
Mass transfer mode is “conduction + convection”.
As B is non-diffusing NB = 0 (as there will be no flux of B)
NA (1 − yA) = JA

We know that:

dCA
JAZ = − DAB
dz

PA
CA =
RT

PA
yA =
P
PA = yAP

Py A
CA =
RT

d  y AP 
NA ( 1 − y A ) =
− DAB  
dz  RT 

− DAB P dy A
NA ( 1 − y A ) =
RT dz

− DAB P dy A
NAdz =
RT (1 − yA )

z2 PD AB y A2 dy A
NA ∫ dz = − ∫ (1 −
z1 RT y A1
yA )

P
.DAB ln ( 1 − y A )
y A2
NA  z2=
− z1  y A1
RT

P  1 − y A2 
NA  z2 − z1  =. DAB ln 
RT  1 − y 
 A21 

z2-z1 = z

13
 Mass Transfer

PD AB  1 − y A2 
NA = RTz ln  1 − y 
 A1 

y y B 2 − y A1
=
ln ( y B 2 / y B 1 )
B log mean

P
=C
RT
CDAB ( y A1 − y A2 )
NA =
z y BLM

Arithmetic mean: Depends upon initial and final value only. Function remain same along
the path (path independent).
Logarithmic mean: Not only depend upon initial and final value but also along path.
Property of the function changes along the path. (path dependent)
• In logarithmic mean difference between end points is large
• When path matters arithmetic mean becomes logarithmic mean
• When path does not matter logarithmic mean becomes arithmetic mean

Within a given system NA does not change with change in Z but with different system NA
changes with change in Z.

Equimolar Counter Diffusion (NA = − NB)

For Gases:
NA + NB = 0 (This is an exception because generally NA + NB ≠ 0)
NA = JA + yA (NA + NB)
We know that
NA + NB = 0
NA = JA

dCA
NA = − DAB
dz

PDAB dy A
NA = −
RT dz

PDAB
NA .dz = − dy A
RT

z2 PDAB y A2
NA .∫ dz = − ∫ dy A
z1 RT y A1

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 Mass Transfer

N ( z − z ) = PDAB
A 2 1
−
RT
( y A2 − y A 1 )

CDAB

=NA
z
(y A1
− y A2 )

NA EMCD
NA DND =
y BLM

NA DND
= A diffusing into non diffusing B
NA EMCD
= Equimolar counter diffusion
yBLM is always less than 1.

Question:
Ammonia gas (A) is diffusing through a uniform tube 0.10m long contain N2 gas(B) at
1.01325 × 105 pa and 298 K. the diagram is given below. At point 1, PA1 = 1.0132 × 104 and at
point 2, PA2 = 0.507 × 104. The diffusivity DAB = 0.230 × 10−4 m2/s.
Calculate the flux JA* at steady state.

Solution:
Z2 − Z1 = 0.1m, DAB = 0.230 × 10−4 m2/s, T = 298K
PA1 = 1.0132 × 104, PA2 = 0.507 × 104

For equimolar counter diffusion NA = J*A

P
NA ( z2 − z1 ) =
− D ( y − y A1 )
RT AB A2

D
NA ( z2 − z1 ) =
− AB ( pA2 − pA1 )
RT

DAB ( pA2 − pA1 )

NA = −
RT ( z2 − z1 )

(
0.230 ∗ 10−4 0.507 ∗ 104 − 1.0132 ∗ 104 )
NA = − 8.314 ∗ 298 ∗ 0.1

0.230 ( 0.507 − 1.0132)

N = −
A
8.314 ∗ 298 ∗ 0.1

NA = 4.7 ∗ 10−4 mol/m2. s

15
 Mass Transfer

Question:
Water in the bottom of a narrow metal tube is held at constant temperature of 293 K.
The total pressure of the air (assumed dry) is 101325 Pa(1atm) and temperature is 293 K.
Water evaporate and diffuse through the air in the tube and the diffusion path is 0.1524m
long. Calculate the rate of evaporation at steady state in lb mol/h. ft2 and kg mol/s. m2.
The diffusivity of water vapor is 0.250*10−4 m2/s. Assume that system is isothermal.
Vapor pressure of water at 293K =2.341 ∗ 103Pa
R = 0.73 ft3.atm/lb mol.0R
DAB = 0.250 ∗ 10−4 m2/s = 0.969 ft2/h

Solution:
DAB = 0.250 ∗ 10−4 m2/s = 0.969 ft2/h
PA1 = 2.341 ∗ 103 Pa = 0.0231 atm
PA2 = 0 Pa
PB1 = P − pA1 = 1 − 0.0231 = 0.9769 atm
PB2 = 1 − 0 = 1atm

PB 2 − PB 1
=PB P=
ln ( PB 2 / PB 1 )
MB log mean

1 − 0.9769
=
ln ( 1 / 0.9769)

= 0.988 atm = 1.001 ∗ 105

C DAB ( y A1 − y A2 ) P DAB (PA1

− PA2 )
=NA =
z y BLM zRT PBM

=
0.969 ∗ 1 ∗ (0.0231 − 0)
0.730 ∗ 528 ∗ 0.5 0.988

= 1.175 ∗ 10−4 lb mol/h. ft2

=
0.250 ∗ 10.1325 ∗ ( 2341)
8314 ∗ 293 ∗ 0.1524 ∗ 1.001 ∗ 105

= 1.595 ∗ 10−7 kg mol/s. m2

For Liquids
Diffusion of A in Non-Diffusing B

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 Mass Transfer

Cavg DAB ( z A2 − x A1 )
NA =
z zBLM

Cz 1 + Cz 2
Cavg =
2

Equimolar Counter Diffusion

Cavg DAB
=
NA
z
(x A1
− x A2 )

Question:
In a single formula both Arithmetic Mean and Logarithmic Mean are used which have
different meaning. Can we use the simultaneously?
Answer:
Yes, we can use, because here Arithmetic Mean and Logarithmic Mean are taken for
different quantities.

Question:
Why in expansion of gases we use C and for liquid use Cavg?
Answer:
Because we are not depending on path in gas but in liquid we depend on path hence, Cavg
i.e., Arithmetic mean is taken.

Question:
An ethanol (A) - water (B) solution in the form of stagnant film 2.0 mm thick at 293K is
in contact with an organic solvent in which ethanol is soluble and water is insoluble.
Hence NB = 0. At point 1 the concentration of ethanol is 16.8% and the solution density is
972.8 kg/m3. At point 2 the concentration of ethanol is 6.8% and density is 988.1kg/m3 the
diffusivity of ethanol is 0.740*10-9 m2/s. calculate the steady state flux NA.

Solution:
The molecular weight of A and B are MA = 46.05 and MB = 18.02.
Basis = 100 kg solution
For 16.8% the mole fraction of ethanol

16.8
x A1 = 46.05 = 0.0732
83.2 16.8
+
18.02 46.05

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 Mass Transfer

xB1 = 1 − 0.0732 = 0.9268

For 6.8% the mole fraction of ethanol

6 .8
x A2 = 46 .05
= 0.0277
93.2 6 .8
+
18.02 46.05

xB2 = 1 − 0.0277 = 0.9723

Molecular weight at point 2:

100
M2 = = 18.75
0.1477 + 5.17

Molecular weight at point 1:

M1 = 20.07

ρ1 ρ2
+
M1 M2
CAvg = = 50.6 kg mol/m3
2

xB 1 + xB 2
xBM =
2

0.9268 + 0.9723
=
= 0.949
2

Cavg DAB x A2 − x A1
NA =
z XBLM

NA =
50.6 ∗ 0.74 ∗ 10−9 (0.0732 − 0.0277 )
0.002 0.949

= 8.99 ∗ 10−7 kg mol/m2. s

Question:
If the area of diffusion is constant then flux?
(A) Constant
(B) Varies
(C) Zero
(D) More data required

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 Mass Transfer

Variation of Flux and Rate of Mass Transfer vs Area

∆Z direction

H
Z of diffusion

(N )
A
A
z
( )
= NAA
z + ∆z

(N )
A
A z + ∆z ( )
− NAA
z 0
lim = = 0
∆z →0 ∆z ∆z

d
NA = 0
dz A
( )
NAA = constant A = constant, NA → constant

1
A = vary, NA → vary NA ∝
A

NA 1 A
= 2
NA 2 A1

(I) For Flat Slab: (Constant Area)

NA 1
= 1 (as A2 = A1)
NA 2

NA1 = NA2

NA2

NA1

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 Mass Transfer

(II) For Cylinder (Varying Area)

NA 1 r
= 2
NA2 r1

(III) For Sphere

NA 1 r22
= 2
NA 2 r1

Question:
Flux in a spherical body is diffusing at steady state. At the center when r = 0 flux of A
starts and as it reaches the point r = 0.5 flux becomes 10 kmol/m2s. And flux becomes 15
kmol/m2s after some time then calculate Radius at which it happens.

Solution:

NA 1 r2 10 r2
= 22 → = 2
NA 2 r1 15 0.25

10 × 0.25
r22 =
15
r2 = 0.40

NA. A = Constant
Rate of mass transfer as well as Rate of heat transfer does not depend upon Area,
whether area remain constant or varies, Rate always remain Constant

Rate Does not Depend Upon “Area of Diffusion”

Rates depend upon “Area of system”, if Area of system doubles Rate doubles.

20
 Mass Transfer

Dependence of Rate and Flux for a Single System

(i) Area of Diffusion is Constant
WA1 = WA2 (Rate of Mass Transfer)
WA1 = WA2 (Flux is Constant as area is Constant)

A (100%)

(ii) Area of Diffusion Varies

WA1 = WA2 (Rate Remains constant)
NA1 ≠ NA2 (Varying areas)
NA1 < NA2 (as A2 < A1)

Comparison of Two Systems with Similar Geometry

R1 R2
(I)

A1

A2

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 Mass Transfer

(i) A2 = 2A1
r2 = 2r1
wA1 ≠ wA2 (as system are different)
Value of flux at all port of (I) & (II) are same (as Systems are different)

W WA2 
=
NA 1 N
=  A1 
A2
 A1 A 2  (flux is constant)
 

(ii) A1 = 2A 2
r1 = 2r2

A1 A2
P P

wA1 ≠ wA2
(NA1)p = (NA2)p

This is a constant varying flux within System.

Comparison of different Systems with different geometry.

(I) (II)

(as Area of entering is Same) Hence flux will vary but Rate, will remain constant

wA1 ≠ wA2
(NA1) = (NA2)
(area of diffusion is different at p)

22
 Mass Transfer

r r

wA1 ≠ wA2
(NA1) = (NA2)

Diffusion of Spherical Naphthalene Ball in Air (Diffusion of A into

Non-Diffusing B)

r1

r2

NA = JA + yA NA & NB = 0

 p  dCA
NA  1 − A  =
− DAB
 p  dr

 p  D dp
NA  1 − A  =
− AB . A
 p  RT dr

PDAB dpA
NA .dr = − .
RT ( p − pA )

r2 PA2 PDAB dpA

∫
r1
NA .dr
= ∫PA 1
− .
RT ( p − pA )

23
 Mass Transfer

1 → Imaginary point having radius as that of ball initial

2 → Point far away from Naphthalene ball
Naphthalene ball is not our area under observation. Now from r1 → r2 area of diffusion
varies.
Hence NA varies →

rate wA
NA
= =
area 4π r 2

wA r2 1 PA2 PDAB dpA

4π ∫r1 r 2 ∫
.dr
= − .
PA 1 RT ( p − pA )

−w A  1 1 PDAB  p − pA2 
 − = + ln 
 p − p 
4π  r2 r1  RT  A1 

r2 ≫≫≫ r1

Hence

1 1
≪≪<
r2 r1

wA PDAB  p − pA2 
= ln 
4π r1 RT  p − p 
 A1 

Dividing both sides by r1,

wA PDAB  p − pA2 
= ln 
4π r 2
RTr1  p − p 
1  A1 

In terms of pressure,

C DAB pA1 − pA2

( N )r = r
A
1
=
r1 pBLM

In terms of yA,

C DAB y A1 − y A2
NA =
r = r1 r1 y BLM

This is a case of “Pseudo Static State” - state where changes with respect to time are
very slow.

24
 Mass Transfer

Condition
Diffusion species is very-very small and diffusion medium is very large
With time radius of naphthalene ball is changing and that’s why rate of mass transfer
also changes with time but modelling of this process is done by using steady state
assumption and neglecting changes with respect to time.
Reason behind this is that diffusing species (naphthalene ball) is very small size and
medium in which it is diffusing is very-very large (atmosphere).
→ PA1 and PA2 are vapor pressure

Diffusion in Solids
Diffusivities 10−5 cm2/s (gas)
10−9 cm2/s (liquids)
10−12 cm2/s (solids)
Diffusivity on case of solid is of magnitude 10−12cm2/s and that’s why diffusing flux which
is obtained by multiplying this diffusivity with gradient is very small.

