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Mass Transfer
Topic 7 Analysis of mass transfer equipment
In this section we will develop the general performance equations, based on mass balances and
rate equations, that govern the behaviour of operating mass transfer equipment. The mass
transfer operations to which such an analysis might pertain may be any of the following:

- Gas-liquid contacting operations: e.g.: gas absorption and desoption, gas-liquid reactors,
distillation.

- Liquid-liquid contacting operations: e.g.: Liquid-liquid extraction, liquid-liquid reactors.

- Gas-solid contacting operations: e.g.: adsorption and desorption.
- Liquid-solid contacting operations: e.g.: adsorption, desorption, leaching
7.1 General considerations:
A. Batch vs continuous operation: Any of the above operations involve transfer of solute(s)
between two immiscible phases, and can be carried out in the batch mode or continuous flow
mode; the former will be in unsteady state with the concentrations in the two phases
changing with time till the required extent of separation is achieved, while the latter will be
typically a steady state operation with the feed phase (sometimes called the raffinate)
entering at a high concentration of the solute to be transferred and leaving with a low
concentration (and vice versa for the receiving phase, sometimes called the extract). (In the
case of gas-liquid operations, the so-called batch operations are usually so only with
respect to the liquid phase, gas being in continuous flow. ) The choice between batch and
flow operation depends on the usual factors of capacity and time requirements - batch
operations being preferred for small capacity, long residence time requirements. The bulk of
mass transfer operations however, operate in the flow mode, and their steady state
performance is what is important in design. Flow equipments are emphasized in what
follows.
B. Equipment and flow configuration: Typical mass transfer operations carried out in the flow
mode are usually carried out in tall towers, in which the two phases in continuous flow
contact each other, and a steady state operation gets established. Although the name
`Tower equipment suggests vertical columns, there are operations such as leaching and
liquid-liquid extraction in which the equipment may be arranged horizontally rather than
vertically, but the principles to be developed below apply equally to these cases as well.
While in principle, the flows could be arranged in co-current or countercurrent manner, the

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latter is by far the dominant mode seen in industry; however, to understand countercurrent
operation, an understanding of co-current operation is necessary.
C. Application of performance equations: The designer might use these principles to size the
equipment for a given mass transfer task. The plant engineer may use the same principles to
establish optimal operating conditions or to trouble-shoot the operation. The focus will be on
developing essential concepts common to all mass transfer operations; the details of each
operation will be studied separately as you consider individual unit operations with their
idiosyncrasies.

D. Two aspects of equipment sizing: Equipment sizing has two aspects - the diameter of the
tower is usually determined based on the flows of the two phases and considerations of
hydrodynamics, so that the two phases move through the equipment in such a way as to
provide good contact and intermixing, but at the same time do not impede each others flows.
We do not dwell on these considerations here. The second aspect has to do with the height
of the equipment, which involves consideration of rates and extents of transfer possible in a
given height or unit of equipment. It is this aspect that this chapter will address.
E. Important parameters that influence the height or length: For a given system (i.e.,
equilibrium considerations being given), the mass transfer coefficients are clearly important
unless they are high enough that a quick attainment of near-equilibrium conditions between
the phases is a possibility. Apart from this, the ratio of the two molar flow rates is always
important - this clearly determines, for a given number of moles transferred, how dilute or
concentrated the receiving phase is; we shall see that this ratio also has a direct bearing on
the length of equipment.
F. Important special cases: While in principle, all components of each phase can transfer in to
the other phase, three important cases commonly occur: (a) the case of dilute phases, in
which case the mass transfer coefficients are concentration-independent and the total molar
flow rates are nearly constant across the equipment (b) the case of one component
transferring, in which case, the molar flowrate of the non-transferred component is constant,
and we shall see that mass transfer equations are conveniently written in terms of mole ratio
units (moles of transferred component per mole of non-tranferred component), mass transfer
coefficients may require correction, and (c) a equimolar counterdiffusion (in binary mixtures)
in which there is no net molar flux engendered by diffusion and dilute phase coefficients
apply. Total molar flowrates remain constant.

