2.

4 Thermal Nonequilibrium and Irreversible Processes

We have seen that the entropy is maximized in a state of thermal equilibrium.
Here we consider the entropy in a state of thermal nonequilibrium.
Thermal-nonequilibrium states are caused by actions from outside the system.
For example, the earth as a whole is not in thermal equilibrium. There is a nearly
constant input of energy from the sun in the form of electromagnetic radiation.
This energy is radiated, in turn, from the earth to the cosmos. In the presence of
this flow of energy, the earth cannot be in an equilibrium state, and various
meteorological phenomena occur and life is supported. Another example is a
conductor connected to a battery. In this case an electric current flows in the
conductor. The systems in these examples are in quasi-stationary nonequilibrium
states. That is, energy is continuously put into the system, and the nonequilibrium
state lasts for a long time. On the other hand, there are also situations where a
nonequilibrium state is prepared by some means or other, and after that the
system is left to evolve by itself without further input of energy from outside. One
example is that of two systems at different temperatures, placed in thermal
contact at some time. Such a nonequilibrium state, when left alone, approaches a
thermal-equilibrium state as time elapses. This process is irreversible. A
thermal-nonequilibrium state changes into an equilibrium state spontaneously,
but not vice versa. We shall argue that in such an irreversible process the entropy
always increases.
For that purpose, we note that a thermal-nonequilibrium state can be created by
imposing various constraints on the system. One example of a typical
nonequilibrium state is a system in which the temperature depends on position.
Another example is that of a cup of water to which a droplet of ink has just been
added. In order to keep these systems in their initial condition, we would need to
divide the system into many small cells with adiabatic barriers between them in
the case of the first example, and to wrap the droplet of ink in the case of the
second example. A thermal-equilibrium state would be approached after these
constraints were removed. The molecules acquire more freedom when the
constraints are removed. Thus, it is evident that the number of microscopic states
increases when this removal happens. Therefore, we can conclude that the
entropy, defined as the logarithm of the number of microscopic states, is larger in
the thermal-equilibrium state. That is, as the system evolves from a
nonequilibrium state to an equilibrium state, the entropy increases.
In other words, the microscopic states allowed in a nonequilibrium state are a
subset of the microscopic states allowed in the equilibrium state. The principle of
equal probability tells us that any microscopic state in the nonequilibrium state is
realized in the equilibrium state with some probability, in principle. However,
when the constraints that are needed to realize the nonequilibrium state are
removed, the number of microscopic states allowed increases so tremendously
that the probability that the system will return to a state in the original subset is
vanishingly small.