wjpls, 2022, Vol.

8, Issue 5, 187-193 Review Article ISSN 2454-2229

Sen et al. World Journal of Pharmaceutical

Worldand LifeofSciences
Journal Pharmaceutical and Life Science
WJPLS
www.wjpls.org SJIF Impact Factor: 6.129

MURPHREE EFFICIENCY IN DISTILLATION BY McCABE THIELE METHOD

1
Prof. Dr. Kishor Dholwani, 2Kushal Nandi, *2Prof. Dr. Dhrubo Jyoti Sen, 2Prodipta Bhattacharyya and 3Dr. Dhananjoy Saha
1
Sardar Patel College of Pharmacy, Bakrol, Anand, Gujarat, India.
2
Department of Pharmaceutical Chemistry, School of Pharmacy, Techno India University, Salt Lake City, Sector V, EM˗4,
Kolkata˗700091, West Bengal, India.
3
Deputy Director, Directorate of Technical Education, Bikash Bhavan, Salt Lake City, Kolkata‒700091, West Bengal, India.

Corresponding Author: Prof. Dr. Dhrubo Jyoti Sen

Department of Pharmaceutical Chemistry, School of Pharmacy, Techno India University, Salt Lake City, Sector V, EM˗4, Kolkata˗700091,
West Bengal, India.

Article Received on 21/03/2022 Article Revised on 11/04/2022 Article Accepted on 01/05/2022

ABSTRACT
Distillation is a unit operation which involves separation of a vaporizable component from a multi˗component
system and subsequent condensation of vapours. The pressure exerted by the vapor at the equilibrium state is
termed as the vapor pressure of the liquid. The opposite process of this vaporization is called condensation. At
equilibrium, the rates of these two processes are same. In order to model the vapor temperature, the Murphree
efficiency equation is used to calculate the change of vapor temperature between vapor inlet temperature and liquid
outlet temperature, which will only be reached at full efficiency. As a result, vapor temperature will be much nearer
to its dew point, which better matches reality.

KEYWORDS: Distillation, theoretical plates, McCabe Thiele method, vapour pressure, equilibrium.

INTRODUCTION fractions, the distillate exit points are located at different

heights on a fractionating column. The bottoms fraction
Continuous distillation, a form of distillation, is an
can be taken from the bottom of the distillation column
ongoing separation in which a mixture is continuously
or unit, but is often taken from a reboiler connected to
(without interruption) fed into the process and separated
the bottom of the column. Each fraction may contain one
fractions are removed continuously as output streams.
or more components (types of chemical compounds).
Distillation is the separation or partial separation of a
When distilling crude oil or a similar feedstock, each
liquid feed mixture into components or fractions by
fraction contains many components of similar volatility
selective boiling (or evaporation) and condensation. The
and other properties. Although it is possible to run a
process produces at least two output fractions. These
small-scale or laboratory continuous distillation, most
fractions include at least one volatile distillate fraction,
often continuous distillation is used in a large-scale
which has boiled and been separately captured as a vapor
industrial process. Stage wise operations for gas/liquid
condensed to a liquid, and practically always a bottoms
contact, such as absorption, desorption and distillations
(or residuum) fraction, which is the least volatile residue
are carried out in trayed columns. The column diameter,
that has not been separately captured as a condensed
tray spacing, and the number of actual trays are the most
vapor. An alternative to continuous distillation is batch
important parameters for tray column design. Column
distillation, where the mixture is added to the unit at the
diameter and tray spacing largely depend upon gas flow
start of the distillation, distillate fractions are taken out
rate and total column pressure; these parameters can be
sequentially in time (one after another) during the
estimated with great accuracy. The most difficult
distillation, and the remaining bottoms fraction is
problem in column design is estimating the actual
removed at the end. Because each of the distillate
number of trays. The simple empirical method for
fractions are taken out at different times, only one
estimating the actual number of trays is to divide the
distillate exit point (location) is needed for a batch
required number of theoretical stages by the overall tray
distillation and the distillate can just be switched to a
efficiency.[1]
different receiver, a fraction-collecting container. Batch
N˳=[Nt/E0]×N0
distillation is often used when smaller quantities are
distilled. In a continuous distillation, each of the fraction
A theoretical stage is defined as one in which the effluent
streams is taken simultaneously throughout operation;
phases are in equilibrium, so that a longer contact time
therefore, a separate exit point is needed for each
will bring no additional change in composition. Another
fraction. In practice when there are multiple distillate

