CY11003 Physical Chemistry 4/3/2023

Fundamental Concepts of
Thermodynamics

CY 11003 CHEMISTRY
Spring 2022-2023

Applications of the Fundamental Concepts of

Thermodynamics

• Mixing of Ideal Gases

• Phase Stability
• Phase Equilibrium
• Chemical Reaction Equilibrium

Srabani Taraphder, Department of Chemistry,

IIT Kharagpur 1
CY11003 Physical Chemistry 4/3/2023

Chemical Equation in Condensed Notation

𝑵𝟐 𝟑 𝑯𝟐 → 𝟐 𝑵𝑯𝟑
Example:
𝑿𝟏 𝟑 𝑿𝟐 𝟐 𝑿𝟑

Alternative 𝟏 𝑿𝟏 𝟑 𝑿𝟐 𝟐 𝑿𝟑 𝟎
representation: 𝝂𝟏 𝝂𝟐 𝝂𝟑

𝝂𝟏 𝑿𝟏 𝝂𝟐 𝑿𝟐 𝝂𝟑 𝑿𝟑 𝟎

𝝂𝒋 𝑿𝒋 0 where 𝝂𝒋 𝟎 (Products); 𝝂𝒋 𝟎 (Reactants)

Balanced equation for any chemical reaction 𝝂𝒋 𝑿𝒋 𝟎

(condensed notation) 𝒋

Chemical Reaction Equilibrium

• Reaction Gibbs energy and chemical potential

• Direction of a spontaneous chemical reaction Concept

• Condition of chemical reaction equilibrium

• Equilibrium constant

• Response of equilibria to external perturbation

Pressure Measure
Temperature -ment
 Concentration

Srabani Taraphder, Department of Chemistry,

IIT Kharagpur 2
CY11003 Physical Chemistry 4/3/2023

Description of Chemical Equilibrium

in terms of
Reaction Gibbs Energy and Chemical Potential

Thermodynamics of Open Systems

Transfer of matter
Mixing of ideal gases Phase Equilibrium Chemical Reaction Equilibrium

From one region to other From one phase From one chemical identity to
to other other

Srabani Taraphder, Department of Chemistry,

IIT Kharagpur 3
CY11003 Physical Chemistry 4/3/2023

Reaction Gibbs Energy ∆𝒓 𝑮

• Let us consider the chemical equilibrium 𝑨 ⇌ 𝑩

• Let an infinitesimal amount 𝒅𝝃 of 𝑨 change in to 𝑩 such that

𝒅𝒏𝑨 𝒅𝝃 and 𝒅𝒏𝑩 𝒅𝝃

• 𝝃 is the extent of reaction (having units in moles)

• The reaction Gibbs energy is defined as

𝝏𝑮
𝚫𝒓 𝑮
𝝏𝝃 𝑻,𝒑

Chemical Potential and Reaction Gibbs Energy ∆𝒓 𝑮

• For the equilibrium 𝑨 ⇌ 𝑩, if the reaction advances by 𝒅𝝃
𝒅𝒏𝑨 𝒅𝝃 and 𝒅𝒏𝑩 𝒅𝝃

𝒅𝑮𝑻,𝒑 𝝁𝑨 𝒅𝒏𝑨 𝝁𝑩 𝒅𝒏𝑩 𝝁𝑩 𝝁𝑨 𝒅𝝃

Therefore, 𝝏𝑮
𝚫𝒓 𝑮 𝝁𝑩 𝝁𝑨
𝝏𝝃 𝑻,𝒑

The reaction Gibbs energy is the difference between the

chemical potential of product and reactant at the composition
of the reaction mixture.

