3 - PHASE EQUILIBRIA

TOPIC OUTLINE
• General Basis of Phase Equilibria
• Phase Rule
• Phase Equilibria of Different Processes
• Gas-Liquid Equilibria
• Liquid-Liquid Equilibria
• Solid-Fluid Equilibria
INTRODUCTION
• The choice of a mass-transfer operation for use in separating a mixture
depends upon the phase characteristics, equilibrium relationships, and
chemical properties of the material to be processed and upon the
economics of the possible separating methods.
• Other unit operations can be used for difficult separations .
INTRODUCTION
• An understanding of the various phase-equilibrium relationships is
necessary in the selection of the mass transfer operation most appropriate
for a given separation.
• The variation of phase equilibria with temperature and pressure is often an
important consideration.
• Furthermore, the number of stages of equipment required to produce a
desired change in phase composition depends upon the distribution of
components between phases at equilibrium.
• Such equilibrium data are determined experimentally.
• In some cases, the equilibrium relationship can be predicted from theory
or from empirical relationships.
• For example, Raoult's law can be used to describe certain vapor-liquid equilibria .
PHASE
• Phase may be defined as a physically distinct and homogeneous
portion of a system.
• A phase may be either a solid, a liquid, or a gas.
• Several solid and liquid phases may coexist ; but , since gases are
totally miscible with each other, there can be only one gas
phase.
INTENSIVE VARIABLE
• An intensive variable is independent of the total quantity of the phase.
• For example , the temperature , pressure , and composition of a phase are
intensive variables .
EXTENSIVE VARIABLE
• Depends upon the quantity
• Example: total volume of the phase, over-all composition of a system of
several phases (depends upon the extent of each phase)
COMPONENTS
• For phase equilibria the number of components of a phase may be
defined as the least number of chemical species necessary to
prepare the phase.
PHASE RULE
• Before the phase relationships for specific systems are discussed , the general
problem of phase equilibria will be considered .
• The phase rule, first stated by J. Willard Gibbs , is a useful tool in the consideration
of phase equilibria . The phase rule is derived by considering the number of
variables in a system together with the number of equations relating them . The
rule may be stated as:

𝐹 =𝐶+2−𝑃 (Eqn 3-1)

• F = number of variables that can be varied independently

• C = number of components in the system
• P = number of phases in the system
GAS-LIQUID EQUILIBRIA
• Calculations for distillation and gas absorption require knowledge of gas-liquid equilibria . A
simple expression of vapor-liquid equilibrium is Raoult's law.
𝑝𝐴 = 𝑃𝐴 𝑥𝐴 (3-2)
𝑝𝐴 𝑃𝐴 𝑥𝐴
Or 𝑦𝐴 = = (3-3)
𝑃 𝑃

• 𝑥𝐴 = mole fraction of component A in the liquid

• 𝑦𝐴 = mole fraction of component A in the vapor
• 𝑝𝐴 = partial fraction of component A in the vapor
• 𝑃𝐴 = vapor pressure of component A at the given temperature
• 𝑃 = total pressure

• Raoult's law
• is accurate only in predicting vapor-liquid equilibria for an ideal solution in equilibrium with an ideal gas mixture.
• Solutions that show negligible deviation from ideality include those whose components have similar structure
and physical properties, (e.g. benzene - toluene, propane-butane , and methanol ethanol .
• Shows that the compositions in an equilibrium mixture depend upon the total pressure of the system and upon
the vapor pressures of the components. The vapor pressures vary with temperature but not with composition or
total pressure.
GAS-LIQUID EQUILIBRIA
• In certain systems , where Raoult's law does not apply, phase compositions can
be predicted by:
𝑦𝐴 = 𝐾𝐴 𝑥𝐴 (3-4)

• 𝐾𝐴 = experimentally determined constant (independent of composition and

dependent only upon the temperature)

• Equation 3-4 expresses Henry’s Law.

