Equilibria, Bubble Points, Dewpoints, Flash Calculations, and Activity Coef Ficients

Chapter 2
Equilibria, Bubble Points, Dewpoints,

Flash Calculations, and Activity
Coefficients
2.1 Vapour Pressure Calculations
The basis for all phase equilibrium calculations are the vapour pressures of the
components. The vapour pressure is derived using the Antoine Equation and
Antoine Constants A, B, and C.
AB
Antoine Equation : lg p0 ¼
C þ tð CÞ
Example 1.1: Calculation of the vapour pressures of benzene and toluene

(Fig. 2.1).
Benzene Toluene
A ¼ 7:00481 A ¼ 7:07581
B ¼ 1196:76 B ¼ 1342:31
C ¼ 219:161 C ¼ 219:187
Temperature Benzene vapour pressure Toluene vapour pressure

50 C p0B ¼ 362 mbar p0T ¼ 123 mbar

98 C p0B ¼ 1704 mbar p0T ¼ 698 mbar

103 C p0B ¼ 1950 mbar p0T ¼ 812 mbar
2.2 Phase Equilibrium of Ideal Binary Mixtures
The equilibrium between the liquid and the vapour phase is calculated according to
the laws of Dalton and Raoult.
© Springer International Publishing AG 2017 39

M. Nitsche and R. Gbadamosi, Practical Column Design Guide,
DOI 10.1007/978-3-319-51688-2_2
40 2 Equilibria, Bubble Points, Dewpoints, Flash Calculations …
Fig. 2.1 Vapour pressure of

different components as a
function of temperature
Dalton:
p1 ¼ y1 Ptot Ptot ¼ p1 þ p2 þ p3 þ . . . pi
Raoult (Fig. 2.2):
p1 ¼ x1 p01 p2 ¼ x2 p02
Ptot ¼ x1 p01 þ x2 p02 þ x3 p03 þ . . .: xi p0i
Equilibrium equation: yi * Ptot = pi = xi * p0i

xi p0i pi
yi ¼ ¼
Ptot Ptot
yi = concentration of the component i in the vapour phase (mole fraction)

xi = concentration of the component i in the liquid phase (mole fraction)
Ptot = total pressure (mbar)
p0i = vapour pressure of the component i (mbar)
pi = partial pressure of the component i (mbar)
Example 2.2.1: Calculation of the partial pressures and the vapour compositions
for an ideal binary mixture.
x1 ¼ 0:6 p01 ¼ 800 mbar

x2 ¼ 0:4 p02 ¼ 1300 mbar
2.2 Phase Equilibrium of Ideal Binary Mixtures 41
Calculation of the partial pressures according to Raoult:
p1 ¼ x1 p01 ¼ 0:6 800 ¼ 480 mbar

p2 ¼ x2 p02 ¼ 0:4 1300 ¼ 520 mbar
Ptot ¼ 1000 mbar
Calculation of the vapour concentration according to Dalton:
p1 480
y1 ¼ ¼ ¼ 0:48 molfr: ¼ 48 mol%
Ptot 1000
p2 520
y2 ¼ ¼ ¼ 0:52 molfr: ¼ 52 mol%
Ptot 1000
In order to simplify the calculation of phase equilibria a separation factor a is

introduced, often also called the relative volatility a, defined as the ratio of the
vapour pressures of the two components, or the ratio of the equilibrium constants,
K, of the components of the ideal mixture.
P01 K1
a1=2 ¼ ¼
P02 K2
Calculation with the relative volatility a assumes that both vapour pressure
curves are fairly parallel in the logarithmic representation (see Fig. 2.3).
In Fig. 2.4 it can be seen that the relative volatility becomes smaller with rising
temperatures. The separation becomes more difficult with increasing temperatures.
Due to the fact that the relative volatility in the rectification section, and in the
stripping section, is different, a geometrical average is formed from the separation
factor aV in the rectification section and the separation factor aA in the stripping
section.
Fig. 2.2 Graphical

representation of the laws of
Dalton and Raoult for an ideal
mixture
Fig. 2.3 Vapour pressure curves of benzene, toluene, and xylene
Fig. 2.4 Relative volatilities for the separation of benzene/toluene and benzene/xylene as a
function of temperature
pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
aav ¼ aV aA
Using the relative volatility a one gets a very simple equation for the calculation
of the phase equilibrium between the composition in the vapour and the compo-
sition in the liquid.
2.2 Phase Equilibrium of Ideal Binary Mixtures 43
ax y
y¼ ðmolfractionÞ x¼ ðmolfractionÞ
1 þ ð a 1Þ x a ð a 1Þ y
Example 2.2.2: Calculation of the vapour composition y1 for a liquid composition

of x1 = 0.2. p01 = 400 mbar p02 = 200 mbar x1 = 0.2 x2 = 0.8
400
a¼ ¼2
200
a x1 2 0:2
y1 ¼ ¼ ¼ 0:33 molfr:
1 þ ða 1Þ x1 1 þ ð2 1Þ 0:2
Ptot ¼ x1 p01 þ x2 p02 ¼ 0:2 400 þ 0:8 200 ¼ 240 mbar
x1 p01 0:2 400
y1 ¼ ¼ ¼ 0:33 molfr:
Ptot 240
Cross-check calculation for x:
y1 0:33
x1 ¼ ¼ ¼ 0:2 molfr:
a ða 1Þ y1 2 ð2 1Þ 0:33
y1 Ptot 0:33 240
x1 ¼ ¼ ¼ 0:2 molfr:
p01 400
In American literature the equilibrium constant K, which is defined as the ratio of

the compositions in vapour and liquid, is often used instead of the relative volatility a.
yi p0i
K¼ ¼
xi Pges
1 K2
y1 ¼ K1 x1 ¼ K1
K1 K2
y1 1 K2
x1 ¼ ¼
K1 K1 K2
Example 2.2.3: Equilibrium calculation with the equilibrium constant K.
x1 ¼ 0:6 p01 ¼ 800 mbar p1 ¼ 0:6 800 ¼ 480 mbar

x2 ¼ 0:4 p02 ¼ 1300 mbar p2 ¼ 0:4 1300 ¼ 520 mbar Ptot ¼ 1000 mbar
Calculation of the equilibrium factor K:
y1 p01 800
K1 ¼ ¼ ¼ ¼ 0:8
x1 Ptot 1000
y2 p02 1300
K2 ¼ ¼ ¼ ¼ 1:3
x2 Ptot 1000
Calculation of the vapour composition y:
y1 ¼ K1 x1 ¼ 0:8 0:6 ¼ 0:48 molfr:

1 K2 1 1:3
y1 ¼ K 1 ¼ 0:8 ¼ 0:48 molfr:
K1 K2 0:8 1:3
Cross-check calculation of x1:
y1 0:48
x1 ¼ ¼ ¼ 0:6 molfr:
K1 0:8
1 K2 1 1:3
x1 ¼ ¼ ¼ 0:6 molfr:
K1 K2 0:8 1:3
2.3 Bubble Point Calculation
The bubble point of a mixture is defined as follows:
Ryi ¼ RKi xi ¼ 1
The bubble pressure Pboil can be calculated directly.
Pboil ¼ x1 p01 þ x2 p02
A simple method for calculating the bubble temperature of a mixture is the

calculation of the bubble pressure from the sum of the partial pressures.
At the bubble temperature the bubble point pressure must be equal to the system
pressure Ptot. The following example shows the procedure.
Example 3.1: Iterative bubble point calculation for a benzene-toluene mixture
30 mol% benzene in the liquid phase (x = 0.3)
70 mol% toluene in the liquid phase (x = 0.7)
Ptot = 1000 mbar p0B = vapor pressure of benzene
p0T = vapor pressure of toluene
First choice : t ¼ 95 C p0B ¼ 1573 mbar p0T ¼ 634:4 mbar
Pboil ¼ 0:3 1573 þ 0:7 634:4 ¼ 916 mbar Pboil is too low!
Second choice : t ¼ 100 C p0B ¼ 1807 mbar p0T ¼ 740 mbar

2.3 Bubble Point Calculation 45
Fig. 2.5 Bubble point determination by graphical interpolation
Pboil ¼ 0:3 1807 þ 0:7 740 ¼ 1060 mbar Pboil is too high!
Third choice : t ¼ 98 C p0B ¼ 1710 mbar p0T ¼ 696 mbar
Pboil ¼ 0:3 1710 þ 0:7 696 ¼ 1000 mbar Pboil ¼ 1000 mbar ¼ correct!
Figure 2.5 shows how the bubble point determination can be simplified by
graphical interpolation. The sum of the two partial pressures must be equal to the
system pressure.
Cross-check calculation of the bubble point at 98 °C:

Vapour pressure of benzene p0B = 1710 mbar
Vapour pressure of toluene p0T = 696 mbar
p0B 1710
K1 ¼ ¼ ¼ 1:71
Ptot 1000
p0T 696
K2 ¼ ¼ ¼ 0:696
Ptot 1000
X
Ki ¼ K1 x1 þ K2 x2 ¼ 1:71 0:3 þ 0:696 0:7 ¼ 1
The bubble point specification is therefore fulfilled.