Srabani Taraphder, Department of Chemistry,

IIT Kharagpur 4
CY11003 Physical Chemistry 4/3/2023

Chemical Potential and Reaction Gibbs Energy ∆𝒓 𝑮

•For the equilibrium 𝝂𝟐 𝑿𝟐 𝝂𝟏 𝑿𝟏 𝟎

•Change in Gibbs free energy 𝒅𝑮𝑻,𝒑 𝝁𝟏 𝒅𝒏𝟏 𝝁𝟐 𝒅𝒏𝟐

• If the reaction advances by 𝒅𝝃 𝒅𝒏𝟏 𝝂𝟏 𝒅𝝃 𝒅𝒏𝟐 𝝂𝟐 𝒅𝝃

𝒅𝑮𝑻,𝒑 𝝁𝟐 𝝂𝟐 𝝁𝟏 𝝂𝟏 𝒅𝝃 𝝏𝑮
𝚫𝒓 𝑮 𝝁𝟐 𝝂𝟐 𝝁𝟏 𝝂𝟏
𝝏𝝃 𝑻,𝒑
In general, for the equilibrium

𝝏𝑮
𝝂𝒊 𝑿𝒊 𝟎 𝚫𝒓 𝑮 𝝁𝒊 𝝂𝒊
𝝏𝝃 𝑻,𝒑 𝒊

Gibbs Free Energy, 𝑮 and Advancement of Reaction, 𝝃

𝝏𝑮 How do we express 𝑮 𝑮 𝑻, 𝒑, 𝝃 ?
𝚫𝒓 𝑮
𝝏𝝃 𝑻,𝒑
For any composition at 𝑻 and 𝒑 𝑮 𝒏𝒊 𝝁𝒊
𝒊
Pure reactant(s)
𝑮
𝑮 𝒏𝒊 𝝁𝒊 ∗ 𝝁𝒊 𝝁𝒊 ∗
Pure product(s)
𝒊
𝟎
𝝁𝒊 ∗ 𝑻, 𝒑 = chemical potential of pure specie 𝒊

𝑮 𝒏𝒊 𝝁𝒊 ∗ 𝒏𝒊 𝝁𝒊 𝝁𝒊 ∗
𝝃 𝒊 𝒊
𝑮𝒑𝒖𝒓𝒆 𝚫𝑮𝒎𝒊𝒙
𝒏𝒊 𝒏𝒊,𝒊𝒏𝒊𝒕𝒊𝒂𝒍 𝝂𝒊 𝝃
𝑮 𝑻, 𝒑, 𝝃 𝑮𝒑𝒖𝒓𝒆 𝑻, 𝒑, 𝝃 𝜟𝑮𝒎𝒊𝒙 𝑻, 𝒑, 𝝃

Srabani Taraphder, Department of Chemistry,

IIT Kharagpur 5
CY11003 Physical Chemistry 4/3/2023

Gibbs Free Energy, 𝑮 and Advancement of Reaction, 𝝃

𝝏𝑮 How do we express 𝑮 𝑮 𝑻, 𝒑, 𝝃 ?
𝚫𝒓 𝑮
𝝏𝝃 𝑻,𝒑
𝑮 𝑻, 𝒑, 𝝃 𝑮𝒑𝒖𝒓𝒆 𝑻, 𝒑, 𝝃 𝜟𝑮𝒎𝒊𝒙 𝑻, 𝒑, 𝝃

𝑮
𝒏𝒊 𝝁𝒊 ∗
Without mixing
𝑮𝒑𝒖𝒓𝒆
𝒊
𝟎

𝒏𝒊 𝒏𝒊,𝒊𝒏𝒊𝒕𝒊𝒂𝒍 𝝂𝒊 𝝃
Mixing

𝚫𝑮𝒎𝒊𝒙 𝒏𝑹𝑻 𝒙𝒊 𝒍𝒏 𝒙𝒊
𝒊

Gibbs Free Energy, 𝑮 and Advancement of Reaction, 𝝃

𝝏𝑮 How do we express 𝑮 𝑮 𝑻, 𝒑, 𝝃 ?
𝚫𝒓 𝑮
𝝏𝝃 𝑻,𝒑
𝑮 𝑻, 𝒑, 𝝃 𝑮𝒑𝒖𝒓𝒆 𝑻, 𝒑, 𝝃 𝜟𝑮𝒎𝒊𝒙 𝑻, 𝒑, 𝝃

𝑮
𝑮𝒑𝒖𝒓𝒆 𝒏𝒊 𝝁𝒊 ∗
𝒊
𝟎

𝒏𝒊 𝒏𝒊,𝒊𝒏𝒊𝒕𝒊𝒂𝒍 𝝂𝒊 𝝃

𝚫𝑮𝒎𝒊𝒙 𝒏𝑹𝑻 𝒙𝒊 𝒍𝒏 𝒙𝒊
𝒊

Srabani Taraphder, Department of Chemistry,

IIT Kharagpur 6
CY11003 Physical Chemistry 4/3/2023

Reaction Gibbs Energy and Composition

of Reaction Mixture at Constant 𝑻 and 𝒑
𝝏𝑮
• 𝚫𝒓 𝑮 𝝁𝑩 𝝁𝑨
𝝏𝝃 𝑻,𝒑

• Chemical potential is a function of composition

of the reaction mixture
• With increasing 𝝃, 𝚫𝒓 𝑮 changes
• A spontaneous reaction proceeds in the
direction of decreasing 𝑮
• The forward reaction is spontaneous if 𝝁𝑨 𝝁𝑩

