MASS TRANSFER

OPERATIONS
Review Lecture Series 2020
MASS TRANSFER: DIFFUSION
MASS TRANSFER:
DIFFUSION
 MASS TRANSFER
Diffusion -transference
of a component in a mixture
from a region where its con-
centration is high to a region
where the concentration is
lower.
 MASS TRANSFER
It can result from:
• molecular diffusion -random velocities of the
molecules
• eddy diffusion or from the circulating or eddy
currents present in a turbulent fluid

Driving force: concentration difference

 MASS TRANSFER OPERATIONS

Mass transfer operations Driving Forces:

• fractional distillation- differences in volatility
• gas absorption-differences in solubility of the
gases in a selective absorbent
• liquid- liquid extraction –based on the
selectivity of an immiscible liquid solvent for
one of the constituents.
 FICK’SFick’s
Rate of Mass Diffusion: LAW Law
Fick’s Law:

where: D = mass diffusivity(L2/t)

ED = eddy diffusivity(L2/t)
 KNUDSEN DIFFUSION

• Knudsen diffusion-main resistance to diffusion

arises from collisions of molecules with the
walls.

T
DKn  97rp
MA

where DKn is the Knudsen diffusivity. MA In g/mol and T in

Kelvins
PHB, Page 5-58
 EFFECTIVE DIFFUSIVITY IN MEMBRANES

1
1 1  
Deff   
 D Dkn  

Where = porosity of membrane 

actual path
= tortuosity if the pores displacement
 FICK’S LAW

BINARY GAS MIXTURES:

For gas mixture of A(solute) and B:
 Equimolecular Counter-diffusion (ECD)

Equimolecular counterdiffusion:

-when the mass transfer rates of the two

components are equal and opposite the
process.(i.e., this what is happening at the
interface between liquid and its vapour at the
surface!)
Equimolecular Counter-Diffusion (ECD)
 Equimolecular Counterdiffusion

Equimolecular counterdiffusion:
 Equimolecular Counterdiffusion

Alternate forms: Equimolecular

Counterdiffusion
 Unimolecular Counter-Diffusion (UCD)

-usually occurs when any solute A diffuses in an

insoluble material, B.
UCD
MASS TRANSFER FOR UCD
 MASS DIFFUSIVITIY
DIFFUSIVITIES OF FLUIDS
For Vapors:
Winkelmann’s Technique- liquid is
allowed to evaporate in a vertical
glass tube over the top of which a
stream of vapour-free gas is passed,
at a rate such that the vapour pres-
sure is maintained almost at zero.
MASS DIFFUSIVITY: GASES and
VAPORS
MASS DIFFUSIVITIY: LIQUIDS
 PROBLEM
Using equation of Fuller et al., estimate the
diffusivity of naphthalene vapour in air at a
temperature of 0°C and a total pressure of 1
atm.

A. 0.0605 cm2/s C. 0.0075 cm2/s

D. 0.0137 cm2/s D. 0.0014 cm2/s
 PROBLEM
The diffusivity in cm2/s of oxygen gas at 80:F
and 1 atm in Nafion membrane with an average
pore radius of 72 Angstroms?

a. 0.0213 c. 0.0152
b. 0.0745 d. 0.1305
 PROBLEM
The molecular diffusivity of nitrogen in
sulphonamide membrane is 0.056 cm2/s. The
average pore radius is 12 angstroms, the
porosity is 0.77 and tortuosity of 2.56. The
effective diffusivity at 25 oC is:
a. 0.1 b. 0.011
c. 0.0011 d. 0.000011 e. 0.0000011
 PROBLEM
In a refinery plant, a binary solution of benzene and o-xylene is
flash-distilled at 120degC so as to separate the more volatile
component. From the differential analysis, it is found that the
transfer of benzene is about 3.25 x 10^-3 kg/m2-s by equimolal
counter-diffusion. If the gas phase contains 65% benzene, and
the total pressure in the column is about 50 kPa, what is the
mole fraction of benzene in the solution?( assume latent heats
to be equal and D = 1.4 x 10^-5 m2/s and vapor pressure of
benzene is 78.3 kPa at 150 degC, and resistance is equivalent to
1 mm film).
a. 0.37 c. 0.54
b. 0.78 d. none of these
 PROBLEM

A pan of 40 mm deep, is filled with water to a level

of 20 mm and is exposed to dry air at 30C. Calculate
the time require for all the water to evaporate. Take,
mass diffusivity is 0.25  10 -4 m2 /s.
a. 6 days c. 5 days
b. 3 days d. 7 days
 PROBLEM
Nitrogen gas at high pressure and 298 K is contained in a 2-m x 2-
m x 2-m cubical container made of natural rubber whose walls
are 4 cm thick. The concentration of nitrogen in the rubber at
the inner and outer surfaces are 0.067 kg/m3 and 0.009 kg/m3,
respectively. The diffusion coefficient of nitrogen through rubber
is 1.5 x 10^-10 m2/s. The mass flow rate of nitrogen by diffusion
through the cubical container is

a. 8.24 x 10-10 kg/s d. 1.35 x 10-10 kg/s

b. 5.22 x 10-9 kg/s e. 9.71 x 10-9 kg/s
c. 3.58 x 10-8 kg/s
 PROBLEM
Pressurized hydrogen gas is stored at 358 K in a 4.8m outer-
diameter spherical container made of nickel. The shell of the
container is 6 cm thick. The molar concentration of hydrogen
in the nickel at the inner surface is determined to be 0.087
kmol/m3 . The concentration of hydrogen in the nickel at the
outer surface is negligible. Determine the mass flow rate of
hydrogen by diffusion through the nickel container. (D = 1.2
 10 12 m2 / s )
a. 2.46  10 10 kg/s c. 1.73  109 kg/s
b. 8.76  10 10 kg/s d. 6.92  10 9 kg/s
GAS ABSORPTION AND
STRIPPING
WHITMANN’S TWO-FILM THEORY
Overall Mass Transfer Coefficient

1 1 m 1 1 1
   
KG kg k KL k mkg

1
Note: Resistance due to mass transfer is
K
 Packed Absorbers/Strippers
• Absorber(or Scrubber) – solute is from gas
phase to liquid phase.

• Stripper- solute is from liquid phase to gas

phase.
 Henry’s Constant
To determine the value of m of the equilibrium
curve from the Henry’s constant KH,
 PAg 
KH  lim  
C 0  C A 

KH 
PAg
, hence KH 
 PAg PT   PT  m  KH
CT
CA (CA CT ) CT PT
ABSORPTION/STRIPPING OF DILUTE
SOLUTIONS
G ' y 2 dy ' G' y 2 dy '
kg aP 1 y i ' y ' KG aP y1 y i ' y '

z 
y

L' x2 dx ' L' x2 dx '

z
kl aCT x1 
x ' xi ' K L aCT x1 x ' x *

Operating Line: L '  x1 ' x '   G '  y ' y1 ' 

Equlibrium Line: y *  mx *

L'
Absorption factor: A
mG '
 SUMMARY OF EQUATIONS (PHB, 14-12 to 15)
1  1   y  mx2  1 
NOG  ln  1    1  
Absorption 1  A 
1 A   y 2  mx2  A 
Packed Column
Z  HOG NOG
1   x  y1 / m  
NOL  ln 1  A   2   A 
Stripping 1  A  x 
 1 1 y / m  
Z  HOL NOL

1  1   y  mx2  1 
Absorption NG  ln  1    1  
ln( A)  A   y 2  mx2  A 

Z  HETP  NG

Tray Column
Stripping 1   x  y1 / m  
NL  ln 1  A   2   A 
ln(1/ A)  x 
 1 1 y / m  
Z  HETP  NL
Minimum Solvent and Gas
Requirement
 HETP, (PHB, Eq. 14-29)
-Height equivalent of a theoretical plate.

ln(1/ A)
HETPg  HOG 
A 1
ln( A)
HETPs  HOL 
1/ A  1
 PROBLEM 1
Gaseous ammonia is absorbed from an ammonia-air stream by water in a wetted-wall column.
Pure water enters the top of the column where the ammonia partial pressure is 2000 Pa. The
OMTC in terms of the partial pressure driving force is 9.2 x 10-3mol/h-m2-Pa. 70% of the total
resistance to mass transfer is found in the gas phase. Equilibrium data is given:

Partial Pressure of
NH3 (Pa) 1533 2039 2572 3252 3945
g NH3/100 g water 1.2 1.60 2.00 2.50 3.00

8. The Henry’s law constant for ammonia in water is most nearly:

a. 1.17 x 10^5 Pa b. 1.24 x 10^5 Pa
c. 1.21 x 10^5 Pa d. 1.28 x 10^5 Pa

9. The individual gas-phase MTC is most nearly:

a. 9.20 x 10-3 mol/h-m2-Pa b. 1.31 x 10-2 mol/h-m2-Pa
c. 6.44 x 10-3 mol/h-m2-Pa d. 1.16 x 10-2 mol/h-m2-Pa

