57

2.2 u The Thermal Properties of Matter

The Fluid State Since the intermolecular spacing is much larger and the
motion of the molecules is more random for the fluid state than for the solid
state, thermal energy transport is less effective. The thermal conductivity of
gases and liquids is therefore generally smaller than that of solids.
The effect of temperature, pressure, and chemical species on the thermal
conductivity of a gas may be explained in terms of the kinetic theory of gases
[4]. From this theory it is known that the thermal conductivity is directly
proportional to the number of particles per unit volume n, the mean molecular
speed c, and the mean free path A, which is the average distance traveled by a
molecule before experiencing a colusin. Henee
kc ncX

Because c increases with increasing temperature and decreasing molecular

mass, the thermal conductivity of a gas increases with increasing temperature
and decreasing molecular weight. These trends are shown in Figure 2.6.
However, because n and A are directly and indirectly proportional to the gas
pressure, respectively, the thermal conductivity is independen! of pressure. This
assumption is appropriate for the gas pressures of interest in this text. Accordingly, although the vales of k presented in Table A.4 pertain to atmospheric
pressure or the saturation pressure corresponding to the prescribed temperature,
they may be used over a much wider range.
Molecular conditions associated with the liquid state are more difficult
to describe, and physical mechanisms for explaining the thermal conductivity

200

400

600

800

1000

Temperature (K)

FIGURE 2.6 The temperature dependence of the thermal

conductivity of selected gases at normal pressures.