# THE SECOND LA W OF THERMODYNAMICS:INTRODUCTION TO THE SECOND LAW

To this point, we have focused our attention on the first law of thermo- dynamics, which requires that energy be conserved during a process. In this chapter, we introduce the second law of thermodynamics, which asserts that processes occur in a certain direction and that energy has quality as well as quantity. A process cannot take place unless it satisfies both the first and second laws of thermodynamics. In this chapter, the thermal energy reservoirs, reversible and irreversible processes, heat engines, refrigerators, and heat pumps are introduced first. Various statements of the second law are followed by a discussion of perpetual-motion machines and the thermodynamic temperature scale. The Carnot cycle is introduced next, and the Carnot principles, idealized Carnot heat engines, refrigerators, and heat pumps are examined. Finally, energy conservation associated with the use of household refrigerators is discussed.

INTRODUCTION TO THE SECOND LAW

In Chap. 5, we applied the first law of thermodynamics, or the conservation of energy principle, to processes involving closed and open systems. As pointed out repeatedly in Chap. 5, energy is a conserved property, and no process is known to have taken place in violation of the first law of thermodynamics. Therefore, it is reasonable to conclude that a process must satisfy the first law to occur. However, as explained here, satisfying the first law alone does not ensure that the process will actually take place.

It is common experience that a cup of hot coffee left in a cooler room eventually cools off (Fig. 6–1). This process satisfies the first law of thermo- dynamics since the amount of energy lost by the coffee is equal to the amount gained by the surrounding air. Now let us consider the reverse process—the hot coffee getting even hotter in a cooler room as a result of heat transfer from the room air. We all know that this process never takes place. Yet, doing so would not violate the first law as long as the amount of energy lost by the air is equal to the amount gained by the coffee.

As another familiar example, consider the heating of a room by the passage of current through an electric resistor (Fig. 6–2). Again, the first law dictates that the amount of electric energy supplied to the resistance wires be equal to the amount of energy transferred to the room air as heat. Now let us attempt to reverse this process. It will come as no surprise that transferring some heat to the wires will not cause an equivalent amount of electric energy to be generated in the wires.

Finally, consider a paddle-wheel mechanism that is operated by the fall of a mass (Fig. 6–3). The paddle wheel rotates as the mass falls and stirs a fluid within an insulated container. As a result, the potential energy of the mass de- creases, and the internal energy of the fluid increases in accordance with the conservation of energy principle. However, the reverse process, raising the mass by transferring heat from the fluid to the paddle wheel, does not occur in nature, although doing so would not violate the first law of thermodynamics. It is clear from these arguments that processes proceed in a certain direction and not in the reverse direction (Fig. 6–4). The first law places no restriction on the direction of a process, but satisfying the first law does not ensure that the process will actually occur. This inadequacy of the first law to identify whether a process can take place is remedied by introducing another general principle, the second law of thermodynamics. We show later in this chapter that the reverse processes discussed above violate the second law of thermo- dynamics. This violation is easily detected with the help of a property, called entropy, defined in the next chapter. A process will not occur unless it satisfies both the first and the second laws of thermodynamics (Fig. 6–5).

There are numerous valid statements of the second law of thermodynamics. Two such statements are presented and discussed later in this chapter in relation to some engineering devices that operate on cycles.

The use of the second law of thermodynamics is not limited to identifying the direction of processes, however. The second law also asserts that energy has quality as well as quantity. The first law is concerned with the quantity of energy and the transformations of energy from one form to another with no regard to its quality. Preserving the quality of energy is a major concern to engineers, and the second law provides the necessary means to determine the quality as well as the degree of degradation of energy during a process. As dis- cussed later in this chapter, more of high-temperature energy can be converted to work, and thus it has a higher quality than the same amount of energy at a lower temperature.

The second law of thermodynamics is also used in determining the theoretical limits for the performance of commonly used engineering systems, such as heat engines and refrigerators, as well as predicting the degree of completion of chemical reactions.