10. The individual liquid-phase MTC is most nearly:

a. 233 mol/h-m2 b. 3620 mol/h-m2
c. 2600 mol/h-m2 d. 3740 mol/h-m2
 PROBLEM 2
Gas, from a petroleum distillation column, has a concentration of H2S
reduced from 0.03 (kmol H2S/kmol of inert hydrocarbon gas) to 1 per
cent of this value by scrubbing with a triethanolamine–water solvent in
a counter-current tower, operating at 300 K and atmospheric pressure.
The equilibrium relation for the solution may be taken as Y = 2X. The
solvent enters the tower free of H2S and leaves containing 0.013 kmol
of H2S/kmol of solvent. If the flow of inert gas is 0.015 kmol/s m2 of
tower cross-section,. The individual mass transfer coefficients may be
taken as 0.04 kmol/s-m3 on the gas phase and 2.43 kmol/s-m3 in the
liquid phase.
the number of transfer units required.
a. 17 b. 21 c. 34 d. 12
the height of the absorber necessary,
a. 5.3 m b. 7.6 m c. 13 m d. 17 m
 PROBLEM 3
Fifty cubic feet/s of flue gas at 80F and 14.7 psia containing 2% by mole CO2 is
scrubbed using optimum water(1.5 times the minimum) in a column containing 25mm
ceramic Pall rings. The overall mass transfer coefficient is 0.15 ft/s in the gas phase.
The equilibria between gas/liquid phases is given by
Y = 3.16X

n designing a 2-feet diameter tower for the 99% absorption of CO2 in the flue gas,
the height of a transfer unit, in feet, is nearly,
a. 1.6 b. 7.3 c. 4.4 d. 0.32

the HETP, in feet, of the packed tower:

a. 0.5 b. 2.3 c. 1.3 d. 0.7

the amount of scrubbing water, in ft3/h required is nearly,

a. 600 b. 300 c. 200 d. 100

the amount of packing, in ft required is nearly,

a. 44 ft b. 30ft c. 26 ft d. 17 ft
 PROBLEM 4
Naptha oil is 99.9% stripped with phenol using superheated recycle
steam at 350K and 1 atm containing no phenol. The oil contains 5.2%
phenol and fed at 20 kmol/h. The column provision is 78 cm in
diameter containing 13 mm Raschig rings (ceramic). The steam to be
used is 1.3 times the minimum value and the Henrys contant is 2.3,

Individual gas phase MTC = 0.077 kmol/h-m2

Individual liquid phase MTC = 0.590 kmol/h-m2

The m3/h steam required is approximately

A. 309 B. 165 C. 409 D. 570

The height of packing needed

A. 6.2 m B. 8.9 m C. 1.32 m D. 2.3 m
 PROBLEM 5
A mixture of ammonia and air is scrubbed in a plate
column with water containing 0.005% ammonia. If
the ammonia concentration is reduced from 5 per
cent to 0.01 per cent, and the water and air rates
are 0.65 and 0.40 lb/m-2s, respectively, how many
theoretical plates are required? The equilibrium
relationship may be written as Y = X, where X is the
mole ratio in the liquid phase

A. 12 B. 9 C. 6 D. 14
 PROBLEM 6
A bubble-cap column with 30 plates is to be used to remove n-
pentane from a solvent oil by means of steam stripping. The inlet
oil contains 6 kmol of n-pentane per 100 kmol of pure oil and it is
desired to reduce the solute content to 0.1 kmol per 100 kmol of
solvent. Assuming isothermal operation and an overall plate
efficiency of 30 per cent, find the specific steam consumption,
that is the kmol of steam required per kmol of solvent oil
treated, and the ratio of the specific and minimum steam
consumptions. The equilibrium relation for the system may be
taken as Y = 3.0X,
a. 1.2 b. 1.4 c. 2.1 d. 2.7
DISTILLATION
 Distillation Operation
DISTILLATION-
separation of liquid
mixtures into their
various components
based on the difference
in their relative
volatilities or boiling
point.
Recall: x-T equilibrium Curve
 Partial Pressures
Daltons Law- in an ideal gas or vapour the partial pressure is
proportional to the mole fraction of the constituent.

Pi  yi PT

Raoult’s Law-can only by applied to ideal mixtures.

0
Pi  xi Pi
 0
Vapor Pressure, P
Antoine’s Equation:

0 B
log(P )  A 
T C
Relative Volatility, α

0
PA
 0
PB
 x-y Equilibrium Curves

 xA
yA 
(  1)x A  1
 NON IDEAL SYSTEMS
0
xi Pi
yi   i
PT

yi  K i xi

where γ is the activity coefficient of the species.

Calculation of the Activity Coefficients
  ln  i 
Gibbs  Duhem Eq.:  xi  x   0
 i 

M arg ules Eq : log  1  x22  A12  2 x1( A21  A12 )

log  2  x12  A21  2 x2 ( A12  A21 )
A12
Van Laar Eq : log  1  2
 A12 x1 
1  
 A21(1  x1 
)
A21
log  2  2
 A21(1  x1 ) 
1  
 A x
12 1 
 Methods of Distillation

Methods of Distillation:

• Differential Distillation
• Flash/Equilibrium Distillation
• Fractionation
 Differential Distillation: Rayleigh
Distillation
Differential
Distillation-a batch
process; the vapour
formed on boiling the
liquid is removed at
once from the system.

 L0  x dx
ln 
 L


x0 xy
 PROBLEM 1
A 500 mols solution containing 14% by mole oil and the rest CCl4 is
differentially distilled such that 42% of the feed is vaporized. The solution can
be assumed as ideal with a relative volatility of 4.32. Compute the recovery of
oil:

A. 84.5% C. 64.4%
B. 95.3% D. 45.5%
 Flash Distillation
Flash/Equilibrium Distillation-a continuous process, it is
vaporising a definite fraction of the liquid feed in such a way
that the vapour evolved is in equilibrium with the remaining
liquid.
 PROBLEM 2
Flash distillation is used to evaporate three-fourth
of a 40 mole% benzene–toluene mixture. Assume a
relative volatility of 2.35.

What is the composition of the resulting distillate?

a. 0.56
b. 0.42
c. 0.45
d. 0.58
 PROBLEM 2-B
A liquid mixture containing 50 mol% n-heptane (A)
and 50 mol% n-octane (B), at 303 K, is to be
continuously flash-vaporized at a pressure of 1 atm
to vaporize 30 mol% of the feed. The average
relative volatility is 2.16. What will be the
composition of the vapor and liquid and the
temperature in the separator if it behaves as an
ideal stage?
a. 0.443 b. 0.233
c. 0.410 d. 0.287
 PROBLEM 3
An equimolal aqueous mixture of an aldehyde is
sprayed in a flash drum such that the ratio of distillate
to the residue liquid is 2:5. The distillate contains 73.4%
of the aldehyde. The relative volatility of the aldehyde
with water is nearly:

A. 2
B. 3
C. 4
D. 5
 Fractionation
Fractionation-occurs
in
continuous
distillation
column and is
capable of
handling high
throughputs.
Cases in Fractionation:

• Binary distillation column- feed contains only

two components
• Multi-component distillation column- feed
contains more than two components the
number of product streams they have
Multi-product
distillation column-
column
has more than two
product
streams where the
extra
feed exits when it is
used
to help with the
separation
 Tray distillation
column- where trays
of various designs are
used to hold up the
liquid to provide
better contact
between vapor and
liquid, hence better
separation.
Packed distillation
column-'packings'
are used to
enhance contact
between vapor and
liquid.
Fractionation Distillation Calculation:
Binary Distillation

F  DB

xf F  xd D  x b B
 McCabe-Thiele Fractionation
• RECTIFYING: R xd
y x
R 1 R 1

• STRIPPING:  Vb  xb
y  x 
 Vb  1 Vb

V ' V D
R  Reflux ratio  
where: V V
L' L  B
Vb  Boil-up ratio  
L B
 McCabe-Thiele Fractionation
• Feed Line:
q xf
y x
q 1 q 1

  Cpf (Tb  Tf )
q

 PROBLEM 4
A 34% -acetone-66 wt.%-water system boils at
223:F. The specific heats of acetone and water
are 0.51 and 0.997 Btu/lb-R, respectively. What
is the feed temperature if the feed line slope in
the McCabe-Thiele plot is -1.5? Assume average
latent heat is 716 Btu/lb

a. 636:F c. 566:F
b. 435:F d. 512:F
 Minimum Reflux
MINIMUM REFLUX- occurs at infinite number of
plates

𝑅𝑚 𝑥𝐷 − 𝑦′
=
𝑅𝑚 + 1 𝑥𝐷 − 𝑥′

Where x’ and y’ are the pinch values being the

intersection of the feed line(or q-line) and the
equilibrium curve
 MINIMUM THEORETICAL STAGES-
 xd (1  xb ) 
MINIMUM ln  

Nm   b d 
x (1 x )
THEORETICAL
ln 
STAGES- occurs when
the reflux ratio is
infinite. That is, no
distillate product is
bled from the system.