• The reverse reaction is spontaneous if 𝝁𝑨 𝝁𝑩

• The reaction reaches equilibrium when 𝝁𝑨 𝝁𝑩

Spontaneity and Equilibrium of the Reaction

at Constant 𝑻 and 𝒑
𝑨 ⇌ 𝑩
exergonic
𝝏𝑮
• 𝚫𝒓 𝑮 𝝁𝑩 𝝁𝑨
𝝏𝝃 𝑻,𝒑 endergonic

𝚫𝒓 𝑮 𝟎 Exergonic Forward reaction is

(work producing) spontaneous
𝚫𝒓 𝑮 𝟎 Endergonic Reverse reaction is
(work consuming) spontaneous
𝚫𝒓 𝑮 𝟎 Neither exergonic nor Reaction is at
endergonic equilibrium

Srabani Taraphder, Department of Chemistry,

IIT Kharagpur 7
CY11003 Physical Chemistry 4/3/2023

Condition of Chemical Equilibrium

For the chemical reaction 𝑨 ⇌ 𝑩

𝚫𝒓 𝑮 𝝁𝑩 𝝁𝑨 𝒆𝒒𝒖𝒊𝒍𝒊𝒃𝒓𝒊𝒖𝒎 𝟎

The values of 𝝁𝑩 and 𝝁𝑨 depend on the composition of the

reaction mixture at equilibrium

For the reaction CH 4 (g)  2 O 2 ( g )  CO 2 (g)  2 H 2 O ( l )

Reaction Gibbs energy

  
 r G  2  H 2 O ( l )   CO 2 ( g )   CH 4 (g)  2O2 (g ) 
Condition of chemical equilibrium

𝟐 𝝁𝑯𝟐 𝑶 𝒍 𝝁𝑪𝑶𝟐 𝒈 𝝁𝑪𝑯𝟒 𝒈 𝟐𝝁𝑶𝟐 𝒈 𝒆𝒒 𝟎

Description of Chemical Equilibrium

in terms of
Equilibrium Constant

1. Perfect gas equilibria

2. General chemical reaction equilibrium

Srabani Taraphder, Department of Chemistry,

IIT Kharagpur 8
CY11003 Physical Chemistry 4/3/2023

Ideal Gas Equilibrium

• For 𝑨 𝒈 ⇌ 𝑩 𝒈 , let both 𝑨 and 𝑩 be ideal gases
𝒑𝒊
• For 𝒊 𝑨, 𝑩 𝝁𝒊 𝝁𝒊 𝟎 𝑹𝑻 𝒍𝒏 ≡ 𝝁𝒊 𝟎 𝑹𝑻 𝒍𝒏 𝒑𝒊
𝒑𝟎

𝝏𝑮 𝒑𝑩
• 𝚫𝒓 𝑮 𝝁𝑩 𝝁𝑨 𝝁𝑩 𝟎 𝝁𝑨 𝟎 𝑹𝑻 𝒍𝒏
𝝏𝝃 𝑻,𝒑 𝒑𝑨

𝜟𝒓 𝑮 𝜟𝒓 𝑮𝟎 𝑹𝑻 𝒍𝒏 𝑸
For any extent of reaction
Reaction quotient 𝑸
𝒑𝑩 ∆𝒇 𝑮𝟎 𝒎
𝒑𝑨
standard molar
Standard Reaction Gibbs energy Gibbs energy of
formation
𝜟𝒓 𝑮𝟎 𝝁𝑩 𝟎 𝝁𝑨 𝟎 ∆𝒇 𝑮𝟎 𝒎,𝑩 ∆𝒇 𝑮𝟎 𝒎,𝑨

Ideal Gas Equilibrium

𝑨 ⇌ 𝑩
exergonic

𝑨 𝒈 ⇌ 𝑩 𝒈 𝜟𝒓 𝑮 𝜟𝒓 𝑮𝟎 𝑹𝑻 𝒍𝒏 𝑸 endergonic

• At equilibrium, 𝜟𝒓 𝑮 𝟎
𝝃

𝒑𝑩
• Let 𝑲 Thus, 𝜟𝒓 𝑮𝟎 𝑹𝑻 𝒍𝒏 𝑲
𝒑𝑨 𝒆𝒒𝒖𝒊𝒍𝒊𝒃𝒓𝒊𝒖𝒎

𝜟𝒓 𝑮𝟎 𝑲 Partial Favoured at
pressures equilibrium
𝟎 𝟏 𝒑𝑨 𝒑𝑩 𝑨

𝟎 𝟏 𝒑𝑨 𝒑𝑩 𝑩

Srabani Taraphder, Department of Chemistry,

IIT Kharagpur 9
CY11003 Physical Chemistry 4/3/2023

A General Chemical Reaction Equilibrium

• For the chemical reaction ∑ 𝒋 𝝂𝒋 𝑿 𝒋 𝟎
𝝏𝑮
𝚫𝒓 𝑮 𝝂𝒋 𝝁𝒋
𝝏𝝃 𝑻,𝒑 𝒋
• In general, 𝝁𝒋 𝝁𝟎 𝒋 𝑹𝑻 𝒍𝒏 𝒂𝒋 [𝒂𝒋 : activity of 𝒋-th specie]

