CHAPTEll 1: Temperaturc and the Zeroth Law of Thermedynamics 7

includes, in addition to the above, such systems as wire resistors. electric

capacitors, and magnetic substances.

1.5
THERMAL EQUILIBRIUM AND THE ZERO'fH LAW

We have seen that a macroscopic description of a pscous mixturc may be

given by specifying such quamities as the composition. the mass, the pressure,
and the volume. The last quantity specified in Sec. 1.1 was temperature, for
which you have an intuitive understanding and some familiarity. This section
begins the analytic development of the quantity. temperature. Experiment
shows that, for a given composition and for a constant mass and temperature,
many different values of pressure and volume are possible for a gas. If the
pressure is kept constant, the volume may vary over a widc range of values,
and vice versa. In other words. the pressure and the volume are independent
coordinates but are related in a simple equation. namely. Boyk's law.
More recently, etcperiment has shown that, for a wirc of constant mass,
the tension and the knph are independent coordinates. whereas. in the case of
a surface film, the surface tension and the arca may be varied independently.
Some systems that, at first sight, seem quite complicated, such as an elecuic
cell with twodifferent electrodes and an electrolyte, may still bc described with
the aid of only two independent coordinmes. On the other hand, some
thermodynamic systems composed of a number of homogeneous parts requirc the
specification of two independent coordinates for each homogeneous pan.
Details of various thermodynamic systems and their thermodynamic
coordinates will be given in Chap. 2. For the mosent, to simpfify our discussion,
we shall deal only with systems of constant mass and composition. each
requiring only one pair of independent coordinates for its description. This
involves no essential loss of generality and results in a considerabk saving of
words. In referring to any unspecified system, we shall use the symbols X and Y
for the pair of independent coordinates, where the symbol X refers to a
generalized force (for instance, the prcssurc of a gas) and Y refers to a
generalized displacement (for inscance. the volume of a gas).
A state of a system in which the coordinates X and Y have definite values
that remain constant so long as the extemal conditions are unchanged is calkd
an equllibrium state. Experiment shows that the existence of an equilibrium
mate in one system depends on the proximity of other systems and on the
nature of the boundary or wall separating the different systems. Walls are said
to be either adiabatic or diathermic in ideal cases. 1f a wall is adiabatic isce
Fig. 1.1(o)l. an equilibrium state for system A may COCXiSl with any equifn
brium state of system B for all attainabk values of the four quantities, X, Y
and X', Y' — provided only that the wall is able to withstand the stress
associatod with the difference between the two sets of coordinates. Thick
layers of wood, concrete, asbestos. felt, or polystyrene, as well as dewars.
are. in this order. increasingly better experimental approximations to ideal
adiabatic walls.