Question:
What is needed to study diffusion in solids if flux is very small?
Answer:
In the case of diffusion in solid magnitude of flux and diffusivity is very low but still it is
important to us because of its practical application.
In case of diffusion in solids flux is only because of molecular diffusion not because of
bulk motion and that’s why

NA = JA or NA + NB = 0

Porosity: Measure of void spaces in medium

Volume of voids
Total volume

Tortuosity: Property of curve being tortuous (twisted, having turns)

(length of curve) = c
(Distance between two ends) = L

c
τ =
L

25
 Mass Transfer

Diffusion Because of Fick’s Law Diffusion Because of Knudsen Law

d>λ
d<λ
Particle - Particle collision matters
• Particle - wall collision matters
• Value of λ < 1, known as KNUDSEN No.
d λ
• Value of > 1 known as KNUDSEN No.
• Governed by Fick's law d

dCA • Governed by Knudsen law

JA = DE
dz
dCA
JAK = − Dk
DE = Effective diffusivity contains dz
(Diffusivity, Porosity and Tortuosity)
Dk = KNUDSEN Diffusivity (does not
depend upon DAB)

2
Dk = r VT
3 p

8RT
VT =
πM
V T = Root mean Sq. Velocity
rp = Radius of Pore

8RT
VT =
πM

M = Molecular weight
KNUDSEN: Name given to all the system
where scale is less than 10−10

Variation of Diffusivity vs Temp & Pressure

(i) For Gases
3
D ∝ T2
AB

1
DAB ∝ P

26
 Mass Transfer

(ii) For liquid

DAB ∝ T
DAB is independent of Pressure

(iii) For solids

1

( )
D ∝ T 2
AB

DAB is independent of Pressure

Question:
What is difference between correlation and fundamental laws?
• Correlation: Extend to which two or more variables fluctuate together (valid only for
a particular range)
• Fundamental law: Generalized rule to explain the observed behavior of bodies.
(Valid always no range is Required)
Flux Varies as Same as Reaction Rate:
(i) A + 2B → 3C

rA r r
− =− B =C
1 1 3

NA N N
− − B =C
=
1 2 3

(ii) A → 2B

−NA NB
=
1 2

NA
= ?
NA + NB

= −1
For EMCD & for solid

NA
= infinite
NA + NB

For diffusion A & Stagnant B

NA
= 1
NA + NB

27
 Mass Transfer

For dilute solution hence

NA
= not defined
NA + NB

28
 Mass Transfer Coefficient (KC)

Chapter 2
Mass Transfer Coefficient (KC)
Rate of Mass Transfer depends upon driving force mainly concentration difference as well
as depends upon the area of system.

wA ∝ A.∆CA
wA = kC A.∆CA

WA
= NA= kC ∆CA
A

Mass Transfer Coefficient is Defined as Ratio of Flux to Driving Force

NA
kC =
∆CA

For Gases,

NA = kC ∆CA

kC
NA = ∆ PA
RT
kC
NA = kG ∆PA, kG =
RT

NA = ky ∆yA ,
ky
kG' =
P

ky kC
kG
= =
P RT
For Liquids,
NA = kL ∆CA
CA
NA = kL Cavg ∆xA, = xA
Cavg
CA = xA Cavg
NA = kx ∆xA
kx = kL Cavg

Mass transfer coefficient is a name given to all those parameters or factors that support
mass transfer flux other than Concentration difference.

29
 Mass Transfer Coefficient (KC)

Comparison Between DAB & kC (MTC)

• DAB is defined only for molecular diffusion, whereas kC is defined for both molecular
diffusion as well as bulk motion, the transport.
• DAB → m2/s, kc → m/s
• DAB is Theoretical quantity given by Fick’s Law and then later on attempts were
made to calculate it experimentally, on the contrary side MTC is an experimental
quantity in origin and then later on attempts were made to define it theoretically.
Heat Transfer Coefficient (h) is unique as driving force for Heat Transfer is unique (Temp.
difference) on other side MTC is not unique and it depends upon driving force as driving
force changes from concentration to partial pressure MTC Coefficient changes from
kc → kg

Theories from Mass Transfer Coefficient

(1) Film Theory (Given by Whitman in 1923)

Area of observation: The region just near to the interface between flowing fluid over
a flat slab.
Flat slab can be of any material but only condition is it should be soluble in fluid
stream flowing over it.
Molecular diffusion occurs at layer just adjacent to flat slab and bulk motion
transport occurs at all other surface.

→ Key Points of Film Theory (Assumption)

(i) Mass transfer takes place at steady state. (mass in = mass out)
(ii) Mass transfer takes place only because of molecular diffusion near the phase
boundary within a confined region named as the Film by Whitman
(iii) Mass transfer takes place within the film only due to molecular diffusion and
outside the film fluid is well mixed having a concentration equal to same as bulk
fluid concentration (Definition of Film Theory)

‘We know’
NA = JA + xa N
xa N → 0 (This is taken as zero because it is not under over Consideration)
NA = JA (This Shows constant flux)

dNA
=0
dz

d  dCA 
 −DAB .  =
0
dz  dz 

30
 Mass Transfer Coefficient (KC)

d 2CA
−DAB . =
0
dz 2

DAB ≠ 0

Hence

d 2CA
=0
dz 2

(This given linear profile)

cA = c1 x + c2

CAi Interface

Solid Liquid

CAi

CAb

Z=0 Z=δ

Here the film is hypothetical and does not exist in real and is just an assumption.
at x = 0 CA = CAi
x=δ CA = CAb

CAi = C2

CAb = c1 δ + CAi

CAb − CAi
c1 =
δ

31
 Mass Transfer Coefficient (KC)

CAb − CAi
=CA
δ
(x) + C Ai

dCA C − CAi
= Ab
dz δ

We know that

dCA
NA = − DAB .
dz

 CAb − CAi 
NA = − DAB .  
 δ 
 

 CAi − CAb 
NA = DAB .  
 δ 
 

DAB
= kL
δ

Using definition of MTC (all factor other than ∆C are MTC)

NA = kL (CAi − CAb)
kL ∝ DAB

1
kL ∝
δ

Question:
Ammonia is diffusing in a confined atmosphere from its original partial pressure of
450 mmHg to 320 mmHg. Length of area of observation of 25 cm in which ammonia is
diffusing. The diffusivity of ammonia is given as 4.5 × 10−5 m2/s and solubility of ammonia
in atmosphere is 1.2 kg/m3. Total pressure is given as 1 atm and T = 25°C. Determine value
of MTC?

Solution:
∆P = 130 mmHg, D = 4.5 × 10−5 m2/s, L = 25 cm
xNHg = 1.2 Kg/m3, PT = 1 atm, T = 298K
NA = KG (∆P)
whenever it is asked to find MTC, simply use this relation:

DAB
kL =
δ

32
 Mass Transfer Coefficient (KC)

4.5 × 10
−5

=
.25
= 18 × 10−5 m/s
This is used for easier calculation answer would otherwise come out to be same.

DAB
NA
=
z
( ∆C )
DAB
=
RTZ
( ∆p)

(2) Penetrating Theory (Higbie in 1935)

Area of Observation: Area of contact of the liquid element with spherical gas bubble.

→ Key points of Penetrating Theory: (Assumptions)

(i) Mass transfer takes place at unsteady state
(ii) Equilibrium exists at gas liquid interface
(iii) Contact time for all liquid element residing on gas bubble is same

B+C
Liquid Bulk

A+C

Gas Bubble

Liquid Bulk

Maximum Achievable Separation is Chemical Equilibrium

Fick’s 2nd Law

∂ 2CA 1 dC
= .
∂z 2
DAB dt

DAB
Instantaneous MTC kL =
πt

33
 Mass Transfer Coefficient (KC)

DAB 1
kL= 2 → kc ∝ ( DAB ) 2
avg
π tc

(3) Surface Renew all Theory: (Danckwerts in 1954)

The drawback of penetration theory is the concept of contact time and in a
turbulent medium any particle from fresh bulk replace particle present on spherical
gas bubble and there is no preference.

Probability of the replacement is same, and replacement is equally likely.

kL ∝ DAB . S

Surface Renewal frequency (S) → fraction of surface area renewed per unit time.

Total area − Travelled area

S=
Total area per unit time

• Contact time of liquid element are not same

• Concept of RTD is used and Age intervals of residence time of liquid element over
spherical bubble were created by Danckwerts

Two Film Theory (By Lewis & Whitman 1924)

Valid for Solid-Solid, Solid-Fluid & Fluid-Fluid interaction
Purpose: To explain process for Mass Transfer.

Gas to Liquid Transport

Liquid Bulk

Gas bulk (yAb − yAi)

yAb xAi
XAb

yAi (yAi − xAb)

δ δ

Equilibrium exist at interface because of its negligible thickness.

NA
= k y ( y Ab − y Ai ) (x Ai
& y Ai )may or may not be an equal)
g

NA
= kx ( x Ai − x Ab )
L

34
 Mass Transfer Coefficient (KC)

y Ai = kx A (Equilibrium Relationship)
i

Three Steps for Mass Transfer

(i) Transport from Gas Bulk to Gas interface
(ii) Diffusion at Interface
(iii) Transport from liquid interface to liquid Bulk

ky (yAb − yAi) = kx (xAi − xAb)

k
− x ( x Ai − x Ab )
y Ai − y Ab =
ky

This equation is similar of equation of line passing through (xAb, yAb)

And having slope of

kx
= −
ky

Question:
Air is concentrated with a solute P having a bulk mole fraction of 0.4. Mass transfer takes
place from gas side to liquid side through diffusion. The bulk concentration of P in liquid
phase xAb = 0.02. The interfacial equilibrium relationship is given as y = 1/2x where x and
y are interfacial Conc. Values of mass transfer coefficient for gas side and liquid side are
identical. Determine value of interfacial concentration.

Solution:
1
=y Ab 0=
.4 , x Ab 0.=
02 , y Ai x
2 Ai
yAi − 0.4 = −1 (xAi − 0.02)

yAi − 0.4 = 0.02 − xAi

3
x = 0.42
2 Ai

0.42 × 2
x Ai =
3
xAi = 0.28, yAi = 0.14

(i) For same data kY = 4.5 × 10−2 Kmol/m2s. Then determine flux

NA = (4.5 × 10−2) (0.4 − 0.14)

= (4.5 × 10−2) (0.26)

= 0.0117 Kmol/m2s

35
 Mass Transfer Coefficient (KC)

Graphical Analysis
At end of separation solute will be present more in liquid than in Gas. Hence x > y

yAb

yAi

XAb XAi

k
(y Ai
− yb ) =
− x ( x Ai − x Ab )
ky

yAb > xAb

This is always true else mass transfer will not take place.

Steps
(i) Eqm curve
(ii) Draw operating line (comes from mass balance)
NA = ky (yAb − yAi) = kx (xAi − xAb)
Relationship at the interface cannot be determined and that’s why interface conc. yAi
calculated cannot be determined accurately. Hence, flux determination is not accurate.

Overall Mass Transfer Coefficient (K)

Ky - overall MTC based on gas side
y
Kx - overall MTC based on liquid side.

yAb

yA = mxA
X
XAb XAb*

36
 Mass Transfer Coefficient (KC)

System Equilibrium Curve

x*Ab → value on Eqm curve corresponding to yAb, does not exist in Reality. (Mathematically
accurate)
Process Equilibrium curve can be determined by the experiment and is now available in
literature also.
yA = mxA

y Ab
x Ab
∗
=
m

y Ab
∗
= mx Ab

Overall driving force is (yAb − xAb) but xAb and yAb are for liquid and gas phase and hence
cannot be compared. Hence, we calculate y Ab ∗
and x Ab
∗

(y Ab
− y Ab
∗
)
Overall gas phase driving force,
(x
∗
Ab
− x Ab ) Overall liquid phase driving force,
(Overall MT Resistance)GAS = (Gas phase MT Resistance)GAS + (Liquid phase MT Resistance)GAS

1 1 m
= +
Ky Ky kx

(Overall mass transfer resistance in gas phase.)

1 1 m
= +
Kx Kx mk y

(Overall mass transfer resistance in liquid phase.)

1 1
and
Ky Kx

(Cannot be compared as their domains are different.)

1 m
>
Ky Kx

This shows gas phase is controlling.

• To increase the overall mass transfer rate, we decrease the resistance of the
controlling side
• If it is given that solute is highly soluble in gas side, it simply means it is less
soluble on liquids or in other words liquid side resistance is high and liquid phase
will control mass transfer process
Absorption: Gas phase controlled
Stripping: Liquid phase controlled

37
 Mass Transfer Coefficient (KC)

Extraction: Raffinate phase controlled

Drying: Solid phase controlled

Distillation
Liquid phase is controlled (This is so because there is no presence of vapor phase. Vapor
phase is formed during distillation process)
Nu = 1 → This means there is no convection
Because of motion, Nu is always > 1
Nusselt considered → convective flux = conductive flux + Motion flux.
For very dilute solution (NA + NB) bulk motion flux becomes zero.

Sherwood No. (Sh)

Sherwood Number is a dimensionless number used in the calculation of Mass transfer. It
is defined as the ratio of “Convective mass transfer rate to Diffusive mass transfer rate”

kl L Convective Mass Transport

=
DAB Molecular Mass Transport

Schmidt No. (Sc)

Schmidt Number is a dimensionless number which is the ratio of momentum Diffusivity
to mass Diffusivity (or) velocity boundary layer to concentration boundary layer.
This is analogous to Prandtl number in heat transfer. This is used to characterize flows
when there is simultaneous momentum and mass transfer.

µ Momentum diffusivity
=
ρ DAB Mass diffusivity

Nusselt Number (Nu)

Nusselt Number is the ratio of heat transferred by convection to the heat transferred by
conduction. It shows how much is heat is transferred due to fluid motion as compared
to the heat transferred by fluid by the process of conduction.
Nusselt Number is the ratio of conduction resistance offered by fluid if it were stable
to the convection resistance offered by fluid. Remember it is always greater than one in
case of fluids.

hA∆T Convective heat transfer

=
KA∆T Conductive heat transfer
L

h Conductive resis tan ce

=
K Convective resis tan ce
L

38
 Mass Transfer Coefficient (KC)

Prandtl No. (Pr)

Prandtl number is a non-dimensional number which gives the ratio of momentum
diffusivity to thermal diffusivity.

