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Vapor/Liquid Equilibrium

- Vapor/liquid equilibrium describes the equilibrium state between coexisting vapor and liquid phases that are in contact. - Processes like distillation rely on vapor/liquid equilibrium to transfer mass between phases and change compositions. - The equilibrium temperature, pressure, and phase compositions must be known to quantitatively model mass transfer.

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109 views20 pages

Vapor/Liquid Equilibrium

- Vapor/liquid equilibrium describes the equilibrium state between coexisting vapor and liquid phases that are in contact. - Processes like distillation rely on vapor/liquid equilibrium to transfer mass between phases and change compositions. - The equilibrium temperature, pressure, and phase compositions must be known to quantitatively model mass transfer.

Uploaded by

mjunaid
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© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Vapor/Liquid Equilibrium:

•Composition changes are the desired outcome, not only


of chemical reactions, but of a number of industrially
important mass-transfer operations.
•Processes such as distillation, absorption, and extraction
bring phases of different composition into contact, and
when the phases are not in equilibrium, mass transfer
between the phases alters their compositions.
•Both the extent of change and the rate of transfer
depend on the departure of the system from equilibrium.
Thus, for quantitative treatment of mass transfer the
equilibrium T, P, and phase compositions must be known.
THE NATURE OF EQUILIBRIUM
•Equilibrium is a static condition in which no changes
occur in the macroscopic properties of a system with
time.
•An isolated system consisting of liquid and vapor
phases in intimate contact eventually reaches a final
state wherein no tendency exists for change to occur
within the system. The temperature, pressure, and
phase compositions reach final values which
thereafter remain fixed. The system is in equilibrium.
•Nevertheless, at the microscopic level, conditions are
not static.
Measures of Composition
Mass or mole fraction

Molar concentration

The molar mass of a mixture or solution is, by


definition, the mole-fraction-weighted sum of the
molar masses of all species present:
THE PHASE RULE. DUHEM'S
THEOREM
Phase Rule
For any system in equilibrium, the number of
independent variables that must be arbitrarily fixed to
establish its intensive state.
F= 2 – π + N
Intensive state of system at equilibrium is established,
when temperature, pressure and compositions of all
phases are fixed.
Thus, no. of variables that may be independently fixed
in a system at equilibrium is

total no. of variables (that characterize the intensive


state of the system) - no. of independent equations
that can be written connecting the variables.
If the system is closed and formed from specified
amounts of the chemical species present, then a
material-balance equation can be written for each of
the N chemical species. These in addition to the
(n - l)N phase-equilibrium equations provide a total
number of independent equations equal to:

The difference between the number of variables and


the number of equations is therefore:
Duhem's theorem is stated as follows:
For any closed system formed initially from given
masses of prescribed chemical species, the
equilibrium state is completely determined when
any two independent variables are fixed.

The two independent variables subject to


specification may in general be either intensive or
extensive. However, the number of independent
intensive variables is given by the phase rule. Thus
when F = 1, at least one of the two variables must be
extensive, and when F = 0, both must be extensive.
VLE
Qualitative Behavior

PT xy diagram for vapor/liquid


equilibrium
Tie line connects points representing phases in
equilibrium.

Bubble Point.
Point where first bubble of the vapor appears
Dew Point
Point where last drop of liquid disappears
Figure 10.2 (a) Pxy diagram for three temperatures. (b) Txy diagram for
three pressures
Dalton's Law of Partial Pressure

Total pressure is equal to summation of partial


pressures.

P =Σ PA

For ideal gases or vapors, the partial pressure is


proportional to the mole fraction of the constituents.
PA= YAP
For ideal mixtures, the partial pressure is related to
the concentration in the liquid phase by Raoult,s law
PA = P˚A XA
Where P˚A is vapor pressure of pure species A at same
temperature.
SIMPLE MODELS FOR VAPORILIQUID EQUILIBRIUM

•When thermodynamics is applied to vapor/liquid


equilibrium, the goal is to find by calculation the
temperatures, pressures, and compositions of phases
in equilibrium. Indeed, thermodynamics provides the
mathematical framework for the systematic
correlation, generalization, evaluation, and
interpretation of data.
•This can not be accomplished without models for the
behavior of systems in vapor/liquid equilibrium. The
two simplest are Raoult's law and Henry's law.
Raoult’s law
Assumptions for Raoult’s law are
•The vapor phase is an ideal gas.
•The liquid phase is an ideal solution.

The first assumption means that Raoult's law can


apply only for low to moderate pressures.
The second implies that it can have approximate
validity only when the species that comprise the
system are chemically similar.
A limitation of Raoult's law is that it can be applied
only to species for which a vapor pressure is known,
and this requires that the species be "subcritical," i.e.,
that the temperature of application be below the
critical temperature of the species.
For Binary system with x2 = 1-x1
P = P2sat + (P1 sat-P2sat) x1
Or

P = x1 P1sat + (1- x1) P2sat

Equation (10.1) may also be solved for xi and summed


over all species. WithΣi xi = 1, this yields:

An equation applied in dew point calculations, where


liquid-phase compositions are not known.
Dew point and Bubble point
Calculations with Raoult's Law
BUBL P: Calculate {yi) and P, given {xi} and T
DEW P: Calculate {xi} and P,given {yi} and T
BUBL T: Calculate {yi} and T, given {xi} and P
DEW T: Calculate {xi} and T, given {yi} and P
VLE BY MODIFIED RAOULT'S LAW
For low to moderate pressures a much more realistic
equation for VLE results when the second major
Raoult's-law assumption is abandoned, and account is
taken of deviations from solution ideality in the liquid
phase by a factor inserted into Raoult's law,

The factor γi is called an activity co-eficient. Activity


coefficients are functions of temperature and liquid-
phase composition.
So

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