Fractional Distillation using

Enthalpy-Concentration Method
molal flow rates need not to be constant
using enthalpy as well as material balances
When the operating lines are plotted with the
equilibrium curve on the x-y diagram, the McCabeThiele step-by-step construction can be used to compute
the number of ideal plates. However, unless Ln and Lm
are constant, the operating lines are curved and can be
plotted only if the change with concentration in these
internal streams is known. Enthalpy balances are
required in the general case to determine the position of
a curved operating line.
The enthalpy-concentration diagram requires the
following data at a constant pressure:
(1) heat capacity of the liquid as a function of
temperature, composition, and pressure.
(2) heat of solution as a function of temperature and
composition.
(3) latent heats of vaporization as a function of
composition and pressure or temperature.
(4) boiling point as a function of pressure, composition
and temperature.
The diagram at a given constant pressure is based on
arbitrary reference states of liquid and temperature,
which is usually taken as the boiling point of the lowerboiling component A.
85

The saturated liquid enthalpy is

H x x AC PLA Tb T0 (1 x A )C PLB Tb T0 H sol
(1)
Tb
= boiling temperature of mixture at xA
= reference temperature
T0
= liquid heat capacity of A
CPLA
CPLB
= liquid heat capacity of B
Hsol
= heat of mixing, usually ignored
The saturated vapor enthalpy is

H y y A HVA C PVA Td T0 (1 y A )HVB C PVB Td T0

(2)
Td
T0
CPVA
CPVB
HVA

= dew temperature of mixture at yA

= reference temperature
= vapor heat capacity of A
= vapor heat capacity of B
= latent heat of A at the reference
temperature T0 & calculated from that
at the normal boiling temperature TbA.

HVA CPLA TbA T0 HVAb CPVA TbA T0 (3)

HVB CPLB TbB T0 HVBb CPVB TbB T0 (4)
That is, the liquid is first changed from temperature T0 to
Tb and then evaporated at Tb , the vapor temperature is finally
changed back from Tb to T0.

86

Example D6. Enthalpy-concentration plot for

benzene-toluene
Prepare an
enthalpyconcentration plot
for benzenetoluene at 1 atm
pressure.
Equilibrium and
physical property
data are given.

For the first point, we select pure toluene (xA=0). For

liquid toluene at the boiling point of 110.6oC,
H x x AC PLA Tb T0 (1 x A )C PLB Tb T0 H sol
0 (1 0)(167.5)(110.6 80.1) 5109 kJ / kmol
For the saturated vapor enthalpy of pure toluene, we first
need to calculate HVB at T0=80.1oC:
HVB C PLB TbB T0 HVBb C PVB TbB T0

Vapor pressure (kPa)

T (K)
353.3
358.2
363.2
368.2
373.2
378.2
383.8

Benzene
101.32
116.9
135.5
155.7
179.2
204.2
240.0

Component

Benzene (A)
Toluene (B)

Boiling
point
(oC)

80.1
110.6

Solution.
We choose a reference temperature of T0=80.1oC so that
the liquid enthalpy of pure benzene (xA=1) at the boiling
point is zero.

Toluene
46.0
54.0
63.3
74.3
86.0
101.32

Mole fraction of
benzene at 101.325 kPa
xA
yA
1.000
1.000
0.780
0.900
0.581
0.777
0.411
0.632
0.258
0.456
0.130
0.261
0
0

Heat capacity
(kJ/kmol K)

Latent heat of
vaporization
Vapor (kJ/kmol)

Liquid
138.2 96.3
167.5 138.2
87

30820
33330

167.5(110.6 80.1) 33330 138.2(110.6 80.1)

34224 kJ/kmol
Hence, at xA = 0,

H y y A HVA C PVA Td T0 (1 y A )HVB C PVB Td T0

= 0 + (1-0)[34224+138.2(110.6-80.1)]
=38439 kJ/kmol
For pure benzene, xA = yA = 1, T = T0=80.1oC, Hx = 0,

H y y A HVA C PVA Td T0 (1 y A )HVB C PVB Td T0

=1[30820+96.3(80.1-80.1)] + 0 = 30820 kJ/kmol

Selecting xA = 0.5, the boiling point Tb = 92oC and the
dew point for yA = 0.5 is Td = 98.8oC from the T-x-y plot.
H x x AC PLA Tb T0 (1 x A )C PLB Tb T0
= 0.5(138.2)(92-80.1)+(1-0.5)(167.5)(92-80.1)
= 1820 kJ/kmol

H y y A HVA C PVA Td T0 (1 y A )HVB C PVB Td T0

= 0.5[30820+96.3(98.8-80.1)]
+(1-0.5)[34224+138.2(98.8-80.1)]
= 34176 kJ/kmol
88

By the similar procedure,

at xA = 0.3 and yA = 0.3,
Hx = 2920 kJ/kmol and Hy = 36268 kJ/kmol
at xA = 0.8 and yA = 0.8,
Hx = 562 kJ/kmol and Hy = 32380 kJ/kmol

Enthalpy-concentration data for benzene-toluene mixture at 1 atm.