Significance
Tells us how fast the thermal diffusion takes place in comparison to momentum
diffusion.
Tells us the relative thickness of thermal boundary layer to momentum boundary layer.
If Prandtl number is small, it tells us that thermal diffusion is dominant in comparison to
momentum diffusion.
That is for a given fluid flow problem, the flow conditions remaining the same, if we want
higher heat transfer rate, we have to use a fluid that has lower Prandtl number.

cp µ ν Momentum diffusivity
= =
K α Thermal diffusivity

Lewis No. (Le)

Lewis Number is also a dimensionless number which is the ratio of thermal Diffusivity to
mass Diffusivity or Schmidt number to Prandtl number. This is used to characterize flows
in which there is simultaneous heat and mass (by convection) transfer.
If Lewis number is greater than one, then explains the predominance of concentration
boundary layer. If it is equal to one it either gives the transfer of both mass and heat or
the presence of velocity boundary layer which hinders the transport of heat and mass.

Sc µK K
= =
Pr PDAB .cp µ PDAB .cp

Reynold’s Analogy
Valid only for turbulent flow and when (Pr) = (Sc) = 1

f kc h
= =
2 Vavg ρ cpVavg

(f, Kc are constant)

Fails when laminar flow is there or fluid is very viscous

J-Factor Analogy / Chilton Colburn Analogy

Valid for turbulent as well as laminar flow.
2 2

f Kc ( Sc ) 3 h ( Pr ) 3
= =
2 Vavg ρ cpVavg

39
 Mass Transfer Coefficient (KC)

b
K 1 d1  V1 d1 
Sh a ( Pr ) ( Sc )
b c
= = 
K 2 d2  V2 d2 

These analogy enables the calculation of the heat transfer coefficient and the mass
transfer coefficient.

40
 Distillation

Chapter 3 – Distillation
Defined as preferential separation of more volatile component from less volatile
component on basis of their relative volatility with help of reboiler followed by a
condenser.

Overhead Condenser

Trim
Cooler

Distillation
Tower
Reflux
Feed Drum

Product
Reboiler

Bottoms Pumps Reflux Pumps

In distillation whenever we talk, we talk only for the more volatile component.

Important Parameters for Distillation

• Temperature
• Pressure
• Liquid Mole fraction
• Vapor Mole fraction

Degree of Freedom
Degree of freedom tells us difference between no. of equation and no. of variables.
For distillation binary DOF = 2, which means either we need 2 more equations, or 2
variables need to be defined by the system.
For distillation pressure value is taken as 1 atm and temperature at particular tray is
constant. Hence, by defining pressure only system can be defined.

41
 Distillation

T-x-y Diagram at Constant Pressure

Boiling temperature
of pure B
Vapour composition
line

Temperature "y" "x"

liquid composition line

Boiling temperature
of pure A

OB 0.5 B I.O B
I.O A 0.5 A OA

Composition of mixture - mol fraction

Vaporization takes place because of latent heat.

Below TB → Cold liquid state ← Below TA
Above TB → Super-heated vapor stage ← Above TA
TB → Boiling point or Bubble point.
→ Liquid at its bubble point - Saturated liquid.
→ Vapor at its dewpoint - Saturated vapor.

For Mixture
Boiling point Range and Dew point Range exist
Partial liquid or vapor – means liquid or vapor are both Saturated.
Nothing is present between the Curves.
At Bubble point curve x APA + ( 1 − x A ) PB =
P
ν ν

Vaporization diagram for mixture

Bubble point curve

42
 Distillation

Bubble Point Curve

Boiling for more volatile component is easier.
Condensation for less volatile component is easier.

Condensation Diagram

Dew point curve

Condensation

Tie Lines
These lines connect liquid mole fraction and vapor mole fraction and gives us
equilibrium relationship between both.

Observation from T-x-y Diagram

(i) Bubble point curve and dew point curve are different for case of mixture and both
are same for case of single component
(ii) For case of mixture dew point is always greater than bubble point as boiling
proceeds by increase in temperature and condensation proceed by decrease in
temperature
(iii) For the initial region of vaporization more volatile vaporizes more and similarly for
initial region of condensation less volatile condenses more
(iv) There can be infinite No. of Tie lines in T-x-y diagram
(v) In T-x-y diagram during vaporization, vapor always forms at its dew point and during
condensation liquid always forms at its bubble point
(vi) For a given feed boiling point range and dew point range are defined and constants
and the difference between them are same

Experimental Determination of T-x-y Diagram

(I) For a given feed F and xf are known
(II) As A and B both components are known. Their corresponding boiling point are also
known from literature and corresponding vapor pressure are known from Antoine
Equation

43
 Distillation

B
Ln p=
ν
A−
C +T

pν = Vapor pressure,
A, B and C are Constant
T = temperature
If T is in °C, pν → mmHg
If T is in K, pν → kPa
(III) Between TA and TB. Let’s assume any temp known as observation temperature.

pA x A pν
yA
= =
P P
(IV) Find A using law of Boiling

P= pνA x A + ( 1 − x A ) pνB

(V) Find yA using

pA x A pν
yA
= =
P P

(VI) Overall Mass Balance & Component Balance

F = L + V, Fxf = LxA + VyA

Relative Volatility
Defined as concentration ratio of component A to component B in vapor phase to same
ratio in liquid phase.

 pA 
 
 p 
yA  pB 
 
yB  P 
α= =
AB
xA pA
xB pAu
pB
PBu

Relative Volatility tells us ease of separation. Where pAu is the vapor pressure of A and pB
u

is the vapor pressure of B.

44
 Distillation

 B 
exp  A − 
pu
 C + T 
α=
AB
=A

Pu
 B' 
B
exp  A' − 
 C ' + T 

α = f(T)
Relative Volatility is Temp. sensitive
Relative Volatility cannot be changed by pressure directly.

Question:
Cyclopentane and Benzene are separated by using distillation. Bubble point of both of
them are given as 49.2°C and 80°C. The Antoine Constant value for Cyclopentane are
A = 15.8602, B = 2589.2 and C = 251.36 and for Benzene are A = 15.9037 B = 2789.0 C =
210.79.
(i) Calculate mole fraction of liquid and vapor, respectively
(ii) Calculate flow rate of liquid and vapor
(iii) Calculated α at this temp

Solution:

 2589.2 
=PAν exp  15.8602 − 
 251.36 + 49.2 


 2789.0 
=PAν exp  15.903 − 
 210.79 + 80 


101.3 kPa = 1 atm.

Pαν = 1436 mmHg, Pν = 551 mmHg
B

760 = (1436)(xA) + (1 − xA) 551

xA = 0.236

yA =
(0.236)( 1436)
( 760)
= 0.446

Feed. F = 100, xF = 0.42

100 = L + V
42 = LxA + VyA
42 = 0.236L + V(0.446)
L = 11.96 V = 88.03

45
 Distillation

pAu
α =
pBu

α = 2.606
With increase in temperature Relative Volatility decreases and with decreases in
temperature Relative Volatility increase.

yA yA

=α
yB
= ,α
(1 − yA )
xA xA
xB (1 − x )A

y (1 − x )
α =
(1 − y ) x
αx
y =
1 + (α − 1) x

y → mole function initial vapor which are in correspondence with x of feed.

When x → xw , then y → mole fraction of final vapor.

PyA = x APAν and

αx
y =
1 + (α − 1) x

(Used to generate x − y data)

Batch Distillation

D, XD

QR
W, XW

Still Pot

Still pot contains a mixture of A + B that needs to be distilled. Steam is introduced into
the still pot which provides necessary heat required for distillation. On introduction of
heat more volatile component starts to vaporize and vapor formation takes place.
Initially these vapors rich in more volatile component but later on less volatile
component also participate in vaporization process. These vapors are then directed
towards condenser. If distillate so obtained is collected in distilled drum. If distillate

46
 Distillation

of different concentration is desired, then this process can be reheated at different

temperature and for different time duration.
Let F be number of moles initially present in the still pot.
Let W be number of moles left in still pot after the distillation and is known as residue.
Let D be number of moles collected in drum known as distillate.
xf → Mole fraction of more volatile present in still pot initially.
xw → Mole fraction of more volatile left in still pot after the distillation and is known as
residue mole fraction.
xD → Mole fraction of more volatile present in distillate stream after distillation, and is
called distillate mole fraction.
L → Number of moles present in still bot at any time t during distillation.
V → Number of moles of vapor formed during distillation in still pot.
x → Mole fraction of more volatile in liquid (L) during distillation in still pot at any time t.
y → Mole fraction of more volatile vapor present in pot at any time t.

F=D+W
Fxf = DxD + Wxw
−dL = dV
−d(Lx) = ydV
−(Ldx + xdL) = y.dV
−Ldx + xdV = y.dV
−Ldx = (y − x)dV
−Ldx = (y − x)(−
−dL)

dL dx
=
L y − x

y.dV → This shows mass of more volatile component formed in vapor.

−d(Lx) → Mass of liquid disappearing.
Batch distillation is also called Differential Distillation (as it is solved using a Differential
Equation) and Simple Distillation

W dL xw dx
∫F L
= ∫x f y − x

W   y − xw 
ln   = − ln 
 y − x 
F   f 

F xf dx
ln
W
= ∫x w y − x
(Rayleigh equation)

47
 Distillation

Question:
A change of 50 kmol of mixture of Benzene and Chlorobenzene having 55% mol of less
volatile is to be batch distilled. If 25 kmol of solution is vaporized and condensate as
distillate. Then calculate concentration of the accumulated distillate. Given relationship
between mole fraction of more volatile in corresponding liquid and vapor as y = 0.7x + 0.15

Solution:
F = 50, W = 25, D = 25

 25  xw dx
ln   =
 50 
∫0.45 0.15 − 0.3 x

 0.15 − 0.3 ( 0.45 ) 

(0.3) ( −ln ( 2) ) =
ln 
 0.15 − 0.3 ( x ) 

  w

 0.015 
−0.3 × 0.693 =
ln  
 0.15 − 0.3 x
 w 

0.015
0.81 =
0.15 − 0.3 xw

0.1215 − 0.243xw = 0.015

xw = 0.44
(50)(0.45) = (25) xD + (25)(0.44)
xD = 0.46

αx
pyA = PAν x A and y =
1 + (α − 1)
x

(Use this equation where a Relationship b/w x and y is not given)

Question: Same question but α = 2

Solution:

2x
y =
1+ x

dx
ln ( 0.5 ) =
xw
∫y s 2x
− x
1+ x

1 + x .dx
ln ( 0.5 ) =
xw
∫y s 2x − x − x 2

48
 Distillation

xw 1 + x .dx xw 1 + x .dx
= ∫= ∫y
y x − x
s
2
s
(
x 1 − x2 )
xw 1 2 
= ∫y  +
x 1 − x
 dx
s
 

x
ln ( x ) − 2ln ( 1 − x )  w
  ys

 0.45   0.55 
ln   − 2ln  
 xw   xw 


( xw ) 
2
0 . 45
ln  × ln ( 0.5 )
 =
 x 2 

 w ( 0 . 55 ) 


0.45
. x = 0 .5
(0.55)(0.55) w
xw = 0.376

(50)(0.45) = (25)(xD) + (0.336)25

xD = 0.564

 FxF   F ( 1 − xF ) 
ln   = α ln  
 WxW   W ( 1 − xW ) 
 

Use this Equation when relation using α is given

Question:
Same data, Calculate value of first vapor mole fraction?

Solution:
This is calculated by putting x = xf in α relation.

y =
( 2)(0.55)
1 + 0.55

y = 0.71

For last vapor put x = xw

49
 Distillation

Question:
For some data determine % of fold vaporized or % change boiled away.
Solution:

F −W
= × 100
F

50 − 25
= × 100 = 50%
50

Question:
Determine avg. value of mole fraction of all vapors so formed during batch distillation?
Solution: xD = 0.564

This is just another name for xD.

Question:
During solution of Rayleigh Equation α is assumed to be constant. We know that α is a
strong function of Temperature and with change in Temperature, α changes and we know
at given temperature and pressure we can obtain only the line and distillation process
cannot be carried at a given Temperature value. Do T − x − y diagram is pointing towards
changes in α for distillation but Rayleigh equation solution pointing towards constant α
for solution, Explain?

Solution:
α which we calculate is already an average hence we treat it as a constant

50
 Distillation

Mass Transfer on a Tray

Diameter of tray = Internal diameter of column

Tray diameter

Flow path lenght

Downcomer
top area
Bottom weir lenght
Top weir lenght

Downcomer
bottom area

Active (bubbling) area

Tray spacing

Weir height

Downcomer
top width

Sloped
Downcomer Downcomer
clearance
Downcomer
bottom width
SINGLE PASS
Kickback

• 10-15% tray part is cut allow flow of liquid.

• Downcomer attaches two trays which allow liquid mounted between two trays.
• Weir allows accumulation of liquid on tray. (height is in mm)
• Vapor travels only through holes.
• At bottom, reboiler produces saturated vapor
• At top, condenser produces saturated liquid
More volatile component vaporizes more at initial phase of vaporization
Less volatile component condenses more at initial phase of condensation
→ Section above Feed Tray - Enriching / Rectifying section as more volatile component is
enriched.

51
 Distillation

→ Section below Feed Tray - Stripping section as lower volatile component is stripped.
Enriching Section - As we go up mole fraction of more volatile component both in liquid
and vapor phase rises.
Stripping Section - As we go down mole fraction of more volatile component both in
vapor and liquid phase decreases.

