Chapter 3 PROPERTIES OF PURE SUBSTANCES W e start this chapter with the introduction of the concept of a pure substance and a discussion of the physics of phase-change processes. We then illustrate the various property diagrams and P-v-T surfaces of pure substances. After demonstrating the use of the property tables, the hypothetical substance ideal gas and the ideal-gas equation of state are discussed. The compressibility factor, which accounts for the deviation of real gases from ideal-gas behavior, is introduced, and some of the best-known equations of state such as the van der Waals, Beattie-Bridgeman, and Benedict-Webb-Rubin equations are presented. Objectives The objectives of Chapter 3 are to: • Introduce the concept of a pure substance. • Discuss the physics of phase-change processes. • Illustrate the P-v, T-v, and P-T property diagrams and P-v-T surfaces of pure substances. • Demonstrate the procedures for determining thermodynamic properties of pure substances from tables of property data. • Describe the hypothetical substance “ideal gas” and the ideal-gas equation of state. • Apply the ideal-gas equation of state in the solution of typical problems. • Introduce the compressibility factor, which accounts for the deviation of real gases from ideal-gas behavior. • Present some of the best-known equations of state.
3–1 N2 AIR FIGURE 3–1 Nitrogen and gaseous air are pure substances. VAPOR LIQUID (a) H2O VAPOR LIQUID (b) AIR FIGURE 3–2 A mixture of liquid and gaseous water is a pure substance, but a mixture of liquid and gaseous air is not. FIGURE 3–3 The molecules in a solid are kept at their positions by the large springlike intermolecular forces. ■ PURE SUBSTANCE A substance that has a fixed chemical composition throughout is called a pure substance. Water, nitrogen, helium, and carbon dioxide, for example, are all pure substances. A pure substance does not have to be of a single chemical element or compound, however. A mixture of various chemical elements or compounds also qualifies as a pure substance as long as the mixture is homogeneous. Air, for example, is a mixture of several gases, but it is often considered to be a pure substance because it has a uniform chemical composition (Fig. 3–1). However, a mixture of oil and water is not a pure substance. Since oil is not soluble in water, it will collect on top of the water, forming two chemically dissimilar regions. A mixture of two or more phases of a pure substance is still a pure substance as long as the chemical composition of all phases is the same (Fig. 3–2). A mixture of ice and liquid water, for example, is a pure substance because both phases have the same chemical composition. A mixture of liquid air and gaseous air, however, is not a pure substance since the composition of liquid air is different from the composition of gaseous air, and thus the mixture is no longer chemically homogeneous. This is due to different components in air condensing at different temperatures at a specified pressure. 3–2 ■ PHASES OF A PURE SUBSTANCE We all know from experience that substances exist in different phases. At room temperature and pressure, copper is a solid, mercury is a liquid, and nitrogen is a gas. Under different conditions, each may appear in a different phase. Even though there are three principal phases—solid, liquid, and gas—a substance may have several phases within a principal phase, each with a different molecular structure. Carbon, for example, may exist as graphite or diamond in the solid phase. Helium has two liquid phases; iron has three solid phases. Ice may exist at seven different phases at high pressures. A phase is identified as having a distinct molecular arrangement that is homogeneous throughout and separated from the others by easily identifiable boundary surfaces. The two phases of H2O in iced water represent a good example of this. When studying phases or phase changes in thermodynamics, one does not need to be concerned with the molecular structure and behavior of different phases. However, it is very helpful to have some understanding of the molecular phenomena involved in each phase, and a brief discussion of phase transformations follows. Intermolecular bonds are strongest in solids and weakest in gases. One reason is that molecules in solids are closely packed together, whereas in gases they are separated by relatively large distances. The molecules in a solid are arranged in a three-dimensional pattern (lattice) that is repeated throughout (Fig. 3–3). Because of the small distances between molecules in a solid, the attractive forces of molecules on each other are large and keep the molecules at fixed positions (Fig. 3–4). Note that the attractive forces between molecules turn to repulsive forces as the
distance between the molecules approaches zero, thus preventing the molecules from piling up on top of each other. Even though the molecules in a solid cannot move relative to each other, they continually oscillate about their equilibrium positions. The velocity of the molecules during these oscillations depends on the temperature. At sufficiently high temperatures, the velocity (and thus the momentum) of the molecules may reach a point where the intermolecular forces are partially overcome and groups of molecules break away (Fig. 3–5). This is the beginning of the melting process. The molecular spacing in the liquid phase is not much different from that of the solid phase, except the molecules are no longer at fixed positions relative to each other and they can rotate and translate freely. In a liquid, the intermolecular forces are weaker relative to solids, but still relatively strong compared with gases. The distances between molecules generally experience a slight increase as a solid turns liquid, with water being a notable exception. In the gas phase, the molecules are far apart from each other, and a molecular order is nonexistent. Gas molecules move about at random, continually colliding with each other and the walls of the container they are in. Particularly at low densities, the intermolecular forces are very small, and collisions are the only mode of interaction between the molecules. Molecules in the gas phase are at a considerably higher energy level than they are in the liquid or solid phases. Therefore, the gas must release a large amount of its energy before it can condense or freeze. 3–3 ■ FIGURE 3–4 In a solid, the attractive and repulsive forces between the molecules tend to maintain them at relatively constant distances from each other. PHASE-CHANGE PROCESSES OF PURE SUBSTANCES There are many practical situations where two phases of a pure substance coexist in equilibrium. Water exists as a mixture of liquid and vapor in the boiler and the condenser of a steam power plant. The refrigerant turns from liquid to vapor in the freezer of a refrigerator. Even though many home owners consider the freezing of water in underground pipes as the most (a) (b) (c) FIGURE 3–5 The arrangement of atoms in different phases: (a) molecules are at relatively fixed positions in a solid, (b) groups of molecules move about each other in the liquid phase, and (c) molecules move about at random in the gas phase.
