Phase Equilibria And Vapour

Liquid Equilibria
 Phase Equilibria
• Equilibrium is a condition in which no
changes occur in the macroscopic properties of
an isolated system with time.
• A system is said to be in a state of equilibrium
if it shows no tendency to depart from that
state either by energy transfer through the
mechanism of heat and work or by mass
transfer across the phase boundary.
• At equilibrium, all potentials that could cause
change are exactly balanced, so no driving
force exists for any change in the system.
• Under equilibrium the net flux is zero.
• Ex: breathing oxygen and dissolve in blood,
preparation of tea or coffee etc..,
The two types of phase equilibrium problems that are frequently encountered are:
1. The determination of composition of phases which exist in equilibrium at a known
temperature and pressure.
2. The determination of conditions of temperature and pressure required to obtain equilibrium
between phases of specified compositions.
CRITERIA OF PHASE EQUILIBRIUM:
• If the system is in thermodynamic equilibrium, mass transfer also should not occur.
• A system can interact with the surroundings reversibly or irreversibly.
• In the reversible process, a state of equilibrium is maintained throughout the process.
• So it can be treated as a process connecting a series of equilibrium states.
• The driving forces are only infinitesimal in magnitude and the process can be reversed by an
infinitesimal change (either increase or decrease) in the potential for the system or the
surroundings.
• The irreversible process, in contrast, occurs with a finite driving force, and it can not be
reversed by infinitesimal changes in the external conditions.
• However, all irreversible processes tend towards a state of equilibrium as discussed in
Clausius inequality.

(1)
• In this equation, the equality sign refers to a reversible process.
• inequality refers to the entropy change for a spontaneous process whose ultimate result
would be an equilibrium state.
• The first law of thermodynamics expressed mathematically as
(2)
Substituting (2) into (1), we get
(3)

• The above equation is valid for cases where external pressure is the only force and
the work is, therefore, the work of expansion on
• By this, we exclude other effects like those due to gravitational and electromagnetic
fields and surface and tensile force
• Equation () can be treated as the combined statement of the first and second law of
thermodynamics applied to a closed system which interact with its surroundings
through heat transfer and work of volume displacement.
• This equation is utilized for deriving the criteria of equilibrium under various sets
of constraints. These different criteria are discussed below
 Activity & Activity Coefficient
Activity:
• Activity of a substance at any given temperature is defined as the ratio of the
fugacity of the substance to its fugacity in the standard state.
• It is denoted by the symbol ‘a’.
• a =f/fo
• Activity is used to allow for the deviation of real solutes from limiting ideal
behavior.
Activity Coefficient:
• Activity coefficients measure the extent to which the real solution departs from
ideality.
• Activity coefficient of the component i in solution is denoted by γ i and is defined
by the following relationship

where fi0is the fugacity in the standard state. For ideal solutions γ i = 1, and we have
• Two types of ideal behaviour are observed; the first conforms to Lewis–Randall
rule (or Raoult’s law) in which case fi0=fi
• The fugacity of the pure species at the system pressure and the second type
conforms to an ideal dilute solution behaviour (the Henry’s law), in which case
fi0=Ki the Henry’s law constant.

• where ai is the activity of i in the solution.