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Study notes on Entropy - Study notes on Entropy EXIT

Day 12 | Second Law of Thermodynamics | Study Notes on Entropy

Entropy
The Clausius Inequality

The rst law is simply an energy balance.

However, the second law leads to an inequality; an irreversible process is less e cient than a
reversible process.
Another important inequality in thermodynamics is the Clausius inequality:

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

The Clausius inequality forms the basis for the de nition of a new property called entropy.
As can be seen in the equation above, for an internally reversible process the cyclic integral of
δQ / T is zero.
A quantity whose cyclic integral is zero depends on the state only and not the process path, and
thus it is a property.
The entropy change of a closed system during an irreversible process is greater than the
integral of dQ/T evaluated for that process
If the energy exchange takes place, dQ will be the energy transfer from the surroundings to the
system.

If the system is isolated, that is, when there is no interaction between the system and the
surroundings, then

ΔS=0 

Now let us rede ne a system which includes our earlier system and its surroundings. Then

(ΔS)sys =0 for an isolated system

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 Through generalization, we can write for an isolated system
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(ΔS)sys>or=0

The Increase of Entropy Principle

Entropy change of a closed system during an irreversible process is greater that the integral of
δQ / T evaluated for the process.
In the limiting case of a reversible process, they become equal.

The entropy generated during a process is called entropy generation, and is denoted by

Note that the entropy generation Sgen is always a positive quantity or zero (reversible process).
Its value depends on the process, thus it is not a property of a system.
The entropy of an isolated system during a process always increases, or in the limiting case of a
reversible process remains constant (it never decreases).
This is known as the increase of entropy principle.
The entropy change of a system or its surroundings can be negative; but entropy generation
cannot.

A process must proceeds in the direction that complies with the increase of entropy principle,
Sgen > 0. A process that violates this principle is impossible.
Entropy is a non‐conserved property, and there is no such thing as the conservation of entropy.
Therefore, the entropy of universe is continuously increasing.
The performance of engineering systems is degraded by the presence of irreversibility. The
entropy generation is a measure of the magnitudes of the irreversibilities present during the
process.

 Entropy change of an ideal gas

The entropy change between two states of an ideal gas canbe obtained from the ideal gas
equation and the combined equation of the rst and second laws.

Tds = du + Pdv
du = cvdT and P = (RT)/v

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Entropy change for different process

Process

Entropy Change S2-S1

Reversible constant volume process

Reversible constant pressure process

Reversible isothermal process

Reversible adiabatic process

Polytropic process

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