www.wjpls.org │ Vol 8, Issue 5, 2022. │ ISO 9001:2015 Certified Journal │ 187

Sen et al. World Journal of Pharmaceutical and Life Science

method for tray number estimation is based on Murphree The McCabe˗Thiele Method: This method uses
tray˗efficiency prediction for each tray. This method can the equilibrium curve diagram to determine the number
be used to calculate the actual number of trays. The of theoretical stages (trays) required to achieve a
definition of overall efficiency strictly applies only when desired degree of separation. The McCabe–Thiele
the Murphree tray efficiencies of all trays are the same method is a chemical engineering technique for the
and when the equilibrium and operating lines are both analysis of binary distillation. It uses the fact that the
straight over the concentrations considered. However, it composition at each theoretical tray (or equilibrium
is more accurate to determine the actual number of trays stage) is completely determined by the mole fraction of
using the procedure based on Murphree tray efficiencies one of the two components and is based on the
(from tray to tray), especially for systems where the assumption of constant molar overflow, which requires
slope of the equilibrium line significantly changes with that:
the liquid˗phase concentration.[2]  The molar heats of vaporization of the feed
components are equal;
In general the efficiency depends upon:  For every mole of liquid vaporized, a mole of vapor
1. Tray variables (geometrical characteristics) such as is condensed; and
column diameter, average flow width, length of  Heat effects such as heat of solution are negligible.
liquid travel, bubbling area
2. Gas and liquid volumetric flow rate The method was first published by Warren L. McCabe
3. Gas and liquid density [Warren Lee McCabe (August 7, 1899 – August 24,
4. Gas and liquid viscosity 1982) was an American Physical Chemist and is
5. Gas and liquid diffusivity considered as one of the founding fathers of the
6. Stripping factor profession of chemical engineering. He is widely known
for the eponymous McCabe–Thiele method for analysis
In a distillation column liquid and vapour are contacted of distillation processes and his book, Unit Operations of
while passing over and through trays (sometimes referred Chemical Engineering, a major textbook.] and Ernest
to as plates). In a theoretical analysis of the column Thiele [Ernest W. Thiele (1895–1993) was an influential
performance such as the McCabe˗Thiele method, the chemical engineering researcher at Standard Oil (then
trays are assumed to operate at maximum efficiency. Amoco, now BP) and Professor of Chemical Engineering
This means that the vapour and liquid phases are at the University of Notre Dame. He is known for his
assumed to reach equilibrium as they interact over the highly impactful work in chemical reaction engineering,
plate. However, in practice there are many reasons why complex reacting systems, and separations, including
the vapour and liquid phases will not reach equilibrium distillation theory] in 1925, both of whom were working
as they pass.[3] at the Massachusetts Institute of Technology (MIT) at
the time.[4]

Figure˗1: Distillation takes place in a column with crossflow trays over which liquid flows in alternate directions
on successive trays. The topmost tray has the highest concentration of the more volatile species and the lowest
tray has the highest concentration of the less volatile species [Left: Warren L. McCabe & Right: Ernest Thiele].

www.wjpls.org │ Vol 8, Issue 5, 2022. │ ISO 9001:2015 Certified Journal │ 188

Sen et al. World Journal of Pharmaceutical and Life Science

Figure 2: Typical bubble cap trays used in industrial distillation column.

Figure 3: Continuous Distillation unit (Left: Industrial Basis, Middle: Laboratory Basis, Right: Diagram).

Construction
A McCabe–Thiele diagram for the distillation of a binary
feed is constructed using the vapor˗liquid equilibrium
(VLE) data for the lower˗boiling component of the
feed.[5]

Figure 4: Typical McCabe–Thiele diagram for distillation of a binary feed.