Saturated Liquid
Saturated Vapor
Enthalpy, Hx,
Enthalpy, Hy,
Mole
Mole
fraction, xA
(kJ/kmol)
fraction, yA
(kJ/kmol)
0
5109
0
38439
0.30
2920
0.30
36268
0.50
1820
0.50
34716
0.80
562
0.80
32380
1.00
0
1.00
30820

Enthalpy-concentration plot for benzene-toluene mixture at 1 atm.

The tie line represents the enthalpies and composition of

the liquid and vapor phases in equilibrium.
89

Distillation in Enriching Section of Tower

Material balances
Vn1 Ln D
(5)
Vn 1 yn1 Ln xn Dx D
(6)
By rearranging Eq. (6) we obtain the operating line
L
Dx
yn1 n xn D
(7)
Vn1
Vn1
Ln and Vn+1 may vary throughout the tower so Eq. (7)
will not be a straight line on an xy plot.

Making an enthalpy balance,

Vn 1 H y,n 1 Ln H xn DH xD qc
(8)
where qc is the condenser duty, kJ/h.
An enthalpy balance for the condenser only gives
qc V1 H y1 LH xD DH xD
(9)
90

Substitute Eq. (9) into Eq. (8) we have

Vn 1H y , n 1 Ln H xn V1H y1 LH xD
Vn 1 D H xn V1H y1 LH xD

Distillation in Stripping Section of Tower

(10)

Eqs. (7) & (10) are the final working equations for the
enriching section.
In order to plot the operating line Eq. (7), the terms Vn+1
and Ln must be determined from Eq. (10). If the reflux
ratio is set, V1 and L are know. The values of Hy1 and
HxD can be determined by Eqs. (1) & (2) or from an
enthalpy-concentration plot. If a value of xn is selected,
it is a trial-and-error solution to obtain Hy,n+1 since yn+1
is unknown. The steps to follow are given below.
1. Select a value of xn. Assume Vn+1 = V1 = L+D, then
Ln = Vn+1 - D.
2. Use Eq. (7) to calculate the approximate value of yn+1.
3. Using this yn+1 to obtain Hy,n+1 and xn to obtain Hxn .
Substitute these values into Eq. (10) and solve for the
new Vn+1. Obtain new Ln from Eq. (5)
4. Substitute the above values into Eq. (7) to get the new
yn+1.
5. If the newly calculated yn+1 the assumed value,
repeat steps 3-4. Usually one iteration is enough.
Assume another xn and repeat steps 2-5.
6. Plot the curved operating line for the enriching section.

91

Material balances
Lm Vm 1 B
Lm x m Vm 1 ym 1 Bx B
so that the operating line is
L
Bx
ym1 m x m B
Vm1
Vm 1

(11)
(12)
(13)

Making an enthalpy balance,

Vm 1H y,m1 Vm 1 B H xm BH xB qr (14)
where qr is the reboiler duty, kJ/h.
An enthalpy balance for the whole distiller gives
(15)
qr DH xD BH xB qc FH F
The final working equations are Eqs. (13) and (15).
Using a method similar to that of the enriching section to
solve the equations.
Component
Benzene
Toluene

Tb ( C)
80.1
110.6

CP (kJ/(kmol K)
Liquid
Vapor
138.2
96.3
167.5
138.2

92

Hvb
(kJ/kmol)
30820
33330

Example D7. Distillation Using EnthalpyConcentration Method

A liquid mixture of benzene-toluene is to be distilled in a
fractionating tower at 101.3 kPa pressure. The feed of
100 kmol/h is liquid, containing 45 mol % benzene and
55 mol % toluene, and enters at 54.4oC. A distillate
containing 95 mol % benzene and 5 mol % toluene and a
bottoms containing 10 mol % benzene and 90 mol %
toluene are to be obtained. The reflux ratio is 1.755. The
average heat capacity of the feed is 159 kJ/(kmol K) and
the average latent heat is 32099 kJ/kmol. Use enthalpy
balances to calculate the flow rates of the liquid and
vapor at various points in the tower and plot the curved
operating lines. Determine the number of theoretical
stages needed.