Note: For report purposes: Subtract 1 from Nm being the reboiler

 Theoretical Number of Stages
Molokanov Equation: N  Nmin
Y
N 1

R  Rmin
X
R 1

 1  54.4 X   X  1  
Y  1  exp    
 11  117.2 X   X  
 Optimum Feeding Tray
Kirkbride Equation:
0.206
   xLK ,B  B
2
NR  zHK
     
NS  zLK   xHK ,D  D 


0.206
NF  1  x   xb  B 
2

 
f
   
N  NF  x f   1  xd  D 

 PROBLEM 5
A continuous fractionating column is to be designed to separate 2.5 kg/s of a
mixture of 60 per cent toluene and 40 per cent benzene, so as to give an
overhead of 97 per cent benzene and a bottom product containing 98 per
cent toluene by mass. A reflux ratio of 3.5 kmol of reflux/kmol of product is to
be used and the molar latent heat of benzene and toluene may be taken as 30
MJ/kmol. Calculate:

The minimum reflux ratio:

A. 1.31 B. 1.22 C. 2.3 D. 2.8
The minimum number of plates required:
A. 6.5 B. 7.2 C. 8.6 D. 9.8
The number of theoretical plates and position of the feed if the feed is liquid
at 295 K, of specific heat capacity 1.84 kJ/kg K for partial condenser
A. 10 B. 14 C. 8 D. 17
 PROBLEM
Isobutanol is separated from n-butanol in a solution containing 60%by mole isobutanol, the rest are n-butanol.
A fractionating column is design to separate 98% of the isobutanol from a capacity of 450 kmols/h of solution,
and bottoms should not contain more than 3% isobutanol. The following data applies:
Specific heat of feed = 2,340 J/kg-K Relative volatility = 2.5
Boiling point of feed = 78degC
Feed temperature = 90 degC
Latent heat of feed = 500 kJ/kg
The distillate concentration(mol%) of isobutanol is:
a. 98% b. 99% c. 93% d. 78%

The number of stages at total reflux:

a. 4 b. 6 c. 8 d. 10

The minimum reflux ratio:

a. 1.03 b. 1.43 c. 2.51 d. 2.1

If the reflux ratio if it is 1.5 times the minimum:

a. 1.54 b. 2.15 c. 3.80 d. 3.2

The number of theoretical plates using partial condenser and a reboiler:

a. 18 b. 26 c. 14 d. 31
 PROBLEM
Benzene is separated from p-xylene in a solution containing 40%by mole benzene, the rest are
xylene. A fractionating column is designed such that the distillate contains 99% benzene from a
capacity of 200 kmols/h of solution, and bottoms should not contain more than 1% benzene. The
following data applies:
• Specific heat of feed = 3,510 J/kg-K Relative volatility = 2.1
• Boiling point of feed = 90 degC
• Feed temperature = 70 degC
• Latent heat of feed = 370 kJ/kg

The recovery of benzene is nearly:

a. 98.5% b. 99.2% c. 93.4% d. 91.9%
The number of stages at total reflux:
a. 5.6 b. 7.8 c. 12.4 d. 15.2
The minimum reflux ratio:
a. 2.04 b. 3.13 c. 2.73 d. 1.62
If the reflux ratio if it is 1.5 times the minimum:
a. 3.06 b. 4.70 c. 3.94 d. 2.72
The number of theoretical plates for a column with partial condenser and a reboiler:
a. 15 b. 20 c. 25 d. 30
 PROBLEM
When the column does not produce distillate
stream,

A. The number of stages is infinite

B. The number of stages is minimum
C. The reflux ratio is zero
D. The reflux ratio is minimum
 PROBLEM
At minimum reflux,

A. The number of stages is infinite

B. The number of stages is minimum
C. The reflux ratio is zero
D. The reflux ratio is minimum
 PROBLEM
The part of the distillation column having the
lowest pressure is at the

A. top
B. bottom
C. Feeding section
D. The pressure is constant althroughout the
column
 PROBLEM
230 kmols/h of acetaldehyde-water system containing 42% by mole aldehyde is
fed in a fractionator such that 95% of the acetaldehyde is removed from the
water, and the bottoms should not contain more than 4 mol% aldehyde. The
following data applies:
Feeding temperature: 65degC
bubble point of mixture: 92 degC
specific heat of feed: 3450 J/kg-K
latent heat of feed at 65degC = 1460 kJ/kg
Vapor pressure of acetaldehyde at 65degC = 43.5 mm Hg
Vpor pressure of water at 65degC = 25.67 mm Hg
Assuming the system is ideal, determine:
The reflux ratio to be used:
a. 4.4 b. 2.34 c. 3.21 d. 2.97

The number of ideal stages of the reflux ratio is optimum with partial condenser
is:
a. 16 b. 9 c. 20 d. 19

The feeding plate is

a. 5th b. 10th c. 16th d. 13th
 PROBLEM
A 100-kmol/h feed consisting of 10, 20, 30, and 40 mol% of propane,
n-butane, n-pentane, and n-hexane, respectively, enters a distillation
column at 100 psia (689.5 kPa) and 200°F (366.5°K). Assuming
equilibrium,

what mole fraction of the feed enters as liquid,

A. 87.8% B. 56.4% C. 93.2% D. 32.5%

and what are the liquid and vapor compositions of n-butane?

A. X = 0.32, Y = 0.14
B. X = 0.057, Y = 0.15
C. X = 0.22, Y = 0.53
D. X = 0.183, Y = 0.32
Tray Efficiency: Murphree

EMV 
 Tray Efficiency: Overall

O’ Conell Correlation-It correlates the overall efficiency

of the column with the product of the feed viscosity
and the relative volatility of the key component in the
mixture

Actual Number of Trays

EOV 
Theoretical Number of Trays

 
0.226
EOV  0.503  f
 PROBLEM
A plate in a distillation column has an incoming
and outgoing vapor compositions of 0.45 and
0.58, respectively. The incoming and outgoing
liquid compositions are 0.23 and 0.20,
respectively. The relative volatility is 5.56.
Determine the Murphree tray efficiency:

A. 40% B. 65% C. 72% D. 88%

LIQUID-LIQUID
EXTRACTION
 Liquid-Liquid Extraction
Liquid-liquid Extraction-separation of the
components of a liquid mixture by treatment
with a solvent in which one or more of the
desired components is preferentially soluble is
known as liquid–liquid extraction.
 Stages in Operation:

(a) Bringing the feed mixture and the solvent

into intimate contact,
(b) Separation of the resulting two phases, and
(c) Removal and recovery of the solvent from
each phase.
Extraction is in many ways preferable over distillation in
the following cases:

(a) Where distillation would require excessive amounts of

heat, such as, for example, when the relative volatility
is near unity.

(b) When the formation of azeotropes limits the degree

of separation obtainable in distillation.

(c) When heating must be avoided.

(d) When the components to be separated are quite

different in nature.
Application of Extraction in Metallurgy:

(a) Those involving cation exchange such as, for

example, the extraction of metals by carboxylic
acids;
(b) Those involving anion exchange, such as the
extraction of anions involving a metal with
amines, and
(c) Those involving the formation of an additive
compound, for example, extraction with neutral
organo-phosphorus compounds. An important
operation of this type is the purification of uranium
from the nitrate with tri-n-butyl phosphate.
The Extraction Process

Extract, E-containing
the required solute in
the added solvent and
the

Raffinate, R- the weaker

solution with some
associated solvent
EQUILIBRIA OF TERNARY SYSTEMS
HUNTER-NASH GRAPHICAL METHOD
MALONEY–SCHUBERT GRAPHICAL
EQUILIBRIUM-STAGE METHOD
 PARTITION RATIO

 solute in Extract 

yi '  solvent of Extract  
Ki  
xi '  solute in Raffinate 
 
 solvent of Raffinate 
Multiple-contact System: Cross-Flow System
Equilibrium Data

Types of Liquid-liquid Mixtures:

A. A homogeneous solution may be formed and the

selected solvent is then unsuitable.
B. The solvent may be completely immiscible with the
initial solvent.
C. The solvent may be partially miscible with the original
solvent resulting in the formation of one pair of partially
miscible liquids.
D. The new solvent may lead to the formation of two or
three partially miscible liquids.
Treybal Eq: Co-current Contact with Fresh
Immiscible Solvents Eq. 15-3
xn '
Recovery, r: 1 r 
xf '
where n is the number of stages.
 xf ' y s / Ki 
ln  
 xn ' y s / Ki 
More generally, N 
 kS 
ln  1  
 F 
E  KS '/ F '
 Problem
A feed of 13,500 kg/h consists of 8 wt% acetic acid in
water. Acetic acid will be removed from the solution by
extraction with pure methyl isobutyl ketone at 298 K. If
the raffinate is to contain only 1 wt% of acetic acid,
estimate the kilograms/hour of solvent required if a
single equilibrium stage is used. Assume that water and
methyl isobutyl ketone are insoluble. For this system, m’
= 0.657 kg water/kg methyl isobutyl ketone (Perry and
Chilton, 1973).

a. 143,800 b. 178,600
c. 120,400 d. 560,780
 PROBLEM
A batch of 1000 lb of wastewater stream
containing 245 ppm of methylmercury is
contacted with iso-octane in order to reduce the
concentration to 12 ppm or less. How much
solvent should be fed in each stage of a 5-stage
co-current extraction? Partition coefficient is 3.

