PART I INTRODUCTION 1 WHAT ARE THE CRITICAL PHENOMENA? A SURVEY OF SOME BASIC RESULTS Our purpose in this first chapter is to provide the reader with a brief qualitative description of what actually happens near the critical point, and with an appreciation of why the study of these critical phenomena has burgeoned in recent years. 1.1. Classical era of critical phenomena Many of the basic facts of critical phenomena were observed fifty or even a hundred years ago, while other aspects have been discovered. only in very recent years. Hence it has become customary to divide the field of critical phenomena into an early ‘classical’ era and a more recent ‘modern’ era. Although a wide variety of physical systems exhibit critical pheno- mena, we shall concentrate on the liquid-gas and magnetic critical points for the sake of simplicity. 1.1.1, Fluid systems Our discussion of fluid systems will focus first on the equation of state, a functional relationship of the form f(P, p, 7) = 0, which relates the thermodynamic parameters—pressure, density, and temperature. The equation of state thus defines a surface in a three-dimensional space whose coordinates are P, p, 7’; each of the points on this surface corresponds to an equilibrium state of the system. In order to aid in visualization of this PpT' surface, it is convenient to consider its pro- jections on to the P7’, Pp, and p7' planes; these are shown schematically in Figs. 1.1(a), 1.2(a), and 1.3(a) respectively. We see from Fig. 1.1(a)2 CRITICAL PHENOMENA: BASIC RESULTS 1,§1 that the projection on to the P7' plane produces three separate regions, corresponding to the three familiar phases of matter—the solid, liquid, and gaseous phases. The solid and gaseous phases are in equilibrium along the sublimation curve, the solid and liquid phases are in equilib- rium along the fusion curve, and the liquid and gaseous phases are in equilibrium along the vapour pressure curve. Each point on these three curves represents an equilibrium state in which two or more phases can coexist—and the triple point represents an equilibrium state in which all three phases coexist. We notice, however, that the vapour pressure curve does not extend forever, as the fusion curve appears to do, but rather that it terminates in a point. This point is called the critical point, and its coordinates are bs | Fusion _ | R curve ony . Solid ttt - Z Vapour H=0) prosure curve rae | Sublimation: Gas Hy st |Surve ' ‘Triple point | (a) Fluid (b) Magnet Fie. L.1. (a) Projection of the PVT’ surface in the PT’ plano. (b) Projection of the HMT’ surface in the HT’ plane. denoted by (P,, p., 7'.), where P,, p,, and 7’, are the critical pressure, critical density, and critical temperature respectively. The fact that the vapour pressure curve terminates in a critical point means that one can convert a liquid to a gas continuously, without crossing the phase transi- tion line, as is indicated by the dotted path shown in Fig. 1.1(a). In this sense there is no fundamental difference between the liquid and gaseous phases. It is widely believed that the fusion curve does not also terminate in a (second) critical point. However, thus far it has not been possible to prove the non-existence of a liquid-solid critical point. That the vapour pressure curve terminates in a critical point was not appreciated until about a hundred years ago. Prior to that time scientists regarded certain gases as being ‘permanent’ in the sense that these gases could not be made to condense no matter how much pres- sure was applied (compressing a gas was a standard laboratory pro- cedure for liquefaction). Presumably the work on these gases was carried.1§1 CLASSICAL ERA OF CRITICAL PHENOMENA 8 out at a temperature 7’ > 7',, while a prerequisite for obtaining droplets of the condensed phase is that the material be brought to a temperature lower than the critical temperature 7',. Thus, for example, helium cannot be liquefied no matter how great the applied pressure unless the temperature is reduced below the critical temperature of 5-2K. In addition to the PT projection, it is also useful to consider the pro- jections in the Pp and pT’ planes; these are shown schematically in Figs. 1.2(a) and 1.3(a) respectively. These projections tell us a great deal (a) Fluid (b) Magnet Fra. 1.2. (a) Isothermal cross-sections of the PVT surface (or, literally, the PpT’ surface). The exponent § is a measure of the degree of the critical isotherm. The fact that 3 > 1 reflects the fact that tho compressibility Ky is infinite at ',. The fashion in which Ky diverges at 1’ -> 7, is described by the exponents y and »/. (b) Isothormal cross- sections of the HM’ surfece. At high temperatures all isotherms approach straight lines, corresponding to the non-interacting limits, P = pkT'/m and H = TM/C, where C is Curic's constant (of. Chapter 6). concerning the qualitative features of the critical point. From Fig. 1.2(a) and also from Fig. 1.3(a) we see that at low temperatures there is a rather large difference between the liquid and gas densities, p,, and pg, but that as the critical temperature is approached this density difference tends to zero. The existence of a quantity which is non-zero below the critical temperature and zero above it will be seen to be a common feature associated with the critical points of a wide variety of physical systems. We say that p,, — pg is the order parameter for the liquid-gas critical point. A second striking feature of Fig. 1.2(a) concerns the shape of the iso- therms as the critical point is approached. At very high temperatures the ideal gas law is obeyed and the isotherms are therefore the straight lines given by the ideal gas equation of state P = pkT/m, (1.1)