Operating Line for enriching section:

V, yN

x N° xrich
N
xlean
x n° + 1 x R°
yn xlean
L D, x D°
V
n
Rectifying section

yn − 1 x n°

• Counting of trays starts from the top

• Leaving streams gets the name of the tray
• Mole fraction gets name of the tray

Applying the Material Balance on Enriching Section

Vn =
+1
Ln + D

yn + 1 Vn + 1 = Lnxn + DxD

 L   Dx 
y n + 1  n  xn +
=  D

 Vn + 1   Vn + 1 
   

{Operating curve of enriching section (as slope is not constant)}

To make the above curve a line, liquid flow rate and vapor flow rate throughout the
section must be same i.e.
L0 = L1 = L2 ... = Ln
V1 = V2 = V3 = ... sVn + 1

 L 
So, let the ratio  n  remains same for each tray.
 Vn + 1 
 

52
 Distillation

Assumption
(1) There should not be any sensible heat transfer
(2) Heat of mixing must be zero
(3) Latent heat of condensation for vapor phase containing (A + B) and latent heat of
vaporization for liquid phase containing (A + B) must be same
(4) Liquid stream must be at its bubble point and vapor stream must be at its dew
point so that only latent transfer takes place
These four assumptions together result in CMO (Constant Molar Overflow)

L  Dx 
y n + 1   xn +  D 
=
V   V 
L
Now this can be compared to y = mx + c where m = and hence is called operating line
for enriching section. V

Reflux Ratio (R)

Defined as ratio of number of moles fed back to column to number of moles withdrawn
from column.

For Enriching Section

L
R =
D

L=Reflux Rate, D=Distillate Rate

Mass Balance
V=L+D
V = RD + D, V = (R + 1) D

RD DxD
=yn + 1 xn +
( R + 1) D ( R + 1) D
R xD
yn + 1
= xn +
( R + 1) ( R + 1)
L R
=
V R + 1

on putting xn = xD

yn + 1 =
( R + 1) x D

R + 1

53
 Distillation

yn + 1 = xD

Hence (xD, xD) is a point that lies on the enriching section operating line.

Operating Line for Stripping Section

ym x mo + 1

V' L' Stripping section

m

ym − 1 x mo + 1
2
V , y1

B, xB
1

Lm = Vm + 1 + W

Lm xm = (Vm + 1) (ym + 1) + WxW

 L   W 
y m + 1  m  xm −
=  x
 Vm + 1   vm + 1  w
   

(Operating curve for stripping section)

Assuming Condition of CMO (Constant Molar Overflow)

 L'  W 
y m + 1   xm −   xW
=
V '  V ' 

Reflux Ratio
v'
R' = = Boil up ratio
w'
V' - Boil up Rate

W = Residue Flow Rate

L' = V' + W & V' = R'W
L' = R' W + W
L' = (R' + 1)W

 ( R' + 1) W   W 
=ym + 1   xm −   xW
 R' W   R' W 
 

54
 Distillation

 ( R' + 1)   1 
=ym + 1   xm −   xW
 R'   R' 
 

 R' + 1 L'
  =
 R'  V'

Put xm = xW

R'
ym + 1 = x
R' m
ym + 1 = xm
(xW, xW ) is the point that lies on stripping section operating line.

Types of Feed
Diameter of Stripping and Rectifying section is never same.

V L

V' L'

q → Fraction of feed that is in liquid

L' = L + qF
V = V' + (1 − q)F
General mass balance at feed tray

(i) Saturated Liquid (q = 1)

This means 100% of feed is liquid.
L' = L + F
V = V'
L' > L

55
 Distillation

This shows load is more in stripping section.

Hence conical section is used to connect two sections.

(ii) Saturated Vapor (q = 0)

This means feed is completely vapor.
L' = L
V = V' + F

(iii) Partial Liquid (0.5 < q <1)

Liquid percentage is between 50-100%.
L' > L
V' < V

(iv) Partial Vapor (0 < q < 0.5)

Vapor percentage is between 50-100%.
L' > L
V' < V

(v) Cold Liquid

It Condenses another stream more but gets vaporized itself less.
On heat basis: q defined as Ratio heat Required to vaporize one mole of feed to one
mole of saturated vapor and heat required to vaporize one mole of saturated liquid
to due hole of saturated vapor

q =
(H ) − (H )
F ν

(H ) − (H )
L ν

Hence for cold liquid q > 1

L' > L
V' > V

(vi) Super-heated vapor q < 0

It vaporized another stream more but condenses itself less.
L > L'
V > V'
Hence Rectifying section will have larger diameter.

56
 Distillation

Equation of Feed Line

L + V' + F = L' + V
(L − L') + F = (V − V')
Rectifying section and stripping section, merge at the feed tray (or freed section).
Graphically it means that operating line for both the section intersects and analytically
this mix or merge is shown by subtraction between operating line of different section.
Let x and y be mole fraction of stream of feed tray then

(L − L' )x + FxF = (V − V')y

L − L' FxF
=y +
V − V' V − V'

Operating Line for Feed Tray

L' = L + qF V = V' + (1 − q)F

 −q  xF
=y  x +
 1 − q  1−q
 

−q
Slope =
1−q

For Saturated liquid slope = ∞ which is equal to slope of Y-axis, hence these are parallel.
For Saturated Vapor slope = 0. Hence it is parallel to X-axis.
For partial liquid or partial vapor, (0 < q < 1)
Slope = −Ve (line will lie in 2nd quadrant.)
Cold liquid (q > 1)
Slope = +Ve (Hence it lies in first quadrant.)

Superheated vapor (q < 0)

Slope = +Ve (lies in 3rd quadrant.)

57
 Distillation

McCabe Thiele Diagram

y = mole fraction of lighter component in vapor phase

1.0
Operating lines:
0.9 Rectifying section
Stripping section
1
0.8 q line

0.7 2
Feed tray
1.6 3
Vapor-liquid
equilibrium x = y line

Distillate composition
0.5 line 4

Feed composition
0.4
5
0.3

0.2 6
Bottoms
0.1 composition
0.0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
x = mole fraction of lighter component in liquid phase

(i) Equilibrium Curve

(ii) F1 xF , q, D1 xD are given values. We calculate W1 xw
Continuous distillation is only done for equimolar or near equimolar feed.
The given value of xD is equal yi (vapor phase Mole Fraction of more volatile component)
xD = x0 = y1 because condenser is total condenser, it only changes phase.

 R  xD
=yn + 1   xn +
R + 1 R + 1


xn = xo yn + 1 = y1
(xo, y1)

 −q  xf
=y   x +
1 − q 1−q
 

At x = xf , y = xf
(xf , xf) lie on feed section operating line

 R' + 1 xW
y m + 1 
=  xm −
 R'  R

x = xw

58
 Distillation

y = xw
Leaving Stream for any tray are in equilibrium and hence lie on equilibrium curve. Stream
on same side of tray lie on operating line.
Number of times we use equilibrium curve is number of trays.

Assumptions
(i) CMO - Constant Molar Overflow
(ii) Heat duty of Condenser and Reboiler are constant & same
Hence no need to apply energy balance
Trays above feed tray are in Rectifying section and below, feed tray are in stripping
section
No. of ideal stages required for given separation is given by McCabe Thiele.
No. of ideal Stages/Trays installed in Column, N

McCabe Answer
(1) N → Total condenser & Total Reboiler
(2) N + 1 → Total condenser & Partial Reboiler
(3) N + 1 + 1 → Partial condenser & Partial Reboiler
Why Reboiler and condenser?
Because these two help to achieve desired effect in given time.

Partial Reboiler Total Reboiler

• Decreases Heat duty • Increases Heat duty

• Less volatile will get vaporized and

• Maintains vapor pressure of each tray
this will increase load on tray

• Separation Increases • Separation Decreases

• Bottom liquid can be purged • Purging cannot be done

• It acts as tray

59
 Distillation

Partial Condenser Total Condenser

• Condenser cost (duty) is less • Very high Condenser cost

• More Separation • Less Separation

• Works as a tray • Does not behave as tray

• Gases vapor as a product and hence

• Very less transportation, reflux, and
with high transportation and storage
storage cost
cost

Due to the last difference (which is major) we use Total Condenser.

There are Three Cases Only when Partial Condenser is Used

(i) Product Required is vapor (Gas) E.g.: LPG
(ii) If a non-condensable component is present in feed
(iii) If difference between boiling point or vapor pressure of less Volatile & more
Volatile is very high

Reflux Ratio
Slope of Enriching Sections:

L R
=
V R + 1

If R = 2
Slope = 2/3 = tanθ1
If R = 3
Slope = 3/4 = tanθ2
θ2 > θ1
For Enriching Section:
Slope ∝ Reflex Ratio
Hence, as reflux ratio increases enriching section curve moves away from equilibrium
curve.
And for stripping section as reflux ratio increases, a stripping section curve moves away
from equilibrium curve.
Slope ∝ (Reflux Ratio)−1
R=2

60
 Distillation

Slope:

L' K' + 1 3
= = = Tan θ 1
V' R 2

R=3
Slope:

4
= Tan θ2
3

θ1 > θ2

No. of Trays
Blue line 8, Red line 5
We can see that reflux ratio of red line is more.
As Reflux Ratio increases number of ideal stages for desired separation decreases.

Reflux Ratio No. of Req. Ideal Stage → Desired Separation

Decreases Increases → Constant

Increases Decreases → Constant

Constant Increases → Increases

Constant Decreases → Decreases

Increases Constant → Increases

Decreases Constant → Decreases

Mass is Changed but Duty is Kept Constant

V = 150
V = 175

D = 75
L = 75, L = 100
F = 200

V' = 150, V' = 175

W = 125
L' = 275, L' = 300

61
 Distillation

Increase in Reflux Ratio

(i) Increases Reflux Rate and hence liquid load on column
(ii) Increases Reboiler size as well as its duty
(iii) Increases Boil up Rate and hence Boil up Ratio
(iv) Increases vapor load on column and hence the column diameter
(v) Increases condenser size and its duty
With increase in Reflux Ratio boil up ratio is automatically increased and vice-versa.

Total Reflux Ratio

In case of Total Reflux condition F = D = W = 0.

V' = 150

F=0 D=0

L = 150

V' = 150
W=0

L' = 250

(v’ cannot be 250 as Reboiler is Partial)

The remaining 100 keeps on circulating in Reboiler

L
R =
D
D = 0, R∞
Slope:

R∞ R
= =  ∞ 1
R∞ + 1 R∞

1 = tanθ
θ = 45°
So, we can say that rectifying and stripping section operating line merges with diagonal
line.

62
 Distillation

Xw XF XD

In case of total reflux ratio number of ideal stages required is minimum.

Fenske equation (only for total reflux ratio)
No. of Stages:

 xD ( 1 − Xw ) 
ln  
 xw ( 1 − XD ) 
=
ln α

= Nmin → Total condenser & Total Reboiler

= Nmin + 1 → Total condenser & Partial Reboiler
= Nmin + 1 + 1 → Partial condenser & Partial Reboiler
Nmin → Minimum Number of ideal stages for desired separation for total Reflux Ratio.

For Total Reflux Ratio

• Maximum Reflux Rate and hence Maximum load
• Maximum Reboiler size and duty
• Total (Maximum) Boil up Ratio
• Maximum vapor load and rate
• Maximum Condenser size and duty
Total Reflux Ratio helps us to achieve maximum achievable separation in the column.
Total Reflux conditions are used in Startup of column or operation as it maximizes reflux
potential in parallel with maximized tray potential.
Total Reflux Ratio also gives us idea about Reboiler size, Condenser size and Reboiler
diameter, as these three cannot be changed later that’s why they are purchased on
maximum sizes.

63
 Distillation

Minimum Reflux Ratio

F D

L = min, Rmin

V' = min, R'min

W=0

L'

1.0 1.0
L
Minimum L
V Minimum
P V P

x = xD
y y =
y
x
=
y x = zF
x = zF
x = xB x = xD x = xB
0 0
0 1.0 0 1.0
x x

Minimum reflux ratio results in minimum reboiler size.

No. of trays = Infinite (and we cannot achieve desired separation)
Slope:

y ' − xD Rmin
=
x ' − xD Rmin + 1

xD − y '
Rmin =
y ' − x'

Only purpose to calculate Rmin is to calculate Ropt.

R_opt=(1.1-1.4) R_min

64
 Distillation

Generally, but it is given in question.

R min
Ropt

YF

Yw
XW XF XD

Feed Section Operating Line on McCabe Thiele Diagram

uid
Cold liq
SL
PL
PV

SV
YF
SHV

XF

y-coordinate always lies between yD and yf

x-coordinate always lies between xD and xf

Types of Feed
Cold Liquid:
xf < x' < xD

Saturated Liquid:
x' = xF

Partial Liquid:
xw < x' < xf

65
 Distillation

yD

YF

Y'

yW

Xw X' XF X' XD

Superheated vapor:
yw < y' < yf

Saturated vapor:
y' = yf

Partial vapor:
yF < y' < yD
(Rmin)Cl < (Rmin)Sl < (Rmin)Pl < (Rmin)PV < (Rmin)SV < (Rmin)(super heated Vapor)
Same trend is followed by Roptimum.

As we go from Cold Liquid Feed to Super-Heated Vapor Feed

(1) Vapor Potential → Increases
(2) Liquid Potential → Increases
(3) Condenser duty and Reflux → Increases
Keeping mass same duty is changed v = 175
condenser duty Increases
V = 150
(i.e., Size Increases)

D = 75
L = 75, L = 75
F = 200

V' = 150, V' = 175

L = 275, L = 300 W = 125

66
 Distillation

Increase on condenser duty means increase in cooling, so saturated liquid will become
cold liquid.
• Change in duty of reflux rate results in those changes that has already seen
previously by changing mass of reflux rate
• Increase in duty of reflux rate is a disturbance that comes by the increase in
condenser duty. And it can be corrected by increase in reflux ratio

Heat Basis
(Duty of Reflux Ratio) (No. of Req. Ideal State) = xD (Required Separation)

Effect of Pressure on Column

Changing pressure will not change temperature and no change in vapor pressure.
But if
Pressure increases then yA decreases
Pressure decreases then yA increases

YP1

YP2 P1' 4-Trays

P2 2-Trays

Xw XF XD

At a given temperature and given liquid mole fraction as pressure decreases the
enrichment of the vapors (yA) increases, and equilibrium curve shifts upwards away from
diagonal line.
Number of Ideal Stages Required also decreases as decrease the pressure.
Number of ideal Stages Decrease with = {Increase in Reflux Ratio or Increase in duty or
Decrease in pressure}
Column running at low pressure have more potential than column running at high
pressure.
Hence, VDU (Vacuum Distillation Unit) is preferred than ADU (Atmospheric Distillation
Unit).
More enriched vapor will occupy more volume than less enriched vapor (both having
same mass).

