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CHAPTER 2 Se oe eee oe SE Simple Thermodynamic Systems 21 THERMODYNAMIC EQUILIBRIUM Suppose that experiments have been performed on a thermodynamic system and that the coordinates necessary and sufficient for a macroscopic descrip- tion have been determined. When these coordinates change in any way what- soever, either spontaneously or by virtue of outside influence, the system is said to undergo a change of state.' When a system is not influenced in any way by its surroundings, it is said to be isolated. In practical applications of ther- modynamics, isolated systems are of little importance. We usually have to deal with a system that is influenced in some way by its surroundings. In general, the surroundings may exert forces on the system or provide contact between the system and a body at some definite temperature. When the state of a system changes, interactions usually take place between the system and its surroundings. When there is no unbalanced force or torque in the interior of a system and also none between a system and its surroundings, the system is said to be in a state of mechanical equilibrium. When these conditions are not satisfied, either the system alone or both the system and its surroundings will undergo a change of state, which will cease only when mechanical equilibrium is restored. When a system in mechanical equilibrium does not tend to undergo a spontaneous change of internal structure, such as a chemical reaction, or a transfer of matter from one part of the system to another, such as diffusion or solution, however slow, then it is said to be in a state of chemical equilibrium. + Notice that in general physics the expression “change of state” is often used to signify a transition from solid to liquid or liquid to gas, etc. Such a change in the language of thermodynamics is called a change of phase. 29 30 parti: Fundamental Concepts A system not in chemical equilibrium undergoes a change of state that, in some cases, is exceedingly slow. The change ceases when chemical equilibrium is reached. Thermal equilibrium exists when there is no spontaneous change in the coordinates of a system in mechanical and chemical equilibrium when it is separated from its surroundings by diathermic walls. In other words, there is no exchange of heat between the system and its surroundings. In thermal equilibrium, all parts of a system are at the same temperature, and this tem- perature is the same as that of the surroundings. When these conditions are not satisfied, a change of state will take place until thermal equilibrium is reached. When the conditions for all three types of equilibrium are satisfied, the system is said to be in a state of thermodynamic equilibrium; in this condition, it is apparent that there will be no tendency whatever for any change of state, either of the system or of the surroundings, to occur. States of thermodynamic equilibrium can be described in terms of macroscopic coordinates that do not involve the time, that is, in terms of thermodynamic coordinates. Thermodynamics does not attempt to deal with any problem involving the rate at which a process takes place. The investigation of problems involving the time dependence of changes of state is carried out in other branches of science, as in the kinetic theory of gases, hydrodynamics, and chemical kinetics. When the conditions for any one of the three types of equilibrium that constitute thermodynamic equilibrium are not satisfied, the system is said to be in a nonequilibrium state. Thus, when there is an unbalanced force or torque in the interior of a system, or between a system and its surroundings, the following phenomena may take place: acceleration, turbulence, eddies, waves, etc. While such phenomena are in progress, a system passes through nonequilibrium states. If an attempt is made to give a macroscopic descrip- tion of any one of these nonequilibrium states, it is found that the pressure varies from one part of a system to another. There is no single pressure that refers to the system as a whole. Similarly, in the case of a system at a different temperature from its surroundings, a nonuniform temperature dis- tribution is set up and there is no single temperature that refers to the system as a whole. Therefore, we conclude that when the conditions for mechanical and thermal equilibrium are not satisfied, the states traversed by a system cannot be described in terms of thermodynamic coordinates referring to the system as a whole. It must not be concluded, however, that we are entirely helpless in dealing with such nonequilibrium states. If we divide the system into a large number of small mass elements, then thermodynamic coordinates may be found in terms of which a macroscopic description of each mass element may be approximated. There are also special methods for dealing with systems in mechanical and thermal equilibrium but not in chemical equilibrium. All these special methods will be considered later. At present, we shall deal exclu- sively with systems in thermodynamic equilibrium. CHAPTER 2: Simple Thermodynamic Systems 31 2.2 EQUATION OF STATE Imagine, for the sake of simplicity, a constant mass of gas, that is, a closed system, in a vessel so equipped that the pressure, volume, and temperature may be easily measured. If we fix the volume at some arbitrary value and cause the temperature to assume an arbitrarily chosen value, then we shall not be able to vary the pressure at all. Once V and T are chosen by us, the value of P at equilibrium is determined by nature. Similarly, if P and T are chosen arbitrarily, then the value of V at equilibrium is fixed. That is, of the three thermodynamic coordinates P, V, and T, only two are independent variables. This implies that there exists an equation of equilibrium which connects the thermodynamic coordinates and which robs one of them of its independence. Such an equation, called an equation of state, is a mathematical function relating the appropriate thermodynamic coordinates of a system in equili- brium. Every thermodynamic system has its own equation of state, although in some cases the relation may be so complicated that it cannot be expressed in terms of simple mathematical functions. For a closed system, the equation of state relates the temperature to two other thermodynamic variables. An equation of state expresses the individual peculiarities of one system as compared with another system and must, therefore, be determined either by experiment or by molecular theory. A general theory like thermodynamics, based on general laws of nature, is incapable of generating an equation of state of any system. An equation of state, therefore, is not a theoretical deduc- tion from thermodynamics, but is usually an experimental addition to thermo- dynamics. It expresses the results of experiments in which the thermodynamic coordinates of a system were measured as accurately as possible, within a limited range of values. An equation of state is, therefore, only as accurate as the experiments that led to its formulation, and holds only within the range of values measured. As soon as this range is exceeded, a different form of equation of state may be valid. For example, a system consisting of a gas at very low pressure has the simple equation of state of an ideal gas, PV =nRT, (2.1) where n is the number of moles and R is the molar gas constant. Equation (2.1) is often rewritten as Pu= RT, where lower-case v indicates the molar volume, that is, volume V per mole n. At higher pressures, the equation of state is more complicated, being fairly well represented by the van der Waals equation, which takes into account particle interactions and the finite size of the particles. Thus, (P+5)e-6) =RT, (2.2)