On a planar graph with the horizontal (x) axis (Figure 4) is used as a graphical aid. The equilibrium line
representing the mole fraction of the lower˗boiling feed (black line in Figure 4), drawn using the VLE data points
component in the liquid phase and the vertical (y) axis of the lower boiling component, represents the
representing the mole fraction of the lower˗boiling feed equilibrium vapor phase compositions for each value of
component in the vapor phase, the 45˗degree x = y line liquid phase composition. Vertical lines from the

www.wjpls.org │ Vol 8, Issue 5, 2022. │ ISO 9001:2015 Certified Journal │ 189

Sen et al. World Journal of Pharmaceutical and Life Science

horizontal axis up to the x = y line indicate the feed and green in Figure 4) starts at the intersection of the
desired compositions of the top distillate product and the distillate composition line and the x = y line and
corresponding bottoms product (shown in red in Figure continues at a downward slope (Δy/Δx) of L / (D + L),
4). where L is the molar flow rate of reflux and D is the
molar flow rate of the distillate product.[6]
The rectifying section operating line for the section
above the feed inlet of the distillation column (shown in

Figure˗5: Examples of q˗line slopes.

The q˗line (depicted in blue in Figure 1) starts at the x = q˗line is infinite (a vertical line). As another example, if
y line and intersects the starting point of the rectifying the feed is all saturated vapor, q = 0 and the slope of the
section operating line. The parameter q is the mole q˗line is 0 (a horizontal line). The typical McCabe˗Thiele
fraction of liquid in the feed, and the slope of the q˗line diagram in Figure 1 uses a q˗line representing a partially
is q / (q – 1). For example, if the feed is a saturated vaporized feed. Example q˗line slopes are presented in
liquid, it has no vapor, thus q = 1 and the slope of the Figure 5.[7]

Figure˗6: McCabe˗Thiele Diagram for Murphree Efficiency.

www.wjpls.org │ Vol 8, Issue 5, 2022. │ ISO 9001:2015 Certified Journal │ 190

Sen et al. World Journal of Pharmaceutical and Life Science

The stripping section operating line for the section below trays, (ii) flow rates and flow paths of vapor and liquid
the feed inlet (shown in purple in Figure 4) starts at the streams, (iii) Compositions and properties of vapor and
intersection of the red bottoms composition line and the liquid streams.
x = y line and continues up to the point where the blue
q˗line intersects the green rectifying section operating Murphree Efficiency: The Murphree plate efficiency is
line. The number of steps between the operating lines therefore expressed as the ratio of the increase in mole
and the equilibrium line represents the number fraction of vapour of a volatile component passing
of theoretical plates (or equilibrium stages) required for through a plate in a column to the same increase when
the distillation. For the binary distillation depicted in the vapour is in equilibrium. In effect, more stages are
Figure 4, the required number of theoretical plates is 6.[8] therefore required to bring about a desired separation.
The efficiency of the tray can also be calculated based on
Constructing a McCabe–Thiele diagram is not always semi˗theoretical models which can be interpreted by the
straightforward. In continuous distillation with a varying Murphree Tray Efficiency EM. In this case it is assumed
reflux ratio, the mole fraction of the lighter component in that the vapor and liquid between trays are well˗mixed
the top part of the distillation column will decrease as the and have uniform composition. It is defined for each tray
reflux ratio decreases. Each new reflux ratio will alter according to the separation achieved on each tray based
the slope of the rectifying section operating line. When on either the liquid phase or the vapor phase. For a given
the assumption of constant molar overflow is not valid, component it is equal to the change in actual
the operating lines will not be straight. If the mixture can concentration in the phase, divided by the change
form an azeotrope, its vapor˗liquid equilibrium line will predicted by equilibrium condition. These definitions of
cross the x = y line, preventing further separation no Murphree tray efficiency are for the overall tray and
matter the number of theoretical plates.[9] involve the average vapor and liquid composition leaving
the tray, this means that both the liquid and vapor leaving
Limitations of McCabe Thiele Method for Distillation a given tray are assumed to be completely mixed and as a
 It is not used when relative volatility is less than 1.3 consequence no concentration gradient exists cross the
or greater than 5. tray. The assumption of complete mixing is unrealistic
 It is not used when more than 25 theoretical except for special cases in very small columns.
stages/plates are required Incomplete liquid mixing and vapor channeling are two
 It is not used when the operating reflux ratio is less common conditions which will result in deviations from
than 1.1 times the minimum reflux ratio. Murphree' s assumption.