A. 75 lb C. 277 lb
B. 1230 lb D. 553 lb
 PROBLEM
Acetic acid is extracted from its aqueous phase
using 1-butanol. The aqueous phase contains 5%
by mass acetic acid. A total of 400 mL of fresh 1-
butanol is contacted for 100 mL of feed. How
many extraction stages must be made in order
to extract more than 99% of the acid?
A. 5 C. 3
B. 7 D. 9
 PROBLEM
An aqueous dilute fermentation broth contains 0.5 wt% of penicillin F.
It is to be extracted with amyl acetate. At room temperature and pH =
3.2. Water and amyl acetate are essentially insoluble, and the
distribution coefficient for the penicillin is K = 80. If 100 kg of the
fermentation broth is extracted with 6 kg of the pure solvent in a single
ideal stage, calculate the fractional recovery of penicillin and the
penicillin concentration in the final raffinate and extract.

a.82.8% b. 56.8% c. 89.4% d. 93.5%

What would be the recovery with two-stage crosscurrent extraction if

6 kg of fresh solvent is used in each stage?
b.97% b. 78.9% c. 95.6% d. 94.5%
 Counter-Current Extraction
Calculation of the Number of Stages:

Analogous to the Kremser-Souders-Brown (Eq. 15-48)

Equation for Stripping:

 x f ' y s / K i  1  1 
ln  1    
 xn ' y s / K i  E  E 
N
ln(E )
Where
KS '
E  extraction factor =
F'
 PROBLEM
In distillery plant, a chemical engineer is tasked
to design a counter-current contact
reciprocating extractor in order to remove
furfural content (1.27%) from water using
toluene as solvent with 99.9% removal. The
toluene is virtually pure and is provided at 1.5
times the minimum amount.
a. 10 b. 14 c. 19 d. 24
 PROBLEM
Methanol is stripped from water using phenol
and distilled. A solution contains 3.2% methanol
is contacted with water in a 16 stage-cross-
current system such that the ratio of feed to
solvent in each stage is 5:1. Compute the %
extraction:
a. 96.4% b. 99.4%
c. 97.7% d. 93.4%
 PROBLEM
Nicotine in an aqueous solution containing 1.5% nicotine is to be
extracted with kerosene at 20°C. Water and kerosene are mutually
insoluble. Determine the percentage extraction of nicotine if 100 kg of
the feed solution is extracted in three ideal stages using 50 kg
kerosene in each stage. The following equilibrium data may be used
where x′ = kg nicotine/kg water, and y′ = kg nicotine/kg kerosene:

x′: 0.001011 0.00246 0.00502 0.00751 0.00998 0.0204

y′: 0.000807 0.00196 0.00456 0.00686 0.00913 0.0187

a. 68.8% b. 45.3% c. 76.1% d. 95.3%

 PROBLEM
The equilibrium of ethanol-water—hexanol system
is given by Y = X; where X is the mass ratio in the
aqueous and Y is the mass ratio in the 1-hexanol
phase. Supposing that 8% ethanol solution is
contacted in a column contactor such that the
solvent is 1.3 times the minimum amount. How
many ideal stages are required in order to recover
90% of the ethanol?
A. 2 C. 4
B. 6 D. 8
DISTILLATION
 Distillation Operation
DISTILLATION-
separation of liquid
mixtures into their
various components
based on the difference
in their relative
volatilities or boiling
point.
Recall: x-T equilibrium Curve
 Partial Pressures
Daltons Law- in an ideal gas or vapour the partial pressure is
proportional to the mole fraction of the constituent.

Pi  yi PT

Raoult’s Law-can only by applied to ideal mixtures.

0
Pi  xi Pi
 0
Vapor Pressure, P
Antoine’s Equation:

0 B
log(P )  A 
T C
Relative Volatility, α

0
PA
 0
PB
 x-y Equilibrium Curves

 xA
yA 
(  1)x A  1
 NON IDEAL SYSTEMS
0
xi Pi
yi   i
PT

yi  K i xi

where γ is the activity coefficient of the species.

Calculation of the Activity Coefficients
  ln  i 
Gibbs  Duhem Eq.:  xi  x   0
 i 

M arg ules Eq : log  1  x22  A12  2 x1( A21  A12 )

log  2  x12  A21  2 x2 ( A12  A21 )
A12
Van Laar Eq : log  1  2
 A12 x1 
1  
 A21(1  x1 
)
A21
log  2  2
 A21(1  x1 ) 
1  
 A x
12 1 
 Methods of Distillation

Methods of Distillation:

• Differential Distillation
• Flash/Equilibrium Distillation
• Fractionation
 Differential Distillation: Rayleigh
Distillation
Differential
Distillation-a batch
process; the vapour
formed on boiling the
liquid is removed at
once from the system.

 L0  x dx
ln 
 L


x0 xy
 PROBLEM 1
A 500 mols solution containing 14% by mole oil and the rest CCl4 is
differentially distilled such that 42% of the feed is vaporized. The solution can
be assumed as ideal with a relative volatility of 4.32. Compute the recovery of
oil:

A. 84.5% C. 64.4%
B. 95.3% D. 45.5%
 Flash Distillation
Flash/Equilibrium Distillation-a continuous process, it is
vaporising a definite fraction of the liquid feed in such a way
that the vapour evolved is in equilibrium with the remaining
liquid.
 PROBLEM 2
Flash distillation is used to evaporate three-fourth
of a 40 mole% benzene–toluene mixture. Assume a
relative volatility of 2.35.

What is the composition of the resulting distillate?

a. 0.56
b. 0.42
c. 0.45
d. 0.58
 PROBLEM 2-B
A liquid mixture containing 50 mol% n-heptane (A)
and 50 mol% n-octane (B), at 303 K, is to be
continuously flash-vaporized at a pressure of 1 atm
to vaporize 30 mol% of the feed. The average
relative volatility is 2.16. What will be the
composition of the vapor and liquid and the
temperature in the separator if it behaves as an
ideal stage?
a. 0.443 b. 0.233
c. 0.410 d. 0.287
 PROBLEM 3
An equimolal aqueous mixture of an aldehyde is
sprayed in a flash drum such that the ratio of distillate
to the residue liquid is 2:5. The distillate contains 73.4%
of the aldehyde. The relative volatility of the aldehyde
with water is nearly:

A. 2
B. 3
C. 4
D. 5
 Fractionation
Fractionation-occurs
in
continuous
distillation
column and is
capable of
handling high
throughputs.
Cases in Fractionation:

• Binary distillation column- feed contains only

two components
• Multi-component distillation column- feed
contains more than two components the
number of product streams they have
Multi-product
distillation column-
column
has more than two
product
streams where the
extra
feed exits when it is
used
to help with the
separation
 Tray distillation
column- where trays
of various designs are
used to hold up the
liquid to provide
better contact
between vapor and
liquid, hence better
separation.
Packed distillation
column-'packings'
are used to
enhance contact
between vapor and
liquid.
Fractionation Distillation Calculation:
Binary Distillation

F  DB

xf F  xd D  x b B
 McCabe-Thiele Fractionation
• RECTIFYING: R xd
y x
R 1 R 1

• STRIPPING:  Vb  xb
y  x 
 Vb  1 Vb

V ' V D
R  Reflux ratio  
where: V V
L' L  B
Vb  Boil-up ratio  
L B
 McCabe-Thiele Fractionation
• Feed Line:
q xf
y x
q 1 q 1

  Cpf (Tb  Tf )
q

 PROBLEM 4
A 34% -acetone-66 wt.%-water system boils at
223:F. The specific heats of acetone and water
are 0.51 and 0.997 Btu/lb-R, respectively. What
is the feed temperature if the feed line slope in
the McCabe-Thiele plot is -1.5? Assume average
latent heat is 716 Btu/lb

a. 636:F c. 566:F
b. 435:F d. 512:F
 Minimum Reflux
MINIMUM REFLUX- occurs at infinite number of
plates

𝑅𝑚 𝑥𝐷 − 𝑦′
=
𝑅𝑚 + 1 𝑥𝐷 − 𝑥′

Where x’ and y’ are the pinch values being the

intersection of the feed line(or q-line) and the
equilibrium curve
 MINIMUM THEORETICAL STAGES-
 xd (1  xb ) 
MINIMUM ln  

Nm   b d 
x (1 x )
THEORETICAL
ln 
STAGES- occurs when
the reflux ratio is
infinite. That is, no
distillate product is
bled from the system.

