Class 11 Chemistry – Thermodynamics
Chapter Notes (Part 1)
Topics Covered
- Introduction to Thermodynamics
- System and Surroundings
- Boundary
- Types of Systems
- State of a System
- State Functions
- Internal Energy
- Work and Heat (Basic Concepts)
Chapter 5: Thermodynamics
What is Thermodynamics?
Thermodynamics is the branch of chemistry that studies the relationship between heat, work, and energy during physical and chemical changes.
It helps us understand:
- How energy changes during a reaction
- Whether a reaction absorbs or releases heat
- Whether a reaction can occur naturally
- How much energy is involved in a process
Examples
- Burning LPG releases heat.
- A battery converts chemical energy into electrical energy.
- An engine converts chemical energy into mechanical energy.
Important Point
Thermodynamics studies only the initial and final states of a system. It does not explain how fast a reaction occurs.
Important Terms
1. System
A system is the part of the universe chosen for study.
Examples
- Water inside a beaker
- Gas inside a cylinder
- Chemicals reacting in a flask
2. Surroundings
Everything outside the system is called the surroundings.
Example:
- If water in a beaker is the system, then the beaker, air, and room are the surroundings.
3. Universe
Universe = System + Surroundings
This is one of the most important definitions in thermodynamics.
Boundary
The surface that separates the system from its surroundings is called the boundary.
It may be:
- Real (glass wall of a flask)
- Imaginary
The boundary controls the exchange of matter and energy.
Types of Systems
Thermodynamic systems are classified according to the exchange of matter and energy.
| System | Matter Exchange | Energy Exchange | Example |
|---|---|---|---|
| Open System | Yes | Yes | Open beaker |
| Closed System | No | Yes | Closed steel vessel |
| Isolated System | No | No | Thermos flask |
1. Open System
Definition
An open system can exchange both matter and energy with the surroundings.
Example
- Tea in an open cup
- Water boiling in an open pan
Memory Trick
Open = Everything can move.
2. Closed System
Definition
A closed system can exchange energy only, but not matter.
Example
- Water in a sealed pressure cooker
- Gas inside a closed cylinder
Memory Trick
Closed = Heat can move, matter cannot.
3. Isolated System
Definition
An isolated system exchanges neither matter nor energy.
Example
- Thermos flask (approximately)
- Perfect insulated container (ideal)
Memory Trick
Isolated = Nothing enters or leaves.
Comparison of Systems
| Property | Open | Closed | Isolated |
|---|---|---|---|
| Matter transfer | ✓ | ✗ | ✗ |
| Energy transfer | ✓ | ✓ | ✗ |
| Example | Open beaker | Closed bottle | Thermos flask |
State of a System
The condition of a system at any moment is called its state.
The state is described using measurable quantities such as:
- Pressure (P)
- Volume (V)
- Temperature (T)
- Amount of substance (n)
These quantities are called state variables.
State Variables
State variables describe the present condition of a system.
Examples:
- Pressure
- Temperature
- Volume
- Number of moles
Changing any one of these changes the state of the system.
State Function
A state function depends only on the initial and final states, not on the path followed.
Examples
- Internal Energy (U)
- Pressure (P)
- Volume (V)
- Temperature (T)
- Enthalpy (H)
Example
If you travel from Delhi to Mumbai:
- by train,
- by bus,
- by plane,
your final location is the same. Similarly, a state function depends only on the initial and final states, not on the route taken.
Internal Energy (U)
Internal energy is the total energy present inside a system.
It includes:
- Kinetic energy of particles
- Potential energy of particles
- Chemical energy
- Electrical energy
- Other microscopic forms of energy
Symbol:
U
Unit:
Joule (J) or kJ
Internal Energy Changes When
- Heat is supplied or removed.
- Work is done on or by the system.
- Matter enters or leaves the system.
Change in Internal Energy
The change in internal energy is represented as:
ΔU = U₂ − U₁
where:
- U₁ = Initial internal energy
- U₂ = Final internal energy
Why is Internal Energy a State Function?
Suppose water is heated:
Method 1:
- Stirring with paddles
Method 2:
- Electric heater
If both methods raise the water to the same final temperature, the change in internal energy is the same.
Therefore,
Internal energy depends only on the initial and final states, not on the method used.
Work (w)
Work is done whenever energy is transferred by applying force.
In thermodynamics:
- Compression → Work is done on the system.
- Expansion → Work is done by the system.
