Entropy

Objectives

By the end of this section, you will be able to:

  • Define entropy
  • Explain the relationship between entropy and the number of microstates
  • Predict the sign of the entropy change for chemical and physical processes

In 1824, at the age of 28, Nicolas Léonard Sadi Carnot ([Figure 1]) published the results of an extensive study regarding the efficiency of steam heat engines. A later review of Carnot’s findings by Rudolf Clausius introduced a new thermodynamic property that relates the spontaneous heat flow accompanying a process to the temperature at which the process takes place. This new property was expressed as the ratio of the reversible heat (qrev) and the kelvin temperature (T). In thermodynamics, a reversible process is one that takes place at such a slow rate that it is always at equilibrium and its direction can be changed (it can be “reversed”) by an infinitesimally small change in some condition. Note that the idea of a reversible process is a formalism required to support the development of various thermodynamic concepts; no real processes are truly reversible, rather they are classified as irreversible.

(a) Nicholas Léonard Sadi Carnot’s research into steam-powered machinery and (b) Rudolf Clausius’s later study of those findings led to groundbreaking discoveries about spontaneous heat flow processes.

Similar to other thermodynamic properties, this new quantity is a state function, so its change depends only upon the initial and final states of a system. In 1865, Clausius named this property entropy (S) and defined its change for any process as the following:

$$ΔS=\frac{q_{rev}}{T}$$

The entropy change for a real, irreversible process is then equal to that for the theoretical reversible process that involves the same initial and final states.