2.4 Dew Point Calculation
The dew point of a mixture is defined as follows:

X
Rxi ¼ yi =Ki ¼ 1
The dew point pressure Pdew can be calculated directly.

X 1
1 y1 y2 yi
¼ þ Pdew ¼
Pdew p01 p02 p0i
The dew point temperature for a specific pressure is calculated iteratively until
the sum of the quotients yi/p0i is equal to the reciprocal value of the system pressure
Ptot. The following example shows the procedure.
Example 2.4.1: Iterative dew point calculation for a benzene-toluene mixture.
30 mol% benzene in the vapour phase (y = 0.3)
70 mol% toluene in the vapour phase (y = 0.7)
Ptot = 1000 mbar
First choice : t ¼ 100 C p0B ¼ 1807 mbar p0T ¼ 740 mbar
1 y1 y2 0:3 0:7
¼ þ ¼ þ ¼ 0:0011 Pdew ¼ 899 mbar is too low!
Pdew p01 p02 1807 740
Second choice : t ¼ 104 C p0B ¼ 2013 mbar p0T ¼ 834:4 mbar
1 y1 y2 0:3 0:7
¼ þ ¼ þ ¼ 0:00099 Pdew ¼ 1012 mbar is too high!
Pdew p01 p02 2013 834:4
Third choice : t ¼ 103:8 C p0T ¼ 2002 mbar p0T ¼ 829 mbar
1 y1 y2 0:3 0:7
¼ þ ¼ þ ¼ 0:001 Pges ¼ 1000 mbar is correct!
Pdew p01 p02 2002 829
Cross-check calculation for the dew point at 103.8 °C:
2002 829
K1 ¼ ¼ 1:99 K2 ¼ ¼ 0:824
1006 1006
X yi 0:3 0:7
¼ þ ¼1
Ki 1:99 0:824
The condition for the dew point is fulfilled.

Figure 2.6 shows how the dew point can be determined by graphical
interpolation.
2.5 Dew Point Calculation of Vapour Containing Inert Gases 47
Fig. 2.6 Dew point determination by graphical interpolation
2.5 Dew Point Calculation of Vapour

Containing Inert Gases
The dew point of a vapour mixturePcontaining inert gas is reached if the sum of the
partial pressures of the vapours ( yi * Pges) reaches the vapour pressure of the
liquid phase by cooling.
X X X
yi PD ¼ zi Ptot ¼ xi p0i
PD ¼ Ptot PIN
PD = sum of the vapours partial pressures (mbar)

PIN = inert gas partial pressure (mbar)
Ptot = total pressure in the system with inert gas (mbar)
yi = vapour composition based on the vapour partial pressure PD
zi = vapour composition based on the total pressure Ptot with inert gas
Calculation of the dew point pressure without inert gas:

X 1 X yi
yi p0i
Pdew ¼ ¼1 Ki ¼
P0i Ki PD
Calculation of the dew point pressure with inert gas:

X 1 X zi
zi p0i
Pdew ¼ ¼1 Ki ¼
P0i Ki Ptot
Example 2.5.1: Dew point pressure calculation without inert gas.

y1 ¼ 0:413 P01 ¼ 3009:3 mbar at 102 C
y2 ¼ 0:587 P02 ¼ 830:8 mbar
X 1
yi 0:413 0:587 1
Pdew ¼ ¼ þ ¼ 1185 mbar
P0i 3009:3 830:8
3009:3 830:8
K1 ¼ ¼ 2:54 K2 ¼ ¼ 0:7
1185 1185
X 0:413 0:587
xi ¼ þ ¼1
2:54 0:7
Example 2.5.2: Dew point pressure calculation with inert gas.
40 Vol% vapour þ 60 Vol% inert gas

y1 ¼ 0:413 molfr: P01 ¼ 3009:3 mbar at 102 C
y2 ¼ 0:587 molfr: P02 ¼ 830:8 mbar
z1 ¼ 0:4 y1 ¼ 0:4 0:413 ¼ 0:165 molfr:

z2 ¼ 0:4 y2 ¼ 0:4 0:587 ¼ 0:235 molfr:
X
Vapour fraction : z1 þ z2 ¼ 0:4
Inert gas fraction : zIN ¼ 0:6
X 1
zi 0:165 0:235 1
Pdew ¼ ¼ þ ¼ 2961:3 mbar
p0i 3009:3 830:8
3009:3 830:8
K1 ¼ ¼ 1:016 K2 ¼ ¼ 0:28
2961:3 2961:3
X 0:165 0:235
xi ¼ þ ¼1
1:016 0:28
With inert gas the dew point pressure is much higher and the dew point tem-
perature lies lower than it would without inert gas. In addition, with inert gas in the
vapour a much deeper cooling must take place in order to condense the vapour.
2.6 Dew and Bubble Point Lines of Ideal Binary Mixtures 49
2.6 Dew and Bubble Point Lines of Ideal Binary Mixtures
The bubble point of a liquid mixture is defined such that the sum of the partial
pressures of the mixture reaches the system pressure with the first droplet being
evaporated. Due to the preferred evaporation of light-boiling components,
high-boiling components increase in concentration and the bubble point rises. The
curve of the boiling temperature as a function of the composition of the
light-boiling components in the mixture is known as the boiling line.
Equation for the boiling point line:
Ptot p02
x1 ¼ f ðtÞ ¼ ðmolfraction light boilers in the liquidÞ
p01 p02
The boiling point temperature increases with decreasing composition of

light-boiling components.
The dew point of a vapour mixture is the temperature at which the first droplet is
condensed. Due to the preferred condensing of high-boiling components the vapour
mixture is enriched with light-boiling components and the dew point temperature
drops.
The representation of the dew point temperature as function of the vapour
composition is referred to as the dew point line.
Equation for the dew point line:
p01 Ptot p02

y1 ¼ f ðtÞ ¼ ðmolfraction light boilers in the vaporÞ
Ptot p01 p02
A diagram with bubble and dew point lines is called a phase diagram or tem-
perature–composition diagram.
Example 2.6.1: Construction of the temperature–composition diagram for
benzene [1]-toluene [2] at 1013 mbar
Procedure:
1. Calculation of the two boiling points with the Antoine Equation.
The two boiling points are the end points in the temperature–composition
diagram.
Bubble point of benzene: 80.1 °C
Bubble point of toluene: 110.6 °C
2. Calculation of vapour pressures at different temperatures with the Antoine
equation.
3. Determination of the liquid composition x and the vapour composition y at the
different temperatures using the equations for the bubble and dew pointo lines.
Calculation results:
Temperature (°C) p01 (mbar) p02 (mbar) x1 (molfr.) y1 (molfr.)