67
 Distillation

Decrease in pressure, increases diameter of column as vapor load increases. Hence, VDU
diameter is more than ADU.
If Separation increases, then relative volatility will also increase.
Hence, decreasing in Pressure, increases the Separation and ease of Separation in case
of distillation is shown by Relative volatility which means α ↑.

Steam Distillation

Heat Sensitive Material

Materials which decompose before reaching their boiling point.
Steam added is either → Miscible (Power add will be less)
→ Immiscible (Power add will be more, as steam will act as a separating component)
Hence, Steam distillation is used only when components are immiscible with steam.
Whenever Steam is miscible with feed, we use vacuum distillation.

P (is reduced as VDU is used)

P = PA + PB + Steam

VDU is used for heat sensitive material in which Steam is miscible with given component
this does not mean steam is used in VDU.
Steam distillation - Changes are made in partial pressure
Vacuum distillation - Changes are made in overall pressure

Flash Distillation
V

Xf

68
 Distillation

The x & y we achieve are maximum achievable and are in equilibrium.

This distillation is called Equilibrium distillation,
→F=L+V
→ FXF = Vy + Lx
Eqm Relationship →
y = mx

αx
=y = or PA x A Py A
1 + (α − 1) x

Enthalpy Balance
FHf + q = VHv + LHL
Analogically flash distillation represents an ideal tray as both given an equilibrium
relationship between x and y. For a continuous distillation unit consist of N trays, it can
be thought of that it is made up of N flash distillation unit connected in series.
Keeping mole fraction same if we change Feed, then L and V changes (Change in feed
quantity changes product quantity).
Keeping Feed Same if we change xF then x and y changes (change in feed quality changes
product quality).

Question:
A binary liquid mixture containing 50 mole% of more volatile component is fed to a
heater where 40% of the feed is flash vaporized. If the liquid and vapor are in equilibrium,
calculate the composition of the liquid product obtained (in mole %), relative volatility of
the system may be taken as 2.0

Solution:
Basis: 100 mole feed
F = L + V, V = 40 mole
100 = 40 + L
L= 60 mole
FXF = Vy + Lx
100*0.5 = 40*y + 60x ---------(1)
αx
y =
1 + (α − 1) x

2x
y =
1 + ( 2 − 1) x

2x
y = -------------------(2)
1+ x

69
 Distillation

From eq 1 & 2

2x
50 =
40 ∗ + 60 x
1+ x

80 x
=
50 + 60 x
1+ x

50 + 50x = 60x + 60x2 + 80x

60x2 + 90x − 50 = 0

x = 0.431
So, 43.1 mole % more volatile composition in liquid.

Efficiencies of Distillation Column

(i) Column Efficiency
Ratio of Required number ideal stages to the required number of actual stages.
It is always less than 100%.

1.0
Pseudo-equilibrium curve
Actual stage
Equilibrium curve Xj*
Equilibrium stage j-1

Yk*
Mole fraction in gas, y

Yk
Working line: rectification
Yk+1

q-line

Working line: stripping

0
0 XB Zf XD 1.0
Mole fraction in liquid, x

Ideal (More Separation achieved)

Actual (Less Separation achieved)
Column efficiency is defined in terms of Number of trays for Calculate purpose only
actually it is in terms of equilibrium or separation

70
 Distillation

Ideal → less trays Required

Actual → More trays Required.
Separation we obtain (Actual) is less than separation that we should obtain (ideal) hence
number of actual trays is more than ideal trays.

(ii) Tray Efficiency

Actual Mass Transfer

=
Ideal Mass Transfer

Yn Y*n

Yn + 1 Xn

n+1

X*n + 1 Xn + 1

yn* = Eqm Vapor mole fraction which is in equilibrium with liquid leaving nth tray.
yn − yn + 1 xn − xn + 1
=
ηTray =
y n* − y n + 1 xn − xn* + 1

(iii) Point Efficiency

yn − yn + 1 xn − xn + 1
=
y − yn + 1
*
n xn − xn* + 1
This does not depend upon any parameter as it comes through equilibrium relation
which remain same.
No mass transfer happens at tray Spacing.

Murphree Efficiency
(For small diameter columns)
Same as point efficiency but it can exceed as 100% as changes are made such that MT
takes place between trays i.e., at tray spacing
Hence, (MT at tray + MT at Spacing) > MT at eqm

71
 Distillation

Hence, it is more than 100%.

Mass transfer became significant at every point.
For Small diameter column, we use spacing, hence mass transfer occurs at spacing
also, so overall efficiency > eqm efficiency

Increasing the reflux ratio is cheapest and hence critical parameter to

increase mass transfer

Problems in distillation column

(Reboiler can both increase and decrease pressure)

(i) Flooding: (Entrainment)

With increase in vapor pressure Entrainment of the liquid in stripping section starts as
vapor potential increases in comparison to liquid potential.
Entrainment in distillation column affects the purity of distillate because liquid in bottom
tray is less enriched that mixes with liquid of top tray.
The worst case of entrainment is flooding which ultimately empties out stripping section.
During flooding pressure drop increase that is an indicator of this situation.

(ii) Weeping
In this case vapor potential decreases because of which it will not be able to hold the
liquid in top section of the column that results into emptying of the rectifying section. It
is indicated by decrease in pressure drop.
Both these situations are hypothetical and can never happen in the industry. Any of the
situations can be corrected by help of a reboiler.
In case of flooding, duty of reboiler decreases to decrease the vapor potential while in
case of weeping, duty of reboiler increases to increase the vapor potential.

Flooding velocity
Velocity of vapors at which flooding occurs.
Operating velocity is generally 60-85% of flooding velocity
In case of flooding, vapor potential refers to some vapor velocity and this vapor velocity
is called flooding velocity. For the operating condition, operating flooding velocity is
calculated by help of flooding velocity

ρL − ρv
uf = K
ρv
ρv = density of vapor, Constant = K
ρL = density of liquid, uf = flooding velocity

72
 Distillation

Total Area →
π 2
A= d
4

d = column internal diameter / tray diameter.

Effective Area = 90% of Total area
Molar flow Rate (in each section)

ρAV
=
MW

Mw => Molecular weight of vapor

ρ = density of vapor
Maximum diameter → Maximum operating velocity (flooding velocity)
Operating velocity → Operating diameter
If down comer cut is mentioned in question, then we use reduce area if not mentioned
then we use total area.

Optimum Reflux Ratio

Minimum Reflux Ratio

Total Costs Operating Costs

Fixed Costs

Cost

Optimal Reflux Ratio

Reflux Ratio

  mV 
ln 1 + ηm  − 1
 L 
Overall efficency ηo = 
 mV 
ln  
 L 
L
→ operating line slope
V
m → Equilibrium Line slope
A → distillation factor

Slope of operating line

A=
Slope of exp . Line

73
 Distillation

74
 Extraction

Chapter 4 – Extraction

S, yS
E (A + B + C)
M, XM
yE

F, yF R (A + B + C)

XR

• Feed comes from distillation unit as more distillation cannot be done to the feed
• Heat is never of concern in extraction
• Extraction is used for mixture where difference between relative volatility is very
less
• Aim is to remove C from (A + C)
B selected such that solubility of B with C is more than that of with A.
To separate solute from feed phase we use a third component B whose solubility with
solute is more than that of A. To create a concentration difference, solvent taken is
generally pure. Both the streams are mixed together in mixture. So that two phases
(heavier & lighter) become.
This mixture contains all the three components, but it is not a homogeneous
mixture. This mixture is then sent to a separator where infinite time is provided for
the separation. Lighter and heavier phase starts to separate out on basis of density
difference. Component B starts to go up and because of higher solubility with C, it
carries C with it.
However, phase (A) tends to go down but because of the miscibility extant of B & C it
takes some B and C with it in heavier phase. Finally, desired separation is achieved and
leaving streams come in equilibrium. The lighter phase is represented by y, Heavier phase
is represented by x.
In extraction whenever we talk, we talk only for the solute.
For example,

xF → Mole fraction of solute in feed.

yS → Mole fraction of solute in solvent.

xM→ Mole fraction of Solute in trinary mixture.

yE→ Mole fraction of solute in Extract.

xR → Mole fraction of solute in Raffinate

75
 Extraction

Difference between Extraction and Distillation

Extraction Distillation
Three Components Two Components
Relative Solubility Relative Volatility
Trinary Mixture Binary Mixture
No Heat is Required Heat is Required

(A + C) & (B + C) miscible than (A + B) must also be miscible.

This is the reason why extraction is trinary at minimum. As it is very difficult to find
components which are miscible with another component but not miscible among each
other.
Why equilateral triangle is used for extraction?
Because if from any point inside the equilateral triangle if we draw perpendicular on each
side, then sum of all perpendicular’s is equal to length of altitude of equilateral triangle.

F E

B C
D

FO + OE + OD = AD

And in Terms of Concentration

xA + xB + xC = 100%

C (100%)

A (100%) B (100%)

Vertices of equilateral triangle represent pure component A, B & C

76
 Extraction

Side AB, BC, AC represent Binary mixture of (A + B), (B + C) & (C + A) respectively

Any point inside of the equilateral triangle represent a trinary mixture of (A + B + C)

Determination of Mole Fraction at Any Point Inside the Triangle

Steps to find ‘C’
• Draw a line parallel to AB opposite to C
• Define direction of increase in C
• Focus on point of intersection which is in direction of increasing C

Similarly Find for all Other Components

C (100%)

A (100%) B (100%)

A B

Equilibrium Triangular Diagram

Mixture

(i) Complete Miscibility

(A) B
100% 100%

77
 Extraction

(ii) Partial Miscibility A B

100% 100%

A B
(iii) Partial Immiscibility
100% 100%

B
(iv) Complete Immiscibility A
100% 100%

85% Falls Under Type-I Category and Rest 15% Under Type-II Category

Type 1

• (A & C) and (B & C) completely Miscible

No Seperation
• (A & B) Partially Immiscible
• Separation Occurs here

A B

All Extraction Operation are Equilibrium Operations

Differences

• Tie Line of Extraction • Tie Line of Distillation

• +ve slope • −ve slope

• Solid line (path is present) • Dotted line (path is imaginary)

Similarity
• Both represent equilibrium mole fraction
• For both tie lines (y > x)
Distillation - vapor phase is enriched (yA > xA).
Extraction - lighter phase is enriched (yE > xA)

78
 Extraction

Type – II

No.sep.
• (B & C) Partially miscible
• (A & C) completely miscible
• Ultimately No extraction is achieved

A B
Tie Line
No Seperation

As temperature increases miscibility increases. Type II gets converted to Type I.

C C

A B
A B

But if temperature is increased for Type-I mixtures, curves shrink and hence separation
decreases.

This is the reason Extraction is carried out at Room Temperature.

Extraction is cheaper but are never carried out alone they are always carried out with
distillation and that is why they are not our first choice.
Solvent which is to be selected must have a difference in relative volatility with C.
• B must be immiscible with C
• B must have volatility difference with C

79
 Extraction

Representation of Extraction as an Ideal Stage

(B + C) SyS E yE (A + B + C)

M xM

(A + B) FxF R xR (A + B + C)

E yE

F xF R xR
Stage

(Mixer + Settler)

S yS

If nothing is mentioned, it is cross current

F+S=E+R
FxF + SyS = EyE + RxR

To covert it into operating curve/line we must drop the suffix

xF & yS Not because they are known value.
xR & yE is unknown
xF & yE Not because they are not
xX & yS Same side of stage
FxF + SyS = Rx + Ey

80
 Extraction

F  S R
y =   xF +   y S −   x
E
  E
  E 

Operating Curve for Extraction as R and E Varies with X And Y

y = mx + c

 −R  F  S
=m  =  c   xF +   y S
 E  E  E 
We will use solute free approach to make it a Binary mixture (i.e., solute will not be
under our observation).

Solute Free Basis

Before

FxF + SyS = yE + RxR

 C   C 
( A + C )F   + ( B + C )S  
 A + C F  B + C S

C
= ( A + B + C )R
( A + B + C )R

C
+ ( A + B + C )E
( A + B + C )E
CF + CS = CR + CE

A and B are Completely immiscible

After solute free approach

C   C 
( A + C )F   + ( B + C )S  
 A + C F  B + C S

 C   C 
= ( A + C )R   + ( B + C )E  
 A + C R  B + C E

CF + CS = CR + CE

A + C → Molar Ratio

C C  C  C 
( A)F   + ( B ) S   = ( A )R   + ( B )E  
 A F  B S  A R  B E

CF + CS = CR + CE

81
 Extraction

(RS) → flow rate of A only (Solute free Raffinate)

(ES) → flow rate of B only (Solute free Extract)

C C 
=( X )F =  (Y )S  
 A F  B S

C 
( X )E = 
 B E

C 
( X )R = 
 A R
So, our third equation becomes

RS XF + ES YS = RS XR + ES YE

RS XF + ES YS = RS X + ES Y

R   RS 
Y  S
=  XF + YS −   X (Operating line of Extraction)
 ES   ES 

 −RS 
  = slope
 ES 

YE

YS

XR XF

 −RS   y − yS 
=  slope
=  E 
 ES   xR − xF 

Question:
A feed solution of 1000 kg/hr contains 25% of solute. It is to be extracted using a
solvent which is pure. It is desired to have 90% of recovery of solute. The equilibrium
relationship is y = 2x where x is mass of C to mass A and y is mass of C to mass of B.
Determine solvent flow rate required for desired separation.

