Thermodynamics

The branch of physics which deals with the study of transformation of heat into other
forms of energy and vice-versa is called thermodynamics.
Thermodynamics is a macroscopic science. It deals with bulk systems and does not go
into the molecular constitution of matter.

Basically a study of interrelation between Heat and Mechanical energy.

The entire branch is based on two laws. 1 st law concerns with energy relation and 2nd
law tells how energy transformation takes place.

 Some common terms used in thermodynamics

 Thermodynamic system: a collection of large number of particles having
specific values of pressure(P), volume(V), temperature(T) that may have
potential to exchange energy with the surroundings. e.g an ideal gas
enclosed in a cylinder connected with a frictionless piston.
 Thermodynamic variables or State: P, V and T; when they change with
time then we say the state of the system has changed or a
Thermodynamic Process (four basic types, as discussed later) has
taken place.
 State Variables -> P, V, T and internal energy U
 Quasi Static Process-> all intermediate states are in equilibrium. In this
the system changes its state very slowly so that it maintains thermal,
mechanical and chemical equilibrium with its surrounding throughout.
 Reversible process -> If the process can be turned back such that both
the system and the surroundings return to their original state, with no other
changes anywhere in the universe. A process is reversible only if it is
quasi-static and there is no dissipative effect.
 Indicator diagram -> A graphical representation demonstrating
interrelation between the thermodynamic variables. Indicates the type of
thermodynamic process. e.g P-V; V-T; P-T diagrams.
 Internal energy(U) -> Sum total of kinetic energy of all constituent
particles and sum of all the potential energies of interaction among these
particles. U = f(T) only for ideal gases and U = f(P,T) for real gases. U of
a system may change (U) if a thermodynamic process takes place. U
for a cyclic process is always zero.
 Work Done -> W = dW = pdV i.e work done in a finite change of volume
from Vi to Vf. Area of P-V curve with the volume axis gives the work done.
Work done by the system depends not only on initial and final states, but
 also on the intermediate states, that is on the path. For a cyclic process
W is calculated as the area enclosed by the closed P-V curve.

A Cyclic Process is eventually a series of operation, after which the system returns
back to its initial P,V and T.

Like in above given situation for the cyclic process ABCA, U = 0 and W = area of
triangle ABC = ½ .(2V0 – V0).(3P0 – P0) = P0V0

First law of Thermodynamics

The first law of thermodynamics is simply the general law of conservation of energy
applied to any system. According to this law, “the total heat energy change in any
system is the sum of the internal energy change and the work done.”
When a certain quantity of heat dQ is subjected to a system, a part of it is used in
increasing the internal energy by dU and a part is used in performing external work dW,
hence dQ = dU + dW

dU is a state function

dQ and dW are path functions

Sign Convention used:

 Heat supplied to the system -> +ve; Heat extracted from system -> -ve
 Work done by the system -> +ve; Work done on the system -> -ve
 Increase in internal energy ->+ve; Decrease on U -> -ve
Way of measurement:

 dQ = nCdT; where n is the number of moles; C is the molar specific heat

capacity and dT is the change in temperature.
 dU = nCvdT ; where Cv is the molar specific heat capacity at constant
value.
 dW = pdV

For gases, there are mainly two principal specific heat capacities. These are specific
heat capacity at constant volume(Cv) and specific heat capacity at constant
pressure(Cp).
From First Law of Thermodynamics we can find a relation between Cp and Cv According
to the relation Cp - Cv = R; R being the universal gas constant.

The specific heat capacity of a gas at constant pressure is greater than the specific heat
capacity of the gas at constant volume i.e. Cp > Cv. Reason is that when heat supplied
to a gas at constant volume, no work would be done by the gas against the external
pressure and all the energy is used to raise the temperature of the gas. On the other
hand when the heat is supplied to the gas at constant pressure, its volume increases
and the heat energy supplied to it is used to increase the temperature of the gas as well
as in doing the work against the external pressure.

Mathematically to find out the relation we proceed as follows:

Let P, V and T be the pressure, volume and absolute temperature initially of one mole of
an ideal gas.
Case (i): Let heat dQ is supplied to the gas at constant volume so that the temperature
increases by dT => dQ = 1 x Cv x dT; Again as per 1st law dQ = dU + dW = dU + PdV =
dU [since dV = 0 here] => dQ = dU

Thus we get dU = CvdT …(i)

If now the same gas is heated at constant pressure so that its temperature increases
by same amount dT only, the corresponding heat supplied can be expressed as
dQ’ = 1 x Cp x dT…(ii); Again as per first law as dQ’ = dU + dW => Cpdt = Cvdt +
PdV…(iii), from eqn (i) and (ii)

Now the ideal gas equation for 1 mole is PV = RT => PdV + VdP = RdT via
differentiating. As dP = 0 for constant pressure process => PdV = RdT

Putting it in eqn (iii), we get CpdT - CvdT = RdT => Cp – Cv = R