Chapter 1

Single stage equilibrium mass

transfer operations

1
 1. Introduction
Definition

Stage: device or a combination of devices in

which two essentially immiscible phases are
brought into intimate contact to allow mass
transfer between them, and then mechanically
separated.

2
Multi-stage mixer-settler for steady-state solid leaching

In general, leaching is the extraction of certain materials from a carrier

into a liquid (usually, but not always a solvent).
Example: the process of extracting minerals from a solid by
3
dissolving them in a liquid.
Tray-type distillation tower

4
 2. Single-stage mixer-settler
(A+C) E1, y1
(A+B) R1, x1

(A+C)
E2, y2

(A+B)
R2, x2
Mixer Settler

Primary assumptions:
Only a single species, A, is transferred from bulk liquid B
(raffinate phase) to bulk liquid C (extract phase), i.e. B and C are
completely immiscible. 5
 Definition

• R = molar flow rate of raffinate phase (A+B) (mol/s)

• Rs = molar flow rate of solute-free B (pure B) (mol/s)
• x = mole fraction of A in raffinate [mol A/mol (A+B)]
• X = molar ratio of A in raffinate (mol A/mol B)
• E = molar flow rate of extract phase (A+C) (mol/s)
• Es = molar flow rate of solute free C (pure C) (mol/s)
• y = mole fraction of A in extract [mol A/mol (A+C)]
• Y = molar ratio of A in extract (mol A/mol C)

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 Relationships
• x=A/(A+B), 1-x=B/(A+B)
• X=A/B=[A/(A+B)]/[B/(A+B)]=x/(1-x)
• x=[A/B]/[1+A/B]=X/(1+X)
• Similarly, Y=y/(1-y) and y=Y/(1+Y)

• Rs=B=(1-x)R=[1-X/(1+X)]R=R/(1+X) and R=(1+X)Rs

• Similarly, Es=(1-y)E and E=(1+Y)Es

• When A is transferred from raffinate to extract,

• R1>R2 and E1<E2
• However, Rs and Es are the same at the inlet and the
outlet, since B and C do not transfer. 7
 Single-stage mixer-settler
(A+C) Es, Y1
(A+B) Rs, X1

(A+C)
Es, Y2

(A+B)
Rs, X2
Mixer Settler
Primary assumptions:
Only a single species, A, is transferred from bulk liquid B
(raffinate phase) to bulk liquid C (extract phase):
Rs and Es remain constant. 8
Mass balance of single stage operation
• Steady state mole balance of species A
• Molar rate of A in = molar rate of A out
R1 x1 + E1 y1 = R2 x2 + E2 y2
• Both R2 and E2 are not known, so a more
useful form of equation is:
Rs X 1 + EsY1 = Rs X 2 + EsY2

Y2 − Y1 Rs
• or =− = constant
X 2 − X1 Es
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 Notes
• The same results are obtained if molar flow
rates, mole fractions and mole ratios are
replaced by corresponding mass flow rates, mass
fractions and mass ratios.
• The same results are also obtained in a batch
contactor where Rs and Es are the solute-free
moles or mass of B and C, respectively, charged
to the device.

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Operating line and equilibrium line
Y

Equilibrium curve
Y*=f(X)
Extract phase

T
Ye (Equilibrium point)

Q (outlet)
Y2
Rs
Slope = − , operating line
Es

Y1
P (inlet)
X
Xe X2 X1
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Raffinate phase
 Observations
• Line PQ, which defines the locus of all possible
exiting concentrations, X2 and Y2, from the
mixer-settler, is called an operating line
• For sufficiently long residence times and high
mass transfer rate, X2 and Y2 approach
equilibrium values, Xe and Ye.
• In theory, it takes an infinite residence time for
the concentration of the two exiting streams to
reach the equilibrium, Xe and Ye.
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 Recovery efficiency
The effectiveness of a single stage or multistage contacting
device in successfully removing the species of interest
from the raffinate phase is called the %Recovery:

Rate of removal of A from raffinate phase

%Recovery = 100%( )
Rate of input of A with raffinate phase
Rs ( X 1 − X 2 )
= 100%
Rs X 1
X2
= 100%(1 − )
X1
which is a function of residence time, stirring speed and
Rs/Es ratio. 13
 Equilibrium stage
• The maximum recovery for given pairs of flow
rates and inlet concentrations is obtained when X2
and Y2 approach the equilibrium concentrations Xe
and Ye.
• An equilibrium (ideal) stage is thus a stage for
which the concentrations of the exiting streams are
in equilibrium.
• % Recovery for an equilibrium stage is thus equal
to 100%(1-Xe/X1)
• How to determine the equilibrium concentrations,
Xe and Ye? 14
 Operating line using R, E, x, y
R1 x1 + E1 y1 = R2 x2 + E2 y2
R2 E1 R1
y2 = − x2 + ( y1 + x1 )
E2 E2 E2
Slope