82
 Extraction

Solution:

F = 1000 kg/hr

xF = 0.25, ys = 1

RS XF + ES YS = RS XR + ES YE

250  25 
( 750 )  
 + ( ES × 0 )=  750 ×  + ESYE
 750   750 

Y = 2X
YE = 2XR

25 50
=
2× =
750 750

250  25   50 
( 750 )   +=

0  750 ×  + ES  
 750   750   750 

 50 
ES 
250 − 25 = 
 750 

225 × 750
ES =
50

Initially there is no solute. Hence ES = S

ES = S = 3375
Equilibrium Approach

YE = 2XR

255  25 
= 2 
ES  750 

ES = 3375

Question:
A Feed solution of 1000 kg/hr contains 25% of solute. It is to be extracted using a solvent
which is pure. If solvent flow rate is 3000 kg. The equilibrium relationship is y = 2x where
x is mass of C to mass A and y is mass of C to mass of B. Determine % recovery of
solute?

Solution:
Let X fraction of c recovered
YE = 2XE

83
 Extraction

X ( 1000 ) ( .25 ) ( 2) ( 1 − X ) ( 1000 ) (.25)

=
3000 ( 1000 ) (0.75)

X
= 1− X
8

9
X = 1
8

8
X= = 88.8%
9

Question:
A Feed solution of 1000 kg/hr contains 25% of solute. It is to be extracted using a
solvent which is pure. It is desired to have 90% of recovery of solute. The equilibrium
relationship is y = 4x where x is mass of C to mass A and y is mass of C to mass of B.
Determine solvent flow rate required for desired separation.

Solution:
YE = 4XR

225 25
= 4×
ES 750

ES = 1687.5

(Solvent Ability) (Solvent Amount) = (Desired Separation)

Y = 4X miscibility is more of solvent

X → solvent amount

Y → Desired Separation

4 → solvent ability

Counter Current Extraction

E yE S yS

Stage

F xF R xR

F+S+=E+R

FxF + Sys = EyE + RxR

84
 Extraction

Now Again we will consider solute free Basis

C  CS  C  C 
( A)F   + ( B ) S   = ( B )E   + ( A )R  
 A F  BS   B E  A R

RS XF + ESYS = RS XR + ESYE

C 
XF =  
 A Feed

C 
YS =  
 B Solute

C 
XR =  
 A Raffinate

C 
YE =  
 B Extract

Solute Free Diagram

ES YE ES YS

Stage

RS XF RS XR

RS XF + ESYS = RS XR + ESYE

XRS + ESYS = RS XR + ESY

RS R
Y= X + YS − S XR
ES ES

RS
Slope =
ES

RS
= YS −
Intercept XR
ES

Equilibrium Curve and Operating line will never intersect (for counter current)

85
 Extraction

YE

YS

XR XF

RS y − yS
= E
ES xF − xR

(Equilibrium Line) (XR , YE)

Operating Line (XF , YE ) & (XR , YS )

Question:
A Feed solution of 1000 kg/hr contains 25% of solute. It is to be extracted using a
solvent which is pure. It is desired to have 90% of recovery of solute. The equilibrium
relationship is y = 2x where x is mass of C to mass A and y is mass of C to mass of B.
Determine solvent flow rate required for desired separation.

Solution:

 5 1 
( XR , YE )  , 
 150 15 

1 
( XF , YE )  , YE 
3 

 5 
( XR , YS )  , 0
 150 

1
−0
5 750
=
1
−
5 ES
3 150

 150 − 15 
( 750 ) ( 15)   = ES
 ( 3) ( 150 ) 

ES = 3375

86
 Extraction

This proves that CROSS, CO-CURRENT or COUNTER CURRENT arrangement does not
matter for single stage.

Optimization in Extraction
(Funding relation between desired and equilibrium separation)

Y*E (XF, Y*E)

YE

YS

XR XF

ES min × 1.5 = ES opt

RS
Slope =
ES opt

For cross current extraction equilibrium line and operating line intersect.

Question:
A Feed solution of 1000 kg/hr contains 25% of solute. It is to be extracted using a solvent
which is pure. It is desired to have 90% of recovery of solute. The eqm relationship is
y = 2x where x is mass of C to mass A and y is mass of C to mass of B. Calculate E
optimum?

Solution:
Y = 2X

 1 2
YE* 2=
= XF 2 = 
3 3

Slope:
500
−0
750 750
=
250
−
25 E S min
750 750

87
 Extraction

ES opt = 337.5 ES min × 1.5 = ES opt

ES opt = 506.25

 225 
YE =  
 506.5 
Optimization in extraction is a choice but not compulsion and is done only when asked
(for GATE) asking a mole Ratio or mass ratio in extraction is a compulsion not a choice
(for GATE).

Equilibrium Approach

 1 2
YE* 2=
= XF 2 = 
3 3

225 2
YE*
= =
ES min 3

225 × 3
ES min
= = 337.5
2

ES min × 1.5 = ES opt

ES opt = 506.25

Kremser Equation
If mixer settler arrangement is replaced by a tray tower, then total number of ideal stages
can be calculated by using Kremser equation.

ES, YE ES, YS

RS, XF RS, XR

ES, Y1 1st Nth ES, Yn + 1

RS, X0 RS, Xn

88
 Extraction

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

m = Slope of Equilibrium Curve

A = Extraction factor

Slope of Optimum Line

A=
Slope of Equilibrium Line

N = Number of ideal stages required to obtain desired separation for a tray tower when
mixer settler arrangement is replaced by tray tower for same feed

RS
ES
A= Use (Eoptimum) for Kremser
m

When A = 1

X0 − X n
N =
Yn + 1
Xn −
m

y = mx

Yn+1 = (m). Xn* + 1

Y
X n* + 1 =n+ 1
m

Entry − Exit
=
Exit − Equilibrium

This is general formula and hence valid for all unit operations

Total work by N trays

N =
Work by 1 Tray

Question:
A Feed solution of 1000 kg/hr contains 25% of solute. It is to be extracted using a
solvent which is pure. It is desired to have 90% of recovery of solute. The equilibrium
relationship is y = 2x where x is mass of C to mass A and y is mass of C to mass of B.
Calculate N?

89
 Extraction

Solution:
 Yn + 1  
 X 0 −  
ln  m  ( 1 − A ) + A
 X − Yn + 1  
 n m 
 
N =
1
ln  
 A

750
=A = 0.740
( 506.5) ( 2)

 250  
 750  
ln   ( 0.26) + 0.74 
 25  
 750  
N =
0.3

N = 4.01
Controlling Parameters

(Distillation → Reflux & Extraction → Solvent Amount)

Cascade Cross Current

ES Y1 ES Y2 ES Y3

RS RS RS RS

1 2 3

X0 X1 X2 X3

ES ES ES

YS YS YS

Known Unknown
RS Y1
X0 Y2
X3 Y3
YS X1
X2
ES

90
 Extraction

Hence, we require 6 equation

- 3 from mass balance (operating line)
- 3 from equilibrium
We will be assuming ES

(X1, Y1)

Y1

(X2, Y2) STAGE-1

Y2 (X3, Y3) STAGE-2

Y3

STAGE-3

YS (X3, YS) (X2, YS) (X1, YS)

X3 X2 X1

Hence will get Slope

GS Yn

RS Nth Stage RS

Xn − 1 Xn

Es

Ys

RS Xn − 1 + ES YS = RS Xn + ES Yn

RS(Xn − 1 − Xn) = ES(Yn − YS)

RS Yn − YS
=
ES Xn − 1 − Xn

91
 Extraction

Assumption
Solvent is pure YS = 0
Equilibrium line y = mx
yn = mXn

RS mX n
=
ES X n− 1 − X n

RS Xn
mE =
S X n− 1 − X n

mES X n− 1 − X n
= + 1 +1
RS Xn

 mES  X n− 1
 + 1 =
 RS  Xn

For n = 1

X0= 1 + mES
X1 RS

X0 X X X Xn − 1
= 0 . 1 . 2 ..........
Xn X1 X2 X3 Xn

n
 mES 
= 1 + 
 RS 

Reduction Ratio
n
X0  mES 
= 1 + 
Xn  RS 

ES Single Stage flow Rate

n = no. of stages

(Solvent Amount) (Number of Stage) = (Desired Sepration)

Increase Decrease Constant

Decrease Increase Constant

92
 Extraction

Counter Current Cascade

ES, Y1 ES, Y2 ES, Y3 ES, YS

RS, X0 RS, X1 RS, X2 RS, X3

6 Unknown, 6 Equation hence system is defined.

Known Unknown
RS ES
X0 Y1
X3 Y2
YS Y3
X1
X2

(X1, Y1)

Y1 (X0 Y1)

(X2, Y2)
(X1, Y2)

Y2

Y3 (X3, Y3) (X2, Y3)

YS

X3 X2 X1 X0

n+ 1
 mES   mES 
  − 
X0  RS   RS 
=
XN  mES 
n+ 1

  −1
 RS 

93
 Extraction

Mixing Rule
F+S=M=R+E

FxF + SyS = MxM = RxR + EyE

F y S − xM R y E − xM
= =
S xM − xF E xM − xR

F xM − y S R xm − y E
= =
M xF − y S M xR − y E

M y S − xF M y E − xR
= =
S xM − xF E xM − xR
F+S=M

F M S

F−S=M

F S M

Actual Equilateral triangular diagram for Mixer Settler arrangement.

C

F D
M E
Slope Always + Ve

R S

A B

Before M there is no equilibrium hence line F-

-S crosses equilibrium curve.
If S is decreases, then M shifts towards F and it can shift maximum up to intersection of
equilibrium curve and F--S.
D represent minimum amount of solvent required.

94
 Extraction

F y − xD
= S at point D
Smin xD − xF

Sopt = 1.5Smin
Then it becomes

F y − xM
= S
Sopt xM − xF

Cross Current Cascade

E1 Y1 E2 Y2 E3 Y3

F R1 R2 R3

XF X1 X2 X3

Sys Sys Sys

Equilateral Diagram

F E1

M1 E2

R1 M2 E3

R2 S
M3
A B

Counter Current Cascade

E1 Y1 E2 Y2 E3 Y3 SYs

F R1 R2 R3

XF X1 X2 X3

95
 Extraction

F + E2 = R1 + E1 F − E1 = R1 − E2 = ∆
R1 + E3 = E2 + R2 R1 − E2 = R2 − F3 = ∆
R2 + S = E3 + F3 R2 − F3 = R3 − S = ∆
R3 − S = Known

F
E1

R1 E2
R2
E3
R3
S
A B

Selectivity

C 
 
 A extr Weight fract of A in R
=(β ) =
C
  Weight fraction of A in E
 
 A Raffinate

96
 Absorption

Chapter 5 – Absorption
G2 Gs L2 X2 L1 X1 G'1

Y2 Y'1

G1 GS LS X1

L1 X1 L2 X2 G'2, Y'2
Y1

Solute should be more in Liquid

Driving Force: Relative solubility

Component B must be highly soluble to C as compared to A
Direction of transport is Gas side to liquid side
In extraction we provide infinite time but for absorption this is not possible. Hence
absorption is never at equilibrium, and absorption product are binary.
Extraction and distillation are done for profit but aim of absorption is to avoid pollution
of environment.
For CNG and LPG absorption is done for purification.
For flue and went gases absorption is unprofitable and packing used is random (clay,
broken glass).
But for profitable process packing material is structural.
A & B for absorption are completely miscible.
Y = C/A
X = C/B

97
 Absorption

(Notation of absorption are opposite to notation of extraction.)

Equilibrium approach cannot be used as absorption is not in equilibrium.
Hence optimization will be used. So, optimization in absorption is a compulsion not a
choice.
As y < x, hence equilibrium curve is always lie below the operating curve.

(Y, Y1) (Y1, Y)

Y1

Y2

X2 X1 X1

Absorption:
Stripping:

Y1

LS
Gs min
Y1

LS
Y2 Gs opt

X2 X1

LS
Slope =
GS opt

Question:
A flue gas of flow Rate 1000 Kmol/hr3 contains 5% Sulphur. To satisfy norms of pollution,
this gas is to be absorbed using absorption column with help of pure solvent (H2O). The
equilibrium relationship is given as y = 4x, where y is moles ratio of C to moles of B and X
is moles ratio of C to moles of A. If 90% of recovery is desired, then determine amount of
water required?

98
 Absorption

Solution:
Gs = 1000
Sulphur = 50
y = 4x This is not for absorption
For absorption
x = 4y y = 0.25x

Y1* = 0.25X1*

50
= 0.25 X 1*
950

50 45
= ( 0.25 )
950 Ls min

45 × 95
Ls min =
5×4

= 213.75
Ls opt = 320.625

Kremser Equation
If absorption tower is replaced by tray tower, then no. of ideal trays required for desired
Separation can be determined by Kremser equation.

Gs Ls Y1 X0

Y2 X2

1th

Nth

Gs Ls

Y1 X1 Xn Yn + 1

99
 Absorption

(Extraction factor should be low)

 Yn + 1 − mX0   1 1
ln  1 −  + 
N =  Y1 − mX0   A A
ln ( A)

Absorption factor (A) should be always > 1

Question:
Calculate no. stages for pervious question.

 50  
 950 − 0   ( 0.25 ) 950  ( 0.25 ) 950 
ln 
5 1 −  + 
  320.62  320.62 
N =  950  
 320.62 
ln  
 ( 0.25 ) 45 

ln ( 10 ) ( 0.26) + 0.74 

N =
ln ( 1.349)

N = 4.01
For A = 1

Yn+ 1 − Y1
N =
Y1 − mX0

LS
GS LS
A
= =
m mGS

A=1 A>1

100
 Absorption

A<1

Extraction problems are always solved in solute free basis.

