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Chemical Engineering Thermodynamics (CHE 303)

Lecture 25: Vapor-Liquid Equilibrium II
Dr. Wael A. Fouad
Assistant Professor
Chemical Engineering Department
King Fahd University of Petroleum and Minerals
 Chapter 13:

Thermodynamic Formulations of
Vapor-Liquid Equilibrium –
Part I

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 Simple models for calculating VLE

• Simple models that can provide good correlation of

experimental VLE data
• Dalton’s law N
p   pi
i 1
• Raoult’s law
yi P  pi  xi pisat i 1,2,..., N

Saturated pressure from Antoine´s equation

B
ln p sat / kPa  A  (T in C ) When are they
T C
applicable? -
• Henry’s law assumptions
yi P  pi  xi H i i 1,2,..., N 3
 VLE calculations

• Pure liquids vaporize at constant T (boiling point)

• Liquid mixtures vaporize over a range of T due to the fact
that as vaporization proceeds liquid composition
changes (richer in the less volatile species), whereby vapor
composition ≠ liquid composition

Tie-lines
(horizontal)

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 VLE calculations (binary mixtures)

• Liquid phase: y1 p  x1 p1sat

y2 p  x2 p2sat +
N
 y1  y2  p  x p sat
1 1  x2 p sat
2
p   xi pisat
=1 i

p  1  x2  p1sat  
 x2 p2sat  p1sat  x2 p2sat  p1sat (= straight line)

y1 p y2 p
• Vapor phase: x1  sat x2  sat
p1 p2
y1 p y2 p 1 1  y2  y2
1  x1  x2  sat  sat  sat
 sat
p1 p2 p p1 p2
(= hyperbole)
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 Raoult’s law - example

• Pxy diagram for acetonitrile(1)/nitromethane(2) at 75C as given

by Raoult’s law

• Liquid phase –
straight line

• Vapor phase –
hyperbole

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 Bubble point and dew point

• When a liquid is heated slowly at constant pressure, the

temperature at which the first vapor bubble forms is the
bubble-point temperature of the liquid at the given pressure
• When a vapor is cooled slowly at constant pressure, the
temperature at which the first liquid droplet forms is the dew-
point temperature of the vapor at the given pressure
• When a liquid is decompressed (pressure decreases) at constant
temperature, the pressure at which the first vapor bubble forms
is the bubble-point pressure of the liquid at the given
temperature
• When a vapor is compressed (pressure increases) at constant
temperature, the pressure at which the first liquid droplet forms
is the dew-point pressure of the liquid at the given
temperature 7

Concepts from Principles of Chemical Engineering

 Bubble/dew point calculations

• Phase equilibrium calculations include:

- Bubble point pressure:
Calculate yi and p, given xi and T
- Dew point pressure:
Calculate xi and p, given yi and T
- Bubble point temperature:
Calculate yi and T, given xi and p
- Dew point temperature:
Calculate xi and T, given yi and p

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 Bubble point calculations

• Bubble point pressure (find pbp and yi for given T and xi):
• Raoult’s law for each species i: pi  yi p  xi p i
sat

• Taking the summation in both sides of the equation: p   xi pisat

i
• Thus, for a known liquid composition and temperature, we calculate
the bubble pressure (pbp)
xi pisat
• The composition of the vapor (bubble) formed is: yi 
pbp
• Bubble point temperature (find Tbp and yi for given p and xi)

• Using: p   xi p i
sat
T 
i
• Trial and Error: Select a T → find pisat (using Antoine equation) →
see if the relation above is satisfied and continue until convergence
xi pisat Tbp 
• The composition of the vapor formed is: yi  9
p
 Dew point calculations

• Dew point pressure (find pdp and xi for given T and yi):
• Raoult’s law for each species i: xi  yi p pi
sat

• Taking the summation in both sides of the equation:

1   yi p p
1
sat
p
i
i
 i i
y
i
p sat

• Thus, for a known vapor composition and temperature T, we calculate

the dew pressure (pdp)
• The composition of the liquid (droplet) formed is: xi  yi pdp pi
sat

• Dew point temperature (find Tdp and xi for given p and

y•i): Using: 1   yi p pisat
i
• Trial and Error: Select a T → find pisat (using Antoine equation) →
see if the relation above is satisfied and continue until convergence
• The composition of the liquid formed is: xi  yi p pisat Tdp  10
 Example 2- Chapter 10

Construction of pxy-diagram:
• Binary system acetonitrile (1) – nitromethane (2) conforms
closely to Raoult’s law. Vapor pressures for the pure species are
given by the following Antoine equations:
2945.47
ln P / kPa 14.2724  o
sat

T / C  224
1

2972.64
ln P2 / kPa 14.2043  o
sat

T / C  209
• Prepare a graph showing p versus x1 and p versus y1 for a
temperature of 75 oC

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 Example 2- Chapter 10

• At 75 oC, Antoine equations predict that:

p1sat  83.21 kPa , p2sat  41.98 kPa
• Bubble point curve:
p  x1 p1sat  x2 p2sat  x1 p1sat  (1  x1 ) p2sat  p2sat  ( p1sat  p2sat ) x1
• Corresponding vapor phase composition:
x1 p1sat
y1 
p
• E.g. For x1=0.6, p=66.72 kPa and y1=0.7483
• Based on the generated p, y1 data for different
values of x1 the pxy-plot is constructed
• Constant T expansion path (abcd)

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 Example 2- Chapter 10

• At 75 oC, Antoine equations predict that:

p1sat  83.21 kPa , p2sat  41.98 kPa
• Dew point curve:
p  1 /( y1 / psat
1  y2 / p )
sat
2
• Corresponding liquid phase composition:
y1 p
x1  sat
p1
• E.g. For y1=0.6, p=59.74 kPa and x1=0.4308
• Based on the generated p, x1 data for different
values of y1 the pxy-plot is constructed

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 Example 3 – Chapter 10

Construction of Txy-diagram:
• Binary system acetonitrile (1) – nitromethane (2) conforms
closely to Raoult’s law. Vapor pressures for the pure species are
given by the following Antoine equations:
2945.47
ln P / kPa 14.2724  o
sat

T / C  224
1

2972.64
ln P2 / kPa 14.2043  o
sat

T / C  209
• Prepare a graph showing T versus x1 and T versus y1 for a
pressure of 70 kPa

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 Example 3 – Chapter 10

• At 70 kPa, Antoine equations predict that:

T1sat  69.84 o C, T2sat  89.58 o C
• Choose a temperature between T1sat and T2sat, e.g. 78 0C:
   
p1sat 78o C  91.76 kPa , p2sat 78o C  46.84 kPa
• Calculate liquid composition:
p  x1 p1sat  x2 p2sat  x1 p1sat  (1  x1 ) p2sat 
p2sat  ( p1sat  p2sat ) x1 x1  0.5156
• Calculate vapor composition:
x1 p1sat
y1  y1  0.6759
p

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