1.

Phase Rule

• Phase rule determines degree of freedom

• Degree of freedom

• Degree of freedom
• Number of components
• Number of phases
• Degree of freedom means, if you want to establish arbitrary state then how
many state variables ( must be fixed.
• In other words, how many state variables can be changed
without changing the phases.
 2. Fundamentals of Vapor - Liquid Equilibria

• Case 1: Ideal gas-phase & Ideal liquid solution:

For mixtures of ideal gases

For mixture of ideal liquids
fugacity is equal to saturation pressure of pure liquid

equation becomes
𝑠
𝑦 𝑖 𝑃 = 𝑥𝑖 𝑃 𝑖
 2. Fundamentals of Vapor - Liquid Equilibria

• Case 2: Low-pressure VLE problems:

• If the pressure is low enough that the assumption of ideal gas behavior for
gas phase.

The equation becomes

• fugacity is equal to saturation pressure of pure liquid;

Therefore
𝑠
𝑦 𝑖 𝑃 =𝛾 𝑖 𝑥 𝑖 𝑃 𝑖
 2. Fundamentals of Vapor - Liquid Equilibria

• There are many Activity coefficient equations are available to correlate

between the activity coefficient and mole fractions;
• Widely accepted and used equations are
1. Wohl’s three-suffix equation
2. Margules equations
3. Van Laar equation
4. Wilson equation

•
 2. Fundamentals of Vapor - Liquid Equilibria

2. Margules Equation:
• Margules equation it is assumed that the term in the Wohl’s equation.
2. Fundamentals of Vapor - Liquid Equilibria
 2. Fundamentals of Vapor - Liquid Equilibria

• They are called Margules three-suffix equation.

 2. Fundamentals of Vapor - Liquid Equilibria

• When
• The above equations becomes
2 2
ln 𝛾 1= 𝑥 A ; ln 𝛾 2= 𝑥 B ;
2 1

• They are called Margules two-suffix equation

• It determines activity coefficient for simple mixtures like argon-oxygen,
benzene-cyclohexane, etc.,
• are constants depends on temperature.
 2. Fundamentals of Vapor - Liquid Equilibria

3. van Laar equation:

• van Laar equation, it is assumed that

• Substitute in the Wohl’s equation;
 2. Fundamentals of Vapor - Liquid Equilibria

• van Laar equations are applicable for solutions like simple,

and non-polar solutions.
 2.1 Phase diagrams for Binary Solutions

• Constant Pressure Equilibria

• Constant Temperature Equilibria
 2.1.1 Constant Pressure Equilibria

• Constant binary system made up of components A & B

• Component A is assumed to be more volatile than B
• Therefore, the vapor pressure of A is more than B any temperature.
• VLE data at constant pressure are represented by boiling point diagrams ()

Fig 2: x-y diagram (Equilibrium

Fig 1: T-x-y diagram distribution boiling diagram)
 2.1 Constant Pressure Equilibria

Fig: Effect of varying the pressure

Fig: Effect of increasing on the equilibrium diagram
pressure on T-x-y diagram
 3. Liquid – liquid Equilibria

Ternary Equilibrium Diagrams

• Consider three components which are in liquid state are in Liquid – liquid
equilibria.
• It is very important in the analysis of extraction operations.
• The extraction process involves bringing a binary mixture of components A
and C into intimate contact with a solvent B.
• Solvent B either partially soluble in liquid A or is immiscible with it.
• The solvent C gets distributed in different proportions between the two
insoluble phases.
• Known as ‘raffinate’ and extract.
• The A-rich phase is ‘raffinate’
• The B-rich phase is ‘extract’.
 3. Liquid – liquid Equilibria

Ternary Equilibrium Diagrams

• The ’raffinate’ phase and ‘extract’ phase both phases have three components.
• The ternary liquid – liquid equilibrium diagrams are usually represented on
equilateral triangular coordinates.
 3. Liquid – liquid Equilibria

Ternary Equilibrium Diagrams

• On the equilateral triangle the length of the altitude is allowed to represent
100% composition.
• The length of the perpendiculars from any point to the bases represent the
percentages of three components.
• The apexes of the triangle represents the pure components A, B and C
• On the sides represent binary mixtures.
 1. Chemical Reaction Equilibrium Constant

• (i) Homogeneous reactions:

(a) Gas Phase reactions:
• Consider a general form of homogeneous gas phase reaction

• Consider equilibrium constant for this reaction.

• Chemical reaction equilibrium constant is defined in terms of activities of
reactants and products.