IUPAC Sign Convention
| Process | Sign of Work |
|---|---|
| Work done on system | Positive (+) |
| Work done by system | Negative (−) |
Heat (q)
Heat is the energy transferred because of a temperature difference.
Sign Convention
| Process | Sign |
|---|---|
| Heat absorbed by system | Positive (+) |
| Heat released by system | Negative (−) |
Important Sign Convention Table
| Quantity | Positive When | Negative When |
|---|---|---|
| Heat (q) | System absorbs heat | System releases heat |
| Work (w) | Work done on system | Work done by system |
Quick Revision Box
Learn These Definitions
System: Part of the universe under study.
Surroundings: Everything outside the system.
Boundary: Surface separating system and surroundings.
Open System: Exchanges matter and energy.
Closed System: Exchanges only energy.
Isolated System: Exchanges neither matter nor energy.
State Function: Depends only on initial and final states.
Internal Energy: Total energy possessed by a system.
Heat: Energy transferred because of temperature difference.
Work: Energy transferred by force.
Important Exam Questions
1. Define system and surroundings with examples.
2. Differentiate between open, closed, and isolated systems.
3. What is a state function? Give four examples.
4. Explain internal energy. Why is it called a state function?
Chapter Notes (Part 3)
Topics Covered
- Enthalpy (H)
- Enthalpy Change (ΔH)
- Relation between ΔH and ΔU
- Heat Capacity
- Molar Heat Capacity
- Specific Heat Capacity
- Relation between Cp and Cv
- Calorimetry
(These notes are rewritten in simple original language for Class 11 students.)
Enthalpy (H)
Why do we need Enthalpy?
Most chemical reactions are performed at constant atmospheric pressure.
At constant volume:ΔU=qv
But in laboratories, reactions usually occur at constant pressure. Therefore, a new thermodynamic function called enthalpy is used.
Definition of Enthalpy
Enthalpy is the heat content of a system at constant pressure.
It is represented by:H
Mathematically:H=U+PV
Where:
- H = Enthalpy
- U = Internal energy
- P = Pressure
- V = Volume
Change in Enthalpy (ΔH)
The change in enthalpy is:ΔH=H2−H1
At constant pressure:ΔH=qp
This means:
Heat absorbed or released at constant pressure is equal to enthalpy change.
Types of Enthalpy Change
1. Exothermic Reaction
A reaction that releases heat is called an exothermic reaction.
Example:C+O2→CO2+heat
For exothermic reactions:ΔH<0
Heat leaves the system.
2. Endothermic Reaction
A reaction that absorbs heat is called an endothermic reaction.
Example:CaCO3+heat→CaO+CO2
For endothermic reactions:ΔH>0
Heat enters the system.
Relationship Between ΔH and ΔU
We know:H=U+PV
Change in enthalpy:ΔH=ΔU+Δ(PV)
At constant pressure:ΔH=ΔU+PΔV
For Gaseous Reactions
Using ideal gas equation:PV=nRT
The relationship becomes:ΔH=ΔU+ΔngRT
Where:
- Δng = moles of gaseous products − moles of gaseous reactants
- R = Gas constant
- T = Temperature
Important Cases
Case 1: No change in number of gas molecules
If:Δng=0
Then:ΔH=ΔU
Example:H2+Cl2→2HCl
Case 2: Solids and Liquids
For reactions involving only solids and liquids:ΔH≈ΔU
because volume change is very small.
Heat Capacity
Definition
Heat capacity is the amount of heat required to increase the temperature of a system by 1 K (or 1°C).
Symbol:C
Formula:q=CΔT
Where:
- q = Heat supplied
- C = Heat capacity
- ΔT = Temperature change
Factors Affecting Heat Capacity
Heat capacity depends on:
- Amount of substance
- Nature of substance
- Composition of substance
Example:
Water has high heat capacity, so it requires more heat to increase its temperature.
Types of Heat Capacity
1. Molar Heat Capacity
The heat required to raise the temperature of one mole of a substance by 1 K.
Formula:Cm=nC
Unit:Jmol−1K−1
2. Specific Heat Capacity
The heat required to raise the temperature of one gram of a substance by 1 K.
Formula:q=mcΔT
Where:
- m = mass
- c = specific heat capacity
- ΔT = temperature change
Heat Capacity at Constant Volume and Pressure
There are two types:
1. Heat Capacity at Constant Volume (Cv)
At constant volume:qv=CvΔT
Since no expansion occurs:ΔU=qv
2. Heat Capacity at Constant Pressure (Cp)
At constant pressure:qp=CpΔT
Since:ΔH=qp
Relation Between Cp and Cv
For an ideal gas:Cp−Cv=R
Where:
- Cp = Heat capacity at constant pressure
- Cv = Heat capacity at constant volume
- R = Gas constant
Calorimetry
Definition
Calorimetry is the experimental technique used to measure heat changes during chemical reactions.