G. Stagewise and continuous contacting: Tower equipment usually fall into two broad
classes. In the first, the two phases involved remain in continuous contact throughout their
traverse through the equipment. Packed towers are typical of such differential contact

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equipment, so called because the operation of the equipment can be understood by making
mass balances on a differential height of equipment and integrating these balances over the
tower height. In the second, the two phases are repeatedly brought into contact and
separated. Such staged equipment can be understood by making mass balances across a
single stage and extending such balances to multiple stages considering the way the flows
are arranged. Gas absorption is typical of an operation that is usually carried out in packed
towers, while distillation, of an operation that is carried out in staged columns, although
examples of either in the other type of equipment are common. Operations such as leaching
and solvent extraction are also carried out in staged equipment, although in these cases the
stages may not be arranged vertically in a tall column. We will think of gas absorption as a
typical mass transfer operation in the development below, but only for the sake of
concreteness; the procedures and methodology are of general applicability.
The general building blocks of our analysis will consist, as mentioned above, of:

- mass balances across a finite height of the equipment in order to define the relationship
between bulk concentration variables through the tower; these are conveniently represented
graphically on diagrams such as Fig. 6.2 above and are called `operating lines.

- (in the case of differential contact equipment) combining these mass balances with the flux
expressions for two-phase transport derived in the previous topic to determine the height of
the tower,

- (in the case of staged equipment) combining the mass balances using the concept of an `ideal
stage in which the leaving streams are in equilibrium, in order to determine how many such
stages are needed in order to accomplish the desired separation task.
We shall first develop the mass balances on the equipment scale.

7.2 Design of a batch mass transfer equipment: Mass balances & rate equations
We shall first develop the performance equations first for the batch case, in which we assume
that both phases (designated L and V; their molar amounts being LB and VB) are introduced into the
equipment at time zero and mass transfer allowed to occur for a time t. Let

al stand for the interfacial area

per unit volume of the continuous phase. Mass transfer coefficients will be denoted by the usual notation.

For the V phase, the change in the moles of solute in a differential time dt may be written as:

d (VB yAb )
= ky0 a L LB (yAb yAi )
dt
where

yAb

and

yAb

.(7.1)
stand for the bulk and interfacial mole fractions of A on the V-side of the

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interface, at time t. Similarly, we have for the L-phase,

d ( LB x Ab )
= kx0 a L LB (x Ai x Ab )
dt

.(7.2)

Since whatever solute is lost from phase V is gained by phase L (there being no accumulation at the
interface), we have:

d (VB yAb )
d ( LB x Ab )
=
dt
dt

.(7.3)

Integrating this from zero time (the mole fractions being to some time t, and rearranging, we get

LB
y 0 yA
= A0
VB
xA xA

....(7.4)

Note that 7.4 is purely a statement of material balance which says that the solute lost by phase V equals
that gained by phase L. No rate information is involved here. On a y-x diagram, eq. (7.4) shows that the
initial composition point and the compositions at different times lie on a straight line of slope

LB
. This is
VB

shown in the figure below, and may be called the Operating line. As shown, if the solutions are not dilute,
this will be a curve rather than a straight line, but we will not belabour the point at this juncture.

Fig 7.1: Operating lines and the construction to locate the interfacial composition.

We may now complete the design using eq. (7.1) (or the equivalent formulation in terms of overall V-side
coefficient), written in the form:

dyAb
L
= ky0 a L B dt
(yAb yAi )
VB

..(7.5)

The left side of this equation requires a numerical or graphical integration: for different values of

yAb , we

evaluate the integrand by performing the kind of construction described in the previous section for locating

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the interfacial concentration, and tabulate

yAb vs.

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1
in order to integrate. A typical construction,
(yAb yAi )

assuming dilute phases (and hence, concentration-independent mass transfer coefficients) is shown in
Fig. 7.1.