Height of Packed Tower

dz

{Absorption process are dilute in nature}

Mass Transfer → Convection
Gas → loss
Liquid → Gains

Gy → No. of Moles of C in Gas phase.

d(Gy) → Transfer of Moles in Gas phase.

d(Ly) → Transfer of mobs in Liquid phase.

−d(Gy) = d(Lx) = WC
Wc → Rate of mass Transfer of Solute from Gas phase to Liquid Side.
In feed.
A = (A + C) − C
GS = G − Gy
GS = G(1 − y)

GS
G =
1− y

y is very very small in comparison to 1, hence is neglected.

101
 Absorption

Whether we work in mole fraction or mole ratio, it is a choice in absorption not a

compulsion and it purely depends upon equilibrium relationship. If equilibrium is in mole
fraction, then solve the question in mole fraction and if equilibrium is a mole ratio, then
solve the question in mole ratio.

−d(Gy) = d(Lx) = WC

GS
G =
1− y

 y   x 
−d  GS d  LS
 =  This remains constant (flow rate of A)
 1− y  1 − x

 y   x 
−GS d  + LS d 
 = 
1 − y  1 − x 

dy LS
−GS . =
+ .dx
(1 − y ) (1 − x )
2 2

dy L
−G =
+ .dx =
WC
(1 − y ) (1 − x )

WC = NC × A

NC → flux

A → Area of cross section

a - Interfacial area: Defined as the surface area created for mass transfer per unit
volume of packed tower.
Hence

WC = NC × a × Adz (Adz → volume)

WC = NC A a dz

ky (y − yi) - for gas

Ky (y − y*) - for gas

kx (xi − x) - for liquid

Kx (x* − x) - for liquid

Ky (y − y*) will be used because this is overall, and we know both entry and exit
composition of gas phase.

−G
= .dy K y ( y − y * ) a. A.dz
( 1 − y )

102
 Absorption

1 G
dz =
− × .dy
( 1 − y ) ( y − y ) a.A.K y
*

y is very very small in comparison to 1, hence y is neglected.

G′ y 1 dy
K y .a. ∫y3 ( y − y * )
z =

G → gas flow rate

G′ =
A → cross section area

G′
→ HTU (unit same as flux)
K y .a.

y1 dy
∫ (y
y2
− y* )
→ NTU

In Questions for absorption (Ky . a) value is given

Calculation and meaning of NTU

y1 dy
NTU = ∫ (y
y2
− y* )

Lengthy method, hence, is not used in Gate.

So, we take (y − y*) average for a particular section. And now we assume this (y − y*)
average remains constant for all sections through the column.

1 y1
NTU =
( y − y* ) ∫ y2
dy
avg

y1 − y2
NTU =
( y − y* ) avg

y1 − y2 Overall Separation

(y − y*)avg Average driving force of a section

So, we now assume that average driving force of a section is equal to separation of single
section.

Height of Transfer Unit (HTU)

Defined as height of packed bed required to achieve a separation equal to average driving
force existing in that section.

103
 Absorption

Y1

Y1*

Y2

Y2*

(y − y ) − (y *
− y 2* )
(y − y *
) av
=
1 1 2

y 1 − y 1*
ln
y 2 − y 2*

NTU on basis of Absorption factor:

 ( y − mx )  1 1
ln  1 2
 1 −  + 
 ( y 2 − mx2 )  A A

NTU =
 1
1 − 
 A

NTU A ln A
=
Nkremser A− 1

This N is a calculated from Kremser Equation,

When A = 1
NTU = N

Height Equivalent to Theoretical Plate (HETP)

Defined as height of hacked tower required to achieve a separation equals to separation
achieved by a theoretical plate.
(i) It eases out quantification process as basis remains same
(ii) Helps us to compare absorption with distillation,

 A ln A 
HETP = HTU  
 A− 1 
If A = 1
HETP = HTU
Z = (NTU) (HTU) (Avg separation basis)

104
 Absorption

OR
Z = (NTU) (HETP) (Theoretical plate separation is basis)

Z NTU HTU
constant ↑ ↓
constant ↓ ↑

Comparison Among Two Different Packing

z1 = NTUp1 × HTUp1

z2 = NTUp2 × HTUp2
Packing having greater height is less effective. Hence packing that gives less height is
preferred.
1
HT=OG HTG + HTL
A

HTOL = HTL + AHTG

Individual

HTL → Height of liquid section.

HTG → Height of liquid section.

Overall

HTOG → Height of tower if we consider whole as gas section.

HTOL → Height of tower if we consider whole as liquid section.

Effect of Pressure in Absorption

Here Henry’s law is used as it is valid for dilute solution:

pA x APA*
yA
= =
p P
pA = HCA

yAP = H(CxA )

yAP = HCxA
Hence more the pressure, more is xA which means more is enrichment.
Hence for a higher pressure, less amount of solvent is required.

105
 Absorption

Y
P1 P2

P2 > P1

XP1 XP2

Y
P1 P2

Y2
P2 > P1

X2 XP1 XP2

Ls opt = (1.4)Ls min Ls min (P1) > Ls min (P2) (or basis of slope)

Ls opt P2 < Ls opt P1

106
 Humidification

Chapter 6 – Humidification
(i) Mass Humidity or Humidity or Absolute Humidity or Specific Humidity - Defined as
ratio of mass of water vapor to mass of dry air
mv
H =
ma

(ii) Molar Humidity - Defined as Ratio of number of moles of water vapor to number of
moles of dry air.
nv
H′ =
na
Assumption: Air and water vapor both behaves as an ideal gas.
Humid air contains one phase and two components: - F = 2 + 2 − 1 = 3
PV = nRT
pa Va = na RTa pa - partial pressures of air
pv Vv = nv RTv pv - partial pressures of water vapor

Dalton’s Law of Partial Pressure

pa + pv = p

nv p
= v
na pa

pv
H′ =
pa

pa + pv = P
pa = P − pv

pv
H′ =
P − pv

mv nv .Mv pv M
H
= = = . v
ma na .Ma P − pv Ma

pv M
H = . v
P − pv Ma

For Water Vapor & Air System

Mv
= 0.622
Ma

107
 Humidification

pv
H = ( 0.622)
P − pv

Partial pressure of water vapor is most important parameter in humidification.

mv pv M
= . v
ma P − pv Ma

Let humidity = 0.065 Then it is called 0.065kg of vapor per kg of dry air
Maximum value of partial pressure is vapor pressure.
For a mixture of two components, partial pressure and vapor pressure are equal at
Saturation.
At saturation
H → Hs (Mass humidity at Saturation)

pvv M
HS = . v
P − pv Ma
v

pvv
H′ = (Saturated Molar Humidity)
P − pvv

Hs gives the maximum amount of vapors present per kg of day air.

Equilibrium is always a multi-phase phenomenon whereas Saturation is a single-phase
phenomenon
 H 
=  100 ×  Percent Saturation or % Humidity.
 HS 

The only parameter required to deal with Humidity is Partial pressure.

If nothing is mentioned, it is mass Humidity

Relative Humidity
Ratio of partial pressure exerted by H2O vapors in air-water vapor system at a given temp
to vapor pressure of pure water at same temp.

pv
RH =
pvv
pv = Partial Pressure
pvv = Vapour Pressure

(Zero humidity is not possible)

pv = pvv Condition of Saturation.
Saturation can be achieved by

108
 Humidification

• Decreasing the temperature

• Increasing the partial pressure
With decrease in temperature relative humidity increases. Specific humidity (H) is
independent of temperature change.

Dry Bulb Temperature (DBT) (Only a theoretical temp. Or DBT can be

assumed but never be calculated)
Temperature recorded by Thermometer whose bulb is perfectly dry and temperature
measurement must not be affected by any moisture content present in the air or by any
radiation.
DBT refers to true temperature of the air and it cannot be calculated. It can only be
assumed when moisture content present is less.

Wet Bulb Temperature (WBT)

Whenever we measure the temp, the temperature is wet bulb temperature as moisture
is always present in the air, wet bulb temperature becomes dry blub temperature when
moisture content present is less.
The bulb of the thermometer is covered with a wetted wick (cloth) and it is moved pass
an unsaturated air at a given speed. A Thin layer of air will surround the wick and is
known as film.
Moisture from wick tends to evaporate and with time that layer of air becomes saturated;
during evaporation temp is going down. When the film becomes saturated or layer of
air comes in equilibrium with the wetted bulk (wick) that point final temp recording is
noted. This decreased temp is known as Wet Bulb Temperature.

Dew Point Temperature (DPT)

Example: Air-H2O vapor system
(I) (Given)
Pressure = 1 atm, T = 350K, Relative humidity = 60%,
Vapor Pressure = 9.6 KPa
Calculation:
pv = 0.6*9.6 = 5.76KPa
Mass Humidity:
H = 0.06 × 0.622 = 0.03732
Hs = 0.06501
Hs − H = Amount of kg of water vapor required to saturate the unit mass of given are
water vapor system at given temp.

109
 Humidification

(II) (Given)
P = 1 atm, T= 325K, RH = 78.9%, pvv = 7.23 kPa
Calculation:
pv = 5.76 kPa (no effect)
Mass Humidity:
H = constant = 0.03732
Hs = decreases = 0.04773
Hs − H = Amount of Kg of H2O water vapor to saturate unit mas of given air water
vapor system

(III) (Given)
P = 1 atm, T = 300K, RH = 100%, pvv = 5.76 kpa
Calculation:
pv = 5.76 (no effect)
Mass Humidity:
H = 0.03732
Hs = 0.03732
This is condition of Saturation.

(IV) (Given):
P = 1 atm, T = 275K, RH = 100%, pvv = 3.76 kpa
Calculation:
pv = 3.71 kpa
Mass Humidity:
H = 0.02358
Hs = 0.02358
0.03732 − 0.02358 = Amount Condensed.

So, in this example (300K) is DPT

DPT: Two ways to define:
(i) Cooling without condensation
(ii) Cooling with condensation
The temperature up to which a given liquid-vapor system can be cooled without
condensation.
Also defined as Temp, after which a given gas-liquid vapor system can be condensed
along with cooling.

110
 Humidification

DPT always calculated at Constant Pressure

→ At DPT Saturation occurs, hence pν = pν
ν

For a mixed mass dew point temperature is Constant.

As mass changes Dew Point Temperature changes.
Dew Point Temperature is unique for a given air water vapor system (for a fixed mass).
DBT, WBT and DPT are all defined only for AIR not for liquid or solid

DBT ← Low moisture – WBT - High moisture → DPT

DBT > WBT > DPT

111
 Humidification

112
 Drying

Chapter 7 – Drying
Removal of moisture from a wet solid.

Air Layer of Air

T, H, Y TW, HW, YW

Heat transfer = hA (T − Tw)

Mass transfer = ky (yw − y)

pA p p 
=y = NA ky  AW − A 
P  P p 

ky
=NA ( pAW − pA )
P
pA → Partial Pressure of drying Air (unsaturated)
pAW → Partial pressure of layer of air adjacent to moisture surface.
v
(Saturated. Hence pAW = pAW )

k y Pw  pA 
=NA 1 − 
P  pW 

k y Pw
=NA (1 − RH )
P

Ma
=NA k y ( HW − H )
Mv

NA → Kmol of water evaporated/m2.s

mA = ky Ma (HW − H)
nA → Kg of water evaporated/m2.s
WA λ = θ
A ky Ma (HW − H)λ = hA (T − Tw)

113
 Drying

T = Dry Bulb Temperature

TW = Wet Bulb Temperature

hA (T − TW )
= ky Ma (HW − H) = Rate of mass transfer
λ

λk y Ma ( HW − H )
(T − TW ) =
hA

λk y Ma ( HW − H )
(T − TW ) =
hA
k y Ma

hA
= Psychometric ratio
k y Ma

(Ma → Molecular weight of air),

(hA → Convective heat transfer coefficient of air)

hA
= Psychometric ratio
KY

Question:
Benzene is evaporated into dry nitrogen. At 297K and 101.3 kN/m2, the resulting mixture
has a percentage relative humidity of 60. It is required to recover 80% of benzene
present by cooling to 283K and compressing to a suitable pressure. What should this
pressure be? The vapor pressure of benzene is 12.2 kN/m2 at 297K and 6 kN/m2 at 283K.

Solution:
RH
pB = PB *
100
At 297 K
60
pB = 12220 *
100
= 7320N/m2

Mass of benzene:
pB MB 7320 * 78
= = 231gm
RT 8.314 * 297
Mass of nitrogen:
pN MB 94000 * 28
= = 1066gm
RT 8.314 * 297
Absolute humidity:
231
= = 0.217
1066

114
 Drying

80% of benzene recovered so new humidity:

= 0.2 * 0.2107 = 0.0434
So,
6000 78
0.434 = *
p − 6000 28

p = 392 kPa

Ways of Moisture Transport (This Deals with Moisture Present Inside Body)

(1) Liquid Diffusion

This happens only in bodies that have affinity towards water. (Hygroscopic bodies)
Solids that have affinity towards water allows transport of moisture due to
concentration difference.

(2) Capillary Transport

Possible in case of only porous sold body such pores in form of Capillary.

(3) Pressure Induced Transport

Possible in those solid bodies that thermally contract on application of heat.

(4) Vapor Diffusion

This happens only when none of above case is possible.
Heat transfer takes place in body of solid by conduction and this heat vaporizes
inside moisture.

Types of Moisture Content

(i) Unbound Moisture

Moisture content which is present at surface of solid body, or moisture content
which is not bounded by solid body.
Moisture content which remains in equilibrium with layer of air adjacent to it and
having a relative humility of 100%.
Moisture content for which Rate of drying is constant.