• 𝚫𝒓 𝑮 𝜟 𝒓 𝑮𝟎 𝐑𝐓 𝐥𝐧 𝐐 , 𝜟 𝒓 𝑮𝟎 ∑𝒋 𝝂𝒋 𝝁𝟎 𝒋 ; 𝑸 ∏ 𝒋 𝒂 𝒋 𝝂𝒋

• At equilibrium, 𝜟𝒓 𝑮𝟎 𝑹𝑻 𝒍𝒏 𝑲, with 𝐊 ∏ 𝒋 𝒂 𝒋 𝝂𝒋
𝒆𝒒

𝒂 𝑵𝟐 𝑶𝟒
Example 𝟐𝑵𝑶𝟐 𝒈 ⇌ 𝑵𝟐 𝑶𝟒 𝒈 𝑲
𝒂𝑵𝑶𝟐 𝟐

• In practical applications, aj is approximated by numerical values of molalities

/ by molar concentration / numerical values of partial pressures
• Equilibrium constant for any reaction can be calculated from tables of
thermodynamic data.

Response of Equilibrium
to
Changes in Pressure and Temperature

Le Châtelier’s Principle

“If a system at equilibrium is disturbed by a change in

temperature, pressure, or the concentration of one of the
components, the system will shift its equilibrium position so as to
counteract the effect of the disturbance.”

Srabani Taraphder, Department of Chemistry,

IIT Kharagpur 10
CY11003 Physical Chemistry 4/3/2023

Temperature dependence of equilibrium constant

 rG 0
  RT ln K d ln K
 
 0
1 d  rG /T 
dT R dT


d  rG 0
/T    r H 0
(Gibbs Helmholtz Equation)
dT 2
T

d ln K rH 0
 van’t Hoff equation
dT RT 2
For exothermic reactions, K decreases with increasing T