7.3 Design/performance of flow equipment: Equipment-scale mass balances:

We shall develop the design/performance equations for flow equipment in two stages for
reasons that will become clear later, and have to do with the distinction between staged and
continuous contact equipment.

7.3.1 (Steady state) Cocurrent contact:

Consider the schematic in Fig. 7.2 (i), which may refer to a co-current tower, or a single stage in
any stage wise contacting equipment.

Fig. 7.1. A co-current mass transfer equipment (i) Schematic (ii) representation of operating and
equilibrium lines on mole fraction co-ordinates.
Let L and V stand for the (phases as well as) the molar flow rates of the two phases, and the
objective of the operation, to transfer solute A from phase V to phase L. y and x represent the
mole fractions of the solute in phases V and L respectively. Position within the equipment is
defined by a single distance variable (say) from end a; at a given position so defined, the
composition is assumed to be the same in the other (perpendicular) direction. Stations a and b
stand for the two ends of the equipment.
A balance for A across envelope I (which covers the part of the equipment from end a to any
general position), gives:

Va ya + La xa = Vy + Lx
which rearranges to

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y=

L
V y + La x a
x+ a a
V
V

Monday, 10 October 2016

(7.6)

This equation relates the bulk compositions of the two phases at any position in the equipment
and is called the equation for the Operating line (OL). As solute is transferred from V to L, V
decreases from left to right and L increases, so that the ratio increases. If solutions are dilute,
the flow rates may be reasonably constant, in which case eq. (7.6) represents a straight line on
x-y co-ordinates. Both cases are shown in Fig. 7.2 (ii), which in fact is the same figure as Fig 7.1.
Note that this curve/line represents the locus of points such as P shown in Fig IMT.2 in
developing the treatment for local interphase mass transfer rates (such a point is shown in Fig
7.2(ii) with the construction to determine the interface concentrations at that location). Equation
7.6 may be applied to the whole equipment (envelope II) to obtain the exit concentrations in
terms of the inlet concentrations - this is useful in fixing the end conditions at the start of design,
since typically three out of the four end compositions are available in a design problem. The
operating line thus ends in b. If the equipment were bigger, the line may extend at most till the
point b, at which the phases get to equilibrium and no more transfer can occur.

Note that the advantage of the straight operating line in locating the limiting situation of b. We
therefore look for such representations as will result in a (nearly) straight operating line. The
mole fraction representation is satisfactory from this point of view when solutions are dilute.
There is one other situation in which we can manage a straight operating line, and that is when A
is the only component being transferred. In this case, we use molar flowrates of the `non-A part
of each phase as the key components, and deal with mole ratios rather than mole fractions.
Thus, if Vs and Ls are the (constant) molar flowrates of the non-transferred components of
phases V and L respectively, and Y and X represent the mole ratio (mole A/mole non-A) in these
phases in general, the material balance can be written as:

Y =

Ls
(X Xa ) + Ya
Vs

(7.7)

and will be linear on X-Y co-ordinates. Of course, the equilibrium curve has also to be recast in
mole ratio units for a representation such as Fig 7.2(ii).

Note that the mass balances work exactly similarly in the co-current flow case to the batch case.
This should call to your mind the correspondence between a batch reactor and a plug flow
reactor.

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7.3.2 (Steady state) Countercurrent contact:

The schematic for this situation is shown in Fig 7.2. Note the notation: `a and `b stand for the
places where phase L enters and leaves respectively (in this case the top and bottom of the
column). We consider transfer of A from V to L.