80.1 1013 390 1.000 1.000
83 1107 430 0.861 0.941
86 1211 476 0.731 0.874
89 1322 525 0.612 0.799
92 1442 578 0.504 0.717
95 1569 636 0.404 0.626
98 1705 698 0.313 0.527
101 1850 765 0.229 0.418
104 2004 836 0.151 0.300
107 2168 913 0.080 0.170
110.6 2378 1013 0.0 0.0
Bubble point line : x1 ¼ f ðtemperatureÞ Dew point line : y1 ¼ f ðtemperatureÞ
p01 = vapour pressure of benzene p02 = vapour pressure of toluene

x1 = liquid composition of the lighter boiling component of benzene (molfraction)
y1 = vapour composition of the lighter boiling component benzene (molfraction)
Figure 2.7 depicts the temperature–composition diagram of the benzene–toluene
mixture.
The dew point of a vapour mixture with 30 mol% benzene and 70 mol% toluene
lies at 104 °C. The bubble point of the mixture lies at 98 °C. The first liquid droplet
Dew line
Bubble line
Dew point
Boiling point
Fig. 2.7 Temperature–composition diagram for the benzene–toluene mixture

2.6 Dew and Bubble Point Lines of Ideal Binary Mixtures 51
condenses at a 104 °C dew point. At the bubble point of 98 °C the total mixture is
liquid. In order to condense the total mixture the mixture has to be cooled down
from 104 to 98 °C. When evaporating, the mixture must on the contrary be heated
from the bubble point to the dew point.
2.7 The Bubble Point and Dew Point

of Immiscible Mixtures
One example of common mixtures of this type is the mixture of hydrocarbons and
water. In an immiscible mixture both liquid phases exert temperature dependent
vapour pressures.
Bubble point:
The bubble point pressure Pboil results from the sum of the hydrocarbon vapour
pressures Porg and the water vapour pressures PW.
Pboil = Porg + PW
This equation is the foundation for steam stripping.

By introducing water or steam the bubble point of hydrocarbons is reduced.
Example 2.7.1: Bubble point of a toluene–water mixture at 1010 mbar.
Temperature: 84 °C.
Toluene vapour pressure at 84 °C = 444 mbar.
Water vapour pressure at 84 °C = 566 mbar.
Pboil = 444 + 666 = 1010 mbar.
The bubble point for the toluene–water mixture is 84 °C at 1010 mbar.
Dew point:
In the dew point calculation the composition of the vapour is used as opposed to the
bubble point calculation. The dew point is defined as the point at which the partial
pressure equals the vapour pressure of the respective component. In a vapour
mixture the component that first condenses out is the component whose partial
pressure reaches the vapour pressure of the component. The higher the vapour
composition the higher the partial pressure and the earlier condensing out of the
component occurs.
Porg ¼ yorg Ptot PW ¼ yW Ptot
The dew point is reached when the vapour pressure of the component falls below
the partial pressure of the component.
P0org < Porg The vapour pressure of the organic component is lower than the
partial pressure, leading to the dew point of the organic component.
P0W < PW The vapour pressure of water is lower than the partial pressure,
leading to the dew point of water.
Example 2.7.2: Determination of the dew point of a toluene–water mixture.

(a) Water condenses first:
Water vapour composition in the vapour yW = 0.63; Ptot = 1 bar.
Water vapour partial pressure PW = 0.63 * 1000 = 630 mbar.
Water has a vapour pressure of P0W = 630 mbar at 87.2 °C.
The dew point is 87.2 °C.
Water condenses first.
(b) Toluene condenses first:
Toluene composition in the vapour yorg = 0.578; Ptot = 1 bar.
Toluene partial pressure Porg = 0.578 * 1000 = 578 mbar.
Toluene has a vapour pressure of P0org = 578 mbar at 92 °C.
The dew point is 92 °C.
Toluene condenses first.
2.8 Flash Calculations for Ideal Binary Mixtures [1]
At the bubble point the total mixture is liquid.

At the dew point the total mixture is vapour.
The vapour and liquid rates change between bubble point and dew point.
When heated to t1 and vaporized at pressure P2 a part of the liquid will be
vaporized (Fig. 2.8).
When cooling the vapour mixture to the temperature t2 a part of the vapour
condenses (Fig. 2.8).
Using the flash calculation the vapour composition of the mixture at tempera-
tures between bubble point and dew point is calculated. The compositions in the
vapour and liquid phase when cooling or heating are also determined with the
equilibrium factors.
How much of the mixture is vapour at temperatures between bubble point and
dew point?
The calculation of the vapour fraction V of the feed F is accomplished with the
use of the equilibrium constants K1 and K2 for the vapour composition of the
light-boiling component z1 as follows:
2.8 Flash Calculations for Ideal Binary Mixtures [1] 53
Fig. 2.8 Flash separation after heating liquid mixtures or cooling vapour mixtures
K1 K2
V z1 1K 1
¼ 2
F K1 1
What is the composition of the liquid and vapour fractions of the mixture?
1 K2
x1 ¼
K1 K2
y1 ¼ K1 x1
V = vapour rate (kmol/h).

F = feed rate (kmol/h).
K1 = equilibrium constant of the lighter component 1.
K2 = equilibrium constant of the heavier component 2.
z1 = composition of the lighter component 1 in the feed (molfraction).
x1 = composition of the lighter component in the liquid phase (molfraction).
y1 = composition of the lighter component in the vapour (molfraction).
Example 2.8.1: Flash calculations for a benzene–toluene mixture with

z1 = 0.3 = 30 mol% benzene in the vapour.
At the bubble point (98 °C) all is liquid.
At the dew point (104 °C) all is vapor.
Feed composition: 30 mol% benzene (z = 0.3 molfr.).
The vapour fraction at 100 °C has to be calculated:
t = 100 °C.
Ptot = 1000 mbar.
Vapour pressure of benzene p0B = 1807 mbar.
Vapour pressure of toluene p0T = 740 mbar.
Ptot = 1000 m:
p0B 1807
Benzene K1 ¼ ¼ ¼ 1:807
Ptot 1000
poT 740
Toluene K2 ¼ ¼ ¼ 0:74
Ptot 1000
V 0:3 1:8070:74
10:74 1
¼ ¼ 0:2864
F 1:807 1
Therefore, 28.64 mol% from the feed is vapour at 100 °C!

Calculation of the compositions in liquid and vapour at t = 100 °C:
1 0:74
x1 ¼ ¼ 0:2437
1:807 0:74
➔ 24.37 mol% benzene in the liquid.

y1 = 1.807 * 0.2437 = 0.44
➔ 44 mol% benzene in the vapour phase.
For the design of condensers and reboilers for mixtures the condensation curve
or the flash curve is required.
In these curves the vapour fraction V/F of the mixture based on the feed rate F is
plotted over the temperature of the mixture.
Example 2.8.2: Calculation of the condensation curve for the mixture ben-
zene–o–xylene.
Inlet composition: z = 0.576 = 57.6 mol% benzene with vapour mixture.
T (°C) K1 K2 V/F x1 y1
96 1.57 0.22 0 0.576 0.906
98.9 1.74 0.25 0.2 0.502 0.874
104 2 0.3 0.4 0.41 0.82
110.2 2.34 0.37 0.6 0.318 0.748
116.2 2.72 0.448 0.8 0.242 0.66
121 3.07 0.52 1 0.188 0.576
Calculation at T = 96 °C:
K1 K2
V z1 1K 1 0:576 1:570:22
¼ 2
¼ 10:22
¼0
F K1 1 1:57 1
1 K2 1 0:22
x1 ¼ ¼ ¼ 0:576 y1 ¼ K1 x1 ¼ 1:57 0:576 ¼ 0:906
K1 K2 1:57 0:22
Calculation at T = 98.9 °C:
V 0:576 1:740:25
10:25 1
¼ ¼ 0:2
F 1:74 1
1 0:25
x1 ¼ ¼ 0:502 y1 ¼ 1:74 0:502 ¼ 0:874
1:74 0:25
Calculation at T = 116.2 °C:
V 0:576 2:720:448
10:448 1
¼ ¼ 0:8
F 2:72 1
1 0:448
x1 ¼ ¼ 0:242 y1 ¼ 2:72 0:242 ¼ 0:66
2:72 0:448
Calculation at T = 121 °C:
V 0:576 3:070:52
10:52 1
¼ ¼1
F 3:07 1
1 0:52
x1 ¼ ¼ 0:188 y1 ¼ 3:07 0:188 ¼ 0:576
3:07 0:52
The condensation curve for the benzene–o–xylene mixture is depicted in

