1.
Introduction
Thermodynamics is the study of energy, its transformations, and the relationships between various macros
2. Key Concepts and Terms
- System: The part of the universe under study.
- Surroundings: Everything else apart from the system.
Types of Systems:
- Open system: Exchanges both energy and matter with surroundings.
- Closed system: Exchanges only energy, not matter.
- Isolated system: Exchanges neither energy nor matter.
State Functions: Properties dependent only on the state of the system (e.g., pressure, volume, temperature
Process Types:
- Isothermal: Constant temperature.
- Adiabatic: No heat exchange.
- Isobaric: Constant pressure.
- Isochoric: Constant volume.
- Cyclic Process: Initial and final states are the same.
Internal Energy (U): The total energy of a system, including kinetic and potential energy.
3. The First Law of Thermodynamics
Statement: Energy can neither be created nor destroyed; it can only be transformed.
Mathematical Expression:
∆U = q + w
Where:
- ∆U: Change in internal energy
- q: Heat absorbed by the system (+ve if absorbed, -ve if released)
- w: Work done on/by the system (+ve if done on, -ve if done by)
Work Done in Isothermal Expansion/Compression (Ideal Gas):
w = -nRT ln(Vf / Vi)
4. Enthalpy (H)
Definition: Enthalpy is the heat content of a system at constant pressure.
H = U + PV
Change in Enthalpy (∆H): At constant pressure, ∆H = qp (heat at constant pressure).
Relationship Between ∆H and ∆U:
∆H = ∆U + ∆ngRT
Where ∆ng is the change in the number of moles of gaseous substances.
5. Heat Capacities
- Specific Heat (c): Heat required to raise the temperature of 1 gram of a substance by 1°C.
- Molar Heat Capacity (C): Heat required to raise the temperature of 1 mole of a substance by 1°C.
Relation Between Cp and Cv:
Cp - Cv = R
For ideal gases, γ = Cp / Cv (ratio of heat capacities).
6. The Second Law of Thermodynamics
Statement: The total entropy of an isolated system always increases for irreversible processes and remain
Entropy (S): A measure of randomness or disorder in a system.
∆S = qrev / T
Where qrev is the reversible heat exchange.
7. Gibbs Free Energy (G)
Definition: Gibbs Free Energy determines the spontaneity of a process.
G = H - TS
Change in Gibbs Free Energy (∆G):
∆G = ∆H - T∆S
- If ∆G < 0: Process is spontaneous.
- If ∆G > 0: Process is non-spontaneous.
- If ∆G = 0: System is in equilibrium.
8. The Third Law of Thermodynamics
Statement: The entropy of a perfectly crystalline substance approaches zero as the temperature approach
9. Hess's Law of Constant Heat Summation
The total enthalpy change of a reaction is the same, irrespective of the pathway taken.
∆Hreaction = Σ∆Hproducts - Σ∆Hreactants
10. Important Applications
- Determination of bond enthalpies.
- Calculation of equilibrium constants (K) using ∆G = -RT ln K.
- Predicting the feasibility of chemical reactions.
11. Sample Numerical Problems
1. Calculate ∆U if a system absorbs 500 J of heat and does 200 J of work.
Solution: ∆U = q + w = 500 + (-200) = 300 J
2. For a reaction with ∆H = -400 kJ and ∆S = -0.2 kJ/K at 300 K, find ∆G.
Solution: ∆G = ∆H - T∆S = -400 - (300 × -0.2) = -340 kJ
