14 Basic concepts of thermodynamics External state variables ‘Thermodynamics is concerned with the state of a system when left alone,and when inter- acting with the surroundings. By ‘system’ we shall mean any portion of the woeld that cas ‘bedefined for consideration of the changes that may oecur under varying conditions. The ‘system may be separated from the surroundings by a real or imaginary wall. The proper ties of the wall determine how the system may interact with the surroundings. The wall itself will not usually be regarded as part of the system but rather as part of the sur- roundings. We shall first consider two kinds of interactions, thermal and mechanical, and we may regard the name ‘thermodynamics’ as an indication that these interactions are of main interest, Secondly, we shall introduce interactions by exchange of matter in the form of chemical species. The name ‘thermochemistry’ is sometimes used as an indication of such applications. The term ‘thermophysical properties’ is sometimes used for thermodynamic properties which de not primarily involve changes in the content of various chemical species, e.g. heat capacity, thermal expansivity and compressibility. ‘One might imagine thatthe contentof mater in the system could be varied in a number ‘of ways equal to the number of species. However, species may react with each ather inside ‘the system. It is thus convenient instead to define a set of independent components, the change of which caa accomplish all possible variations of the content. By denoting the ‘number of independent components as ¢ and also considering thermal and mechanical interactions with the surroundings, we find Iby definition that the state of the system may vary in ¢ +2 independeat ways, For metallic systems it is usually most convenient to +regard the elements as the independent components. For systems with covalent bonds it ‘may sometimes be convenient to regard a very stable molecular species as a component. For systems witha strongly ionic character it may be convenient to select the independent components from the neutral compounds rather than from the ions, By waiting for the system to come to rest after making a variation we may hope to establish a state of equilibrium. A criterion that a state is actually a state of equilibrium: ‘would be that the same state would spontaneously be established from different starting points. After a system has reached a state of equilibrium we can, in principle, measure ‘the values of many quantities which are uniquely defined by the state and independent of ‘the history of the system. Examples are temperature T, pressure P, volume Vand content ‘ofeach component Vj. We may call such quantities state variables or state functions, depending upon the comtext. [tis possible to ideatify a particular state of equilibrium byBasic concepts of thermodynamics. P Figure 11. Property diagram for comstant amount of a salid material at a constant temperature showing volume as a finction of pressure. Notice that F has kere been plotted in the newative direction. The reason will be explained later. giving the values of a number of state variables under which it is established. As might be expected, ¢ + 2 variables must be given. The values of all other variables are fixed, provided that equilibrium has really been established. There are thus ¢ + 2 independent variables and, after they have been selected and equilibrium has been established, the rest are dependent variables. As we shall see, there are many ways to select the set of independent variables. For each application a certain set is usually most convenient. For any selection of independent variables it is possible to change the value of each one, independent of the others, butoaly if the wall containing the system is open for exchange of e +2 kinds, ie. exchanges of mechanical work, heat and c components, ‘The equilibrium state of a system can be represented by a point in ac +2 dimensional diagram. In principle, all points in such a diagram represent possible states of equilibrium although there may be practical difficulties in establishing the states represented by some region. One can use the diagram to define a state by specifying a point or a series of states by specifying a line. Such a diagram may be regarded as a state diagram. It does not give any information on the properties of the system under consideration unless such information is added to the diagram, We shall later see that some vital information con the properties can be included in the state diagram but in order to show the value of some dependent variable a new axis must be added. For convenience of illustration we shall now decrease the number of axes in the ¢ +2 dimensional state diagram by scetioning at constant values of ¢ + 1 of the independent variables All the states to be considered will thus be situated along a single axis, which may now be regarded as the state diagram, We may then plot a dependent variable by introducing a second axis. That property is thus represeated by a line. We may call such a diagram a property diagram. An example is shown in Fig. 1.1. Of course, we may arbitrarily choose to consider any one of the two axes as the independent variable. The shape of the line is independent of that choice and itis thus the Line itself that represents the property of the system, In many cases the content of matter in a system is kept constant and the wall is only ‘open for exchange of mechanical work and heat. Such a system is ofien called a closed system and we shall start by discussing the properties of such a system. In other cases the content of matter may change and, in particular, the composition of the system by which we mean the relative amounts of the various components independent of the size of the system. In materials science such an open system is called an ‘alloy system’ and its behaviour as a function of composition is often shown in so-called phase diagrams,12 12 Internal state variables a which are state diagrams with same additional information on what phases are present in ‘various regions. We shall later discuss the properties of phase diagrams in considerable detail. ‘The state variables are of two kinds, which we shall call intensive and extensive. ‘Temperature T and pressure P are intensive variables because they can be defined at each point of the system. As we shall see later, 7 must have the same value at all points in a ‘system at equilibrium, An inteasive variable with this property will be called potential, ‘We shall later meet intensive variables, which may have different values at different parts of the system. They will not be regarded as potentials. ‘Volume Vis an extensive variable because its value for a system is equal to the sum of its values of all parts of the system. The content of component i, usually denoted by n; or Nj, isalso an extensive variable. Such quantities obey the law of additivity. For a ‘homogeneous syste their values. are proportional to the size of the system. ‘One can imagine variables, which depend upon the size of the system but do not always obey the law of additivity. The use of such variables is complicated and will not ‘be much considered, The law of additivity will be further discussed in Section 3.4. Ifthe system is contained inside a wall that is rigid, thermally insulating and imperme- able to matter, then all the interactions mentioned are prevented and the system may be regarded as completely closed to interactions with the surroundings. Itis left ‘completely alone’. It is often called an isolated system, By changing the properties of the wall we ‘can open the system to exchanges of mechanical work, heat or matter. A system open to all these exchanges may be regarded as a completely open system, We may thus control the values of ¢ +2 variables by interactions with the surroundings and we may regard ‘them as external variables because their values can be changed by interaction with the external world through the surroundings. "After some or all of the e+ 2 independent variables have been changed to new values and before the system has come to rest at equilibrium, it is also possible to describe the state of the system, at least in principle. For that description additional variables are ‘required. We may call them internal variables because they will change due to internal processes as the system approaches the state of equilibrium under the new values of the +2 extemal variables. An internal variable § (pronounced *xeye") is illustrated in Fig. 1.2(a)where ¢ + 1 of the independent variables are again kept constant in order to obtain a two-dimensional diagram. The equilibrium value of § for various values of the remaining independent variable T is represented by a curve. In that respect, the diagram is a property diagram, ‘On the other hand by a rapid change of the independent variable T the system may ‘be brought to a point away from the curve. Any such point represents a possible non- ‘equilibrium state and in that sense the diagram is a state diagram. In order to define such 4 point one must give the value of the internal variable in addition to T. The quantity § is thus an independent variable for states of non-equilibrium.