Note: For report purposes: Subtract 1 from Nm being the reboiler

 Theoretical Number of Stages
Molokanov Equation: N  Nmin
Y
N 1

R  Rmin
X
R 1

 1  54.4 X   X  1  
Y  1  exp    
 11  117.2 X   X  
 Optimum Feeding Tray
Kirkbride Equation:
0.206
   xLK ,B  B
2
NR  zHK
     
NS  zLK   xHK ,D  D 


0.206
NF  1  x   xb  B 
2

 
f
   
N  NF  x f   1  xd  D 

 PROBLEM 5
A continuous fractionating column is to be designed to separate 2.5 kg/s of a
mixture of 60 per cent toluene and 40 per cent benzene, so as to give an
overhead of 97 per cent benzene and a bottom product containing 98 per
cent toluene by mass. A reflux ratio of 3.5 kmol of reflux/kmol of product is to
be used and the molar latent heat of benzene and toluene may be taken as 30
MJ/kmol. Calculate:

The minimum reflux ratio:

A. 1.31 B. 1.22 C. 2.3 D. 2.8
The minimum number of plates required:
A. 6.5 B. 7.2 C. 8.6 D. 9.8
The number of theoretical plates and position of the feed if the feed is liquid
at 295 K, of specific heat capacity 1.84 kJ/kg K for partial condenser
A. 10 B. 14 C. 8 D. 17
 PROBLEM
Isobutanol is separated from n-butanol in a solution containing 60%by mole isobutanol, the rest are n-butanol.
A fractionating column is design to separate 98% of the isobutanol from a capacity of 450 kmols/h of solution,
and bottoms should not contain more than 3% isobutanol. The following data applies:
Specific heat of feed = 2,340 J/kg-K Relative volatility = 2.5
Boiling point of feed = 78degC
Feed temperature = 90 degC
Latent heat of feed = 500 kJ/kg
The distillate concentration(mol%) of isobutanol is:
a. 98% b. 99% c. 93% d. 78%

The number of stages at total reflux:

a. 4 b. 6 c. 8 d. 10

The minimum reflux ratio:

a. 1.03 b. 1.43 c. 2.51 d. 2.1

If the reflux ratio if it is 1.5 times the minimum:

a. 1.54 b. 2.15 c. 3.80 d. 3.2

The number of theoretical plates using partial condenser and a reboiler:

a. 18 b. 26 c. 14 d. 31
 PROBLEM
Benzene is separated from p-xylene in a solution containing 40%by mole benzene, the rest are
xylene. A fractionating column is designed such that the distillate contains 99% benzene from a
capacity of 200 kmols/h of solution, and bottoms should not contain more than 1% benzene. The
following data applies:
• Specific heat of feed = 3,510 J/kg-K Relative volatility = 2.1
• Boiling point of feed = 90 degC
• Feed temperature = 70 degC
• Latent heat of feed = 370 kJ/kg

The recovery of benzene is nearly:

a. 98.5% b. 99.2% c. 93.4% d. 91.9%
The number of stages at total reflux:
a. 5.6 b. 7.8 c. 12.4 d. 15.2
The minimum reflux ratio:
a. 2.04 b. 3.13 c. 2.73 d. 1.62
If the reflux ratio if it is 1.5 times the minimum:
a. 3.06 b. 4.70 c. 3.94 d. 2.72
The number of theoretical plates for a column with partial condenser and a reboiler:
a. 15 b. 20 c. 25 d. 30
 PROBLEM
When the column does not produce distillate
stream,

A. The number of stages is infinite

B. The number of stages is minimum
C. The reflux ratio is zero
D. The reflux ratio is minimum
 PROBLEM
At minimum reflux,

A. The number of stages is infinite

B. The number of stages is minimum
C. The reflux ratio is zero
D. The reflux ratio is minimum
 PROBLEM
The part of the distillation column having the
lowest pressure is at the

A. top
B. bottom
C. Feeding section
D. The pressure is constant althroughout the
column
 PROBLEM
230 kmols/h of acetaldehyde-water system containing 42% by mole aldehyde is
fed in a fractionator such that 95% of the acetaldehyde is removed from the
water, and the bottoms should not contain more than 4 mol% aldehyde. The
following data applies:
Feeding temperature: 65degC
bubble point of mixture: 92 degC
specific heat of feed: 3450 J/kg-K
latent heat of feed at 65degC = 1460 kJ/kg
Vapor pressure of acetaldehyde at 65degC = 43.5 mm Hg
Vpor pressure of water at 65degC = 25.67 mm Hg
Assuming the system is ideal, determine:
The reflux ratio to be used:
a. 4.4 b. 2.34 c. 3.21 d. 2.97

The number of ideal stages of the reflux ratio is optimum with partial condenser
is:
a. 16 b. 9 c. 20 d. 19

The feeding plate is

a. 5th b. 10th c. 16th d. 13th
 PROBLEM
A 100-kmol/h feed consisting of 10, 20, 30, and 40 mol% of propane,
n-butane, n-pentane, and n-hexane, respectively, enters a distillation
column at 100 psia (689.5 kPa) and 200°F (366.5°K). Assuming
equilibrium,

what mole fraction of the feed enters as liquid,

A. 87.8% B. 56.4% C. 93.2% D. 32.5%

and what are the liquid and vapor compositions of n-butane?

A. X = 0.32, Y = 0.14
B. X = 0.057, Y = 0.15
C. X = 0.22, Y = 0.53
D. X = 0.183, Y = 0.32
Tray Efficiency: Murphree

EMV 
 Tray Efficiency: Overall

O’ Conell Correlation-It correlates the overall efficiency

of the column with the product of the feed viscosity
and the relative volatility of the key component in the
mixture

Actual Number of Trays

EOV 
Theoretical Number of Trays

 
0.226
EOV  0.503  f
 PROBLEM
A plate in a distillation column has an incoming
and outgoing vapor compositions of 0.45 and
0.58, respectively. The incoming and outgoing
liquid compositions are 0.23 and 0.20,
respectively. The relative volatility is 5.56.
Determine the Murphree tray efficiency:

A. 40% B. 65% C. 72% D. 88%

LIQUID-LIQUID
EXTRACTION
 Liquid-Liquid Extraction
Liquid-liquid Extraction-separation of the
components of a liquid mixture by treatment
with a solvent in which one or more of the
desired components is preferentially soluble is
known as liquid–liquid extraction.
 Stages in Operation:

(a) Bringing the feed mixture and the solvent

into intimate contact,
(b) Separation of the resulting two phases, and
(c) Removal and recovery of the solvent from
each phase.
Extraction is in many ways preferable over distillation in
the following cases:

(a) Where distillation would require excessive amounts of

heat, such as, for example, when the relative volatility
is near unity.

(b) When the formation of azeotropes limits the degree

of separation obtainable in distillation.

(c) When heating must be avoided.

