Entropy The second law leads to the definition of a new property called entropy.

The Clausius Inequality The first law is simply an energy balance. However, the second law leads to an ine quality; an irreversible process is less efficient than a reversible process. Another im portant inequality in thermodynamics is the Clausius inequality:

That is, the cyclic integral of Q / T is always less than or equal to zero. This is val id for all cycles, reversible or irreversible. For internally reversible cycles, it can be shown that:

Entropy The Clausius inequality forms the basis for the definition of a new property called entropy. As can be seen in the equation above, for an internally reversible process the cy clic integral of Q / T is zero. A quantity whose cyclic integral is zero depends on t he state only and not the process path, and thus it is a property. Clausius in 1865 realized that he discovered a new property and he called it entrop y:

Entropy per unit mass is designated by s (kJ/kg.K). The entropy change of a system during a process can be calculated: (kJ/K)

To perform this integral, one needs to know the relation between Q and T during th e process. Note that the cyclic integral of Q / T will give us the entropy change only if the integration carried out along an internally reversible path between two states. For irreversible processes, we may imagine a reversible process between the two st ates (initial and final) and calculate the entropy change (since entropy is a property).

Principle of increase of entropy

Let a system change from state 1 to state 2 by a reversible process A and return to state 1 by another reversible process B. Then 1A2B1 is a reversible cycle. Therefore, the Clausius inequality gives:

If the system is restored to the initial state from 1 to state 2 by an irreversible process C, then 1A2C1 is an irreversible cycle. Then the Clausius inequality gives:

Subtracting the above equation from the first one,

Since the process 2B1 is reversible,

Where the equality sign holds good for a reversible process and the inequality sign holds good for an irreversible process. Now let us apply the above result to evaluate the entropy change of the universe when a system interacts with its surroundings and exchanges energy as heat with the surroundings.

Let Tsur and Tsys be the temperatures of the surroundings and the system such that Tsur >Tsys.Let dQ represent the energy transfer as heat from t he surroundings to the system during the given irreversible process. dSsys = dQ/Tsys dSsur = -dQ/Tsur dSuni = dSsys + dSsur = (dQ/T)sys (dQ/T)sur >0 Suni >0 (since Tsur>Tsys) If the system is isolated, there is no change in the entropy of the surroundings and S 0, for an isolated system Therefore the entropy of an isolated system either increases or, in the limit, remains constant. The equality sign holds good when the process undergone by the system is reversible, the inequality sign holds good if there is any irreversibility present in the process. This statement is usually called the principle of entropy increase.

Irreversible or spontaneous processes can occur only in that direction for which the entropy of the universe or that of an isolated system, increases. These processes cannot occur in the direction of decreasing entropy. For an isolated system, S > 0, for irreversible processes S = 0, for reversible processes S < 0, the process is impossible