For a non-ideal system, where the molar latent heat is

no longer constant and where there is a substantial

heat of mixing, the calculations become much more
tedious.
For binary mixtures of this kind a graphical model has
been developed by RUHEMANN, PONCHON, and
SAVARIT, based on the use of an enthalpy-composition
chart.
It is necessary to construct an enthalpy-composition
diagram for particular binary system over a
temperature range covering the two-phase vaporliquid region at the pressure of the distillation.

The following data are needed:

1. Heat capacity as a function of temperature,
composition and pressure.
2. Heat of mixing and dilution as a function of
temperature and composition.
3. Latent heats of vaporization as a function of
composition and pressure or temperature.
4. Bubble-point temperature as a function of
composition and pressure.

Enthalpy of liquid:
n

hm hi

(1)

In regular / ideal mixtures:

hi x i hio

(2)

For gaseous / vapor mixtures at normal T and P:

n

Hm hi y i i
i

(3)

Enthalpy-composition diagram

The equations used to calculate enthalpy of liquid and

vapor are:
hmix x A hA xB hB Hsol

(3)

hmix x A CP ,A T Tref x B CP ,B T Tref Hsol

(4)

Hmix hmix mix

(5)

mix x A A xB B

(6)

EXAMPLE 2
Devise an enthalpy-concentration diagram for the
heptane-ethyl benzene system at 760 mm Hg, using the
pure liquid at 0C as the reference state and assuming
zero heat of mixing.
SOLUTION

TB (C)
CP (cal/mole K)
(cal/mole)

heptane
136.2
51.9
7575

ethyl benzene
98.5
43.4
8600

t, C
136.2

xH
0.000

yH
0.000

H
--

EB
1.00

129.5
122.9
119.7
116.0
110.8
106.2
103.0
100.2
98.5

0.080
0.185
0.251
0.335
0.487
0.651
0.788
0.914
1.000

0.233
0.428
0.514
0.608
0.729
0.834
0.904
0.963
1.000

1.23
1.19
1.14
1.12
1.06
1.03
1.00
1.00
1.00

1.00
1.02
1.03
1.05
1.09
1.15
1.22
1.27
--

t = 136.2C
xH = 0.0

xEB = 1.0

h x H CP ,H t tref x EB CP ,EB t tref Hsol

= 0 + 1.0 (43.4) (136.2 0) + 0 = 5,911 cal/mole

mix = xH H + xEB EB = 0 + 1.0 (8,600) = 8,600
H = h + mix = 5,920 + 8,600 = 14,511 cal/mole

t = 129.5C
xH = 0.08

xEB = 0.92

h x H CP ,H t tref x EB CP ,EB t tref Hsol

= 0.08 (51.9) (129.5) + 0.92 (43.4) (136.2)

= 5,708 cal/mole
mix = xH H + xEB EB = 0.08 (7,575) + 0.92 (8,600) = 8,518
H = h + mix = 5,708 + 8,518 = 14,226 cal/mole
The computations are continued until the last point
where xH = 1.0 and xEB = 0.0

t, C

xH

136.2

h
H
(cal/mole) (cal/mole)
0.000
5,911
14,511

129.5
122.9
119.7

0.080
0.185
0.251

5,708
5,527
5,450

14,226
13,937
13,793

116.0
110.8
106.2
103.0
100.2
98.5

0.335
0.487
0.651
0.788
0.914
1.000

5,365
5,267
5,197
5,160
5,127
5,112

13,621
13,368
13,129
12,952
12,790
12,687

20,000
18,000

Vapor

16,000

Saturated vapor

14,000

12,000
10,000

2 Phase

8,000
6,000
4,000

Saturated liquid

Liquid

2,000
0
0

0.2

0.4

0.6

0.8

The enthalpy-concentration diagram may be used to evaluate

graphically the enthalpy and composition of streams added
or separated.
Over-all material balance:
V
F=V+L
(7)

Component material balance

F

F xF = V y + L x

(8)

Enthalpy balance:

L
Steady-state flow system
with phase separation
and heat added

F hF = V H + L h

(9)

For adiabatic process, q = 0:

Substituting eq. (7) to (9) gives:

V L hF V H L h
V (H hF) = L (hF h)

(10)

L H hF

V hF h

(11)

Substituting eq. (7) to (8) gives:

V (y xF) = L (xF x)

(12)

L y xF

V xF x

(13)

Substituting eq. (12) to (13) gives:

H hF y x F

hF h x F x

(14)

Eq. (14) can be rearranged:

H hF hF h

y xF xF x

(15)

H hF
The slope of line VF is :
y xF
___

hF h
The slope of line FL is :
xF x

hF

___

xF

Enthalpy-concentration
lines adiabatic, q = 0

According to eq. (15), the

slopes of both lines are the
same.
Since both lines go through
the same point (F), the lines
lie on the same straight line.

