McCabe-Thiele Diagrams for

Binary Distillation
Tore Haug-Warberg
Dept. of Chemical Engineering
August 31st, 2005

The McCabe–Thiele diagram for solving bi-

Q̇ < 0 nary distillation problems represents a pillar-
V1 stone in every chemical engineering class. The
reason for this is not its practical importance—
D which in the era of modern computer technol-
V2 L0 ogy has become very modest—but its educa-
L1 tional value based on a very illustrative graph-
ical picture of a complicated physical process.
The McCabe–Thiele diagram in its most simple
Vn form represents a graphical solution to the clas-
F Ln−1 sical separation problem of N + 1 ideal equilib-
Vn+1 rium stages connected with countercurrent va-
Ln por and liquid flows as illustrated in Fig.1. The
streams are shown as separated flows except at
certain distinct locations (trays) where complete
mixing and thermodynamic equilibrium is as-
sumed. This is a useful abstraction but it must
VN be understood that the situation in a real plant
LN−1 V deviates in two respects: First of all there is
N+1
Q̇ > 0 no one-to-one correspondance between a physi-
B cal tray (or plate) and a thermodynamic equilib-
LN
rium stage1. Secondly, many columns have their
F 1: Simplified pic-
plates replaced by a structured packing which
ture of a counter-current gives intimate contact between the vapor and liq-
distillation column. uid phases at all locations in the column. The
simplified picture is still valid, however, if each
tray is considered to be one theoretical equilib-
rium stage regardless of the physical realization of it.

1It is common practice to talk about tray efficiencies which is the fraction of a theoret-

ical equilibrium stage reached for each physical plate. This efficiency may reach values as
high as 0.80-0.90 but is in many cases much lower.
1
2

1. The energy balance

To calculate the solution of the complicated separation problem in Fig.1
we need 3 sets of mass balances, one for the rectifying, one for the feed and
one for the stripping section of the column. In addition there is an overall
energy conservation assumption known as constant molar overflow. The
origin and importance of this assumption is clearified below. Let i
n
represent any of the internal stages in the the column except the feed tray.
The energy balance for an adiabatic stage is
vap liq liq
Ḣi+1 + Ḣi−1 = Ḣivap + Ḣi
Since enthalpy is an Euler homogenous function of first order (extensive
state variable) the energy balance can also be written
liq liq
i+1 Vi+1 + hi−1 Li−1 = hi Vi + hi Li
hvap vap

where h, and V and L denote the molar enthalpy and molar flows of the
vapor and liquid streams respectively2. Combined with the mass balance
Vi+1 + Li−1 = Vi + Li for stage i the last equation becomes

liq 
vap 
liq 
hi−1 − hvap
i+1 Li−1 = h i − h vap
i+1 V i + h i − h vap
i+1 Li

Adding and subtracting hvap vap

i−1 Li−1 and hi Li brings the equation on the fol-
lowing form:

liq 
vap 
vap 
hi−1 − hvap vap
i−1 Li−1 + hi−1 − hi+1 Li−1 = hi − hvap
i+1 Vi


vap 
+ hliq
i − h vap
i Li + h i − h vap
i+1 Li

The enthalpy function has no absolute zero, and it is only the enthalpy dif-
ferences that matter in the energy balance. But, the importance of the tem-
perature dependency of enthalpy is usually much smaller than the heat of
vaporization3. The assumption that hvap i−1 = hi
vap
= hvap i+1 is therefore quite
legitimate and the energy balance can be simplified to:

liq 
liq 
hi−1 − hvap
i−1 Li−1 = h i − h vap
i Li
Finally, assuming that the heat of vaporization is constant for the two-phase
mixture makes hliq vap liq
i−1 − hi−1 = hi − hi
vap
and consequently Li−1 = Li . The last
argument can easily be extended to yield
L0 = L1 = L2 = . . . = Ln−1
V1 = V2 = V3 = . . . = Vn
2The dot-notation has been dropped for the rate symbols.
This is according to common
practice in this field.
3
Typical changes per stage are 100–500J/mol for sensible heats and 25000–
35000J/mol for heats of vaporization
 2. OPERATING LINES 3