Fig. 2.9. The molar vapour fraction V/F drops from V/F = 1 at dew point at 121 °C
to V/F = 0 at bubble point 96 °C. The concentration of the light components of
benzene in the vapour and liquid phase against temperature are plotted in Fig. 2.10.
The required heat loads for the condensation of the benzene–o–xylene mixture
result from the enthalpies for the cooling of the vapour mixture along with the con-
densing and the cooling of the condensate. Figure 2.11 gives the calculated heat loads
for condensing a mixture of 1000 kg/h benzene and 1000 kg/h o–xylene as function
of temperature. In condensing and cooling from the dew point (121 °C) to the bubble
point (96 °C) of the mixture the required heat load increases from 0 to 230 kW.
Fig. 2.9 Condensation curve for the benzene–o–xylene mixture given in Example 2.8.2
Fig. 2.10 Benzene compositions in the vapour and liquid phase as function of temperature
Fig. 2.11 Heat load curve for the condensation of 2 tonnes/h of the benzene–o–xylene mixture as
a function of temperature
Example 2.8.3: Flash calculations for a mixture of 30 mol% butane and

70 mol% pentane.
Pressure (bar) Boiling point temperature (°C) Dew point temperature (°C)
xBut ¼ 0:3 xPen ¼ 0:7 yBut ¼ 0:3 yPen ¼ 0:7
1 19.5 28.9
2 41 50
3 55.3 64
4 66.3 74.7
Flash calculation at 4 bar:
Temperature (°C) Molar ratio V/F

66 0.0
67 0.061
68 0.149
69 0.242
70 0.341
71 0.448
72 0.567
73 0.703
74 0.861
75 1.0
V = vapour rate (kmol/h); F = feed rate (kmol/h)

Figure 2.12 depicts the bubble points and dew points of the mixture as a function
of pressure.
The flash curve of the mixture of 30 mol% butane and 70 mol% pentane at a
pressure of 4 bar is shown in Fig. 2.13.
Fig. 2.12 Bubble points and dew points of the butane–pentane mixture as function of pressure
Fig. 2.13 Flash curve for the V/F ratio of the butane–pentane mixture at 4 bar as a function of
temperature
2.9 Calculation of the Equilibrium and the Bubble and Dew Point … 59
2.9 Calculation of the Equilibrium and the Bubble

and Dew Point Temperatures of Ideal
Multi-component Mixtures
In principle the same laws and equations hold as in the calculations for binary
component mixtures.
Ptot ¼ x1 p01 þ x2 p02 þ x3 p03 þ xi p0i

p0i Ptot yi
yi ¼ K i xi ¼ xi xi ¼ yi ¼
Ptot p0i Ki
With the relative volatility a based on the vapour pressure p0h of the heaviest
component
p01 p02 p03
a1 ¼ a2 ¼ a3 ¼
p0h p0h p0h
a1 x 1 ax
y1 ¼ P ¼P
ð a1 x 1 þ a2 x 2 þ a3 x 3 Þ ai x i
y1 =a1 y=a
x1 ¼ P ¼P
ðy1 =a1 þ y2 =a2 þ y3 =a3 Þ yi =ai
Example 2.9.1: Calculation of the vapour phase composition for a benzene–

toluene–xylene mixture.
Benzene : 30 mol% x1 ¼ 0:3 p01 ¼ 1795 mbar at 100 C

Toluene : 60 mol% x2 ¼ 0:6 p02 ¼ 732 mbar at 100 C
Xylene : 10 mol% x3 ¼ 0:1 p03 ¼ p0S ¼ 306 mbar at 100 C
Calculation of the bubble pressure:
Pboil ¼ 0:3 1795 þ 0:6 732 þ 0:1 306 ¼ 1008 mbar
The bubble point lies at 100 °C and 1008 mbar total pressure.
What is the composition of the vapour?
p01 1795
Benzene y1 ¼ x1 ¼ 0:3 ¼ 0:534 molfr:
Ptot 1008
732
Toluene y2 ¼ 0:6 ¼ 0:435 molfr:
1008
306
Xylene y3 ¼ 0:1 ¼ 0:031 molfr:
1008
Cross-check calculation for the liquid composition x1 of benzene:
y1 Ptot 0:534 1008

x1 ¼ ¼ ¼ 0:3 molfr:
P01 1795
Alternative calculation of the vapour composition using the relative volatility a

based on the vapour pressure of the heaviest component xylene with
P0h = 306 mbar:
1795 732 306

a1 ¼ ¼ 5:87 a2 ¼ ¼ 2:39 a3 ¼ ¼1
306 306 306
0:3 5:87
y1 ¼ ¼ 0:534 molfr:
0:3 5:87 þ 0:6 2:39 þ 0:1 1
0:6 2:39
y2 ¼ ¼ 0:435 molfr:
0:3 5:87 þ 0:6 2:39 þ 0:1 1
0:1 1
y3 ¼ ¼ 0:031 molfr:
0:3 5:87 þ 0:6 2:39 þ 0:1 1
Cross-check calculation for x1:
y1 =a1 0:534=5:87
x1 ¼ P ¼ ¼ 0:3 molfr:
y=a 0:534=5:87 þ 0:435=2:39 þ 0:031=1
The calculation of the bubble and dew points follows using the equations from
Sects. 2.3 and 2.4.
The bubble point of a mixture is defined as follows: Ryi ¼ RKi xi ¼ 1
The bubble pressure can be calculated directly: Pboil ¼ x1 p01 þ x2 p02 þ x3 p03
The dew point of a mixture is defined as follows: R xi ¼ R yi= Ki ¼ 1
The dew pressure for the vapour composition z can be calculated directly:
X 1
1 z1 z2 z3 z4 zi
¼ þ þ þ Pdew ¼
Pdew p01 p02 p03 p04 p0i
Example 2.9.2: Calculation of the bubble point for a four-component mixture

C14–C17 at a pressure of 100 mbar.
x1 ¼ 0:315 x2 ¼ 0:276 x3 ¼ 0:227 x4 ¼ 0:182
The vapour pressures of the individual

P components are calculated.
The sum of the partial pressures Pi is plotted against temperature.
2.9 Calculation of the Equilibrium and the Bubble and Dew Point … 61
P P
Temperature (°C) Vapour pressure (mbar) xi p0i ¼ Pi
C14 C15 C16 C17
175 116.4 68.7 40.7 24.5 69.3 mbar
180 137.2 82.3 49.5 29.9 82.6 mbar
184 156.1 94.6 57.5 34.9 94.7 mbar
186 166.3 101.4 62 37.6 101.3 mbar
A bubble point temperature of 185.5 °C at 100 mbar is achieved by interpolation

(Fig. 2.14).
Fig. 2.14 Bubble point determination for the C14–C17 mixture
Example 2.9.3: Calculation of the dew point for a four-component C14–C17

mixture at 100 mbar.
Vapor composition : z1 ¼ 0:315 z2 ¼ 0:276 z3 ¼ 0:227 z4 ¼ 0:182
The vapour pressures

P are calculated using the Antoine Constants.
The quotient zi/p0i is calculated for different temperatures. P
At total pressure P = 100 mbar the dew point lies at the quotient zi/p0i =
1/100 = 0.01.
P
Temperature (°C) Vapor pressure (mbar) zi/p0i
C14 C15 C16 C17
200 255.0 160.2 101.3 62.7 0.0081
198 240.3 150.4 94.7 58.4 0.00866
196 226.4 141.1 88.4 54.4 0.00925
194 213.0 132.3 82.5 50.6 0.00985
192 200.5 123.9 76.9 47.1 0.0106
Fig. 2.15 Determination of the dew point temperature for a C14–C17 mixture
A dew point temperature of 193.6 °C at 100 mbar is achieved by interpolation

(Fig. 2.15).
2.10 Flash Calculations for Ideal Multi-component

Mixtures [2]
For mixtures with more than two components the calculation must be performed
iteratively. The individual V/F values of the different components are calculated
with an estimate of V/F. The sum of the V/F values of the component must equal
the V/F estimate.
V X zi L F 1
¼ ¼ 1¼
F 1 þ VK
L
i
V V V=L
! !
F zi F zi
yi ¼ xi ¼
V 1 þ VK
L
i
V Ki þ L
V
The following is required for the calculation: the vapour composition zi of the
individual components as mole fractions and the equilibrium constants Ki = p0i/Ptot.
The calculation is carried out iteratively with an estimate of V/F value.
L F
¼ 1
V V
2.10 Flash Calculations for Ideal Multi-component Mixtures [2] 63
V/F = molar ratio of the vapour rate V to the feed rate F.