LEVER-ARM RULE PRINCIPLE

L H hF

V hF h

V
H
F

xF

Consider triangle LBV

___

V LF
___
F LV

___

H hF L

___ ___
LF BA hF h V

FV
h

AV

___

___

Similarly:

hF

L FV
___
V LF
___

L FV
___
F LV

Over-all material balance:

V1

qD

F=D+B

D, xD, HLD

L0
x0
HL0

(16)

Component material balance:

F
xF
HF

qB
B, xB, HLB

F x F = D xD + B x B

(17)

F xF = D xD + (F D) xB

(18)

F x F x B
D
xD xB

(19)

Enthalpy balance:
F hF qB D hD qD B hB

(20)

A
qD

Material balance around condenser:

V1 = L 0 + D

V1
L0

L1

D
xD

(21)

Component material balance:

V1 y1 = L0 x0 + D x0

(22)

Enthalpy balance:
qD + V1 H1 = L0 h0 + D hD

(23)

Designating:

qD
QD
D

V1 H1 = L0 h0 + D (hD QD)

(24)

Combining eqs. (21) and (24):

L 0 hD Q D H1

D
H1 hD

(25)

Internal reflux is shown as:

L 0 hD Q D H1

V1 hD Q D h0

(26)

A
qD

Internal reflux between

each plate, until a point
in the column is reached
where a stream is added
or removed, can be
shown as:

Lm
hD QD Hm1

Vm1
hD QD hm

D
xD

L0

Lm
Vm+1

(27)

(hD QD), xD

hD QD H1

H or h

H1

V1
H1 hD
L0, D

h0, hD

y1, x0, xD

Material balance:

D, yD
qD

V1 = L 0 + D

(28)

Component material balance:

v1
v2
v3

L0

L1
L2

y1 V1 = x0 L0 + yD D

(29)

Enthalpy balance:
qD + V1 H1 = L0 h0 + D HD

(30)

q
Designating: Q D D
D
F
xF

vF

LF-1
LF

V1 H1 = L0 h0 + D (hD QD) (31)

Combining eqs. (28) and (30):

L 0 HD Q D H1

D
H1 h0

(32)

Internal reflux is shown as:

L 0 HD Q D H1

V1 HD Q D h0

(33)

Internal reflux between each plate, until a point in the

column is reached where a stream is added or removed,
can be shown as:
Lm HD Q D Hm1

Vm1 HD Q D hm

(34)

(HD QD), yD

H D QD H 1
V1

H or h

HD, yD

H 1 h0

h0, x0

y1, x0, yD

qD

V1
V2
V3

Vn+1

D
xD

L0
L1
L2

The material balance equation

maybe rearranged in the from
of difference:
L 0 V1 = L 1 V 2 = L 2 V3
= . . . . = Lm Vm+1
=D =
L 0 V1 = D =

Ln
LF

(35)

For the component material balance:

L0 x0 V1 y1 = L1 x1 V2 y2

= L2 x2 V3 y3 = . . . .
= Lm xm Vm+1 ym+1
= D x D = x
L0 x0 V1 y1 = D xD = x

(36)

Combining eqs. (35) and (36):

xD = x

(37)

For the enthalpy balance:

L0 h0 V1 H1 = L1 h1 V2 H2 = L2 h2 V3 H3 = . . . .
= Lm hm Vm+1 Hm+1 = D (hD QD) = h

(38)

Combining eqs. (23) and (35):

h = hD QD

(39)

These 3 independent equations [eqs. (35), (36), and (37)] can be

written for rectifying section of the column between each plate.
On the enthalpy scale and on the composition scale, the
differences in enthalpy and in composition always pass through
the same point, ([xD, (hD QD)]
This is designated as point , the difference point, and all lines
corresponding to the combined material and enthalpy balance
equations (operating line equations) for the rectifying section of
the column pass through this intersection.

PLATE-TO-PLATE GRAPHICAL PROCEDURE FOR DETERMINING

THE NUMBER OF EQUILIBRIUM STAGES:
1. Use R, xD, HD or hD to establish the location of point with x = xD
and h = hD QD or h = HD QD
2. Use Equilibrium data alone to establish the point L1 at (x1, h1).
Since L1 is assumed to be a saturated liquid, x1 must lie on the
saturated-liquid line.

3. Draw the operating line between L1 and . This line intersects the
saturated-vapor line at V2 (y2, H2).
4. Repeat steps 2 and 3 until the feed plate is reached.

 (x, h)

V3

V2

V1

H or h

V4

L3

L2

x or y

L1

Lm

V m1

VM
V M 1

L M 1
LM

qB

B
xB

The material balance equation maybe rearranged in

the from of difference:

LM V M1 B LM1 V M
L M 2 L M 1 . . .

