The one-way character of irreversible processes is so pervasive that we take it for granted. If these processes were to occur spontaneously (on their own) in the wrong way, we would be astonished. Yet none of these wrong-way events would violate the law of conservation of energy.
For example, if you were to wrap your hands around a cup of hot coffee, you would be astonished if your hands got cooler and the cup got warmer. That is obviously the wrong way for the energy transfer, but the total energy of the closed system (hands + cup of coffee) would be the same as the total energy if the process had run in the right way. For another example, if you popped a helium balloon, you would be astonished if, later, all the helium molecules were to gather together in the original shape of the balloon. That is obviously the wrong way for molecules to spread, but the total energy of the closed system (molecules + room) would be the same as for the right way.
Thus, changes in energy within a closed system do not set the direction of irreversible processes. Rather, that direction is set by another property that we shall discuss in this lesson—the change in entropy ΔS of the system. The change in entropy of a system is defined in the next section, but we can here state its central property, often called the entropy postulate:
If an irreversible process occurs in a closed system, the entropy S of the system always increases; it never decreases.
Entropy differs from energy in that entropy does not obey a conservation law. The energy of a closed system is conserved; it always remains constant. For irreversible processes, the entropy of a closed system always increases. Because of this property, the change in entropy is sometimes called “the arrow of time.” For example, we associate the explosion of a popcorn kernel with the forward direction of time and with an increase in entropy. The backward direction of time (a videotape run backwards) would correspond to the exploded popcorn re-forming the original kernel. Because this backward process would result in an entropy decrease, it never happens.
There are two equivalent ways to define the change in entropy of a system: (1) in terms of the system’s temperature and the energy the system gains or loses as heat, and (2) by counting the ways in which the atoms or molecules that make up the system can be arranged. We use the first approach in the next section and the second in Section 20-8.
Fig. 20-1 The free expansion of an ideal gas. (a) The gas is confined to the left half of an insulated container by a closed stopcock. (b) When the stopcock is opened, the gas rushes to fill the entire container. This process is irreversible; that is, it does not occur in reverse, with the gas spontaneously collecting itself in the left half of the container.
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