Fig 7.2: Schematic of a mass transfer tower of the differential contacting type. (a) Tower
schematics, (b) y-x diagram with operating and equilibrium line information.
A balance on the solute across envelope 1 shown, which extends from station a to some level z
gives, for steady state operation,

La xa + V y = Lx + Va ya
which, on rearrangement, gives

y=

L
V x

V a ya L a x a
V

(7.8)

This is the operating line equation for this case, and is of positive slope. The equation is shown
plotted in Fig 7.2(b), which also shows the equilibrium curve. Note

- that the operating line is above the equilibrium line, consistent with the direction of transfer
assumed. A typical point on the operating line may be identified with the point P (see
construction shown to locate the interfacial concentration) in Fig IMT.2 in our discussion of
interphase mass transfer rates.

- in general, for the direction of transfer assumed, L and V both have their minimum values at
the top of the column and increase down the column; the operating line is therefore usually a

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curve, as indicated in the figure. If the mixtures are dilute, the variation in flow rates may be
small and we may use an average value for the ratio L/V , and a straight operating line
results.

- As the ratio L/V is reduced with the top point fixed, the composition point at the bottom
(station b) moves closer to the equilibrium value. The value of L/V for which the two curves
touch at some point between a and b is thus the minimum value of the ratio of flow rates for
which the desired separation is possible; for this ratio, the tower height required will be infinite.
(In the figure shown, the two curves touch for the minimum ratio at the top of the column, but
this is because of the shape of the equilibrium curve chosen for illustration).
The existence of a limiting value as shown above is characteristic of countercurrent operation.
The choice of an appropriate phase flow rate ratio has implications on the economics of the
operation. The higher the ratio, the shorter the tower, but more dilute will be the liquid solution at
the bottom and hence larger will be the cost of recovering the solute from it. Typical ratios used
are 1.1 to 1.5 times the minimum.
As in the previous case of co-current devices, a straight operating line can be achieved even if
the solutions are not dilute (or the amounts transferred, small) provided only one component is
being transferred. In this case, we choose mole ratio co-ordinates, and use molar flow rates of
the non-A component in each phase, resulting in:

Y=

Ls
(X Xa ) + Ya
Vs

. (7.9)

7.4 Stagewise contacting: Calculation of Number of ideal stages:

Material balances on the equipment length scale give us relationships between the bulk phase
concentrations as the phases move through the equipment. For equipment sizing, we need to
look at what is happening within the equipment, i.e., examine the process on a smaller length
scale. We do this for stage wise contacting in this section, and for continuous contacting in the
next.

A stage is any device in which the two phases (between mass transfer has to be engineered) are
brought into contact, allowed to proceed towards equilibrium, and then separated. A staged
device has a number of stages linked up in some manner, and the equipment height depends on
the number of stages. Here the standard is the Ideal stage, in which the contacting phases get to
equilibrium, and leave the stage. The ideal stage is also referred to as the Equilibrium stage or
the Theoretical stage. The number of ideal stages required to achieve a required separation
depends on the mode of contacting.

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Clearly, the co-current process studied in a previous section is a single stage, and the operating
line will terminate in the equilibrium line if the stage is ideal. This is therefore taken as the model
for an ideal stage. A real stage can be described in terms of a stage efficiency, which compares
the actual separation achieved with what an ideal stage would achieve in some manner. While
different definitions are possible, the Murphree efficiency is the most frequently used, and
compares the actual separation achieved to what would be achieved if the leaving phase were to
be in equilibrium with the exit composition of the other phase. Thus, for phase V, it is:

EMV =

Ya Yb
,
Ya Yb*

(7.10)

and for the phase L, it is:

EMV =

Xb X a
.
Xb* Xa

(7.11)

The two are clearly not equal, but are related through the slopes of the operating and equilibrium
lines. Further, while mole ratio units have been employed in the above definitions, the choice of
units depends on what gives a straight (or nearly straight) operating line. One has to therefore
specify (a) the units employed as well as (b) the reference phase while mentioning Murphree
efficiencies.
Since the separation achievable in a single stage is limited by what is possible in an ideal
stage, stages are usually combined in cascades in order to achieve the desired separation. The
phases then flow from one stage to the next. Since co-current devices are always a single stage,
while combining stages, it is usually counter-current or cross-current contact that is of interest.