(d) When the components to be separated are quite

different in nature.
Application of Extraction in Metallurgy:

(a) Those involving cation exchange such as, for

example, the extraction of metals by carboxylic
acids;
(b) Those involving anion exchange, such as the
extraction of anions involving a metal with
amines, and
(c) Those involving the formation of an additive
compound, for example, extraction with neutral
organo-phosphorus compounds. An important
operation of this type is the purification of uranium
from the nitrate with tri-n-butyl phosphate.
The Extraction Process

Extract, E-containing
the required solute in
the added solvent and
the

Raffinate, R- the weaker

solution with some
associated solvent
EQUILIBRIA OF TERNARY SYSTEMS
HUNTER-NASH GRAPHICAL METHOD
MALONEY–SCHUBERT GRAPHICAL
EQUILIBRIUM-STAGE METHOD
 PARTITION RATIO

 solute in Extract 

yi '  solvent of Extract  
Ki  
xi '  solute in Raffinate 
 
 solvent of Raffinate 
Multiple-contact System: Cross-Flow System
Equilibrium Data

Types of Liquid-liquid Mixtures:

A. A homogeneous solution may be formed and the

selected solvent is then unsuitable.
B. The solvent may be completely immiscible with the
initial solvent.
C. The solvent may be partially miscible with the original
solvent resulting in the formation of one pair of partially
miscible liquids.
D. The new solvent may lead to the formation of two or
three partially miscible liquids.
Treybal Eq: Co-current Contact with Fresh
Immiscible Solvents Eq. 15-3
xn '
Recovery, r: 1 r 
xf '
where n is the number of stages.
 xf ' y s / Ki 
ln  
 xn ' y s / Ki 
More generally, N 
 kS 
ln  1  
 F 
E  KS '/ F '
 Problem
A feed of 13,500 kg/h consists of 8 wt% acetic acid in
water. Acetic acid will be removed from the solution by
extraction with pure methyl isobutyl ketone at 298 K. If
the raffinate is to contain only 1 wt% of acetic acid,
estimate the kilograms/hour of solvent required if a
single equilibrium stage is used. Assume that water and
methyl isobutyl ketone are insoluble. For this system, m’
= 0.657 kg water/kg methyl isobutyl ketone (Perry and
Chilton, 1973).

a. 143,800 b. 178,600
c. 120,400 d. 560,780
 PROBLEM
A batch of 1000 lb of wastewater stream
containing 245 ppm of methylmercury is
contacted with iso-octane in order to reduce the
concentration to 12 ppm or less. How much
solvent should be fed in each stage of a 5-stage
co-current extraction? Partition coefficient is 3.

A. 75 lb C. 277 lb
B. 1230 lb D. 553 lb
 PROBLEM
Acetic acid is extracted from its aqueous phase
using 1-butanol. The aqueous phase contains 5%
by mass acetic acid. A total of 400 mL of fresh 1-
butanol is contacted for 100 mL of feed. How
many extraction stages must be made in order
to extract more than 99% of the acid?
A. 5 C. 3
B. 7 D. 9
 PROBLEM
An aqueous dilute fermentation broth contains 0.5 wt% of penicillin F.
It is to be extracted with amyl acetate. At room temperature and pH =
3.2. Water and amyl acetate are essentially insoluble, and the
distribution coefficient for the penicillin is K = 80. If 100 kg of the
fermentation broth is extracted with 6 kg of the pure solvent in a single
ideal stage, calculate the fractional recovery of penicillin and the
penicillin concentration in the final raffinate and extract.

a.82.8% b. 56.8% c. 89.4% d. 93.5%

What would be the recovery with two-stage crosscurrent extraction if

6 kg of fresh solvent is used in each stage?
b.97% b. 78.9% c. 95.6% d. 94.5%
 Counter-Current Extraction
Calculation of the Number of Stages:

Analogous to the Kremser-Souders-Brown (Eq. 15-48)

Equation for Stripping:

 x f ' y s / K i  1  1 
ln  1    
 xn ' y s / K i  E  E 
N
ln(E )
Where
KS '
E  extraction factor =
F'
 PROBLEM
In distillery plant, a chemical engineer is tasked
to design a counter-current contact
reciprocating extractor in order to remove
furfural content (1.27%) from water using
toluene as solvent with 99.9% removal. The
toluene is virtually pure and is provided at 1.5
times the minimum amount.
a. 10 b. 14 c. 19 d. 24
 PROBLEM
Methanol is stripped from water using phenol
and distilled. A solution contains 3.2% methanol
is contacted with water in a 16 stage-cross-
current system such that the ratio of feed to
solvent in each stage is 5:1. Compute the %
extraction:
a. 96.4% b. 99.4%
c. 97.7% d. 93.4%
 PROBLEM
Nicotine in an aqueous solution containing 1.5% nicotine is to be
extracted with kerosene at 20°C. Water and kerosene are mutually
insoluble. Determine the percentage extraction of nicotine if 100 kg of
the feed solution is extracted in three ideal stages using 50 kg
kerosene in each stage. The following equilibrium data may be used
where x′ = kg nicotine/kg water, and y′ = kg nicotine/kg kerosene:

x′: 0.001011 0.00246 0.00502 0.00751 0.00998 0.0204

y′: 0.000807 0.00196 0.00456 0.00686 0.00913 0.0187

a. 68.8% b. 45.3% c. 76.1% d. 95.3%

 PROBLEM
The equilibrium of ethanol-water—hexanol system
is given by Y = X; where X is the mass ratio in the
aqueous and Y is the mass ratio in the 1-hexanol
phase. Supposing that 8% ethanol solution is
contacted in a column contactor such that the
solvent is 1.3 times the minimum amount. How
many ideal stages are required in order to recover
90% of the ethanol?
A. 2 C. 4
B. 6 D. 8
Solid Liquid Extraction:
LEACHING
 Leaching
Leaching -the preferential solution of one or
more compounds from a solid mixture by
contact with a liquid solvent. The solvent
partially dissolves the solid material so that the
desired solute can be carried away.
Industrial Leaching

• the metals industry for removing mineral

from ores (acid solvents)
the sugar industry for removing sugar from
beets (water is solvent)
The Leaching Mechanism

1. The solvent is transferred from the bulk solution

to the surface of the solid.
2. The solvent penetrates or diffuses into the solid
(intraparticle diffusion).
3. The solute dissolves from the solid into the
solvent.
4. The solute diffuses through the mixture to the
surface of the solid (intraparticle diffusion).
5. The solute is transferred to the bulk solution.
Factors Affecting Rate of Leaching:
• Particle Size
• Solvent
• Temperature
• Fluid Agitation Strategy
EQUILIBRIUM IN LEACHING
 SOLID RETENTION

mass of solids
R or
mass of solvent
mass of solids
R
mass of solution
SINGLE STAGE LEACHING
MULTI-STAGE COUNTERCURRENT
LEACHING
MULTI-STAGE COUNTERCURRENT
LEACHING
Number of Stages: Tiller-Tour
Equation

y n  xn
ln
y1  x1
N 1
y n  y1
ln
xn  x1
 Problem
Crushed olives containing its oil is 85% by mass inert
solids and 15% oil is leached with diethyl ether that is 5%
of in oil(because it is recycled). 200 kg of this slurry is
contacted with 250 kg of the ether in a single stage so
that the value of retention for the outlet underflow is 1.5
kg of insoluble solid per kg solvent in the adhering
solution. The composition of the resulting leachate in
terms of oil by mass is nearly:

a. 15.2% c. 34.7%
b. 23.5% d. 11.2%
 Problem
Cod liver oil is obtained from crushed livers by extraction
with an organic solvent. A sample that contains 0.335 kg
of oil per each kg of exhausted liver is fed into a
multistage extractor that operates under countercurrent,
where pure organic solvent is employed. It is desired to
recover 90% of the oil in the final overflow, with a
composition 60% in weight of oil. If retention of the
solution is 2 kg per each 3.2 kg of insoluble solids,
calculate the number of ideal stages required to carry out
the desired extraction:
a. 1 c. 5
b. 2 d. 6
 PROBLEM
A treated ore containing inert solid gangue and copper
sulfate is to be leached in a counter multistage extractor
using pure water to leach the CuSO4. The solid charge
rate per hour consists of 10,000 kg of inert gangue, 1200
kg of CuSO4, and 400 kg of H2O. The exit wash solution is
to contain 92 wt % water and 8 wt % CuSO4. A total of
95% of the CuSO4 in the inlet ore is to be recovered. The
number of stages required if underflow is constant at 0.5
kg inert gangue solid per kg aqueous solution is
a. 6 b. 5
c. 12 d. 9
 PROBLEM
To extract copper, pyrite cinders are subjected to
chlorinating roasting with sodium chloride. The copper is
contained in the roasted material in the form of cupric
chloride (CuCl2) whose content is 11%. The roasted
product is leached in a counter-current battery using
acidified water obtained as a result of washing the flue
gases. The inert solid material retains 2 kg of water per
kg. of solid. Equilibrium is reached in each stage. How
many stages are needed in the battery to produce a
solution containing 12% (mass) of CuCl2 and extract 98%
of the copper from the roasted product?

a.8 stages b. 11 stages c. 17 stages d. 3 stages

 PROBLEM
A 100 lbs/day ore feed containing 75% gangue, 20% zinc oxide
and balance water is leached by process water containing no
zinc oxide, all in mass basis. The recovery is 98% in the extract
with limiting concentration of 20% zinc oxide such that the
underflow retention is 3 lbs solid/lb of solution.