which is known as the constant molar overflow assumption4. The same

assumption is valid for the bottom section as well, but not across the feed
tray, where a discontinuity occurs because of the feed stream entering from
outside the control volume.
2. Operating lines
This section (and the rest of the paper) is restricted to the distillation
of binary mixtures. In the top section of the column an enrichment of the
lighter of the two components takes place and in the bottom section the
heavier component is enriched5. The next task is to express the mass bal-
ances of the column and have them integrated with the energy balance from
the previous section into something called an operating line. The com-
position of the lighter component is designated by y and x for the vapor
and liquid phases respectively. By convention these symbols stand for the
lighter component.
2.1. The rectifying section. We shall write the mass balances as one
total balance and one component balance. For the top section these equa-
tions are
Vi = D + Li−1
yi Vi = x0 D + xi−1 Li−1
which means the heavier component is never considered explicitly6. The
equations are easily solved for the vapor composition:
D Li−1
yi = x0 + xi−1
Vi Vi
D Li−1
= x0 + xi−1
D + Li−1 D + Li−1
The constant molar overflow assumption yields L0 = L1 = . . . = Ln−1 ≡ L.
Furthermore, it is customary to define the external reflux ratio of the column
as R ≡ L/D ∈ [0, ∞:
1 R
yi = x0 + xi−1 , i ∈ [1, n]
1+R 1+R
This is the so-called operating line representing the combined mass and
energy balances in the rectifying section of the column.
The equation is valid for all of the internal stages i = 1, 2, . . . , n and in
particular for i = 1 which yields y1 = x0 = xD . A bit surprising maybe,
4Valid for any number of the chemical components in the mixture.
5This means that the temperature profile of the column decreases from the bottom
towards the top.
6
For binary mixtures it can easily be eliminated from the given equations.
4

y1
y2
y3
y4

slope = R
1+R

x0
1+R

x3 x2 x1 xD

F 2: Rectifying section of a benzene–

toluene column (R = 2).

but from Fig.1 we see that the condenser has no separating effect—it only
condenses the vapor into a liquid phase7,8. For i = 2 the operating line
connects the vapor composition from stage 2 with the liquid composition
from stage 1, but here the calculation stops. We cannot move on before the
liquid composition from stage 1 is known! The answer to this problem lies
in the assumption of thermodynamic equilibrium from which we can derive
x1 = xeq (y1 ), x2 = xeq (y2 ) and so on. With this relationship in mind we got
all three ingredients of the McCabe–Thiele graphical method:
(1) Constant molar overflow assumption
(2) Operating line
(3) Equilibrium curve
The diagram is conventionally drawn with the heavier component to the left
and the lighter component to the right. That means the equilibrium curve is
located above the main 45◦ diagonal in the diagram. Fig.2 shows a typical
example for an almost ideal mixture of benzene (light) and toluene (heavy).

7
This is referred to as a total condenser. In some cases the column is equipped with
a partial condenser which makes xD
x0 . The condenser must then be treated like an
additional equilibrium stage, see the discussion of the stripping section below.
8
Prove that the heat duty of the condenser is in the range R ≤ Q/(D∆vap h) ≤ R + 1 for
partial versus total operation.
 2. OPERATING LINES 5

The staircase (red) shows the interaction between the equilibrium curve
(vertical step) and the operating line (horisontal step). Note that the op-
erating line (black) crosses the equilibrium line (blue) at one point in the
diagram. The column cannot operate to the left of this cross-over point be-
cause that would be in the one-phase region of the phase diagram. Hence,
the number of theoretical stages approaches infinity as the column strives
towards a singular condition9.
2.2. The stripping section. The operating line for the bottom section
follows the same receipe as for the top section. The two mass balances are
principally the same,
Vi + B = Li−1
yi Vi + xB B = xi−1 Li−1
and again we solve for the vapor composition on the left hand side:
B Li−1
yi = −xB + xi−1
Vi Vi
B Vi + B
= −xB + xi−1
Vi Vi
The constant molar overflow assumption yields Vn+1 = Vn+2 = . . . = VN+1 ≡
V. Furthermore, we may characterize the heat duty10 of the reboiler as
S ≡ V/(V + B) ∈ 0, 1] and write
1−S 1
yi = −xB + xi−1 , i ∈ [n + 1, N + 1]
S S
where S is the fraction of the downcoming liquid which is being evaporated.
Alternatively we can define S as the heat duty of the reboiler divided by the
heat which is needed to evaporate all the downcoming liquid.
The operating line is valid for all the internal stages i = n + 1, n +
2, . . . , N and also for the reboiler i = N + 1. The stripping section has
therefore one external equilibrium stage in addition to the internal stages
of the column (the situation is similar to that of a partial condenser in the
rectifying section). The cross-over between the operating line and the main
diagonal is given by yN+2 = xN+1 = xB . The index i = N + 2 is strictly
speaking outside the control volume but it does still serve as an easy-to-
remember construction point of the diagram, see Fig.3.
At this point it is possible to count the number of theoretical stages
from the specifications of the top and bottom products together with the
condenser and reboiler duties. It is more common, however, to specify
9
This is barely visible in the current diagram but an infinitly large magnifying glass
would reveal an infinite number of successively smaller steps.
10
Prove that the heat duty of the reboiler is Q = S (1 − S )−1 B∆vap h.
6

y5
slope = 1
S
y6

y7

y8

xB x7 x6 x5 x4

F 3: Stripping section of a benzene–

toluene column (S = 2/3). Tray numbers are
rounded to the nearest integer.

the feed stream rather than the reboiler duty. To manage this we need the
operating line for the feed tray which is discussed in the next section.