(ii) Bound Moisture

Moisture content which is present in body of solid or moisture content which is
bounded by solid body.
Moisture content which remains in equilibrium with a layer of air adjacent to it and
having a relative humidity of less than 100%.
Moisture content for which rate of drying varies.

115
 Drying

(iii) Critical Moisture

Just defined as point of intersection between unbound moisture line and bound
moisture line in drying equilibrium curve. Also defined as point at which unbound
moisture get over and bound moisture Starts.

(iv) Equilibrium Moisture

Moisture content that cannot be removed or moisture content for which partial
pressure exerted by water vapor in adjacent layer of air become same as partial
pressure of water vapor in drying air.

(v) Free Moisture

Moisture content that can be removed from solid body, or above the equilibrium
moisture content, content present is known as free moisture content.

Unbound Moisture

Bound Moisture

Free Moisture

X* XC Xi

kg of moisture
X =
kg of drysolid

Time of Drying
1 dX
Nα
A dt

Ws dX
N = − .
A dt

Ws - Weight of bone dry (completely dry solid)

Ws dX
dt = − .
A N

tf XF Ws dX
∫0
dt = − ∫
Xi
.
A N

116
 Drying

[Unbound = N constant]
[Bound = N varies]
XC − Ws dX XF − Ws dX
=tf ∫Xi A
.
N
+ ∫
XC A
.
N

XC − Ws dX
∫Xi A
.
N
→ Unbuonded

XF − Ws dX
∫XC A
.
N
→ Buonded

Ws W XC dX
tf
= ( X i − Xc ) + S ∫ .
ANC A Xf N

Ws
( Xi − Xc ) → tC (Constant drying time )
ANC

Ws XC dX
∫ . → tv (Variable drying time )
A Xf N

tf = tc + tv

For tv
Let

N = pX + q

X = X*,N = 0

0 = pX* + q

q = − pX*

N = p(X − X*)

X = Xc

N = Nc

NC = p(Xc − X*)

NC
p =
XC − X *

WS  ( XC − X * ) 
=tv
ANC
( XC − X ) ln  X − X * 
*

 f 

117
 Drying

t = tc + tu t = tc

X* XF XC Xi X XC XF Xi

t = tV
t = tC

X* Xc = XF Xi X* XF Xc = Xi

Ws and A are always given together → Either kg/m2 or m2/kg

A = Area of cross section (Surface Area of Solid)

Factors on Which Drying Depends

→ Gas Temperature: As gas temperature rises the rate of drying decreases.
→ Gas humidity: As gas humidity increases rate of drying decreases
→ Velocity of air along with direction:
(1) Air flows parallel to surface Rate ∝ (v).7
(2) Air flows perpendicular to surface Rate ∝ (v).37
→ Thickness of solid: There will be no effect on constant drying time, but variable drying
time increase as thickness increases.

Question:
A 100kg batch of granular solid contains 30% moisture is to be dried to 15.5% of moisture
by passing air at 350K. If the constant rate of drying under condition is 0.00070 kg/m2.s
and the critical moisture content are 15%, what is the approximate drying time in hours.
Assume the dry surface to be 0.03 m2/kg dry mass and assume all percentage on wet
basis.

Solution:
Mass of water in feed = 30 kg

118
 Drying

Mass of dry solids in feed = 70 kg

WS W XC dX
tf
= ( X i − XC ) + S ∫ .
ANC A Xf N

Xf < Xc

So, drying takes place in constant periods

WS
=tf ( X i − Xf )
ANC

For kg of water in dry product the percentage

x
= 15.5
70 + x
x = 12.84kg

Surface area available for drying = 0.3 * 70 = 2.1 m2

Thus, initial moisture content on a dry basis = 30/70 = 0.429

Final moisture content on a dry basis = 15.5/70 = 0.183

70
=tf
2.1 ∗ 0.007
(0.429 − 0.183)
Drying time = 11700 second =3.25 hours

Humid Heat (Cs )

Heat energy necessary to increase the temperature of unit mass gram of dry air plus
whatever vapor it may contain by 1°C at constant pressure.

Cs = CPB + CpA (H)

CPB → Specific heat of gas

CpA → Specific heat of vapor

 Kg H2O 
H → Humidity  
 Kg dry air 

Humid Volume (VH )

Total volume of unit mass of dry air plus whatever vapor it may contain at 1 atm and
given temperature.

22.4T  1 H 
=VH  + 
273  MB MA 

119
 Drying

22.4 (TG0 + 273 )  1 H  m3 

=VH  +  
273  29 18   kg dry air 

TG0 → dry bulb temp of gas,

 kg H2O 
H → Humidity  
 kg dry air 

Total Enthalpy
Enthalpy of unit mass of dry air plus whatever vapor it may contain.

Hy = CPB(T − T0) + CpA H(T − T0) + Hλ0

Hy = CS(T − T0) + Hλ0

CPB → Specific heat of gas

CpA → Specific heat of vapor

CS → Humid heat

Psychometric Chart
Psychrometric chart (or humidity chart) is a chart on which several properties of a
gas-vapor mixtures are cross-plotted, providing a concise compilation of a large quantity
of physical property data.
r)
Ai

Psychrometric Chart
y
Dr
/g

SI (metric) units 140

120
(J

35
n

Barometric pressure 101.325 kPa (Sea level)

tio
ra

based on data from

tu
Sa

Carrier Corporation Cat. No. 794-001,

at

dated 1975 0.030

py

100
al
th

Humidity Ratio(gm water /gm of Dry Air)

En

C)

30
(°

0.9
re
tu

0.025
ra
pe
m

80
Te
n
tio

25
ra
tu

0.020
Sa

90 %

ity
or

Spe

60
0

id
80 %
b

10
ul

m
70 %

cifi
B

hu
%
et

20
c
la %
W

0.015
tiv
Re 60

val
u
me

40 %
%

15 40
0.9
50

30% 0.010
m3
0.85

10
/kg

20 5 20%
Dry

0.005
A

0 10%
ir
0.80

0 -5
0.75

0%
0.000
-10 -5 0 5 10 15 20 25 30 35 40 45 50 55

120
 Drying

Dry Bulb Temperatures

These lines are indicated vertical, and Air temperature increases from left to right.

Relative Humidity
These lines are curved and begin at 100% along the top of the chart, and decrease
moving downward.

Humidity Ratio
Humidity ratio is found on the vertical, y-axis with lines of constant humidity ratio
running horizontally across the chart.

Dewpoint Temperature
Dewpoint temperature is determined by moving from a state point horizontally to the
left along lines of constant humidity ratio until the upper, curved, saturation temperature
boundary is reached.

Enthalpy
The enthalpy scale is located above the saturation, upper boundary of the chart. Lines of
constant enthalpy run diagonally downward from left to right across the chart. Lines of
constant enthalpy and constant wet bulb are the same on this chart, but values are read
from separate scales. More accurate psychrometric charts use slightly different lines for
wet-bulb temperature and enthalpy.

Wet-Bulb Temperature
Determination of wet-bulb temperature on this psychrometric chart follows lines of
constant enthalpy, but values are read off the upper, curved, saturation temperature
boundary.

Specific Volume
On this chart, values range from 12.5 to 15.0 cubic feet/ pound of dry air. Greater specific
volume is associated with warmer temperatures (dry bulb).

Wet-Bulb
Temparature

Enthalpy Relative
Humidity

Dewpoint
Temparature
Humidity
Ratio

Dry-Bulb Specific
Temparature Volume

121
 Drying

Sensible Heating or Cooling

A psychrometric process that involves the increase or decrease in the temperature of air
without changing its humidity ratio.
Example: passing moist air over a room space heater and of kiln air over the heating coils

Heating and Humidifying

A psychrometric process that involves the simultaneous increase in both the dry bulb
temperature and humidity ratio of the air.

Cooling and Dehumidifying

A psychrometric process that involves the removal of water from the air as the air
temperature falls below the dewpoint temperature.

Adiabatic or Evaporative Cooling

A psychrometric process that involves the cooling of air without heat loss or gain.
Sensible heat lost by the air is converted to latent heat in the added water vapor.

Humdifying
Heating and
Evaporative Cooling Humdifying

Sensible Cooling Sensible Heating

Cooling and Chemical

Dehumdifying Dehumdifying
Dehumdifying

122
 Adsorption

Chapter 8 – Adsorption
The phenomena of attracting and retaining the molecules of a substance on the surface
of a solid resulting into a higher concentration of molecule on the surface is known as
adsorption.
In adsorption the molecules of a substance are present in higher concentration at the
surface of solid material. (surface phenomena)
In absorption, the molecules of substance are uniformly distributed throughout the body
of liquid. (bulk phenomena)
The substance on the surface of which adsorption takes place is called adsorbent and
the substance adsorbed is called adsorbate.
The process of removal of adsorbed substance from the surface on which it is adsorbed
is known as desorption.
Some time adsorption and absorption process take place simultaneously and this
process is known as sorption.

Types of Adsorption
(1) Chemical adsorption
(2) Physical adsorption

Difference Between These Two Types of Adsorption

Physical Adsorption Chemical Adsorption

Adsorbate held on the surface by weak Adsorbate held on the surface by chemical
wander-wall forces bond

The enthalpy of adsorption is of the order The enthalpy of adsorption is of the order
of 20 KJ/Mole of 200 KJ/Mole

Usually takes place at low temperature

Usually takes place at relatively high
and decreases with increase in
temperature
temperature

It is not specific, all the gases adsorbed to

Highly specific in nature
some extent on all solid

Multi molecular layer my form Single layer will form

Enthalpy of Adsorption
Enthalpy change for adsorption of 1 mole of adsorbent on the surface of adsorbate.

123
 Adsorption

Adsorption Isotherm
The extent of adsorption of a gas on solid is expressed by x .
m
Here x → no. of moles of adsorbate.
m → mass of adsorbent.
x
A relation between and pressure of gas at constant temperature is known as
m
adsorption isotherms.

Freundlich Adsorption Isotherm

x
=K
m
T
1
x
= KP n
x
1
x m
  = kP
n

 m m

P Ps

1
Slope =
n
x 1 x
log
ln  = ln k + ln p m
 m n
log k

log p

When pressure is very high then Freundlich adsorption isotherm will fail.

Langmuir Adsorption Isotherm

x  aP 
= 
m  1 + bP 
x a
At very high Pressure → =
m b

Low pressure → x = aP
m
1  1 + bP 
= 
x  ap 
m

124
 Adsorption

1 1 bp
= +
x ap ap
m a b
b Slope =
q a
1 1 b
= + a
x ap a P
m x /m
1
Intercept =
p 1 bp a
= + O P
x a a
m

Adsorption Isobar
Relation between extend of adsorption and temperature of gas at constant pressure is
known as adsorption isobar.

Azeotrope
An azeotrope is a mixture of chemical components that has identical compositions of the
liquid & vapor phases in equilibrium with each other. This occurs because of molecular
interactions between different chemical components.
If the element contains similar structures and elementary molecules, then the molecular
interaction will be very much less hence azeotrope do not occur. Examples: mixture of
hydrocarbons (propane, butane, pentane, etc.)

Types of Azeotropes
(1) Positive azeotrope or Minimum boiling azeotrope
(2) Negative azeotrope or Maximum boiling point azeotrope

(1) Positive Azeotrope or Minimum Boiling Azeotrope

The azeotrope boils at a temperature that is lower than the boiling point of the
lighter component, positive azeotrope also called minimum boiling azeotrope.
For minimum boiling azeotrope pressure goes through maxima.
Example: ethanol-water, benzene-water.

o r M Vap
Vap o r
PA0
id
Liqu Liqu PB0
id
Vapor Pressure

Fig.1.1 Phase diagram of positive

azeotrope at constant temperature.
XA= 1 XA= 0
XB= 1
XB = 0 Mole Fraction

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 Adsorption

TB0
T 0 Vapor
A

Liquid

0 XB 1

Fig.1.2 Phase diagram of positive azeotrope at constant pressure.

The point at which both curves touch each other that point shows the azeotropic point
of the mixture. At this point liquid composition in the mixture and vapor composition in
the mixture are equal in amount.

(2) Negative Azeotrope or Maximum Boiling Point Azeotrope

The boiling point of this azeotrope is higher compared to the boiling points of its
components. Negative azeotrope is also called maximum boiling point azeotrope.
For maximum boiling azeotrope pressure goes through minima.
Example: hydrochloric acid-water, acetone-chloroform.

Vapo
Vapor Pressure

r
PAo r
Vapo
Liqu PBo
id d
N Liqui

XA = 1 XA = 0
XB = 0 XB = 1
Mole Fraction

Fig.2.1 Phase diagram of negative azeotrope at constant temperature.

Vapor
TBo

Liquid
o
T B

0 XB 1

Fig.2.2 Phase diagram of negative azeotrope at constant pressure.

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 Adsorption

Types of Distillation Precesses for Azeotropic Mixtures

• Extractive Distillation
At the top of the column solvent which has high boiling point is added to similarly
change the relative volatility to make separation. Bottom is separated by the
second column to recycle the solvent.

• Azeotropic Distillation
Where another compound which is entrainer is added to the mixture, this entrainer
affects the relative volatility of the one compound and separation becomes easier.

• Distillation Using Salts

The salts dissolve in the mixtures of liquid and changes the relative volatilities such
that separation becomes possible.

• Pressure Swing Distillation

To separate binary azeotropes two columns which are operated at different
pressures are used which change appreciably in composition over a moderate
pressure range or where a separating agent which forms a pressure-sensitive
azeotrope is added to separate a pressure-insensitive azeotrope.

• Reactive Distillation
The separating agent reacts very good and reversibly with one of the azeotropic
constituents in the mixture. To recover the initial component reaction is reversed
by the distillation of the product from the non-reacting components.

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