What amount of solvent is required in lbs/day?

a. 85 b. 99 c. 150 d. 200

ow many counter current stages including the leaching stage,

are required?
a. 1 b. 3 c. 5 d. 7
 LEACHING EQUIPMENT
BOLLMAN EXTRACTOR -contains a bucket elevator in a closed
casing.
•The buckets are loaded with flaky solids such as
soybeans
•The solids are sprayed with appropriate amount of
half miscella as they travel downward.
•Half miscella- intermediate solvent containing
some extracted oil and some small solid particles.
•As solids and solvent flow concurrently down the
right-hand side of the machine, the solvent extracts
more oil from the beans.
Rotocel Extractor
•A horizontal basket is divided into walled
compartments with a floor that is permeable to the
liquid
•The basket rotates slowly about a vertical axis
•Solid are admitted to each compartment at feed
point
•The compartments then pass a number of solvent
sprays, a drainage section and a discharge point.
•To give countercurrent extraction, the fresh
solvent is fed only to the last compartment before
the discharge point.
Rotocel Extractor
Heap Leaching
Dump Leaching
BIOLEACHING
MEMBRANE SEPARATION
Membrane-an
interphase
separating two phases
and selectively
controlling the
transport of materials
between those phases.
Membranes

-Usually synthetic meterials such as polyamide,

polysulphone, polycarbonate, etc.
MEMBRANE SEPARATIONS
 REJECTION

• Solute Rejection Coefficient:

where: R = rejection coefficient

Cf = solute concentration in feed
Cp = solute concentration in permeate
 MWCO

• MWCO(Molecular Weight Cut-Off)- The

nominal molecular weight cut-off is normally
defined as the molecular weight of a solute for
which R = 0.95

• -A parameter designated by the manufacturer.

 Permeability, Pm

Pm
NA   (driving force)

Deff
Pm 
RT
Unit: cm3 (STP)  cm
1 barrer = 10 10
cm2  s  cmHg
 PROBLEM
A gas mixture of hydrogen (H) and ethane (E) is to be partially separated with
a composite membrane having a 1-mm-thick porous skin with an average
pore size of 20 A and a porosity of 30%. Assume tortousity = 1.5. The pressure
on either side of the membrane is 10 atm and the temperature is 100degC.
Estimate permeability of ethane in barrer units:
a. 128,430 b. 63,400
c. 245,700 d. 12,640
 Liquid Permeation: Dialysis
c1  c2
NA 
1 k1  1 pm  1 k2

DK '
permeance = pm 
L

Where K’ = distribution constant

 PROBLEM
A membrane process is being designed to recover solute A
where c1 =0.02 kg/m3 by dialysis through a membrane to a
solution where c2 =0.002. The membrane thickness is 1.59 x
10-5 m, K = 0.75, DAB = 3.5 x 10-11 m2/s in the membrane.The
mass transfer coefficients in the solution are kc1 = 3.5 x 10-5
and kc2 = 2.1 x 10-5 m/s. Calculate the area (sq. m) to recover
0.01 kgmol/h of solute A:
a. 106 b. 175
c. 231 d. 432
 Gas Permeation

qA qp y p  Pm 
    (ph x0  pl y p )
Am Am  t 

Pm  gas permeability

y  [ x  (Pl / Ph )y]

1  y (1  x)  (Pl / Ph )(1  y)
 PROBLEM
A membrane is to be used to spate gas mixtures A and B whose feed flow rate is 1 x
104 cm3 (STP)/s and feed composition of A is 0.5. The desired composition of the reject
is 0.25. The membrane thickness is 2.54 x 10-3 cm. The pressure in the feed side is 80
cm Hg and the permeate side is 20 cmHg. The permeabilities are PA = 50 x 10-10
cm3(STP)-cm/s-cm2-cmHg and PB = 5 x 10-10. Assuming complete mixing:

The permeate composition:

a. 0.604 b. 0.706 c. 0.532 d. none of these

Fraction permeated:
a. 0.604 b. 0.706 c. 0.532 d. none of these

Membrane area required(m2):

a. 0.384 x104 b. 1.053 x103 c. 8.232 x103 d. 2.735 x104
 PROBLEM
A membrane with a thickness of 2 x 10^-3 cm, and a
permeability of A equal to 400 x 10^-10 cm3(STP)-cm/(s-
cm2-cmHg), and selectivity of 10 is to be used to separate
a gases A and B. The flowrate of feed is 2 x 10^3
cm3(STP)/s and its composition is 0.413 mol of A. The
feed side pressure is 80 cmHg and the permeate side is 20
cmHg. The reject composition is 0.30 in A

Compute the average permeate composition:

a. 0.738 b. 0.262 c. 0.523 d. 0.642

Compute the area in sq. m required:

a. 140 b. 250 c. 600 d. 790
 PROBLEM
The selectivity over a membrane is 8 and the
permeate composition is 0.35. If the pressure in
the upstream side of a membrane is very much
higher compared to that in the permeate side,
then the concentration of the feed is:
a. 0.063
b. 0.20
c. 0.15
d. 0.26
 REVERSE OSMOSIS
Pw
Nw  (P   )  Aw (P   )
Lm
Ds K s
Ns  (c1  c2 )  As (c1  c2 )
Lm
c2
Solute rejection = R  1 
c1
B(P   )

Pw 1  B(P   )
B
DsK sCw
 REVERSE OSMOSIS
Polarization Factor:

C si  C sF Nw R
 
C sF AsCw
 PROBLEM
A reverse osmosis is used at 25degC for NaCl solution containing
2.5 g/L has water permeability of 4.81 x 10-4 kg/s-m2-atm and
solute permeability of 4.42 x 10-7 m/s. The transmembrane
pressure is 27.2 atm. Compute:

the solute rejection:

a. 0.965 b. 0.892 c. 0.983 d. 0.913

The solute flux in kg/s-m2 :

a. 1.066 x 10-6 b. 2.303 x 10-6
c. 7.211 x 10-5 d. 9.93 x 10-8
 PROBLEM
At standard conditions, the permeability of cellulose acetate membrane is determined by reverse
osmosis. The membrane area is 0.002 m2. The inlet feed contains 10 g NaCl/L solution. The
product contains 0.39 g NaCl/Li at 1.92 x 10-8 m3 solution/s. A pressure differential of 5514 kPa is
applied.

Compute the permeability constant of water in cellulose acetate in kg/s-m2-atm :

a. 0.03 b. 0.002 c. 0.0002 d 0.00001

Compute the retention of NaCl:

a. 0.45 b. 0.96 c. 0.86 d. 0.98

the polarization factor is:

a. 23.7 b. 16.3 c. 0.32 d. 0.011
 PROBLEM 4
An experimental hollow fiber (do = 500 um, di = 400 um) inside a tube with ID = 900
um is used for desilination of water. Salt water flow at velocity of 1 cm/s at the annular
space at a pressure of 40 atm while the permeate pressure is 2 atm. The osmotic
pressure difference between feed and product may be taken as 5 atm. The dense layer
of the membrane is about 0.1 um with a salt rejection of 99.5%. The water content is
about 0.2 g/mL and the diffusivity of water and salt are 10^-6, and 5 x 10^-8 cm2/s,
respectively.

The operating temperature is 30degC, the diffusion flux of water is:

a. 9 x 10-4 b. 1.2 x 10^-4 c. 4.8 x 10^-4 d. 1.33 x 10^-4

The polarization factor of the process is nearly:

a. 43 b. 0.056 c. 3.5 d. 0.13
ELECTRODIALYSIS
 ELECTRODIALYSIS
FQc
Area: Am 
i
Number of Pairs: FQc
N
I
where: Am = total area of all cell pairs
F = 96,500 A/equiv
i = current density = current/area
I = current
Q = flow rate of feed
ξ = current efficiency
N = number of cell pairs
 PROBLEM
What number of stack required for an electrodialysis process to
reduce the NaCl content of 50,000 m3/day of brackish water
from 1,500 mg/L to 200 mg/L with a 60% conversion. Assume
each membrane has a surface area of 1 m2 and each stack
contains 500 cell pairs. A reasonable current density is 5
mA/cm2, and the current efficiency is 0.9 (90%).
a. 41
b. 34
c. 78
d. 87
 PROBLEM
A total of 86,000 gal/day of an aqueous solution of 3,000 ppm of NaCl is to be desalinized to 400
ppm by electrodialysis, with a 40% conversion. The process will be conducted in four stages, with
three stacks of 150 cell pairs in each stage. The fractional desalinization will be the same in each
stage and the expected current efficiency is 90%. The applied voltage for the first stage is 220 V.
Each cell pair has an area of 1,160 cm2.

Calculate the current density in A/m2 for stage 1:

a. 32 b. 73 c. 56 d. 98

Calculate the power at the first stage:

a. 5.6 kW b. 6.8 kW c. 2.3 kW d. 17.3 kW
 PROBLEM
For an electrodialysis process to reduce the salt (NaCl)
content of 24,000 m3/day of brackish water from 1,500
mg/L to 300 mg/L with a 50% conversion. Assume each
membrane has a surface area of 0.5 m2 and each stack
contains 300 cell pairs. A reasonable current density is 5
mA/cm2, and the current efficiency is 0.8 (80%). Assume
1 volt source.