0
rH  1 1 
 ln K 1    
ln K 2 T  T 
R  2 1 

Standard Reaction Enthalpy and Entropy

∆𝒓 𝑮𝟎
𝑲 𝒆𝒙𝒑 ∆𝒓 𝑯𝟎 𝟎
𝑹𝑻

∆𝒓 𝑯𝟎 𝑻∆𝒓 𝑺𝟎
𝑲 𝒆𝒙𝒑
𝑹𝑻
∆𝒓 𝑯𝟎 ∆𝒓 𝑺𝟎
𝑲 𝒆𝒙𝒑 𝒆𝒙𝒑
𝑹𝑻 𝑹

∆𝒓 𝑯𝟎 𝟎
∆𝒓 𝑯𝟎 ∆𝒓 𝑺𝟎
𝒍𝒏 𝑲
𝑹𝑻 𝑹

∆𝒓 𝑯𝟎 𝝂𝒊 𝑯𝒊 𝟎 ∆𝒓 𝑺𝟎 𝝂𝒊 𝑺𝒊 𝟎
𝒊 𝒊

Srabani Taraphder, Department of Chemistry,

IIT Kharagpur 11
CY11003 Physical Chemistry 4/3/2023

Change in Equilibrium Constant K with pressure

• 𝜟𝒓 𝑮𝟎 𝑹𝑻 𝒍𝒏 𝑲

• 𝜟𝒓 𝑮𝟎 is defined at a single standard pressure

• Therefore,

𝝏𝑲
𝟎
𝝏𝒑 𝑻

Change in Equilibrium Constant K with pressure

𝑨 𝒈 ⇌ 𝟐𝑩 𝒈  : degree of dissociation of A

Le-Chatelier’s principle
As pressure is increased, 𝜶 should decrease

From standard reaction Gibbs energy

𝝏𝑲
𝟎
𝝏𝒑 𝑻

Srabani Taraphder, Department of Chemistry,

IIT Kharagpur 12
CY11003 Physical Chemistry 4/3/2023

Change in Equilibrium Constant K with pressure

 : degree of
𝑨 𝒈 ⇌ 𝟐𝑩 𝒈 dissociation of A

𝑨 𝑩
𝒕 𝟎 1 0
At equilibrium 𝟏 𝜶 𝟐𝜶
Mole fraction 𝒙𝒊 𝟏 𝜶 𝟐𝜶
𝟏 𝜶 𝟏 𝜶
Partial pressure, 𝟏 𝜶 𝟐𝜶
𝒑 𝒑
𝟏 𝜶 𝟏 𝜶
𝒑𝒊 (bar)
𝟏/𝟐
𝟏
𝒑𝒊
𝝂𝒊
𝟒 𝜶𝟐 𝒑 𝝏𝑲 𝜶
𝑲𝒑 𝟎⇒ 𝟒𝒑
𝝏𝒑 𝑻 𝟏
𝒑𝟎 𝟏 𝜶𝟐 𝒑𝟎 𝑲𝒑
𝒊

Change in Equilibrium Constant K with pressure

 : degree of
𝑨 𝒈 ⇌ 𝟐𝑩 𝒈 dissociation of A

𝝏𝑲 𝟏/𝟐
𝟏
𝟎 𝜶
𝝏𝒑 𝟒𝒑
𝑻 𝟏
𝑲𝒑

As the pressure 𝒑 is increased, 𝜶 decreases

Even if the equilibrium constant 𝑲𝒑 is independent of pressure, 𝒑,

amounts of the reactant and product are dependent on the pressure

Srabani Taraphder, Department of Chemistry,

IIT Kharagpur 13
CY11003 Physical Chemistry 4/3/2023

Reaction Gibbs Energy and Composition of Reaction

Mixture at Constant 𝑻 and 𝒑
𝝏𝑮
𝚫𝒓 𝑮 𝝁𝑩 𝝁𝑨 𝑵𝟐 𝑶𝟒 𝒈 ⇌ 𝟐 𝑵𝑶𝟐 𝒈
𝝏𝝃 𝑻,𝒑
Assumption: both reactant and product behave ideally
𝑵𝟐 𝑶 𝟒 𝒈 𝑵𝑶𝟐 𝒈

𝝂𝒊 -1 +2

Initial mole number 1 0

For an advancement 𝝃 of the reaction

Mole number 1-𝝃 2𝝃

Total mole number 1+𝝃

Mole fraction 𝟏 𝝃 𝟐𝝃
𝟏 𝝃 𝟏 𝝃
Partial pressures 𝟏 𝝃 𝟐𝝃
𝒑 𝒑
𝟏 𝝃 𝟏 𝝃

Reaction Gibbs Energy and Composition of Reaction

Mixture at Constant 𝑻 and 𝒑
𝝏𝑮 𝑵𝟐 𝑶𝟒 𝒈 ⇌ 𝟐 𝑵𝑶𝟐 𝒈
𝚫𝒓 𝑮 𝝁𝑩 𝝁𝑨
𝝏𝝃 𝑻,𝒑
Assumption: both reactant and product behave ideally
𝑵𝟐 𝑶 𝟒 𝒈 𝑵𝑶𝟐 𝒈

𝝂𝒊 -1 +2

Initial mole number 1 0

For an advancement 𝝃 of the reaction

Partial pressures 𝟏 𝝃 𝟐𝝃
𝒑 𝒑
𝟏 𝝃 𝟏 𝝃

Reaction quotient 𝟒𝝃𝟐 𝒑

𝟏 𝝃𝟐

𝚫 𝒓 𝑮𝟎 𝟒. 𝟕𝟕 𝒌𝑱 𝒎𝒐𝒍 𝟏 At 298 K, 1.0 bar

𝟏
𝚫𝒓 𝑮 (𝒌𝑱 𝒎𝒐𝒍 ) 𝟒. 𝟕𝟕 𝑹𝑻 𝐥𝐧 𝑸

Srabani Taraphder, Department of Chemistry,

IIT Kharagpur 14
CY11003 Physical Chemistry 4/3/2023

Applications of Equilibrium Constants

Predicting the Direction of Reaction

• If Q > K the reverse reaction must occur to reach equilibrium

• If Q < K the forward reaction must occur to reach equilibrium

Chemical Equilibrium – A Dynamic Equilibrium

• Upon addition of reactants and/or products, they react until a constant
amount of reactants and products are present
equilibrium w.r.t ‘matter flow’ from reactant to product state

• Equilibrium is dynamic since product is constantly made (forward reaction),

but at the same rate it is consumed (reverse reaction)

Srabani Taraphder, Department of Chemistry,

IIT Kharagpur 15