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Lecture 24 CHE303

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31 views16 pages

Lecture 24 CHE303

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Abdullah Altwirqi
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Chemical Engineering Thermodynamics (CHE 303)


Lecture 24: Vapor-Liquid Equilibrium I
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

2
Systems with variable composition

• The majority of processes in chemical industry (distillation,


absorption, extraction, reaction) involves phases of
different composition into contact
• Mass transfer depends heavily on the departure of the
system from equilibrium
• Phase equilibrium is a strong function of temperature and
pressure
• Most common type of phase equilibrium in chemical
industry is the Vapor / Liquid Equilibrium (VLE)
• Other types of phase equilibria include:
• Liquid / Liquid Equilibrium (LLE)
• Solid / Liquid Equilibrium (SLE)
• Solid / Vapor Equilibrium (SVE)
• Vapor / Liquid / Liquid Equilibrium (VLLE) 3
Nature of equilibrium

• Equilibrium: A static condition where no changes occur in


the macroscopic properties of a system with time
• An isolated system consisting of liquid and vapor phases
in contact eventually reaches a final state where no tendency
exists for change to occur within the system
• Temperature, pressure and composition of each phase reach
their equilibrium values and remain unchanged
• At the microscopic (molecular) level, molecules still cross the
interface from vapor to liquid and vice versa, but at the same
rate

4
Measures of composition

mi mi
• Mass fraction:  N
 mi
m
i 1

ni ni
• Mole fraction: xi   N
n n
i
i 1

N
• Molar mass of mixture: M   xi M i
i 1

5
Phase rule (Gibbs)

• Degrees of freedom (number of variables that may be


independently fixed in a state at equilibrium) = (Total
number of variables that characterize the intensive state
of the system) – (number of independent equations
connecting the variables):
• For N chemical species and π phases of a PVT system in
equilibrium, the total number of variables is T, P and N-1
compositions per phase (=2+(N–1).π)
• A phase-equilibrium equation can be written to connect
intensive variables for each of the N species for each pair of
phases present (=(π–1).N)
• F = 2 + (N–1).π – (π–1).N = 2 – π + N (phase rule)
• For example, for VLE of binary systems: F = 2
6
Phase rule - examples

F=2-+N number of variables that may be independently


fixed in a state at equilibrium
• Water
2 phases (vapor-liquid equilibria) – F?
3 phases (vapor-liquid-solid) – F?

• Ethane/decane binary mixture


2 phases (vapor-liquid equilibria) – F?
1 (liquid) – F?

• Ethane/butane/hexane ternary mixture


2 phases (vapor-liquid equilibria) – F?
1 (liquid) – F?
7
VLE behavior
• Pure fluid • pTxy diagram for VLE of binary mixture
Two phase equilibrium: F = 2 (surfaces)

8
Chapter 3, SvNA
New, CHEG332
VLE behavior - projections

• Pxy diagram and Txy diagram for VLE of binary mixture

Solid line:
Saturated liquid
Dashed line:
Saturated vapor
C: Mixture’s
critical point

Key to interpret
phase diagrams!

Tie-lines: connecting the composition of the two phases at 9


equilibrium at a given T,P – horizontal in Pxy, Txy diagrams
VLE behavior - projections

• pTxy diagram illustrating the phase transition lines in a


binary mixture.

Key to interpret
phase diagrams!

10
VLE behavior

• pT diagram for VLE of binary mixture


Solid line: Bubble curve (liquid)
Dashed line: Dew curve (vapor)
• xy diagram for VLE of
binary mixture

11
Dalton’s law

• A mixture contains nA moles A, nB moles B and


nC moles C, occupying a volume of V at T, p
• Partial pressure (pA): the pressure which
would be exerted by the component alone in
the same V and at the same T
p A nA pA  yA p
p AV  n A RT   yA
p n
• Thus, the partial pressure of a component in an ideal gas
mixture is the mole fraction of that component times the
total pressure N
y A  y B  ...  1 p A  pB  ...  p p   pi
i 1
• Dalton’s Law: The partial pressures of the components of
an ideal gas mixture add up to the total pressure 12
Raoult’s law
• Raoult’s law:
• Major assumptions:
- The vapor phase is an ideal gas → good for low to moderate
pressures
- The liquid phase is an ideal solution (enthalpy of mixing is zero and
volume change on mixing is zero) → valid for mixtures of chemically
similar molecules
yi P  pi  xi p sat
i i 1,2,..., N
• Only applicable to subcritical species
• Saturated vapor pressure (psat) is a function of
temperature (Antoine’s equation)
B
ln p sat / kPa  A  (T in C ) (Table B.2)
T C
13
Henry’s law

• Henry’s law: yi P  pi  xi H i i 1,2,..., N


• Major assumption:
• For a species in very low concentration in the liquid
phase (dilute), the partial pressure in the vapor phase is
proportional to its liquid-phase mole fraction

• Applicable even when i is at supercritical state


• Henry’s constant (H) is a function of temperature

14
Example 1 – Chapter 10
Use either Raoult’s law or Henry’s law to solve the following
problems and justify the selection:
a) A gas containing 1.0 mol% ethane is in contact with water at 20 °C and
20.0 atm. What is the mole fraction of the dissolved ethane?
b) An equimolar liquid mixture of benzene (B) and toluene (T) is in
equilibrium with its vapor at 30 °C. What is the system’s pressure and
the composition of the vapor?
Solution:
• Which law (Raoult or Henry) should be applied for each problem?
a) Hydrocarbons are normally insoluble in water. Thus the solution of
ethane in water is very dilute. Therefore Henry’s law is
appropriate.
• Henry’s constant for ethane in water at 20 °C is 2.63.104 atm/mole
fraction (from Perry’s handbook)
yi p 0.01 20
pi  yi p  xi H i T  xi    7.60  10 6

H i 2.63 10 4 15
Example 1 – Chapter 10
b) Benzene and toluene are structurally similar compounds and thus
miscible. Therefore, Raoult’s law can be applied.
• Vapor pressures for benzene and toluene at 30 °C are needed using
Antoine’s equation (Table B.2):

• From Raoult’s law:

16

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