F/V = molar ratio of the feed rate F to the vapour rate V.
L/V = molar ratio of the liquid rate L to the vapour rate V.
Example 2.10.1: Calculation of the L/V ratio.

V/F = 0.5 which means that 50% of the feed in kmol/h is vapour.
L F 1
¼ 1¼ 1¼1
V V 0:5
Example 2.10.2: Flash calculation for a four-component C14–C17 mixture.
Pressure: 100 mbar
Temperature: 188 °C
First estimate: V/F = 0.3; L/F = 2.33
zi
Component zi (molfr.) P0i (mbar) Ki 1 þ 2:33K1
i
C14 0.315 177 1.77 0.1359

C15 0.276 109 1.09 0.0879
C16 0.227 67 0.67 0.0507
C17 0.182 41 0.41 0.0272
0.3017 = V/Fi
P
V/Fi = 0.3017 > V/Fchosen ! choose the higher value for V/F ! V/
F = 0.32 ! L/V = 2.125
zi
Component zi (molfr.) 1 þ 2:125K1
i
C14 0.315 0.14315

C15 0.276 0.09357
C16 0.227 0.05442
C17 0.182 0.02944
0.32058 = V/Fi
P
V/Fi > V/Fchosen ! choose the higher value for V/F ! V/F = 0.33 !
L/V = 2.03
zi
Component zi (molfr.) 1 þ 2:03K1
i
C14 0.315 0.14671

C15 0.276 0.09641
C16 0.227 0.05632
C17 0.182 0.03058
0.33002 = V/Fi
Fig. 2.16 Flash curve for the C14–C17 mixture with a molar V/F ratio as a function of temperature
P
If the ratio PVi/Fi < V/F ! choose the lower value of V/F!
If the ratio Vi/Fi > V/F ! choose the higher value for V/F!
A deviation of 0.0005 is sufficiently accurate!
The flash curve for the C14–C17 mixture is depicted in Fig. 2.16.
2.11 Phase Equilibrium of Non-ideal Binary Mixtures
With non-ideal mixtures the laws of Raoult and Dalton are invalid. The partial
pressure lines are non-linear. Instead they curve upward or downward. Figure 2.17
shows the real partial pressures of methanol and water at 60 °C, considering the
activity coefficient and also the total pressure resulting from the partial pressures as
functions of the methanol composition.
With the ideal calculation the curves are linear according to the laws of Raoult
and Dalton. This is shown in Fig. 2.2. With the real calculation, considering the
activity factor c for the non-ideal behavior, the curves of partial pressure and total
pressure curve upward. A higher total pressure and a lower bubble point temper-
ature results for the mixture.
With azeotropic mixtures vapour pressure maxima and vapour pressure minima
can occur. This is shown in Figs. 2.18 and 2.19 for a mixture from A and B. The
calculation must be performed with a correction factor for the interaction of
the partial pressures. This correction factor is termed the activity coefficient c. The
activity coefficient is dependent on the composition in the liquid phase and the
temperature.
2.11 Phase Equilibrium of Non-ideal Binary Mixtures 65
Fig. 2.17 Partial pressure

and total pressure for the
non-ideal methanol–water
mixture at 60 °C as function
of methanol composition in
the liquid
Fig. 2.18 Partial pressures

for A and B and total pressure
A + B for an azeotropic
mixture with a bubble point
minimum
In the calculation of the equilibria for two-component and multi-component

mixtures the interactions of the partial pressures are considered using the activity
coefficients. Section 2.12 shows how the activity coefficient is calculated using
different models. The following table of activity coefficients for methanol and water
at 60 °C illuminates the influence of the composition on the activity coefficient.
Fig. 2.19 Partial pressures

for A and B and total pressure
A + B for an azeotropic
mixture with a bubble point
maximum
Methanol composition Activity coefficient of methanol Activity coefficient of water

(molfraction)
0.01 2.3069 1.002
0.05 2.0657 1.0035
0.1 1.8356 1.0131
0.2 1.5263 1.0462
0.4 1.2113 1.152
0.6 1.0737 1.2967
0.8 1.0153 1.4737
0.9 1.0035 1.5737
0.99 1.000 1.67
The correction of the partial pressures of the components of a mixture using the
activity coefficient c influences the vapour–liquid equilibrium as follow:
Ptot ¼ c1 x1 p01 þ c2 x2 p02 ðmbarÞ
y1 Ptot ¼ c1 x1 p01
Vapor composition:
x1 p01 c1 x2 p01 c2
y1 ¼ ðmolfr:Þ y2 ¼ ðmolfr:Þ
Ptot Ptot
Equilibrium constant:
p01 c1 p02 c2
K1 ¼ K2 ¼
Ptot Ptot
Separation factor = Relative volatility a:
K1 c1 P01
a¼ ¼
K2 c2 P02
K1 = equilibrium factor for component 1

K2 = equilibrium factor for component 2
Ptot = total pressure in the system (mbar)
p01 = vapour pressure of component 1 (mbar)
p02 = vapour pressure of component 2 (mbar)
x1 = liquid composition of component 1
y1 = vapour composition of component 1
x2 = liquid composition of component 2
y2 = vapour composition of component 2
c1 = activity coefficient of component 1
c2 = activity coefficient of component 2
The activity coefficient c is strongly dependent on composition and can be
calculated using different models: Wilson, NRTL, Uniquac, and Unifac.
Example 2.11.1: Non-ideal equilibrium for methanol–water
Below is the equilibrium calculation for a methanol [1]–water [2] mixture at
92.1 °C and Ptot = 1000 mbar.
Required data for calculation:
x1 ¼ 0:0535 x2 ¼ 0:9465
c1 ¼ 1:848 c2 ¼ 1:004
p01 ¼ 2:817 mbar p02 ¼ 756:4 mbar
1:848 0:0535 2817

y1 ¼ ¼ 0:279
1000
1:004 0:9465 756:4
y2 ¼ ¼ 0:721
1000
1:848 2817 1:004 756:4
K1 ¼ ¼ 5:218 K2 ¼ ¼ 0:761
1000 1000
K1 5:218
a¼ ¼ ¼ 6:853
K2 0:761
For comparison purposes the ideal relative volatility, without considering the
activity coefficient, is calculated below:
p01 2:817
aideal ¼ ¼ ¼ 3:724
p02 756:4
Conclusion: The influence of c is substantial! Due to the activity coefficient

the separation factor is nearly doubled. The activity coefficient c depends on the
temperature and very strongly on the composition in the liquid phase.
Example 2.11.2: Activity coefficient at different compositions.

Influence of the composition on the activity coefficient of methanol [1] in water [2]
at 30 °C.
x1 = methanol composition in the liquid c1 = activity coefficient of methanol
x1 0.001 0.01 0.1 0.15 0.2

c1 2.596 2.521 1.968 1.765 1.609
The dependency on the temperature is shown in the following table for x = 0.1.
Temperature 30 °C 60 °C 85 °C
c according to Wilson 1.968 1.836 1.744
Remark At an azeotropic composition y = x and a = 1. Thus it follows that )

p01/p02 = c2/c1
An azeotropic point is reached if the activity coefficient in the diluted phase is
greater than the vapour pressure ratio. In the following Figs. 2.20, 2.21, 2.22 and
2.23 some vapour–liquid equilibria of non-ideal mixtures are depicted. To illumi-
nate the pressure dependency of the phase equilibrium the equilibria at different
pressures are shown.
Fig. 2.20 Vapour–liquid

equilibrium of acetone–water
at different pressures
Fig. 2.21 Equilibrium of the

azeotropic ethanol–water
mixture at different pressures

azeotropic ethanol–benzene
mixture with a minimum
bubble point
Other examples for azeotropes with minimum bubble points are:

