ENGINEERING THERMODYNAMICS CE 360

7.0 SECOND LAW OF THERMODYNAMICS

Considering the first law of thermodynamics earlier discussed, it can be noticed that the first
law merely reflects the conservation of energy and indicates that energy is always conserved
but can undergo transformation from one form to another. However, the first law does not
impose any restriction on the process direction yet all experience indicates that there should
exist such a restriction depending on the entropy of the system, the concise statement of
which constitutes the second law of thermodynamics. General observation suggests a general
restriction on the processes beyond that imposed by the first law. The second law is equally
well expressed in two statements that describe this restriction:

7.1 Word Statements of the Second Law of Thermodynamics

Statement 1:
No process is possible whose sole effect (in system and surroundings) is to convert heat
absorbed by a system completely into work done by the system. This is sometimes referred to
as the Kelvin Planck statement on the second law.

From the first statement, it means that there is no apparatus that can operate in such a way
that its only effect (in system and surroundings) is to convert heat absorbed by a system
completely into work done by the system. This means that it is not possible to achieve 100%
efficiency. There is a limit in the efficiency of every system or engine.

Statement 2:
No process is possible whose sole effect is the transfer of heat from a lower temperature level
to a higher one. This is sometimes referred to as the Clausius statement on the second law.

Using the above statements, the second law has been defined in a more specific way. Let us
now try to define the second law in a more general way using entropy.

7.2 Entropy and the Second Law of Thermodynamics

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Entropy is defined as the measure of the inherent disorder of a system.

Consider a system at a constant temperature T to which a small amount of energy flows as

heat Q as shown below,

- The entropy change within the system can be expressed as follows:

- Suppose the temperature is not constant, then the infinitesimal change in entropy can be
expressed as follows:

Integrating equation 7.2 for a system reversibly taken from state a to b, we get the following:

With T being the uniform temperature of the closed system and delta Q the incremental
reversible transfer of heat energy into that system.

Entropy is a state variable and is not path dependent.

7.2.1 The mathematical Statement of the Second Law of Thermodynamics

The key ingredient in the mathematical statement of the Second Law of Thermodynamics is
entropy S and it is usually derived as follows:

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- Consider the total entropy change for an isolated system consisting of two bodies labelled
H at a higher temperature TH and L at a lower temperature TL. as shown below.

Case 1: Deriving the total entropy change immediately the two bodies H and L are
brought closer to each other

- Let a quantity of heat IQI be transferred from the body at a higher temperature to the body
at a lower temperature.
- The entropy changes of the bodies at TH and TL are given as:

- Adding the two entropy changes, we get the total entropy change

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The total entropy change of the reversible process is positive as seen from equation 7.5
because TL ˂ TH. Also, ∆S Total becomes smaller as the difference TH and TL gets smaller. If TH
is only infinitesimally higher than TL, the heat transfer is reversible, and ∆STotal approaches
zero as the process becomes reversible.
Case 2: Expressing the total entropy change when the two bodies H and L finally reach
temperature equilibrium at Tf

Eventually the two bodies will attain the same temperature and they are said to have reached
temperature equilibrium.

For the total entropy change at equilibrium, equation 7.5 becomes

According to the Clausius equality, for a closed homogeneous system in which only
reversible processes take place,

With T being the uniform temperature of the closed system and delta Q the incremental
reversible transfer of heat energy into that system.

Equations 7.5 and 7.6 can be combined to give equation 7.7 as shown below,

Equation 7.7 gives the mathematical statement of the second law of thermodynamics and can
be stated in terms of entropy as follows:

The entropy of a system is always greater or equal to zero but can never be negative.

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If we consider the surrounding to be the entire universe, equation 7.7 can also be expressed
as follows:

Equation 7.8 implies that the entropy of the universe is always greater or equal to 0 (zero)
since the surrounding associated with the system can be the entire universe.