Solution:
F = 100 kg mol/h, xF = 0.45, xD = 0.95, xB = 0.10,
R = 1.5Rm = 1.5(1.17) = 1.755,
D = 41.2 kg mol/h, B = 58.8 kmol/h
The feed enters at 54.5oC so q = 1.195.
The flows at the top of the tower are calculated as
follows.
R = L/D = 1.755; L = 1.755D = 1.755(41.2) = 72.3;
V1 = L+D = 72.3+41.2 = 113.5
The latent heats of vaporization of benzene and toluene
at the reference temperature of 80.1oC are
HVA = HVAb = 30820 kJ/kmol
93

HVB CPLB TbB T0 HVBb CPVB TbB T0

= 167.5(110.6-80.1) + 33330 - 138.2(110.6-80.1)
= 34224 kJ/kmol
The saturation temperature (dew point) at the top of the
tower for y1 = xD = 0.95 is 82.3oC.
Hy1 = 0.95[30820+96.3(82.3-80.1)]
+(1-0.95)[34224+138.2(82.3-80.1)] = 31206 kJ/kmol
The boiling point of the distillate D is obtained as
81.1oC.
HxD = 0.95(138.2)(81.1-80.1)
+ (1-0.95)(167.5)(81.1-80.1) = 139 kJ/kmol

Step 1: select xn = 0.55 and guess yn+1 from Eq. (7)

yn1

Ln
Dx D 72. 3
41. 2
( 0. 55)
( 0. 95) 0. 695

xn
Vn1 113. 5
113. 5
Vn1

Step 2: using the Figure in Example D6 for xn = 0.55

obtain Hxn = 1590 and for yn+1 = 0.695, Hy,n+1 = 33240.
Substituting into Eq. (10)
Vn+1 (33240) = (Vn+1 - 41.2)1590
+113.5(31206) - 72.3(139)
Vn+1 =109.5
Using Eq. (5),
109.5=Ln +41.2 or Ln =68.3
Step 3: substituting into Eq. (7),
68. 3
41. 2
yn1
( 0. 55)
( 0. 95) 0. 700
109. 5
109. 5
94

This calculated value is close enough to the approximate

value of 0.695 so that no further trials are needed.
Select other values of xn and calculate the responding
yn+1, plot the curved operating line in the enriching
section.
The condenser duty is obtained from Eq. (9)
qc V1 H y1 LH xD DH xD

113. 5(31206) 72. 3(139) 41. 2(139) 3526100 kJ / h

For xB = 0.10, HxB = 4350 from the Figure in page 89.

The feed is at 54.5oC, using Eq. (1), we have
HF = 0.45(138.2)(54.5-80.1)
+ (1-0.45)(167.5)(54.5-80.1) = -3929 kJ/kg mol
Using Eq. (15),
qr = 41.2(139) + 58.8(4350) + 3526100 - 100(-3929)
= 4180500 kJ/h
Making a material balance below the bottom tray and
around the reboiler we have
(16)
LN B Vb
Enthalpy balance
Vb H yb Vb B H xN BH xB qr
(17)
From the equilibrium diagram we find that for xB = 0.10,
yB = 0.207, which is the vapor composition leaving the
reboiler.
For the equimolal overflow in the stripping section,
Lm Ln qF 72. 3 1.195(100 ) 191. 8
(18)
Vm 1 Vn 1 (1 q ) F 113. 5 (1 1.195)100 133. 0
95

Selecting ym+1 = yB = 0.207 and using Eq. (13), an

approximate value of xm = xN is obtained.
L
Bx
ym1 m x m B
Vm1
Vm 1
191. 8
58. 8
0. 207
xN
( 0.10 )
133. 0
133. 0
Solving xN =0.174. From the Figure in example D6 for
xN =0.174, HxN =3800, and for yB = 0.207, Hyb =37000.
Substituting into Eq. (17),
Vb (37000) Vb 58.83800 58.8(4350) 4180500
Solving Vb = 125.0. Using Eq. (16) we get LN = 183.8.
Substituting into Eq. (13) and solving for xN.
183. 8
58. 8
0. 207
xN
( 0.10 )
125. 0
125. 0
xN = 0.173
This value is quite close to the approximate value of
0.174.
Assuming other values of ym+1 and solving for xm using
the same procedure, the curved operating line for the
stripping section can be constructed.
The number of theoretical stages is determined to be
10.4, compared with 9.9 steps using the constant flow
method.

96

Ponchon and Savarit method

Rectifying section
We rearrange Eq. (8) as
Vn1H y,n1 Ln H xn DH xD qc DQ' (16)
DH xD qc
where Q'
D
The left hand side is the net rate flow of heat upwards
through the enriching section, while the right hand side
is constant. This means that the net rate of flow of heat
is constant and independent of the tray number in the
rectifying section.

Solid line: enthalpy-concentration method

Dashed line: constant molal overflow
The solid line is slightly above the dashed line.