Ethylacetate–ethanol
Isopropanol–water
Methanol–benzene
Water–butanol
Methanol–trichlorethylene
Sulphur carbon–acetone

azeotropic acetone–
chloroform mixture at
1013 bar with a maximum
bubble point
Other examples of azeotropes with maximum bubble points are:

Saltpetre acid–water
Water–formic acid
2.12 Calculation of the Activity Coefficients
The calculation of the activity coefficients using different models is described in the
Refs. [3–6]. The required data for the calculations are given in [7]. In the following
text the calculation of the activity coefficients using 3 models is shown. A fourth
method is the Unifac Model, a group contribution method which does not require
measured equilibrium data.
2.12 Calculation of the Activity Coefficients 71
2.12.1 Calculation According to Wilson for Miscible

Components [8]

V2 k12
K1;2 ¼ exp
V1 RT

V1 k12
K2;1 ¼ exp
V2 RT

K1;2 K2;1
ln c1 ¼ ln ðX1 þ X2 K1;2 Þ þ X2
X1 þ X2 K1;2 X2 þ X1 K2;1
ln c1
1 ¼ 1 ln K1;2 K2;1
Required data:
k12 and k21 = interaction parameter.
v1 and v2 = molar volume of the liquid.
Example 2.12.1: Methanol [1]–water [2] at 30 °C and x1 = 0.1.
k12 ¼ 107:389 v1 ¼ 40:73

k21 ¼ 469:578 v2 ¼ 18:07

18:07 107:389
K1;2 ¼ exp ¼ 0:371
40:73 1:987 303

40:73 469:578
K2;1 ¼ exp ¼ 1:033
18:07 1:987 303

0:371 1:033
ln c1 ¼ ln ð0:1 þ 0:371 0:9Þ þ 0:9
0:1 þ 0:371 0:9 1:033 0:1 þ 0:9
Fig. 2.24 Activity coefficients of methanol and water at 60 °C as a function of the methanol
composition in the mixture
ln c1 = 0.677 ) c1 = 1.968
ln c∞ = 1 - ln 0.371 – 1.033 = 0.958 c∞ = 2.607
c∞ = activity coefficient at infinite dilution.
In Fig. 2.24 the activity coefficients of methanol and water at different compo-
sitions are shown.
Example 2.12.2: Calculation of the vapour–liquid equilibrium at 75.7 °C.
Methanol composition x1 = 0.3909
Water composition x2 = 0.6091
Methanol vapour pressure p01 = 1.526.8 mbar
Water vapour pressure p02 = 413.8 mbar
K1,2 = 0.47525
K2,1 = 0.98356
Ptot = 1013 mbar
Calculation of the activity coefficient c1 of methanol:

K1;2 K2;1
ln c1 ¼ ln x1 þ x2 K1;2 þ x2
x1 þ x2 K1;2 x2 þ x1 K2;1
ln c1 ¼ lnð0:3909 þ 0:6091 0:47525Þ

0:47525 0:98356
þ 0:6091
0:3909 þ 0:6091 0:47525 0:6091 þ 0:3909 0:98356
ln c1 ¼ 0:2076 c1 ¼ 1:231
Calculation of the activity coefficient c2 of water:

K1;2 K2;1
ln c2 ¼ ln x2 þ x1 K2;1 x1
x1 þ x2 K1;2 x1 K2;1 þ x2
ln c2 ¼ ln ð0:6091 þ 0:3909 0:98356Þ

0:47525 0:98356
0:3909
0:3909 þ 0:6091 0:47525 0:6091 þ 0:3909 0:98356
ln c2 ¼ 0:120359 c2 ¼ 1:128
Calculation of the methanol composition y1 and the water composition y2 in the

vapour:
x1 p01 c1 0:3909 1526:8 1:231
y1 ¼ ¼ ¼ 0:72 molfr:
Ptot 1013
x2 p02 c2 0:6091 413:8 1:128
y2 ¼ ¼ ¼ 0:28 molfr:
Ptot 1013
Calculation of the vapour composition with relative volatility a:
c1 p01 1:231 1526:8

a¼ ¼ ¼ 4:027
c2 p02 1:128 413:8
a x 4:027 0:3909
y1 ¼ 1;2 1 ¼ ¼ 0:72
1 þ a1;2 1 x1 1 þ ð4:027 1Þ 0:3909
Fig. 2.25 Relative volatility a for methanol–water as function of the methanol composition in the
liquid phase
From Fig. 2.25 it can be seen that the separation factor a for the non-ideal
mixture methanol–water decreases with increasing methanol composition.
2.12.2 Calculation According to NRTL for Partially

Miscible Components with Two Liquid Phases [9]
g12 g21
s12 ¼ s21 ¼
RT RT
G12 ¼ expða12 s12 Þ G21 ¼ expða21 s21 Þ
" 2 #
G21 s12 G12
ln c1 ¼ X2 s21
2
þ
X1 þ X2 þ G21 ðX2 þ X1 G12 Þ2
c1 ¼ s21 þ s12 G12
Required data:
g12 and g21 = interaction parameter
a12 = a21 = non-randomness factor
Example 2.12.2.1: Methanol [1]–water [2] at 30 °C and x1 = 0.1.
g12 = −253.965 cal/mol g21 = 845.16 cal/mol a12 = 0.299
253:965 845:16
s12 ¼ ¼ 0:422 s21 ¼ ¼ 1:4
1:987 303 1:987 303
G12 ¼ expð0:299 0:422Þ ¼ 1:134
G21 ¼ expð0:299 1:404Þ ¼ 0:657
" 2 #
0:657 0:422 1:134
ln c1 ¼ 0:9 1:404
2
þ
0:1 þ 0:9 0:657 ð0:9 þ 0:1 1:134Þ2
ln c1 = 0.65 ) c1 = 1.915
ln c∞ ∞
1 = 1.404 + (−0.422) * 1.134 = 0.925 ) c1 = 2.522
2.12.3 Calculation According to Uniquac for Components

with a Miscibility Gap
u
u
12 21
s12 ¼ exp s21 ¼ exp
RT RT
r i xi qi x i
ui ¼ P #i ¼ P
r i xi qi x i
z
li ¼ ðri qi Þ ðri 1Þ
2
ln c1 ¼ ln c1C þ ln c1R
u1 z #1 r1
ln c1C ¼ ln þ q1 ln þ u2 ðl1 l2 Þ
x1 2 u1 r2
ln c1R ¼ q1 lnð#1 þ s21 #2 Þ

s21 s12
þ #2 q 1
#1 þ s21 #2 #2 þ s12 #1
Required data:
u12 and u21 = interaction parameters.
r = volume parameter (van der Waals).
q = surface parameter (van der Waals).
z = coordination number (mostly = 10).
Example 2.12.3.1: Calculation of activity coefficient of methanol in a metha-
nol–water mixture at 30 °C.
u12 ¼ 328:451 cal=mol u21 ¼ 506:088 cal=mol

r1 ¼ 1:4311 r2 ¼ 0:92
q1 ¼ 1:432 q2 ¼ 1:40
Methanol composition xMeth = 0.1 molfr. = 10 mol%

0:1 1:4311
u1 ¼ ¼ 0:147
0:1 1:4311 þ 0:9 0:92
u2 ¼ 1 0:1473 ¼ 0:853
0:1 1:432
#1 ¼ ¼ 0:102
0:1 1:432 þ 0:9 1:4
#2 ¼ 1 0:102 ¼ 0:898
l1 = 10/2 * (1.4311 − 1.432) − (1.4311 − 1) = −0.4356

l2 = 10/2 * (0.92 − 1.40) − (0.92 − 1) = −2.32

328:451
s12 ¼ exp ¼ 1:7255
1:987 303

506:088
s12 ¼ exp ¼ 0:4314
1:987 303
0:147 10 0:102
ln c1C ¼ ln þ 1:4311 ln
0:1 2 0:147
1:4311
þ 0:853 0:4356 ð2:32Þ ¼ 0:471
0:92
ln c1R ¼ 1:432 ln ð0:102 þ 0:4314 0:898Þ þ 0:898 1:432

0:4314 1:7255
¼ 0:0908
0:102 þ 0:898 0:4314 0:898 þ 0:102 1:7255
ln c1 = 0.477 + 0.0908 = 0.5678 ) c1 = 1.764
2.12.4 Critical Comparison of the Activity Coefficients