Tray Efficiency: Tray efficiency in general is The Murphree point vapor efficiency describes the
considered to be a measure of the degree of approach to degree of approach to equilibrium between the vapor and
an ideal tray ˗˗ an ideal or equilibrium tray being defined liquid at a single point on a tray. The plate efficiency is
as one on which both the vapor and. liquid phases lower in the columns operated at high velocity because
leaving the tray are in mutual thermodynamic of significant entrainment.[10]
equilibrium. For the analysis of theoretical stage required
for the distillation, it is assumed that the the vapor The traditional Murphree efficiency approach to tray
leaving each tray is in equilibrium with the liquid leaving design
the same tray and the trays are operating at 100% The section efficiency is calculated based on
efficiency. In practice, the trays are not perfect. There are fundamental mass˗transfer considerations, including the
deviations from ideal conditions. The equilibrium with approach to equilibrium both locally on the tray (point
temperature is sometimes reasonable for exothermic efficiency) and on the tray as a whole (tray efficiency).
chemical reaction but the equilibrium with respect to The conventional method of designing trays employs
mass transfer is not often valid. The deviation from the Murphree’s definition of efficiency to quantify the
ideal condition is due to: (1) Insufficient time of contact approach to equilibrium. The overall number of transfer
(2) Insufficient degree of mixing. To achieve the same units for the gas phase (NOG) is (1):
degree of desired separation, more trays will have to be (NOG)˗1=[(NG)˗1+λ(NL)˗1]
added to compensate for the lack of perfect separability.
The concept of tray efficiency may be used to adjust the where NG and NL represent the number of transfer units
the actual number of trays required. in the gas and liquid phases (a measure to quantify mass
transfer), respectively, and λ is the stripping factor
Overall Efficiency calculated as λ = mG/L, where m is the slope of the
The overall tray efficiency, EO is defined as equilibrium line and G and L are the gas and liquid flow
E˳= (Number of theoretical trays)/(number of actual rates per cross˗sectional bubbling area in kmol/m2/s.
trays)
The approach to equilibrium that can be achieved with a
It is applied for the whole column. Every tray is assumed given number of transfer units depends on the
to have the same efficiency. The overall efficiency concentration profile — the driving force for mass
depends on the (i) geometry and design of the contacting transfer, which, in turn, depends on the flow pattern of