• activity of component ;
• stoichiometric number of component
 1. Chemical Reaction Equilibrium Constant

• The above expression is in terms of fugacity; therefore, the Reaction

equilibrium constant is

• The fugacity coefficient () is defined as

 1. Chemical Reaction Equilibrium Constant

• Substitute the above expression in the reaction equilibrium constant expression,

then

• We can write above expression

• If the gas mixture behaves as ideal gas

𝐾 =𝐾 𝑓 =𝐾 𝑃 ;
 2. Standard Free Energy Change

• Consider chemical reaction

• The criteria of equilibrium for chemical reaction is

• chemical potential of compound

• stoichiometric values of compound in the reaction
 2. Standard Free Energy Change

• In the reaction equilibrium, the chemical potential can be expressed in terms of

fugacity.

• The chemical potential at standard state

• constant; (depends on only on Temperature)

• Subtract from equation (1) – (2)

 2. Standard Free Energy Change

• Constant is same because standard state temperature and equilibrium state

temperature are same. Therefore, can be eliminated

• We know that
 2. Standard Free Energy Change

• Substitute equation (3) in the equation of equilibrium criteria;

 2. Standard Free Energy Change

• Rearrange the above expression

 2. Standard Free Energy Change

• We can write
 2. Standard Free Energy Change

• The left-hand side is equal to standard free energy change

• The right-hand side is equal to reaction equilibrium constant

• Therefore,
0
Δ 𝐺 =− 𝑅𝑇 ln 𝐾 ;
• This is relationship between the equilibrium constant and standard free energy
change
• The equilibrium constant can be determined form standard free energy and
Temperature ;
 3. Equilibrium Conversion in Single Reactions

• Equilibrium conversion in thermodynamics refers to the extent to which

reactants are converted to products when a chemical reaction reaches
equilibrium.
• The approach to calculating equilibrium conversion differs for single-stage
reactions and multi-stage reactions.
• (i) Single Reactions:
• Consider a single, a reversible reaction

• If the initial concentration of A, B & C are

• If is assumed conversion
 3. Equilibrium Conversion in Single Reactions

• The equilibrium conversion will be

• The equilibrium constant in terms of concentration

 3. Equilibrium Conversion in Single Reactions

• Solving this equation for X gives the Equilibrium conversion

 3. Equilibrium Conversion in Single Reactions

− 𝐾 ± √ 𝐾 2 + 4 𝐾 [ 𝐴 ]0
𝑋=
2 [ 𝐴 ]0

• The equilibrium conversion for single reactions is this.

 1. Partial Molar Properties

• = The partial molar property of the component in the solution.

• = Total number of moles
• = Molar property of the solution
• = number of moles of component , here
• = total value of any extensive thermodynamic property of a solution,
• = Temperature
• = Pressure
• = the number of moles of all components in the solution other than the number
of moles of are kept constant.
 1.2 Determining Methods for Partial Molar Properties

• Method 1: Analytical
• Method 2: Graphical
• Method 3: The tangent-intercept method
 1.2 Determining Methods for Partial Molar Properties

• Method 1: Analytical
 1.2 Determining Methods for Partial Molar Properties

• Method 2: Graphical
Constant
Volume of the solution
moles of ith component 𝑡
𝑀
moles of other components are constant
Tangent Slope =

Slope of the tangent which is drawn to the curve

𝑛1
 1.2 Determining Methods for Partial Molar Properties

• Method 3: The Tangent-Intercept Method

• It is widely used method for the determination of

𝐵
polar properties of both components in a binary
solution. 𝑀 𝜕𝑀
• Plot molar property vs mole fraction of any 𝑠𝑙𝑜𝑝𝑒=
𝜕 𝑥1
component
• Draw the tangent to the curve at the desired mole 𝐴 𝐷
𝐶
fraction. 0 𝑥1 1
• The intercept that this tangent makes with the
vertical axis at &
 2. Chemical Potential

• Temperature is index for thermal equilibrium

• Pressure is index for mechanical equilibrium
• In the same way, chemical potential is the index for chemical equilibrium.
• Chemical potential is change in free energy with change in number of
particles / moles.
 2. Chemical Potential

• The total differential is

2. Chemical Potential
 2. Chemical Potential

• For closed system, change in free energy can be written as

• The above expression can be rewrite for total change in free energy

• Partial derivation of above expression with respect to the

 2. Chemical Potential

• Substitute them in the following equation

• This is the fundamental relationship for change in free energy of a solution.

 2. Chemical Potential

• At constant temperature and pressure, the change in energy is due entirely to the
changes in the number of moles.

• In other words, we can write the above equation by integrating

• For binary solution

 3. Concept of Fugacity

• Compound pressure which is there in the ideal solution is described by partial

pressure.
• Whereas compound pressure which is there in the non-ideal mixture (real
solution) is described by fugacity.
• It is another thermodynamics concept.
• Fugacity is defined as effective pressure of compound in the non-ideal
mixture.

• Pure compound fugacity;

• mole fraction of compound of gas phase & liquid phase
 3. Fugacity Coefficient

• The ratio of fugacity to pressure is referred to as fugacity coefficient.

