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Thermodynamics Notes

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26 views2 pages

Thermodynamics Notes

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rjkey70
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We take content rights seriously. If you suspect this is your content, claim it here.
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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

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