Calculated Using Different Models
The available models for equilibria calculations of distillation and absorption plants
or the design of condensers and evaporators can be simplified with the use of
computer. Substantial discrepancies can be seen if the results of the different cal-
culation methods are compared. This is shown in the following Examples 2.12.4.1
and 2.12.4.2.
Example 2.12.4.1: Activity coefficients for a pentane–toluene mixture.
Composition: 10 mol% Pentane, 90 mol% Toluene
Fig. 2.26 Activity coefficient of pentane in toluene as function of temperature, using different
models
Interaction parameters:
Wilson: k11 = 0 k12 = −296.9388 k21 = 1145.5506 k22 = 0

NRTL g11 = 0 g12 = 1401.7145 g21 = −490.4151 g22 = 0 a = 0.298
Uniquac u11 = 0 u12 = 869.1587 u21 = −436.4687 u22 = 0
Conclusion: The activity coefficients calculated using different models for

pentane in toluene deviate considerably (Fig. 2.26). The activity coefficient of
pentane becomes greater with increasing temperature. Additionally the
non-temperature dependent activity coefficients of pentane are calculated according
to Margules and van Laar.
Margules: c = 1.44 for Pentane.
van Laar: c = 1.47 for Pentane.
The activity coefficient of toluene lies constantly at 1.
Example 2.12.4.2: Activity coefficients for the a hexane, ethyl acetate, and
toluene mixture
Composition:
Hexane: x = 0.3 = 30 mol%.
Ethyl acetate: x = 0.3 = 30 mol%.
Toluene: x = 0.4 = 40 mol%.
Interaction parameter Wilson Uniquac NRTL Alpha

1/1 0 0 0 0
1/2 107.1217 302.7052 427.6309 0.2995
1/3 21.0210 112.6399 130.3146 0.3016
2/1 618.7792 −83.8122 255.6205 0.2995
2/2 0 0 0 0
2/3 135.1766 −62.3228 63.3896 0.3021
3/1 246.4956 −57.7374 131.5420 0.3016
3/2 15.6079 63.3994 86.1714 0.3021
3/3 0 0 0 0
Calculation results:
Wilson Uniquac NRTL

20 °C 30 °C 20 °C 30 °C 20 °C 30 °C
Hexane 1.373 1.36 1.37 1.358 1.376 1.363
Ethyl acetate 1.264 1.257 1.251 1.246 1.269 1.26
Toluene 1.031 1.03 1.017 1.018 1.029 1.028
The deviations range 0.2–1%!
2.13 Bubble Point, Dew Point, and Flash Separation

for Non-ideal Binary Mixtures
For non-ideal mixtures the influence of the activity coefficient c must be considered
in the calculation of the partial pressure.
Example 2.13.1: Bubble point calculation with the activity coefficient for the
methanol [1]–water [2] mixture.
x1 ¼ 0:1 x2 ¼ 0:9 t ¼ 87:8 C Ptot ¼ 1000 mbar

c1 ¼ 1:705 c2 ¼ 1
p01 ¼ 2438 mbar p02 ¼ 646 mbar
Pboil = x1 * c1 * p01 + x2 * c2 * p02 = 0.1 * 1.705 * 2438 + 0.9 * 1 *

646 = 997 mbar 1 bar
Cross-check calculation of the bubble point:
c1 p01 1:705 2438 1 646

K1 ¼ ¼ ¼ 4:167 K2 ¼ ¼ 0:64
Ptot 1000 1000
R Ki * xi = 0.1 * 4.167 + 0.9 * 0.64 = 1

Therefore, the bubble point condition is fulfilled at 87.8 °C!
Without considering the activity coefficient c a bubble point temperature of

93.1 °C rather than one of 87.8 °C is obtained.
Example 2.13.2: Dew point calculation with the activity coefficient c for the
methanol [1]-water [2] mixture.
y1 ¼ 0:1 y2 ¼ 0:9 t ¼ 97:1 C Ptot ¼ 1:000 mbar
c1 ¼ 2:2 c2 ¼ 1:0
p01 ¼ 3:343 mbar p02 ¼ 910:3 mbar
1 y1 y2 0:1 0:9
¼ þ ¼ þ ¼ 0:001 Pdew ¼ 1 bar
Pdew c1 p01 c2 p02 2:2 3343 910:3
Cross-check calculation of the dew point:
2:2 3343 1 910:3

K1 ¼ ¼ 7:373 K2 ¼ ¼ 0:9125
1000 1000
X yi 0:1 0:9
¼ þ ¼1
Ki 7:373 0:9125
Therefore, the dew point condition is fulfilled at 97.1 °C!

Example 2.13.3: Flash calculation for the methanol [1]–water [2] mixture
Ptot ¼ 1 bar ¼ 1000 mbar t ¼ 92:1 C Feed rate ¼ 100 kmol=h
Feed compositions: z1 ¼ 0:1 molfr: z2 ¼ 0:9 molfr:
c1 ¼ 1:848 c2 ¼ 1:004
p01 ¼ 2823:7 mbar p02 ¼ 758:3 mbar
1:848 2823:7 1:004 758:3

K1 ¼ ¼ 5:218 K2 ¼ ¼ 0:7614
1000 1000
K1 K2
V z1 1K 1 0:1 5:2180:7614
10:7614 1
¼ 2
¼ ¼ 0:2058
F K1 1 5:218 1
At 92.1 °C 20.58% of the feed is vapour.

Vapour rate V = 0.2058 * 100 = 20.58 kmol/h
Liquid rate L = 100–20.58 = 79.42 kmol/h
Composition calculation in the liquid and the vapour:
1 K2 1 0:7614
x1 ¼ ¼ ¼ 0:0535 molfr:
K1 K2 5:218 0:7614
x2 ¼ 10:0535 ¼ 0:9465ðmolfr:Þ ¼ 94:65 mol%
y1 ¼ K1 x1 ¼ 5:218 0:0535 ¼ 0:279 molfr: ¼ 27:9 mol%

y2 ¼ K2 x2 ¼ 0:7614 0:9465 ¼ 0:721 molfr: ¼ 72:1 mol%
2.13 Bubble Point, Dew Point, and Flash Separation … 79
Without consideration being given to the activity coefficient c, the following

incorrect results at 92.1 °C are obtained:
K1 ¼ 2:74 K2 ¼ 0:758
V ¼0 L ¼ 100 kmol/h
Nothing is vaporized because the bubble point lies with c = 1 at 93.1 °C above
92.1 °C.
2.14 Non-ideal Multi-component Mixtures
The equilibria calculation of mixtures with more than two components is very
complex and therefore done using computers. The compositions, the temperature,
and the Antoine Constants for the vapour pressure and the interaction parameters
for the equilibrium must be input. The activity coefficients are strongly dependent
on the composition of the liquid phase. Example 2.14.1 shows how strongly the
activity coefficient of water increases with decreasing water composition in the
liquid phase.
Example 2.14.1: Activity coefficient of water at different compositions.
Activity coefficient c
x (molfr.) 30 °C 50 °C
n-Heptane 0.2 1.1 1.014
Methyl ethyl ketone 0.2 1.138 1.13
Ethyl acetate 0.2 1.14 1.142
Toluene 0.2 1.63 1.606
Water 0.2 4.287 4.22
x (molfr.) 30 °C 50 °C
n-Heptane 0.225 1.138 1.128
Ethyl acetate 0.225 1.102 1.104
Toluene 0.225 1.338 1.323
Water 0.1 6.055 5.912
x (molfr.) 30 °C 50 °C
n-Heptane 0.2475 1.262 1.243
Ethyl acetate 0.2475 1.096 1.098
Toluene 0.2475 1.133 1.125
Water 0.01 8.912 8.578
Example 2.14.2: Flash calculation for a four-component mixture with differ-

ent compositions at 1 bar total pressure as function of temperature.
Mixture 1 x (molfr.) Activity coefficient
n-Heptane 0.25 1.65
Methyl ethyl ketone 0.25 1.331
Ethyl acetate 0.25 1.273
Toluene 0.25 0.974
Mixture 2 x (molfr.) Activity coefficient
n-Heptane 0.1 1.83
Methyl ethyl ketone 0.1 1.314
Ethyl acetate 0.4 1.112
Toluene 0.4 1.013
In Fig. 2.27 the flash curves for both of the different compositions are shown.
Figure 2.28 shows how the composition of a non-ideal mixture of n-heptane,
methyl ethyl ketone, ethyl acetate, and toluene changes in nine consecutive vapor-
ization stages. After four vaporization stages the compositions scarcely change.
If toluene is distilled off then the composition of the mixture remains constant:
Ethyl acetate: 45:7 mol%