Estimate the membrane area m2:

a. 6876 b. 9430 c. 1300 d. none
Estimate the electrical energy required:
a. 344 kW b. 120 kW c. 470 kW d.none
 Membrane Filtration
• Waste water treatment particularly for removal of stable oil -water
emulsions to meet today’s effluent standards
• Production of chlorine-and bacteria-free water.
• Production of ultra pure water for electronic and pharmaceutical industries.
• Preparation of sterile fluids for medicinal uses.
• Dairy industry particularly in fractionation of cheese, whey and pre-
concentration of milk for production of cheese.
• Clarification of fermentation products
• Microfiltration : 0.02-10 micron
• Ultrafiltration : 0.001-0.02 micron
• Nanofiltration (Pore size) : 0.001-0.002 micron
• Reverse Osmosis : 0.0001-0.001 micron
 Ultrafiltration

dC A Nw  C AG 
D  JC A   k ln  
dZ  C
 AB 
Lk
 0.33(Re Sc)0.5 for Laminar flow
D
Lk
 0.33(Re Sc) for Turbulent flow
D
 PROBLEM
In a cross-flow ultrafiltration unit, a protein of molecular weight 3000 da is separated from
the fermentation broth by using a UF membrane. The shell-side of the filter is at 0.3 atm.
The flow rate of liquid through a tube of diameter 2 cm and length 50 cm is 200 L/min. The
flow regime is turbulent, the Fanning’s friction factor, f = 0.0005. The inlet pressure is 2 atm.
Protein concentrations in the solution and on gel film are 30 mg/L and 100 mg/L,
respectively. The mass transfer coefficient for protein flux is 0.05 cm/s

Determine the exit pressure, atm

A. 1.8989 B. 1.9722 C. 1.9845 D. 1.8935

Determine the transmembrane pressure, atm

A. 1.6861 B. 1.4453 C. 1.7431 D. 0.9956

How much filtrate is obtained from the UF membrane. Li/min

C. 0.7 B. 1.13 C. 1.46 D. 0.3
 PROBLEM
Tertiary treatment of water in hollow-fibre UF units purified such that the
inlet concentration is 40 ppm of insolubles and will be reduced to 0.5 ppm at
a rate of 500 m3/h. The temperature of operation in a UF cell is 25degC. The
flux of clean water from each cell is 0.0811 m3/h arranged in a parallel
cascade. The diffusivity of water in the membrane is 0.0007 m2/s. One cell is
1 m long and 2 cm in diameter. Assuming turbulent flow, Compute:

The number of cells required

a. 100 B. 200 C. 500 D. 700

The total throughput of clean water from the plant, m3/h:

a. 30 B. 40 C. 60 D. 70
ADSORPTION
ADSORPTION

-the process through

which a substance,
originally present in one
phase, is removed from
that phase by
accumulation at the
interface between that
phase and a separate
(solid) phase.
Adsorbent- the surface molecules composing the solid

Adsorbate-molecules adsorbed from the fluid phase

Physisorption-adsorption in which the forces
involved are intermolecular (i.e., van der Waals,
hydrogen bonding) of the same kind as those
responsible for the non-ideality of real gases and
the condensation of vapours etc.

Chemisorption –a chemical process in which a

reacting molecule forms a definite chemical
bond with an unsaturated atom, or a group of
atoms (an active centre) on a catalyst surface.
Adorbent Solids Porosity
Properties of Adsorbents:

it should have a large internal surface area.

Properties of Adsorbents:
admit the molecules to be adsorbed. It is a
bonus if the pores are also small enough to
exclude molecules which it is desired not to
adsorb.
 Industrial Adsorbents

Molecular Sieves-are naturally occurring zeolites

with lattice structures composed of tetrahedral
of silica and alumina arranged in various ways
 Industrial Adsorbents

Activated Carbon-coal, wood, coconut shells or

bones treated (or activated) with zinc chloride
or phosphoric acid (in order to induce porosity)
and decomposed at 800 K.

Surface area of Activated C:

106 m2/kg
 Industrial Adsorbents

Silica Gel-polymeric material from the

acidification of sodium silicate.

S.A. of Silica Gels:

500,000 m2/kg
 Industrial Adsorbents

Activated Alumina- more thermally stable than

silica gel. Has high affinity to water due to
hydroxyl groups

S.A.: of Activated Alumina:

350,000 m2/kg
 PROBLEM
The volume of nitrogen gas at 1 atm and 273K
required to cover 1g of the silica gel is 0.129
dm3. Calculate the surface area(sq. m.) of the gel
if each nitrogen molecule occupies an area of
16.2 X 10-20 m2:

A. 561.7 c. 212
B. 789.3 d. 234
ADSORPTION ISOTHERMS

-adsorption isotherms that is the amount of

adsorbate on the adsorbent as a function of its
pressure (if gas) or concentration (if liquid) at
constant temperature.
ADSOPRTION ISOTHERMS: LIQUIDS
FREUNDLICH ISOTHERM
-mainly used for liquid state-
adsorption

1/n
y  mx
adsorbate
y
solvent
adsorbate
x=
solid
 PROBLEM
The adsorption of glutamic acid in a cation exchanger(CE) can be
modelled as Freundlich relation with n = 0.417. Supposing that
60% of the glutamic acid from the feed is adsorbed by 2 grams of
CE. What mass of CE is required for 98% adsorption?
a. 11.4 g c. 23.5 g
b. 15.6 g d. 7.6 g
 PROBLEM

Laboratory data shows that 70% of color from a 250 mL of wastewater is

adsorbed using 50 grams of zeolite, and 90% for 150 grams of zeolite. What
mass of zeolite is required on to treat 45 cubic meters of wastewater in order
to reduce the concentration by 97%?
a. 17,400 kg c. 51, 000 kg
b. 26,900 kg d. 73,500 kg
 PROBLEM
The adsorption of cadmium from a stream occurs through two adsorption column in
series. The overall removal is 99%. The adsorption can be modelled by Freundlich
equation
Cs  3.21CL0.5

Where Cs is the mg of Cd per m3 of adsorbent, and CL is the mg of Cd per m3 of

liquid. What total mass of adsorbent is required to process 200 m3/h of stream
containing 2000 mg/m3 of Cd, if each stage is loaded with equal masses of adsorbent?
a. 5100 m3 c. 6800 m3
b. 3400 m3 d. 10,200 m3
 ay
x
by
adsorbate
y
solvent
adsorbate
x=
solid
Assumptions of Langmuir Isotherm:
(a) these are no interactions between adjacent
molecules on the surface.
(b) the energy of adsorption is the same all over
the surface.
(c) molecules adsorb at fixed sites and do not
migrate over the surface.
 PROBLEM
Supposing that the adsorption of trace Pb2+ from a solution with a cationic resin can
be described by Langmuir model.The following data applies:
Liquid(ppm) resin loading(mg Pb/mg resin)
4500 16.5%
2500 9.5%
800 3.1%
what mass of cationic resin is required in order to reduce the concentration of Pb2+ in
water by 95% in a 2 m3 batch volume of solution containing 500ppm Pb2+?

a. 21 kg b. 48 kg c. 13 kg d. 76 kg
FIXED-BED ADSORPTION
 tb  c 
tu  time for usable capacity of bed is reached (c = 0) = 0  1 
 c0 
dt  tb

 c 
tt  total time inside the bed = 0  1  dt
 c0 
tu
used height of bed: Hb   HT
tt
 t 
unused height of bed: HUN   1  u   HT
 tt 
 PROBLEM
A polysulphone adsorption resin is studied in a bench-scale adsorption column of diameter 5 cm, and height of 30 cm long
containing 100 grams of the resin. The inlet solution contains 200 ppm of H2S to be adsorbed (s.g. = 1.064) at a rate of 20 cm3/s.
The breakthrough is assumed when c/c0 = 0.02.The breakthrough concentrations with are given:
t(h): 0 1 2 3 4 5 6
C (ppm): 1 3 5 7 67 155 200

Determine the capacity of unused bed in the bench scale:

A. 43% B. 65% C. 78% D. 24%

If the plant adsorber column will have a break-through time of 24 hours, what height of bed is required?
A. 1.87 m B. 2.33 m C. 0.76 m D. 1.04 m

Determine the mass of resin required to process 500 cm3/s of solution in the plant adsorber column.
A. 10.2 kg B. 15.5 kg C. 4.7 kg D. 18.5 kg
 Regeneration Techniques

Pressure Swing- uses pressure as the

thermodynamic variable to be changed with
adsorption taking place at high pressure and
desorption at low pressure.