www.wjpls.org │ Vol 8, Issue 5, 2022. │ ISO 9001:2015 Certified Journal │ 191

Sen et al. World Journal of Pharmaceutical and Life Science

the vapor and liquid phases. Most models for crossflow shown in the adjacent diagram, better contacting is
trays assume that the vapor flows vertically in plug flow achieved by installing bubble˗caps or valve caps at each
and the liquid is vertically well mixed. With these perforation to promote the formation of vapor bubbles
assumptions, the Murphree point efficiency on a tray is flowing through a thin layer of liquid maintained by
defined as (1). a weir on each tray. To design a distillation unit or a
similar chemical process, the number of theoretical trays
The Murphree vapor˗phase tray efficiency (ηtray) defines or plates (that is, hypothetical equilibrium stages), Nt,
the fractional approach to equilibrium for a single required in the process should be determined, taking into
crossflow tray based on the vapor concentrations on the account a likely range of feedstock composition and the
operating and equilibrium lines. When the equilibrium desired degree of separation of the components in the
line is steeper than the operating line, as is typically the output fractions. In industrial continuous fractionating
case for the stripping section of a column, the stripping columns, Nt is determined by starting at either the top or
factor is greater than one and the section efficiency is bottom of the column and calculating material balances,
less than the tray efficiency. When the stripping factor is heat balances and equilibrium flash vaporizations for
less than one, the section efficiency is higher than the each of the succession of equilibrium stages until the
tray efficiency, which typically occurs in the rectifying desired end product composition is achieved. The
section. When the stripping factor is exactly one the calculation process requires the availability of a great
section and tray efficiencies are equal. deal of vapor–liquid equilibrium data for the components
present in the distillation feed, and the calculation
LIMITATIONS procedure is very complex.
Several limitations of the Murphree efficiencies have
In an industrial distillation column, the Nt required to
been discussed by Standard. Murphree efficiencies are
achieve a given separation also depends upon the amount
concerned only with mass transfer on the tray and ignore
of reflux used. Using more reflux decreases the number
the transfer of heat. Constant molal flow rates along the
of plates required and using less reflux increases the
column were assumed when Murphree defined the
number of plates required. Hence, the calculation of Nt is
efficiencies and application includes this assumption
usually repeated at various reflux rates. Nt is then divided
since the variable is mole fraction of each component
by the tray efficiency, E, to determine the actual number
and not total moles of each component. The vapor and
of trays or physical plates, Na, needed in the separating
liquid efficiencies are related but not equivalent.[11]
column. The final design choice of the number of trays to
be installed in an industrial distillation column is then
CONCLUSIONS
selected based upon an economic balance between the
The concept of theoretical plates in designing distillation cost of additional trays and the cost of using a higher
processes has been discussed in many reference reflux rate.
texts. Any physical device that provides good contact
between the vapor and liquid phases present in industrial REFERENCE
scale distillation columns or laboratory scale glassware
1. McCabe, W. L. & Smith, J. C. Unit Operations of
distillation columns constitutes a "plate" or "tray". Since
Chemical Engineering (3rd ed.). McGraw˗Hill,
an actual, physical plate can never be a 100% efficient
1976.
equilibrium stage, the number of actual plates is more
2. A b Perry, Robert H. & Green, Don W. Perry's
than the required theoretical plates. Where the number of
Chemical Engineers' Handbook (6th ed.).
actual, physical plates or trays is, is the number of
McGraw˗Hill, 1984.
theoretical plates or trays and is the plate or tray
3. Beychok, Milton (May 1951). "Algebraic Solution
efficiency. So-called bubble cap or valve cap trays are
of McCabe˗Thiele Diagram". Chemical Engineering
examples of the vapor and liquid contact devices used in
Progress.
industrial distillation columns. Another example of vapor
4. W.L. McCabe & E.W. Thiele (June). "Graphical
and liquid contact devices are the spikes in
Design Of Fractionating Columns". Industrial and
laboratory Vigreux fractionating columns. The trays or
Engineering Chemistry, 1925; 17: 605–611.
plates used in industrial distillation columns are
5. King, C. Judson Separation Processes.
fabricated of circular steel plates and usually installed
McGraw˗Hill, 1971.
inside the column at intervals of about 60 to 75 cm (24 to
6. McCabe, W. L. and Smith, J. C., Unit Operations of
30 inches) up the height of the column. That spacing is
Chemical Engineering, (3rd ed.), McGraw˗Hill,
chosen primarily for ease of installation and ease of
1976.
access for future repair or maintenance.
7. O’Connell, H. E., ―Plate Efficiency of Fractionating
Columns and Absorbers,‖ Transactions of the
An example of a very simple tray is a perforated tray.
American Institute of Chemical Engineers, 1946; 42:
The desired contacting between vapor and liquid occurs
741–775.
as the vapor, flowing upwards through the perforations,
8. Lewis, W. K., ―Rectification of Binary
comes into contact with the liquid flowing downwards
Mixtures,‖ Industrial and Engineering Chemistry,
through the perforations. In current modern practice, as
1936; 28(4): 399–402.

www.wjpls.org │ Vol 8, Issue 5, 2022. │ ISO 9001:2015 Certified Journal │ 192

Sen et al. World Journal of Pharmaceutical and Life Science

9. Lockett, M. J., ―Distillation Tray Fundamentals,‖

Cambridge Univ. Press, New York, NY, 1986.
10. Chen, G. X., and K. T. Chuang,―Liquid˗Phase
Resistance to Mass Transfer on Distillation
Trays,‖ Industrial and Engineering Chemistry
Research, 1995; 34(9): 3078–3082.
11. Chan, H., ―Tray Efficiencies for Multicomponent
Distillation Columns,‖ PhD Dissertation, the Univ.
of Texas at Austin (May), 1983.

www.wjpls.org │ Vol 8, Issue 5, 2022. │ ISO 9001:2015 Certified Journal │ 193