GAS-LIQUID EQUILIBRIA
• Binary System
• Has two components
• More volatile component – component with the higher vapor pressure at a
given temperature
• Less volatile component - component with the lower vapor pressure
• By convention, the composition of a binary mixture will be expressed as the
concentration of the more volatile component.
GAS-LIQUID EQUILIBRIA
• For binary systems where A is the more volatile component and B is the less volatile
component, assuming Raoult’s law is valid:
𝑦𝐴 𝑥𝐵 𝑃𝐴
= (3-5)
𝑥𝐴 𝑦𝐵 𝑃𝐵

• Since 𝑦𝐵 = 1 − 𝑦𝐴 and 𝑥𝐵 = 1 − 𝑥𝐴
𝑦𝐴 1−𝑥𝐴 𝑃𝐴
= = 𝛼𝐴𝐵 (3-6)
𝑥𝐴 1−𝑦𝐴 𝑃𝐵

• 𝛼𝐴𝐵 = relative volatility of component A relative to B

𝐾𝐴
• 𝛼𝐴𝐵 = (for systems which do not follow Raoult’s law)
𝐾𝐵
• 𝛼𝐴𝐵 = constant if both Raoult’s and Henry’s law holds, varies with composition in other cases
GAS-LIQUID EQUILIBRIA

Figure 3.1 Typical vapor-liquid

equilibrium curves
Example 3-1
• A mixture of butane and pentane is at equilibrium at 3
atm pressure and 100 ° F . Calculate the compositions of
the liquid and vapor : (a) using Raoult’s law, (b) using
experimental values of 𝐾𝐴 , and Equation 3-4.
Example 3-2
• What is the relative volatility of butane to pentane at 100 ° F and 465
psia?
GAS-LIQUID EQUILIBRIA
• Bubble Point
• Temperature at which a liquid mixture of a given composition
begins to vaporize as the temperature is increased
• Dew point
• Temperature at which a vapor mixture begins to condense on
cooling

• Note: For a pure liquid the bubble point and dew point are identical and equal to the
boiling point, since a pure component vaporizes or condenses at one temperature.
Example 3-3
• Calculate the dew point of a gaseous mixture containing 20 mole
percent benzene, 30 mole percent toluene, and 50 mole percent o-
xylene at 1 atm total pressure.
GAS-LIQUID EQUILIBRIA
• The region below the bubble-point curve represents the
liquid phase. A liquid at a temperature below its bubble
point may be referred to as a subcooled liquid, whereas
one at its bubble point is called a saturated liquid.
• Similarly, a vapor at its dew point is called a saturated
vapor.
• Between the bubble-point and dew-point curves is a
region of two phases where both a saturated liquid and a
saturated vapor coexist . The relative quantities
• of liquid and vapor in the two-phase region can be
calculated by a material balance.
• Above the dew -point curve lies the region of superheated
vapors.

Figure 3.2 Temperature-composition

diagram for liquid-vapor equilibrium of
benzene and toluene at 1 atm
 GAS-LIQUID EQUILIBRIA

• An azeotrope is a mixture which has an equilibrium vapor

of the same composition as the liquid.
• Such a characteristic is undesirable if a separation of the
mixture into its components by distillation is necessary,
since no composition richer than the azeotrope can be
attained.
• At the azeotropic composition the dew point and bubble
point are equal, and the mixture vaporizes at a single
temperature.
• Often called “constant-boiling mixtures”

Figure 3-3. Temperature-composition diagram for mixtures forming an azeotrope at 1 atm

Seatwork 1
• Calculate the dew point and bubble point of the
following mixture at a total pressure of 2 atm:
• Hexane 40 mole percent
• Heptane 25 mole percent
• Octane 35 mole percent
Seatwork 2
• An equilibrium mixture of liquid and vapor has an over-all composition of 0.55
mole fraction benzene and 0.45 mole fraction toluene at 1 atm total pressure and
205 °F .
• (a) Calculate the compositions of liquid and vapor and check the values with
Figure 3.2 .
• What percentage of the vapor will condense if the total pressure is increased
to 2 atm ?
Seatwork 3
• Determine the composition of the phases specified for each of the following vapor - liquid
equilibria :
• The vapor phase in equilibrium with a liquid of 30 mole percent ethanol and 70 mole percent water at 1 atm
• The vapor phase in equilibrium with a liquid of 40 mole percent a and 60 mole percent b , where the relativity
volatility of a to b is 2.7.
• The liquid and vapor phases for a mixture of acetone and chloroform at a temperature of 140oF and at a total
pressure of 1 atm
• The liquid and vapor phases for a mixture of ammonia and water with an overall composition of 40 mole
percent ammonia at 200oF and 100 psia