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)