Thermodynamics

• Thermal equilibrium and definition of temperature

  • Zeroth law of thermodynamics

• Heat, work and internal energy

• First law of thermodynamics

• Isothermal and adiabatic processes

• Second law of thermodynamics −

  • Reversible and irreversible processes

• Heat engine and refrigerator

SUMMARY

1. The zeroth law of thermodynamics states that ‘two systems in thermal equilibrium with a third system separately are in thermal equilibrium with each other’. The Zeroth Law leads to the concept of temperature.

2. Internal energy of a system is the sum of kinetic energies and potential energies of the molecular constituents of the system. It does not include the over-all kinetic energy of the system. Heat and work are two modes of energy transfer to the system. Heat is the energy transfer arising due to temperature difference between the system and the surroundings. Work is energy transfer brought about by other means, such as moving the piston of a cylinder containing the gas, by raising or lowering some weight connected to it.

3. The first law of thermodynamics is the general law of conservation of energy applied to any system in which energy transfer from or to the surroundings (through heat and work) is taken into account. It states that ∆Q = ∆U + ∆W where ∆Q is the heat supplied to the system, ∆W is the work done by the system and ∆U is the change in internal energy of the system.

4. For an ideal gas, the molar specific heat capacities at constant pressure and volume satisfy the relation Cp – Cv = R where R is the universal gas constant.

5. Equilibrium states of a thermodynamic system are described by state variables. The value of a state variable depends only on the particular state, not on the path used to arrive at that state. Examples of state variables are pressure (P ), volume (V ), temperature (T ), and mass (m ). Heat and work are not state variables. An Equation of State (like the ideal gas equation PV = µ RT ) is a relation connecting different state variables.

6. A quasi-static process is an infinitely slow process such that the system remains in thermal and mechanical equilibrium with the surroundings throughout. In a quasi-static process, the pressure and temperature of the environment can differ from those of the system only infinitesimally.

7. The second law of thermodynamics disallows some processes consistent with the First Law of Thermodynamics. It states Kelvin-Planck statement No process is possible whose sole result is the absorption of heat from a reservoir and complete conversion of the heat into work. Clausius statement No process is possible whose sole result is the transfer of heat from a colder object to a hotter object. Put simply, the Second Law implies that no heat engine can have efficiency η equal to 1 or no refrigerator can have co-efficient of performance α equal to infinity.

8. A process is reversible if it can be reversed such that both the system and the surroundings return to their original states, with no other change anywhere else in the universe. Spontaneous processes of nature are irreversible. The idealised reversible process is a quasi-static process with no dissipative factors such as friction, viscosity, etc.

9. If Q > 0, heat is added to the system

If Q < 0, heat is removed to the system

If W > 0, Work is done by the system

If W < 0, Work is done on the system

POINTS TO PONDER

1. Temperature of a body is related to its average internal energy, not to the kinetic energy of motion of its centre of mass. A bullet fired from a gun is not at a higher temperature because of its high speed.

2. Equilibrium in thermodynamics refers to the situation when macroscopic variables describing the thermodynamic state of a system do not depend on time. Equilibrium of a system in mechanics means the net external force and torque on the system are zero.

3. In a state of thermodynamic equilibrium, the microscopic constituents of a system are not in equilibrium (in the sense of mechanics).

4. Heat capacity, in general, depends on the process the system goes through when heat is supplied.

5. In isothermal quasi-static processes, heat is absorbed or given out by the system even though at every stage the gas has the same temperature as that of the surrounding reservoir. This is possible because of the infinitesimal difference in temperature between the system and the reservoir.