• The formula

• = fugacity coefficient;
• For ideal mixture, Therefore
 4. Concept of activity and its calculations

• In ideal mixtures, the compound concentration is referred by concentration.

• In non-ideal mixtures, the compound concentration is referred by activity.
• It is another thermodynamic property.
• Activity (a) is defined as effective concentration of compound in the non-ideal
mixture.
• In ideal mixtures, the compound activity equal to its concentration or mole
fraction.
 4. Concept of activity and its calculations

• Whereas, non-ideal mixtures, the compound activity is equal to its

concentration through activity coefficient.

= compound activity coefficient of gases & liquids respectively;

 4. Concept of activity and its calculations

• Activity can be expressed in terms of fugacity

• Activity of compound in the mixture;

• fugacity of compound in the mixture;
• standard fugacity of a compound which is there at standard phase.

For ideal Gas mixtures:

 4. Concept of activity and its calculations

• For Ideal Liquids mixtures:

• Whereas, for non-ideal gases and liquid mixtures

 5. Ideal & Non -Ideal Solutions

Lewis-Randall rule:
• It is applicable to ideal liquids and ideal gases.
• Fugacity of each constituent is directly proportional to the number of moles of
the constituent in the solution.

= fugacity of component in the solution.

= mole fraction of component in the solution.
= fugacity of in the pure state.

• It is applicable to all gas mixtures for moderate temperature & pressure.

• Whereas few liquid mixtures only follow the above rule.
• Same isotherms (ex: ortho-, meta-, para-xylene), adjacent members of
homogeneous series of organic compounds (ex: n-hexane & n-heptane;
ethanol & propanol; benzene & toluene; ethyl bromide & ethyl iodide, etc.,)
 5. Ideal & Non -Ideal Solutions

• Raoult’s Law:
• When ideal solution is equilibrium with its vapor state.
• The Lewis-Randall rule modified

• It says that partial pressure of constituent is directly proportional to the mole

fraction in the liquid solution.
• Ideal solutions which conform to Raoult’s law over the entire range of
concentrations are rare.
• Examples for ideal solution (frequently cited) optical isomers of organic
compounds.
 5. Ideal & Non -Ideal Solutions

• Henry’s Law:
• A solution any of whose components does not obey Raoult’s law is designated
as non-ideal solution.
• It says that the fugacity or partial pressure is directly proportional to the
concentration in the liquid. This behavior exhibited when the solute
concentration approaches to zero;

= Henry’s constant.
• Henry’s law deviate for all solutions where the solute mole fraction > 0.1
 6. Gibbs – Duhem’s Equation

• In a mixture, the partial molar properties of the components are related to one
another by one of the most useful equations in thermodynamics:
• That is Gibbs – Duhem’s equation
• We know already the total molar property at constant Temperature and
constant pressure is equal to

Derive above expression

 6. Gibbs – Duhem’s Equation

• We know that total molar property is function temperature, pressure, number

of moles of various compounds in solution.
• Whereas at constant temperature and pressure

Substitute this in the above expression

 6. Gibbs – Duhem’s Equation

This is called general form of Gibbs-Duhem’s equation;

Sum of product of change in partial molar property of constituent and number of

moles in the solution is equal to zero.

For example for Gibbs free energy

 7. Property Change of Mixing

• For Ideal solution, the total molar property is equal to sum of partial molar
properties of constituents.

• Even it is not exactly true for ideal solutions also;

• We introduce correction term i.e. property change of mixing;
 7. Property Change of Mixing

• Here difference in the property of the solution M and sum of the properties of
the sum components (at same temperature and pressure).

• A more general definition of can be written as

Molar property of pure in a specified standard state;

If the components exists in the pure form in the same state of aggregation as the
solution at temperature and pressure, then
 7. Property Change of Mixing

• Property change of mixing is function of temperature and pressure and

standard state specified for the components;
• Now substitute in the equation
 7. Property Change of Mixing

• The quantity can be treated as the change in the property of components

when one mole of pure in its standard state is brought to the given
composition at the same temperature and pressure.
 8. Excess Properties

• Property of a real solution and property of ideal solution very important in

pharmaceutical Industry.
• The excess property is defined as the difference between an actual property
and the property that would be calculated for the same temperature, pressure
and compositions by the equations for an ideal solutions

Excess molar property

Molar property of solution
Molar property of ideal solution.
 8. Excess Properties

• The excess property change of mixing is defined as in a similar manner.

• Excess property change of mixing;

• = Property change of mixing for a real solution;
• = Property change of mixing for a ideal solution;

But we know that property change of mixing

In the same way

 8. Excess Properties

• Substitute them in above expression

We know that

• Means excess property change of mixing is equal to excess property.