Second and Third Laws of Thermodynamics

The first law of thermodynamics states that energy is conserved. There are, however, many processes we can imagine that conserve energy but are not observed to occur in nature. For example, when a hot object is placed in contact with a cold object, heat flows from the hotter one to the colder one, never spontaneously the reverse. If heat were to leave the colder object and pass to the hotter one, energy could still be conserved. Yet it does not happen spontaneously. As a second example, consider what happens when you drop a rock and it hits the ground. The initial potential energy of the rock changes to kinetic energy as the rock falls. When the rock hits the ground, this energy in turn is transformed into internal energy of the rock and the ground in the vicinity of the impact;
the molecules move faster and the temperature rises slightly. But have you seen the reverse happen-a rock at rest on the ground suddenly rise up in the air because the thermal energy of molecules is transformed into kinetic energy of the rock as a whole? Energy could be conserved in this process, yet we never see it happen.

There are many other examples of processes that occur in nature but whose reverse does not. Here are two more. (1) If you put a layer of salt in a jar and cover it with a layer of similar-sized grains of pepper, when you shake it you get a thorough mixture. But no matter how long you shake it, the mixture does not separate into two layers again. (2) Coffee cups and glasses break spontaneously if you drop them. But they do not go back together spontaneously.

broken cup
Have you ever observed this process, a broken cup spontaneously reassembling and rising up onto a table? This process could conserve energy and other laws of mechanics.

The first law of thermodynamics (conservation of energy) would not be violated if any of these processes occurred in reverse. To explain this lack of reversibility, scientists in the latter half of the nineteenth century formulated a new principle known as the second law of thermodynamics.

The second law of thermodynamics is a statement about which processes occur
in nature and which do not. It can be stated in a variety of ways, all of which are
equivalent. One statement, due to R. 1. E. Clausius (1822-1888), is that

heat can flow spontaneously from a hot object to a cold object; heat will not
flow spontaneously from a cold object to a hot object.

Since this statement applies to one particular process, it is not obvious how it applies to other processes. A more general statement is needed that will include other possible processes in a more obvious way.

The development of a general statement of the second law of thermodynamics was based partly on the study of heat engines. A heat engine is any device that changes thermal energy into mechanical work, such as a steam engine or automobile engine. We now examine heat engines, both from a practical point of view and to show their importance in developing the second law of thermodynamics.

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