Thermodynamics Unit 5

Dr.
Ravi B
Assistant Professor
Department of
Pharmaceutical Engineering
B V Raju Institute Of Technology

Narsapur
Course Name
Chemical & Process Thermodynamics
Topic Name
Unit-5 (Chemical Equilibrium)
Unit – 5 Objective
1) To study reaction equilibrium constants and their correlations with properties

for homogeneous, heterogeneous, single and multiple reactions.
Unit – 5 Outcomes
Student able to
1) understand reaction equilibrium constants and their correlations with
properties for homogeneous, heterogeneous, single and multiple reactions.
Mapping
Mapping of Course Outcomes with Program Outcomes
Course PO1 PO2 PO3 PO4 PO5 PO6 PO7 PO8 PO9 PO10 PO11 PO12
Outcomes
CO1 3 3 2 2 2 2 2 -- -- -- 2 3
CO2 3 3 2 2 2 2 2 -- -- -- 2 3
CO3 3 3 2 2 2 2 2 -- -- -- 2 3
CO4 3 3 2 2 2 2 2 -- -- -- 2 3
CO5 3 3 2 2 2 2 2 -- -- -- 2 3
Content of Unit – 5
1. Chemical Reaction Equilibrium Constant

i. Homogeneous reactions
a) Gas phase reactions
b) Liquid phase reactions
ii. Heterogeneous reactions
2. Standard Gibbs free energy Change
3. Equilibrium conversion for
i. Single-stage reactions
ii. Multi-stage reactions
Introduction
• The Pharmaceutical process industries are concerned with the transformation of

raw materials into drug products.
• Such transformation in most cases is achieved by means of chemical reactions.
• The design and operation of reaction equipment are therefore quite an important
field in the Pharmaceutical Engineering Profession.
• To be successful in this profession, the Pharmaceutical Engineers should be
versatile with the thermodynamics and kinetics of chemical reactions.
Introduction
• Thermodynamics predicts the equilibrium conversion in chemical reaction,

operating conditions, and feasibility of chemical reactions.
• The kinetics deals with the rate with which the desired conversion is attained
in practice.
• (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
• We know the formula of activity for ideal solutions in terms of fugacity
• substitute in the equilibrium constant formula
• For gases mixtures, the standard state fugacity is equal to the

pure compound fugacity which is unity () at a Pressure.
Therefore
• The above expression is in terms of fugacity; therefore, the Reaction

equilibrium constant is
• The fugacity coefficient () is defined as

• 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 ;
• (b) Liquid Phase reactions:

• Consider a general form of homogeneous liquid phase reaction
• Equilibrium constant which is defined can be used for all types of reactions.
• Therefore, Chemical reaction equilibrium constant in terms of activity
• We know that activity in terms of fugacity

• Substitute activity formula in terms of fugacity in the equation (1), Then

equation becomes
• Generally, the standard state of a compound in liquid state reactions may be

calculated at 1 bar pressure and reaction temperature.
• Therefore, the fugacity in this state is not much
difference from pure state
• Therefore, equation (2) becomes as
• Fugacity of a compound can be written as Substitute this in the equation (3)
• Equilibrium constant in terms of activity coefficient

• Equilibrium constant in terms of mole fraction
• For practical calculations we set therefore, the above expression become
𝐾 =𝐾 𝑥;
• (ii) Heterogeneous reactions

• Heterogeneous reactions occur in more than one phase, such as reactions
involving solids and gases or liquids.
• The equilibrium constant can be expressed in terms of activity
• Whereas, we consider the solid and liquid phase activities are 1, because with
respective to the gas, solid and liquid phase concentrations do not change
much.
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
• 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)

• Constant is same because standard state temperature and equilibrium state

temperature are same. Therefore, can be eliminated
• We know that
• Substitute equation (3) in the equation of equilibrium criteria;

• Rearrange the above expression

• We can write
• 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
• The equilibrium conversion will be
• The equilibrium constant in terms of concentration

• Solving this equation for X gives the Equilibrium conversion

− 𝐾 ± √ 𝐾 2 + 4 𝐾 [ 𝐴 ]0
𝑋=
2 [ 𝐴 ]0
• The equilibrium conversion for single reactions is this.

• (ii) Multiple reactions:

• Consider following reactions
• Let the initial concentration of A, B, & C are
• For the first reaction, the change in concentrations at equilibrium

can be defined by the conversion
• For the second reaction, the equilibrium concentrations depend on another

conversion
• Apply equilibrium constant expression

• For the first reaction:
• For the Second reaction:
• These equations can be solved simultaneously to find the values

of and that satisfy both equilibrium conditions.
• From the first reaction solve for

• From the first reaction solve for

• From the second reaction solve for by substituting

Unit-4 Outcome
Student able to
1) understand reaction equilibrium constants for homogeneous and
heterogeneous reactions and equilibrium conversion for single and multiple
reactions.
Thank You

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Dr.

B V Raju Institute Of Technology

1) To study reaction equilibrium constants and their correlations with properties

1. Chemical Reaction Equilibrium Constant

• The Pharmaceutical process industries are concerned with the transformation of

• Thermodynamics predicts the equilibrium conversion in chemical reaction,

• (i) Homogeneous reactions:

• Consider equilibrium constant for this reaction.

• We know the formula of activity for ideal solutions in terms of fugacity

• substitute in the equilibrium constant formula

• For gases mixtures, the standard state fugacity is equal to the

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

• The fugacity coefficient () is defined as

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

• We can write above expression

• If the gas mixture behaves as ideal gas

• (b) Liquid Phase reactions:

• We know that activity in terms of fugacity

• Substitute activity formula in terms of fugacity in the equation (1), Then

• Generally, the standard state of a compound in liquid state reactions may be

• Fugacity of a compound can be written as Substitute this in the equation (3)

• Equilibrium constant in terms of activity coefficient

• For practical calculations we set therefore, the above expression become

• (ii) Heterogeneous reactions

• The equilibrium constant can be expressed in terms of activity

• Consider chemical reaction

• The criteria of equilibrium for chemical reaction is

• chemical potential of compound

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

• The chemical potential at standard state

• constant; (depends on only on Temperature)

• Subtract from equation (1) – (2)

• Constant is same because standard state temperature and equilibrium state

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

• Rearrange the above expression

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

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

• Equilibrium conversion in thermodynamics refers to the extent to which

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

• The equilibrium conversion will be

• The equilibrium constant in terms of concentration

• Solving this equation for X gives the Equilibrium conversion

• The equilibrium conversion for single reactions is this.

• (ii) Multiple reactions:

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

• For the first reaction, the change in concentrations at equilibrium

• For the second reaction, the equilibrium concentrations depend on another

• Apply equilibrium constant expression

• For the first reaction:

• For the Second reaction:

• These equations can be solved simultaneously to find the values

• From the first reaction solve for

• From the first reaction solve for

• From the second reaction solve for by substituting

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