important phase-change process, attention in this section is focused on the liquid and vapor phases and their mixture. As a familiar substance, water is used to demonstrate the basic principles involved. Remember, however, that all pure substances exhibit the same general behavior. STATE 1 Compressed Liquid and Saturated Liquid P = 1 atm T = 20°C Heat FIGURE 3–6 At 1 atm and 20°C, water exists in the liquid phase (compressed liquid). STATE 2 P = 1 atm T = 100°C Consider a piston–cylinder device containing liquid water at 20°C and 1 atm pressure (state 1, Fig. 3–6). Under these conditions, water exists in the liquid phase, and it is called a compressed liquid, or a subcooled liquid, meaning that it is not about to vaporize. Heat is now transferred to the water until its temperature rises to, say, 40°C. As the temperature rises, the liquid water expands slightly, and so its specific volume increases. To accommodate this expansion, the piston moves up slightly. The pressure in the cylinder remains constant at 1 atm during this process since it depends on the outside barometric pressure and the weight of the piston, both of which are constant. Water is still a compressed liquid at this state since it has not started to vaporize. As more heat is transferred, the temperature keeps rising until it reaches 100°C (state 2, Fig. 3–7). At this point water is still a liquid, but any heat addition will cause some of the liquid to vaporize. That is, a phase-change process from liquid to vapor is about to take place. A liquid that is about to vaporize is called a saturated liquid. Therefore, state 2 is a saturated liquid state. Saturated Vapor and Superheated Vapor Heat FIGURE 3–7 At 1 atm pressure and 100°C, water exists as a liquid that is ready to vaporize (saturated liquid). STATE 3 P = 1 atm T = 100°C Saturated vapor Saturated liquid Heat FIGURE 3–8 As more heat is transferred, part of the saturated liquid vaporizes (saturated liquid–vapor mixture). Once boiling starts, the temperature stops rising until the liquid is completely vaporized. That is, the temperature will remain constant during the entire phase-change process if the pressure is held constant. This can easily be verified by placing a thermometer into boiling pure water on top of a stove. At sea level (P 1 atm), the thermometer will always read 100°C if the pan is uncovered or covered with a light lid. During a boiling process, the only change we will observe is a large increase in the volume and a steady decline in the liquid level as a result of more liquid turning to vapor. Midway about the vaporization line (state 3, Fig. 3–8), the cylinder contains equal amounts of liquid and vapor. As we continue transferring heat, the vaporization process continues until the last drop of liquid is vaporized (state 4, Fig. 3–9). At this point, the entire cylinder is filled with vapor that is on the borderline of the liquid phase. Any heat loss from this vapor will cause some of the vapor to condense (phase change from vapor to liquid). A vapor that is about to condense is called a saturated vapor. Therefore, state 4 is a saturated vapor state. A substance at states between 2 and 4 is referred to as a saturated liquid–vapor mixture since the liquid and vapor phases coexist in equilibrium at these states. Once the phase-change process is completed, we are back to a singlephase region again (this time vapor), and further transfer of heat results in an increase in both the temperature and the specific volume (Fig. 3–10). At state 5, the temperature of the vapor is, let us say, 300°C; and if we transfer some heat from the vapor, the temperature may drop somewhat but no condensation will take place as long as the temperature remains above 100°C