The instrument used is called a calorimeter.
Types of Calorimetry
1. Constant Volume Calorimetry
Used to measure:ΔU
Instrument:
Bomb Calorimeter
Working:
- Reaction occurs inside a strong steel container.
- Container is surrounded by water.
- Heat released increases water temperature.
- Temperature change is used to calculate heat.
Because volume remains constant:ΔU=qv
2. Constant Pressure Calorimetry
Used to measure:ΔH
At constant pressure:ΔH=qp
Used for reactions occurring in open containers.
Important Differences
| ΔU | ΔH |
|---|---|
| Change in internal energy | Change in enthalpy |
| Measured at constant volume | Measured at constant pressure |
| ΔU = qv | ΔH = qp |
| Used in bomb calorimeter | Used in pressure calorimeter |
Quick Revision Formula Sheet
First Law:
ΔU=q+w
Enthalpy:
H=U+PV
Enthalpy Change:
ΔH=ΔU+PΔV
Gas Reaction:
ΔH=ΔU+ΔngRT
Heat Capacity:
q=CΔT
Specific Heat:
q=mcΔT
Ideal Gas:
Cp−Cv=R
Important Exam Questions
1. Define enthalpy and write its mathematical expression.
2. Differentiate between ΔH and ΔU.
3. Derive the relationship between ΔH and ΔU.
4. What is calorimetry? Explain bomb calorimeter.
5. Explain Cp and Cv relationship.
Chapter Notes (Part 4)
Topics Covered
- Reaction Enthalpy (ΔrH)
- Standard Enthalpy of Reaction
- Enthalpy of Phase Transformations
- Standard Enthalpy of Formation
- Thermochemical Equations
- Hess’s Law of Constant Heat Summation
Reaction Enthalpy (ΔrH)
Definition
The heat change that occurs during a chemical reaction at constant pressure is called reaction enthalpy.
It is represented as:ΔrH
For a reaction:Reactants→Products
Reaction enthalpy is:ΔrH=Enthalpy of products−Enthalpy of reactants
orΔrH=∑Hproducts−∑Hreactants
Meaning of Reaction Enthalpy
If:
ΔrH<0
Reaction is exothermic.
- Heat is released.
- Products have lower enthalpy than reactants.
Example:CH4+2O2→CO2+2H2O
If:
ΔrH>0
Reaction is endothermic.
- Heat is absorbed.
- Products have higher enthalpy.
Example:CaCO3→CaO+CO2
Standard Enthalpy of Reaction (ΔrH°)
The enthalpy change when a reaction occurs with all substances in their standard states is called standard enthalpy of reaction.
Symbol:ΔrH∘
Standard State
The standard state of a substance is its pure form at:
- Pressure = 1 bar
- Specified temperature (usually 298 K)
Examples:
- Pure liquid water at 298 K and 1 bar
- Solid iron at 1 bar pressure
Enthalpy Changes During Phase Transformation
A phase change involves energy change.
Examples:
- Melting
- Boiling
- Sublimation
1. Enthalpy of Fusion (ΔfusH°)
Definition
The heat required to convert one mole of solid into liquid at constant temperature and standard pressure is called standard enthalpy of fusion.
Example:H2O(s)→H2O(l) ΔfusH∘=+6.00kJmol−1
Important Point
Melting is an endothermic process.
Therefore:ΔfusH∘>0
2. Enthalpy of Vaporisation (ΔvapH°)
Definition
The heat required to convert one mole of liquid into vapour at constant temperature and pressure is called standard enthalpy of vaporisation.
Example:H2O(l)→H2O(g) ΔvapH∘=+40.79kJmol−1
3. Enthalpy of Sublimation (ΔsubH°)
Definition
The enthalpy change when one mole of a solid changes directly into vapour is called standard enthalpy of sublimation.
Example:CO2(s)→CO2(g)
Factors Affecting Phase Change Enthalpy
The amount of heat required depends on:
- Strength of intermolecular forces
- Nature of substance
Stronger intermolecular forces require more energy.
Example:
- Water has strong hydrogen bonding.
- More heat is needed to vaporise water compared with many organic liquids.
