Thermodynamics and Propulsion

6.8 Some Overall Comments on Entropy, Reversible and Irreversible Processes

[Mainly excerpted (with some alterations) from: Engineering Thermodynamics, William C. Reynolds and Henry C. Perkins, McGraw-Hill Book Company, 1977.]

6.8.1 Entropy

1. Entropy is a thermodynamic property that measures the degree of randomization or disorder at the microscopic level. The natural state of affairs is for entropy to be produced by all processes.
2. A macroscopic feature which is associated with entropy production is a loss of ability to do useful work. Energy is degraded to a less useful form, and it is sometimes said that there is a decrease in the availability of energy.
3. Entropy is an extensive thermodynamic property. In other words, the entropy of a complex system is the sum of the entropies of its parts.
4. The notion that entropy can be produced, but never destroyed, is the second law of thermodynamics.

6.8.2 Reversible and Irreversible Processes

Processes can be classed as reversible or irreversible. The concept of a reversible process is an important one which directly relates to our ability to recognize, evaluate, and reduce irreversibilities in practical engineering processes.

Consider an isolated system. The second law says that any process that would reduce the entropy of the isolated system is impossible. Suppose a process takes place within the isolated system in what we shall call the forward direction. If the change in state of the system is such that the entropy increases for the forward process, then for the backward process (that is, for the reverse change in state) the entropy would decrease. The backward process is therefore impossible, and we therefore say that the forward process is irreversible.

If a process occurs, however, in which the entropy is unchanged by the forward process, then it would also be unchanged by the reverse process. Such a process could go in either direction without contradicting the second law. Processes of this latter type are called reversible.

The key idea of a reversible process is that it does not produce any entropy.

Entropy is produced in irreversible processes. All real processes (with the possible exception of superconducting current flows) are in some measure irreversible, though many processes can be analyzed quite adequately by assuming that they are reversible. Some processes that are clearly irreversible include: mixing of two gases, spontaneous combustion, friction, and the transfer of energy as heat from a body at high temperature to a body at low temperature.

Recognition of the irreversibilities in a real process is especially important in engineering. Irreversibility, or departure from the ideal condition of reversibility, reflects an increase in the amount of disorganized energy at the expense of organized energy. The organized energy (such as that of a raised weight) is easily put to practical use; disorganized energy (such as the random motions of the molecules in a gas) requires ``straightening out'' before it can be used effectively. Further, since we are always somewhat uncertain about the microscopic state, this straightening can never be perfect. Consequently the engineer is constantly striving to reduce irreversibilities in systems, in order to obtain better performance.

6.8.3 Examples of Reversible and Irreversible Processes

Processes that are usually idealized as reversible include:

• Frictionless movement
• Restrained compression or expansion
• Energy transfer as heat due to infinitesimal temperature nonuniformity
• Electric current flow through a zero resistance
• Restrained chemical reaction
• Mixing of two samples of the same substance at the same state.

Processes that are irreversible include:

• Movement with friction
• Unrestrained expansion
• Energy transfer as heat due to large temperature non uniformities
• Electric current flow through a non zero resistance
• Spontaneous chemical reaction
• Mixing of matter of different composition or state.