CONCEPTS FROM GASKINETICS

361

(1) Since no direction in velocity space is preferred, 4>{u, v, w) must be independent of any rotation of axes. Hence 4 > { u , v , ' w ) depends only on u^+v^ + w^. Thatis, TO) = / w ( 2 + 1,24-^2). (2) Assuming that u, v, w are statistically independent,! i.e., that (j){u, V, w) = (j>{u)4>(v)(l){w), i t follows that 4,{u)4>{v)4>{w) = + 2 -)- ^2) (14.10)

The only nonsingular function 4> which satisfies this relation has the form of Eq. 14-9. For our purposes, i t is important to remember that, once (^( M, V,W) is known, we can obtain mean values of all functions of u, v, w. Furthermore, these mean values can be interpreted as time averages or as ensemble averages. 144 The Virial Theorem of Clausius

One way to obtain the equation of state of a perfect gas is to compute the total momentum transferred to a portion of a wall. I t is very instructive, however, to consider also the problem from a somewhat different point of view which is due to Clausius, and in which the mechanical equations of motion are explicitly used. Consider the motion of a single molecule of a gas. Let m be its mass, r its position vector measured from an arbitrary origin, and F(r, t) the forces acting on it. These forces are due to the other molecules and to the wall of the vessel containing the gas. The equation of motion is w J = F (14-11)

We now form the scalar product with r and slightly transform the left side of the resulting equation. dh d ( mt = m-\t dt^ dt\ or, with dr/dt = c. d . - ( r c) - c2 = F - r dt (14-13) dx \m dt. 2 F r (14-12)

We shall now average this equation. To do this we imagine a large number of replicas of our gas. I n each of these systems, we pick a molecule and write Eq. 14-13 for i t . We then add all these equations and divide by the
fTMs is certainly the simplest assumption, and may be legitimately tried for comparison with experience. In the apphcation of classic mechanics to kinetic theory, the assumption of independence is rigorously justified from a discussion of collision processes.

362

ELEMENTS OF GASDYNAMICS

number of systems. The result is an equation between ensemble averages j w - ( F ^ - w ^ = F ^ dt (14-14)

I n the first term, differentiation with respect to t and summation over aU the members of the ensemble are independent linear operations and can be interchanged. But we are considering a macroscopically stationary system, and hence all mean values must be independent of time. The first term then vanishes, and we obtain one form of the virial theorem of Clausius; m? = -T^t (14-15)

F - r is called the virial of the forces. The virial theorem was obtained by averaging over an ensemble. We can now use the ergodic property and consider the mean values to be time averages. Thus mc^ is twice the average of the kinetic energy of a single molecule observed over a long time, and F r is the time average of the force times displacement in the direction of the force for this single molecule. 145 The Equation of State of a Perfect Gas

We shall now apply the virial theorem to the molecules of a gas enclosed in a vessel of volume V. For simpUcity, we may choose a spherical vessel of radius ro and use its center as origin. The size of each molecule and the range of its force field are assumed to be vanishingly small. This implies the assumption of point masses for the molecules, and leads, as we shall see, to the perfect gas equation. For point molecules, the contribution to the vurial of the intermolecular forces is zero. This is so because the force vector F at any point is randomly distributed, in direction, and thus the average F r is zero. Thus the only contribution comes from th.^ force at the wall. To find this we multiply the virial equation by N, the number of molecules in V, and write Nm'^ = -iVF^

At the wall, the force F is related to the pressure. I n magnitude i t is equal to the pressure times the area of the wall, and is directed radially inward. Furthermore, |r| = ro. Thus, Nm'^ = p'^Trro^ ro = 3pV or t = p
P

(14-16)

This becomes identical with the thermal equation of state for the gas

CONCEPTS FROM GASKINETICS

if we put RT = p

363
(14-17)

Now fc^ = CT is the mean kinetic energy in translation per unit mass of gas. Thus ^ = i?r = f e r
P

(14-18)

We have thus succeeded i n expressing the temperature i n mechanical terms. Furthermore, if the gas consists of mass points without internal structure, then CT accounts for its total energy per unit mass and hence is equal to the internal energy of thermodynamics. Thus e = ^RT (14-19)

Equation 14-19 is the caloric equation of state of a monatomic gas. The specific heat c and the ratio of specific heats y are determined from
de

3 (14-20)

'^-TT=2^
and ^ = = ^

(14.21)

These values agree with observations on the noble gases, e.g.. He, A, etc., over a fairly large temperature range. Multiatomic gases will have other energies besides the kinetic energy of translation, for example, rotational and vibrational energies. I n this case
e=

|i?r-H

rot

+ evib

etc.

(14-22)

Thus c for multiatomic gases is larger than ^R, and 7 is smaller than f . 14>6 The Maxwell-Boltzmaiin Distribution The virial theorem has led us to a relation between the mean square of the absolute velocity of a molecule c^, the thermodynamic pressure p, and the temperature T. We can now combine these results with the distribution function <i>{u, v, w) and bring the latter into its final form, 4>{u, V, w) was given by:
<i>{u, V, w ) du dv dw

= ^e -P ('+"W)

du dv dw

(14-23)

where A and (3 are constants, independent of u, v, w. We first relate A and (3 by normalizing 0, i.e., by choosing A so that

Iff

A e-f'('''+^^)

du d v d w = l

(14-24)