97

Using Eq. (5) to eliminate Vn+1 in Eq. (6), we have

Ln D yn 1 Ln xn DxD
Ln y n 1 x n D x D y n 1
(17)
Hence,
Ln x D y n 1

internal reflux ratio

(18)
D y n 1 x n

98

This can be explained by the lever rule. A vapor of Vn+1

of composition y n+1 is separated into a distillate D of xD,
and a liquid Ln of xn. (Vn+1, yn+1) is at the fulcrum of a
beam, balanced by the distillate (D, xD) and liquid (Ln,
xn). In order for the beam to be balance, the moments
about the fulcrum must be equal. Hence, we have Eq.
(17).
A similar analysis for Eq. (16) gives
Ln D H y,n1 Ln H xn DQ'
Ln H y,n1 H xn D Q' H y,n1
or
Q' H y ,n 1
Ln

internal reflux ratio (19)

H
D
H

y ,n 1

xn

Again this obeys the lever rule.

Combining Eqs. (18) & (19), we have

Q' H y,n1
Ln x D y n 1

(20)
D y n 1 x n H y ,n 1 H xn
On the H-x-y diagram, this is a straight line through the
points (Hy,n+1, yn+1) at Vn+1, (Hx,n, xn) at Ln, and (Q, xD)
at D as linked above and shown in the figure below. D
is termed the difference point.
99

Since the heat and mass balances apply to any tray, then
at the top plate, n = 0, we have
line length Q ' H y ,1
L
x y1 Q ' H y ,1
R 0 D

D y1 x D H y ,1 H xD line length H y ,1 H xD
The line length H y ,1 H xD is the latent heat of
vaporization at a distillate composition xD. If the reflux
ratio is specified, then the length of Q Hy,1 can be
calculated, and hence Q determined.

100

Equilibrium data are used to determine the liquid and

vapor compositions leaving the first theoretical plate.
The graphical solution of Ponchon and Savarit is
continued using the equilibrium data and the H-x-y
diagram until the reboiler composition is reached. In the
following case, a total of 4 theoretical plates is shown, 3
in the column and 1 for the reboiler having an enthalpy
HR and composition xR.

Stripping section
The same analytical techniques used in the rectifying
section can be applied to the stripping section and the
entire column.

We rearrange Eq. (14 ) as

Lm H xm Vm1H y,m1 BH xB qr BQ' '
where Q = HxB qr/B, by eliminating B (B=Lm Vm+1),
y x H y ,m1 Q"
Lm
m 1 B
(21)
x B xm
H x,m Q"
Vm 1
On the H-x-y diagram, this is a straight line passing
throught (Hy,m+1, ym+1) at Vm+1, (Hx,m, xm) at Lm, and (Q,
xB) at B as shown in the figure above. B is also termed
the difference point. B is W in the figure.

Eq. (21) applies to every plate in the stripping section.

On the H-x-y diagram, this is a line from VZ+1 (vapor
leaving the reboiler and entering the bottom tray Z of the
101

102

tower) to B, intersects the saturated liquid enthalpy

curve at LZ, the liquid leaving the bottom plate. Vapor
VZ leaving the bottom plate is in equilibrium with the
liquid LZ and is located on the tie line Z.
The number of theoretical plates in the stripping section
can be determined from the H-x-y diagram by
alternatively constructing lines to B and tie lines. Each
tie line is a theoretical plate.
The complete column

The overall mass balance is

F=D+W
The more volatile component mass balance is
FxF = DxD + WxW
The heat balance is
FHF = QC + DHyD + WHxW QR = DQ+WQ
Eliminating F yields
D x F xW H F Q"

W x D x F Q ' H F
This is a straight line on the H-x-y diagram passing
through (Q, xD) at D, (HF, xF) at F, and (Q, xW) at W
and is shown in the above figure for a case of liquid feed
below its boiling point (cold liquid).
The procedure to determine the number of theoretical
plates is summarized below.
1. Locate the feed enthalpy and composition
2. Locate xD and xW
3. Locate D by computation of Q or for a specific
reflux ratio as R = L0/D
4. The line D, F is extended to x = xW and thus locates
W whose coordinates can be used to calculate QR.
5. The number of theoretical plates is then determined
by application of the straight line relationship on the
H-x-y diagram and the equilibrium data of the y-x
diagram.

103

104

Example D8. Distillation Using Ponchon Savarit

Method

Re-calculate the number of theoretical stages required

for example D7 using Ponchon Savarit method.
xF = 0.45, HF = -3929 kJ/kg mol
xD = 0.95, xB = 0.10
DH xD qc 41.2(139) 3526100

85724 kJ/kmol
Q'
41.2
D

Q = HxB qr/B =435 -4180500/58.8 = -66747 kJ/kmol

or in the H-x-y diagram, draw the line from D (xD=0.95,
Q=85724) through (xF=0.45, HF=-3929) to intersect
xB=0.10 gives Q = -66747 kJ/kmol from B.
The number of theoretical plates is then determined by
application of the straight line relationship on the H-x-y
diagram and the equilibrium data of the y-x diagram.
10.4 plates, or 9.4 plates plus 1 reboiler are needed. The
feed is at plate 6.

105

106

107