Standard Enthalpy of Formation (ΔfH°)
Definition
The enthalpy change when one mole of a compound is formed from its elements in their most stable forms under standard conditions is called standard enthalpy of formation.
Symbol:ΔfH∘
Examples
Formation of Water:
H2(g)+21O2(g)→H2O(l) ΔfH∘=−285.8kJmol−1
Formation of Methane:
C(graphite)+2H2(g)→CH4(g) ΔfH∘=−74.81kJmol−1
Important Rule
The standard enthalpy of formation of an element in its most stable state is:0
Examples:
- H₂(g) = 0
- O₂(g) = 0
- C(graphite) = 0
Calculation of Reaction Enthalpy Using Formation Enthalpies
Formula:ΔrH∘=∑ΔfH∘(products)−∑ΔfH∘(reactants)
Steps:
- Write balanced equation.
- Multiply each substance by its coefficient.
- Add product enthalpies.
- Add reactant enthalpies.
- Subtract.
Thermochemical Equation
A balanced chemical equation along with its enthalpy change is called a thermochemical equation.
Example:C2H5OH(l)+3O2(g)→2CO2(g)+3H2O(l) ΔrH∘=−1367kJmol−1
The physical states of substances must be mentioned.
Rules for Thermochemical Equations
Rule 1
Coefficients represent number of moles, not molecules.
Rule 2
If the equation is multiplied by a number, ΔH is also multiplied by that number.
Example:
If:ΔH=−100kJ
For half reaction:ΔH=−50kJ
Rule 3
If a reaction is reversed, the sign of ΔH changes.
Example:
Forward:N2+3H2→2NH3 ΔH=−91.8kJ
Reverse:2NH3→N2+3H2 ΔH=+91.8kJ
Hess’s Law of Constant Heat Summation
Statement
If a reaction occurs in several steps, the total enthalpy change is equal to the sum of enthalpy changes of all steps.ΔHoverall=ΔH1+ΔH2+ΔH3+…
Why Hess’s Law Works?
Because enthalpy is a state function.
It depends only on:
- Initial state
- Final state
It does not depend on the path followed.
Example of Hess’s Law
Formation of CO₂:
Direct method:C+O2→CO2
or through two steps:
Step 1:C+21O2→CO
Step 2:CO+21O2→CO2
Total:ΔH=ΔH1+ΔH2
Applications of Hess’s Law
It is used to calculate:
- Enthalpy of formation
- Enthalpy of combustion
- Bond energies
- Heat changes that cannot be measured directly
Quick Revision Table
| Quantity | Meaning |
|---|---|
| ΔrH° | Standard reaction enthalpy |
| ΔfH° | Formation enthalpy |
| ΔfusH° | Melting heat |
| ΔvapH° | Vaporisation heat |
| ΔsubH° | Sublimation heat |
Important Exam Questions
1. Define standard enthalpy of formation.
2. What is a thermochemical equation?
3. State Hess’s law of constant heat summation.
4. Why is enthalpy a state function?
5. Explain the difference between exothermic and endothermic reactions.
Chapter Notes (Part 5 – Final Part)
Topics Covered
- Entropy (ΔS)
- Second Law of Thermodynamics
- Spontaneous and Non-spontaneous Processes
- Gibbs Free Energy (ΔG)
- Relation Between ΔG and Spontaneity
- Complete Chapter Revision Sheet
Entropy (S)
Definition
Entropy is a measure of the randomness or disorder of a system.
Symbol:S
A system with greater disorder has higher entropy.
Understanding Entropy
Particles in matter can be arranged differently:
Solid
- Particles are tightly arranged.
- Movement is limited.
- Disorder is low.
Therefore:Ssolid<Sliquid
Liquid
- Particles have more freedom of movement.
Gas
- Particles move freely.
- Disorder is maximum.
Therefore:Ssolid<Sliquid<Sgas
Change in Entropy (ΔS)
The change in entropy is:ΔS=Sfinal−Sinitial
Cases
1. Increase in Entropy
ΔS>0
Example:H2O(l)→H2O(g)
Liquid changes into gas, so disorder increases.
2. Decrease in Entropy
ΔS<0
Example:H2O(g)→H2O(l)
Gas changes into liquid, so disorder decreases.
Factors Affecting Entropy
1. Physical State
Entropy order:Gas>Liquid>Solid
2. Temperature
Higher temperature increases molecular movement.
Therefore:
Higher temperature → Higher entropy
3. Number of Gas Molecules
More gas molecules generally mean more randomness.
Example:N2+3H2→2NH3
Gas molecules decrease, so entropy decreases.