Lm V m1

(40)

For the component material balance:

L M x M V M 1 y M 1 B x B L M 1 x M 1 V M y M
L M 2 x M 2 V M 1 y M 1 . . .
L m x m V m 1 y m 1 x

(41)

Combining eqs. (40) and (42):

x xB

(42)

For the enthalpy balance:

LM hM V M 1 HM 1 B hB QB LM 1 hM 1 V M HM
LM 2 hM 2 V M 1 HM 1 . . .
L m hm V m1 Hm1 h

(43)

Combining eqs. (40) and (43):

h hB QB

(44)

 These 3 independent equations [eqs. (40), (41), and

(43)] can be written for stripping section of the column
between each plate.
On the enthalpy scale and on the composition scale,
the differences in enthalpy and in composition always
pass through the same point, [xB, (hB QB)].
This is designated as point , the difference point, and
all lines corresponding to the combined material and
enthalpy balance equations (operating line equations)
for the stripping section of the column pass through
this intersection.

QB is usually not known. It can be derived from over-all

material balance:
F=D+B

(45)

Combining eq. (45) with eqs. (35) and (40) gives:

F

(46)

Equation (46) implies that lies on the extension of the

straight line passing through F and .

PLATE-TO-PLATE GRAPHICAL PROCEDURE FOR

DETERMINING THE NUMBER OF EQUILIBRIUM STAGES:
1. Draw a straight line passing through F and .
2. Draw a vertical straight line at xB all the way down until it
intersects the extension of line F in
3. Assuming the reboiler to be an equilibrium stage, the vapor
VM+1 is in equilibrium with the bottom stream.
4. Use equilibrium data alone to establish the value of ym+1 on
the saturated-vapor line.
5. Draw the operating line between Lm(xm, hm) and VM+1. This
line intersects the saturated-liquid line at

6. Repeat steps 4 and 5 until the feed plate is reached.

VM1 VM VM1

H or h

hB LM LM-1

x or y

, x B

V1

qD
D

L0

The construction may start from

either side of the diagram,
indicating either the condition at
the top or the bottom of the
column.
Proceed as explained in previous
slides.

qB

In either case, when an equilibrium

tie line crosses the line connecting
the difference points through the
feed condition, the other
difference point is used to
complete the construction.

H or h

9 8 7 6

xB

xF

xD

V1

H or h

L1

y1

x1

EXAMPLE 3
Using the enthalpy-concentration diagram from Example 2,
determine the following for the conditions in Example 1, assuming a
saturated liquid feed.
a. The number of theoretical stages for an operating reflux ratio of
R = L0/D = 2.5
b. Minimum reflux ratio L0/D.
c. Minimum equilibrium stages at total reflux.
d. Condenser duty feeding 10,000 lb of feed/hr, Btu/hr.
e. Reboiler duty, Btu/hr.

SOLUTION
(a)

From the graph: hD = h0 = 5,117 cal/mole

H1 = 12,723 cal/mole
L0 hD QD H1

D
H1 hD

5,117 QD 12,723
2.5
12,723 5,117

QD = 26,621 cal/mole

The coordinate of point is:

x = xD = 0.97
h = hD QD = 5,117 ( 26,621) = 31,738 cal/mole

Draw a straight line passing through and F.

Extend the line until it intersects a vertical line passing
through xB, at
Draw operating lines and equilibrium lines in the whole
column using the method explained in the previous slides.
Number of stages = 11

35,000

30,000
25,000

20,000
15,000
10,000

5,000
01
0.9 0

0.2

0.4

0.6

0.8

0.2

0.4

0.6

0.8

0.8
0.7

0.6
0.5
0.4
0.3
0.2
0.1
0
0

 = 21,700 cal/mole

20,000

(b)

18,000

L0 hD QD H1

D
H1 hD

16,000
14,000

10,000

8,000
6,000
4,000

2,000
0
1

0.9

0.8

0.2

0.4

0.6

0.8

0.7

0.5
0.4
0.3
0.2
0.1
0
0

h H1
H1 hD

21,700 12,723
L0

D min 12,723 5,117

= 1.18

0.6

12,000

0.2

0.4

0.6

0.8

20,000

(c)

18,000
16,000

14,000

2 1

10,000
8,000
6,000

4,000
2,000

N=7

0
1

0.9

0.2

0.4

0.6

0.8

0.2

0.4

0.6

0.8

0.8
0.7
0.6

12,000

0.5
0.4
0.3
0.2
0.1
0
0

(d)

hD QD = h = 31,738 cal/mole
hD = 5,117 cal/mole

QD = 26,621 cal/mole
QD 26,621

cal
1.8 Btu lb mole
mole D 10,000 lb F hr

0.426
mole
cal mole
mole F 103 lb mole F

= 1,981,843 Btu/hr
(e)

hB QB = 14,350 cal/mole
hB = 5,886 cal/mole
QB = 14,350 + 5,886 = 20,236 cal/mole

QD 26,236

cal
1.8 Btu lb mole
mole B 10,000 lb F hr

0.574
mole
cal mole
mole F 103 lb mole F

= 2,631,751 cal/mole