2.3. The feed tray. The operating line for the feed tray (q-line) re-
quires four mass balances and two energy balances (including the con-
stant molar overflow assumption). The extra mass and energy balances are
needed to characterize the physical state of the feed stream. To begin with
we have the component balances

yn Vn = xD D + xn−1 Ln−1
xn Ln = yn+1 Vn+1 + xB B

for the rectifying and stripping sections respectively. At the feed tray there
will in general be sudden jumps in all the stream variables, but for an opti-
mal placement of the feed tray the intensive state variables (temperature and
composition) are continuous. Hence, we shall require that yn = yn+1 ≡ y and
that xn = xn−1 ≡ x in the equations above. Summation plus reorganization
yields:
y (Vn+1 − Vn ) = x (Ln − Ln−1 ) − (xD D + xB B)



















xF F
 2. OPERATING LINES 7

Note that the total mass balance xF F = xD D+ xB B is substituted on the right

side. The q-line is first written on the preliminary form:
Ln − Ln−1 F
y=x − xF
Vn+1 − Vn Vn+1 − Vn
The feed stream is subsequently replaced by the mass balance for the feed
tray F = (Ln − Ln−1 ) − (Vn+1 − Vn ). A little manipulation yields
 
Ln − Ln−1 Ln − Ln−1
y=x − xF −1
Vn+1 − Vn Vn+1 − Vn
 
∆L ∆L
≡x − xF −1
∆V ∆V
where ∆V and ∆L measure the differences in the vapor and liquid flows
across the feed tray (top-down). This could serve as our final result, but it
is customary to characterize the feed quality by
∆L
q≡
∆L − ∆V
where q = 1 ⇔ ∆V = 0 (saturated liquid feed) and q = 0 ⇔ ∆L = 0
(saturated vapor feed). Hence, the feed quality can be interpreted as the
fraction of saturated liquid in the feed. The definition of the feed quality is
easily inverted to give ∆L/∆V = q/(q − 1) which puts the q-line on the final
form:
q 1
y=x − xF
q−1 q−1
This is the last of the three operating lines used in a McCabe-Thiele dia-
gram, but it should be mentioned that the optimal feed tray location causes
a slight redundancy in the calculation of the diagram: E.g. in most cases
the composition specifications xF and xD are given in addition to the reflux
ratio R and the feed quality q. This specifies the upper part of the column
and the conditions of the stripper will be fixed once xB or S is known (the
other parameter is fixed by the common cross-over point of the operating
lines). Anyway, the calculation is complete in the sense that it reveales all
the significant figures of a binary distillation column (see also Fig.4):
(1) Compositions of the top and bottom products
(2) Composition and quality of the feed stream
(3) Reflux ratio (and condenser duty)
(4) Reboiler duty
2.4. Extreme specifications. The condition of minimum reflux is reached
then i) the cross-over between the operating lines is located at the phase
boundary as illustrated in Fig.2 or ii) the upper operating line is tangent to
the equilibrium curve while the cross-over point is inside the phase diagram
8

0.8
Ntop = 4.03
q
0.6 slope = q−1

0.4
Nbot = 4.42
0.2

0
0 0.2 0.4 0.6 0.8 1

F 4: Complete McCabe-Thiele diagram

for a benzene–toluene column with parame-
ters xD = 0.9, xF = 0.55, xB = 0.1, R = 2 and
q = 0.2 (consistent with S = 2/3).

(applies to mixtures with concave equilibrium curves). In both cases the

number of theoretical stages approaches infinity. The other extreme is then
the reflux is infinite and the operating lines for the column overlap with the
main diagonal. This yields the smallest number of theoretical stages for a
given separation.
There are also cases when the stripping section or the rectifying section
is missing or ineffective. These cases include batch distillation (no strip-
per) and degassing units (no rectifyer). Mathematically, there is also the
possibility that a section becomes ineffective because of an extreme feed
condition. This is readily verified from the q-line which has slope ±1 for
q = ±∞. The first case (q = ∞) corresponds to a liquid feed so cold that it
condenses all the vapor coming up from the reboiler (ineffective rectifying
section). The second case (q = −∞) corresponds to a superheated vapor
so hot that it evaporates all the liquid coming down from the condenser
(ineffective stripping section).