4. Molecular Complexity
Larger molecules generally have more possible arrangements and higher entropy.
Second Law of Thermodynamics
Statement
A spontaneous process is accompanied by an increase in the total entropy of the universe.
Mathematically:ΔSuniverse>0
For an equilibrium process:ΔSuniverse=0
Spontaneous Process
Definition
A process that occurs naturally under given conditions is called a spontaneous process.
Examples:
- Flow of heat from hot object to cold object
- Expansion of gas
- Burning of fuel
Important Point
A spontaneous process:
- Does not always occur quickly.
- Depends on thermodynamic conditions.
Example:
Conversion of diamond into graphite is thermodynamically possible but occurs extremely slowly.
Non-spontaneous Process
A process that does not occur naturally and requires continuous energy supply is called a non-spontaneous process.
Examples:
- Electrolysis of water
- Formation of glucose by photosynthesis
Factors Affecting Spontaneity
Spontaneity depends on:
- Enthalpy change (ΔH)
- Entropy change (ΔS)
- Temperature
Gibbs Free Energy (G)
Definition
Gibbs free energy is the energy available in a system that can be used to perform useful work.
Symbol:G
Gibbs Energy Change (ΔG)
The equation is:ΔG=ΔH−TΔS
Where:
- ΔG = Gibbs energy change
- ΔH = Enthalpy change
- T = Temperature in Kelvin
- ΔS = Entropy change
Significance of ΔG
Case 1: ΔG Negative
ΔG<0
Reaction is spontaneous.
Example:
Heat-releasing reactions.
Case 2: ΔG Positive
ΔG>0
Reaction is non-spontaneous.
Energy must be supplied.
Case 3: ΔG = 0
System is at equilibrium.
No net change occurs.
Relationship Between ΔH, ΔS and ΔG
| ΔH | ΔS | Spontaneity |
|---|---|---|
| Negative | Positive | Always spontaneous |
| Positive | Negative | Never spontaneous |
| Negative | Negative | Depends on temperature |
| Positive | Positive | Depends on temperature |
Temperature Effect on Spontaneity
Case 1
ΔH<0,ΔS>0
Both terms favour spontaneity.
Reaction is spontaneous at all temperatures.
Case 2
ΔH>0,ΔS<0
Both terms oppose spontaneity.
Reaction is never spontaneous.
Case 3
ΔH<0,ΔS<0
Spontaneous at low temperature.
Case 4
ΔH>0,ΔS>0
Spontaneous at high temperature.
Relation Between Gibbs Energy and Equilibrium Constant
For a reaction:aA+bB→cC+dD
The relationship is:ΔG∘=−RTlnK
Where:
- R = Gas constant
- T = Temperature
- K = Equilibrium constant
Meaning of Equilibrium Constant
If:
K>1
Products are favoured.ΔG∘<0
Reaction is spontaneous.
If:
K<1
Reactants are favoured.ΔG∘>0
Reaction is non-spontaneous.
Complete Thermodynamics Formula Sheet
1. First Law
ΔU=q+w
2. Work
w=−PextΔV
3. Enthalpy
H=U+PV
4. Enthalpy Change
ΔH=ΔU+PΔV
5. Gas Reaction
ΔH=ΔU+ΔngRT
6. Heat Capacity
q=CΔT
7. Specific Heat
q=mcΔT
8. Heat Capacity Relation
Cp−Cv=R
9. Entropy Change
ΔS=S2−S1
10. Gibbs Energy
ΔG=ΔH−TΔS
11. Gibbs-Energy and Equilibrium
ΔG∘=−RTlnK
Chapter One-Page Revision
Thermodynamics studies:
Heat + Work + Energy changes
System:
Part being studied
Surroundings:
Everything outside the system
First Law:
Energy is conservedΔU=q+w
Enthalpy:
Heat change at constant pressureΔH=qp
Entropy:
Measure of disorder
Spontaneous Process:
Natural process
Gibbs Energy:
Predicts spontaneityΔG<0
means spontaneous.
Most Important Board Exam Questions
1. State and explain the first law of thermodynamics.
2. Derive the relationship between ΔH and ΔU.
3. Explain Hess’s law with an example.
4. Define entropy and explain factors affecting it.
5. What is Gibbs free energy? Explain its importance.
6. Explain conditions for spontaneity using ΔG.
7. Differentiate between:
- Open, closed and isolated systems
- Exothermic and endothermic reactions
- ΔH and ΔU
- Reversible and irreversible processes