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Chapter 11: Thermodynamics

Unit VIII – Thermodynamics


11.1 Thermal Equilibrium and Zeroth Law

Thermal equilibrium: Two bodies are in thermal equilibrium when they are at the same temperature and no net heat flows between them.

Zeroth Law of Thermodynamics:

If body A is in thermal equilibrium with body C, and body B is also in thermal equilibrium with body C, then A and B are in thermal equilibrium with each other.

This defines temperature as a fundamental measurable quantity.


11.2 Internal Energy, Heat, and Work

  • Internal energy (U): Total kinetic + potential energy of all molecules of a system.
  • Heat (Q): Energy transferred due to temperature difference between system and surroundings.
  • Work done by gas (W): \(W = \int P,dV\) = area under P-V curve.

Sign Convention:

  • Q positive: heat given to the system
  • W positive: work done by the system

11.3 First Law of Thermodynamics

The change in internal energy of a system equals the heat supplied to it minus the work done by it.

\[ \boxed{\Delta U = Q - W} \]

Consequences:

  • For a cyclic process: \(\Delta U = 0 \Rightarrow Q = W\)
  • For isochoric (\(\Delta V = 0\)): \(W = 0 \Rightarrow \Delta U = Q\)
  • For isobaric (\(\Delta P = 0\)): \(W = P\Delta V\)

11.4 Thermodynamic Processes

11.4.1 Isothermal Process (constant temperature)

For ideal gas: \(PV = \text{constant}\) (Boyle’s Law)

\[ W = nRT\ln\frac{V_2}{V_1} \]

Since \(T\) is constant: \(\Delta U = 0 \Rightarrow Q = W\)

11.4.2 Adiabatic Process (no heat exchange, Q = 0)

\[ PV^\gamma = \text{constant}, \quad TV^{\gamma-1} = \text{constant} \]

\[ W = \frac{P_1 V_1 - P_2 V_2}{\gamma - 1} = \frac{nR(T_1 - T_2)}{\gamma - 1} \]

Since \(Q = 0\): \(\Delta U = -W\)

11.4.3 Isochoric Process (constant volume)

\[ W = 0 \Rightarrow \Delta U = Q = nC_V\Delta T \]

11.4.4 Isobaric Process (constant pressure)

\[ W = P\Delta V = nR\Delta T \]

\[ Q = nC_P\Delta T, \quad \Delta U = nC_V\Delta T \]

Table: \(C_P - C_V = R\) and \(\gamma = C_P/C_V\)


11.5 P-V Diagrams

P-V Diagrams for Different Processes V → P Isothermal (T=const) Adiabatic (steeper) Isobaric (P=const) Isochoric (V=const) Area under P-V curve = Work done by gas Adiabatic curve is steeper than isothermal (γ > 1)

11.6 Second Law of Thermodynamics

Kelvin-Planck Statement:

No heat engine can convert heat entirely into work without rejecting some heat to a colder reservoir.

Clausius Statement:

Heat cannot spontaneously flow from a colder to a hotter body.

Both statements are equivalent.


11.7 Heat Engine and Efficiency

A heat engine takes heat \(Q_1\) from a hot source, does work \(W\), and rejects heat \(Q_2\) to a cold sink:

\[ W = Q_1 - Q_2 \]

\[ \eta = \frac{W}{Q_1} = 1 - \frac{Q_2}{Q_1} \]

Carnot engine (maximum efficiency):

\[ \eta_{Carnot} = 1 - \frac{T_2}{T_1} \]

where \(T_1\) = temperature of hot source, \(T_2\) = temperature of cold sink (in Kelvin).


Key Formulas Summary

FormulaQuantity
\(\Delta U = Q - W\)First Law
\(W = \int P,dV\)Work done by gas
\(PV^\gamma = \text{const}\)Adiabatic process
\(W_{iso} = nRT\ln(V_2/V_1)\)Isothermal work
\(\eta = 1 - T_2/T_1\)Carnot efficiency
\(C_P - C_V = R\)Mayer’s relation

Practice Questions

Section A – MCQ (1 mark each)

Q1. In an isothermal expansion of an ideal gas:

(a) Temperature increases   (b) Internal energy increases   (c) Internal energy remains constant   (d) Heat exchanged is zero

Answer

(c) Internal energy remains constant — For ideal gas, U depends only on T; isothermal means T = const.


Q2. A Carnot engine works between 500 K and 300 K. Its efficiency is:

(a) 20%   (b) 30%   (c) 40%   (d) 60%

Answer

(c) 40% — \(\eta = 1 - 300/500 = 1 - 0.6 = 0.4 = 40%\)


Section B – Short Answer (2–3 marks)

Q3. In an adiabatic process, a gas is compressed from V to V/2. If \(\gamma = 1.4\) and initial pressure is \(10^5\) Pa, find the final pressure.

Answer

\(PV^\gamma = P’V’^\gamma\)

\[ P’ = P\left(\frac{V}{V’}\right)^\gamma = 10^5 \times (2)^{1.4} = 10^5 \times 2.639 \approx \mathbf{2.64 \times 10^5 \text{ Pa}} \]


Section D – Competency-Based Questions

Q4. (Case Study) A gas undergoes the cycle: Isothermal expansion → Isochoric cooling → Isobaric compression → Isochoric heating.

(i) Sketch the P-V diagram.

(ii) In which process is work done by the gas positive?

(iii) State the First Law for the adiabatic process.

(iv) Why is the efficiency of a heat engine always less than 100%?

Answer

(i) P-V diagram: A→B is hyperbola (isothermal expand), B→C is vertical line going down (isochoric cool), C→D is horizontal line going left (isobaric compress), D→A is vertical line going up (isochoric heat).

(ii) Work done by gas is positive during isothermal expansion (A→B) — gas expands, does positive work.

Work done during isobaric compression is negative (work done on gas).

(iii) For adiabatic: \(Q = 0 \Rightarrow \Delta U = -W\) — if gas is compressed adiabatically, internal energy increases (temperature rises).

(iv) By the second law of thermodynamics, some heat (\(Q_2\)) must always be rejected to the cold sink. Hence, \(\eta = 1 - Q_2/Q_1 \lt 1\) always.