• As the residence time increases, R2 decreases

and E2 increases as x2 decreases
• Therefore, the operating line is not straight
with a decreasing slope.
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 Graphical method (R, E, x, y)
y

Equilibrium curve
Extract phase

y*=f(x)

T
ye
Q (outlet)
y2
R2
Slope = − , operating line
E2

y1
P (inlet)
x
xe x2 x1
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Raffinate phase
General design problems for a single
stage mass transfer operation
• Given the inlet concentrations and flow rate
of the two phases, what is the maximum
recovery obtainable?
• Given the inlet concentration of the two
phases and the flow rate of the raffinate
phase, what flow rate of the extract phase is
needed to achieve a specific recovery?
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 General approaches
• Many stage-wise problems require graphical
solution methods. Construction procedures are
simplest if the co-ordinate system selected
yields straight operating lines, e.g. mole or mass
ratio co-ordinate for contact of mutually
insoluble phases.
• In some problems, it is impossible to avoid
using a curved operating line, and consequently
graphical solution procedures become more
tedious and less accurate. Analytical/numerical
can then be used.
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Analytical/numerical method for
equilibrium stage analysis
R1, x1 (Rs, X1) R2, x2 (Rs, X2)
E1, y1 (Es, Y1) E2, y2 (Es, Y2)

Mass balance of A:

Rs ( X 1 − X 2 ) = Es (Y2 − Y1 )
Y2 = f eq ( X 2 ) Equilibrium at exit

Solve using root-finding method 19

Similarly one can derive:
R1 x1 + E1 y1 = R2 x2 + E2 y2
Rs = (1 − x1 ) R1 = (1 − x2 ) R2
Es = (1 − y1 ) E1 = (1 − y2 ) E2

 x1 − x2   y1 − y2 
R1   + E1   = 0
 1 − x2   1 − y2 
y2 = f eq ( x2 )
x2 and y2 are obtained using root-finding method 20
 Non-equilibrium stage
• Non-equilibrium stage is the one where the exiting
streams are not in equilibrium.
• The degree of approach of non-equilibrium stage
to equilibrium exiting condition could, in theory,
be determined from residence time and mass
transfer considerations.
• To keep the analysis of the device as simple as
possible, the designer simply assigns an efficiency
to each stage where the stage efficiencies are
usually determined from appropriate correlations
of experimental data.
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 Stage efficiencies
Y

Equilibrium curve
Y*=f(X)
Extract phase

Y2*
T
Ye
Q (outlet)
Y2
Rs
Slope = − , operating line
Es

Y1
P (inlet)
X
X2 * Xe X2 X1
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Raffinate phase
• Stage efficiency: fractional approach to equilibrium
attained in a real, non-equilibrium stage
PQ X 1 − X 2 Y2 − Y1
Estage = = =
PT X 1 − X e Ye − Y1

• Murphree stage efficiency: fractional approach of

one exiting stream, to equilibrium with the actual
bulk concentration of the other exiting stream
Extract phase Raffinate phase
Y2 − Y1 X1 − X 2
EME = * EMR =
Y2 − Y1 X 1 − X 2* 23
• Simple stage efficiency is more useful for
single-stage operation.
• Murphree stage efficiencies are more
commonly used in multi-stage operations.
• Murphree efficiencies are, in general, not
the same as each other, nor they are the
same as the simple stage efficiency.

EME ≠ EMR ≠ Estage

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 Example 1
Liquid extraction at 25°C with benzene as the solvent is
to be used to separate p-dioxane (a cyclic diether) from
water. The aqueous solution contains 20 mol% p-dioxane
and is to be treated in a single stage of mixer-settler at a
flow rate of 60 mol/min. A flow of 100 mol/min of pure
benzene is available to carry out the extraction. At 25 °C,
the equilibrium curve for the distribution of p-dioxane
between water and benzene is
Y = 1.25 X
where Y and X are the mole ratios of p-dioxane in
benzene and water, respectively. Determine the percent
recovery obtained. 25
Solution

R1 = 60 mol/min, E1=100 mol/min, x1= 0.2, y1= 0

Rs = 60*(1-0.2) = 48 mol/min, Es = E1 = 100 mol/min
X1 = 0.2/(1-0.2) = 0.25, Y1 = 0
Operating line: (Y2-Y1)/(X2-X1)=-Rs/Es=-48/100=-0.48
or (Y2-0)/(X2-0.25)=-0.48, Y2=-0.48(X2-0.25)
Equilibrium line: Y2 = 1.25X2
Get Y2: 1.25X2=-0.48X2+0.12, X2=0.12/1.73=0.0693
Y2=1.25X2=0.101
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% recovery = 1-X2/X1 = 1-0.0693/0.25 = 0.7225 = 72.25%