Methyl ethyl ketone: 37:5 mol%
n-Heptane: 16:8 mol%
The composition curves in Fig. 2.28 result from Fig. 2.29 with the equilibrium
constants K of the different components. After four vaporization stages the toluene
has vanished and the K values lie at 1. At K = 1 the vapour composition y equals
the liquid composition x. This is a ternary azeotropic mixture.
Fig. 2.27 Flash curves for two non-ideal mixtures as a function of temperature
2.14 Non-Ideal Multi-component Mixtures 81
Fig. 2.28 The behaviour of the compositions of the four components with increasing number of
vaporization stages
Fig. 2.29 Equilibrium constants of the components as a function of the vaporization stages
Although the three light components have different vapour pressures the sepa-
ration factor a is set to 1 by the activity coefficient.
The determining factor for the separation is the relative volatility.
Bubble point (°C) Mole weight

Ethyl acetate 77 88
Methyl ethyl ketone 80 72
Heptane 98.4 100
Toluene 110.6 92
Example 2.14.3: Calculation of the relative volatility a at 73 °C and

Ptot = 977 mbar.
p0 (mbar) p0/Ptot c K
1. n-Heptane 448.7 0.459 2.155 0.99
2. Methyl ethyl ketone 800.5 0.827 1.206 0.998
3. Ethyl acetate 878.8 0.899 1.117 1.005
4. Toluene 302.4 0.309 1.017 0.315
c1 P01 2:155 448:7

a1=2 ¼ ¼ ¼1
c2 P02 1:206 800:5
c P02 1:206 800:5
a2=3 ¼ 2 ¼ ¼ 0:98
c3 P03 1:117 878:8
c P01 2:155 448:7
a1=3 ¼ 1 ¼ ¼ 0:985
c3 P03 1:117 878:8
c P03 1:117 878:8
a3=4 ¼ 3 ¼ ¼ 3:19
c4 P04 1:017 302:4
c P01 2:155 448:7
a1=4 ¼ 1 ¼ ¼ 3:19
c4 P04 1:017 302:4
c P02 1:206 800:5
a3=4 ¼ 2 ¼ ¼ 3:19
c4 P04 1:017 302:4
Conclusion
The first three components with a separation factor a = 1 do not allow separation.
However, toluene with a separation factor a = 3.19 allows very simple separation.
Figures 2.30 and 2.31 show the calculation results for another non-ideal
four-component mixture with non-ideal behaviour.
Fig. 2.30 Equilibrium

factors K for the different
components of the mixture
dependent of the temperature
References 83
Fig. 2.31 Flash curve for the

non-ideal, four-component
mixture as function of
temperature
References
1. E.J. Henley, J.D. Seader, Equilibrium Stage Separations in Chemical Engineering (Wiley,
New York, 1981)
2. B.D. Smith, Design of Equilibrium Stage Processes (McGraw-Hill, New York, 1963)
3. J. Gmehling, B. Kolbe, Thermodynamik (Georg Thieme Verlag, Stuttgart, 1988)
4. J.M. Prausnitz, J. Gmehling, Thermische Verfahrenstechnik Phasengleichgewichte
(vt-Hochschulkurs III, Krausskopf-Verlag Mainz, 1980)
5. J. Gmehling, B. Kolbe, M. Kleiber, J. Rarey, Chemical Thermodynamics for Process
Simulation (Wiley-VCH Verlag, Weinheim, 2012)
6. G. Mehos, Estimate binary equilibrium coefficients. Chem. Eng. 101 (1996)
7. J. Gmehling, U. Onken, Vapor-Liquid Equilibrium Data Collection, in DECHEMA-Chemistry
Data Series ab (1977)
8. M. Hirata, Sh. Ohe, K. Nagahama, Vapor-Liquid Equilibria (Elsevier, New York, 1975)
9. H. R. Null, Phase Equilibrium in Process Design (Wiley-Intercsience, New York, 1970)
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Chapter 2

Equilibria, Bubble Points, Dewpoints,

2.1 Vapour Pressure Calculations

Example 1.1: Calculation of the vapour pressures of benzene and toluene

Temperature Benzene vapour pressure Toluene vapour pressure

2.2 Phase Equilibrium of Ideal Binary Mixtures

© Springer International Publishing AG 2017 39

Fig. 2.1 Vapour pressure of

Raoult (Fig. 2.2):

Equilibrium equation: yi * Ptot = pi = xi * p0i

yi = concentration of the component i in the vapour phase (mole fraction)

x1 ¼ 0:6 p01 ¼ 800 mbar

Calculation of the partial pressures according to Raoult:

p1 ¼ x1 p01 ¼ 0:6 800 ¼ 480 mbar

Calculation of the vapour concentration according to Dalton:

In order to simplify the calculation of phase equilibria a separation factor a is

Fig. 2.2 Graphical

Fig. 2.3 Vapour pressure curves of benzene, toluene, and xylene

Example 2.2.2: Calculation of the vapour composition y1 for a liquid composition

In American literature the equilibrium constant K, which is deﬁned as the ratio of

Example 2.2.3: Equilibrium calculation with the equilibrium constant K.

x1 ¼ 0:6 p01 ¼ 800 mbar p1 ¼ 0:6 800 ¼ 480 mbar

Calculation of the vapour composition y:

y1 ¼ K1 x1 ¼ 0:8 0:6 ¼ 0:48 molfr:

Cross-check calculation of x1:

2.3 Bubble Point Calculation

The bubble point of a mixture is deﬁned as follows:

The bubble pressure Pboil can be calculated directly.

Pboil ¼ x1 p01 þ x2 p02

A simple method for calculating the bubble temperature of a mixture is the

First choice : t ¼ 95 C p0B ¼ 1573 mbar p0T ¼ 634:4 mbar

Second choice : t ¼ 100 C p0B ¼ 1807 mbar p0T ¼ 740 mbar

Fig. 2.5 Bubble point determination by graphical interpolation

Third choice : t ¼ 98 C p0B ¼ 1710 mbar p0T ¼ 696 mbar

Cross-check calculation of the bubble point at 98 °C:

The bubble point speciﬁcation is therefore fulﬁlled.

2.4 Dew Point Calculation

The dew point of a mixture is deﬁned as follows:

The dew point pressure Pdew can be calculated directly.

First choice : t ¼ 100 C p0B ¼ 1807 mbar p0T ¼ 740 mbar

Second choice : t ¼ 104 C p0B ¼ 2013 mbar p0T ¼ 834:4 mbar

Third choice : t ¼ 103:8 C p0T ¼ 2002 mbar p0T ¼ 829 mbar

Cross-check calculation for the dew point at 103.8 °C:

The condition for the dew point is fulﬁlled.

Fig. 2.6 Dew point determination by graphical interpolation

2.5 Dew Point Calculation of Vapour

PD = sum of the vapours partial pressures (mbar)

Calculation of the dew point pressure without inert gas:

Calculation of the dew point pressure with inert gas:

Example 2.5.1: Dew point pressure calculation without inert gas.

40 Vol% vapour þ 60 Vol% inert gas

z1 ¼ 0:4 y1 ¼ 0:4 0:413 ¼ 0:165 molfr:

2.6 Dew and Bubble Point Lines of Ideal Binary Mixtures

Equation for the boiling point line:

The boiling point temperature increases with decreasing composition of

p01 Ptot p02

Temperature (°C) p01 (mbar) p02 (mbar) x1 (molfr.) y1 (molfr.)

Bubble point line : x1 ¼ f ðtemperatureÞ Dew point line : y1 ¼ f ðtemperatureÞ