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Huang, Kerson 1987 Statistical Mechanics 2ed PDF
Huang, Kerson 1987 Statistical Mechanics 2ed PDF
0. This number is v, f(p) d3p, with v, > 0. Therefore the pressure is,THE EQUILIBRIUM STATE OF A DILUTE GAS 7 for a gas with zero average velocity ‘ Laat? 2pasfolo) = f d*ppv.fol) c 2 Cc 2 = 3p pip AP? 35 pe AP’ —fa ppze“? al ppe (4.20) where the last step comes about because f,(p) depends only on |p| so that the average values of p2, p?, and p} are all equal to one-third of the average of P? = pz + p, + pz. Finally we notice that 2 P P=3cfd'p mn 2ne (4.21) This is the equation of state. Experimentally we define the temperature T by P = nkT, where k is Boltzmann’s constant. Hence e= kT (4.22) In terms of the temperature T, the average momentum po, and the particle density n the equilibrium distribution function for a dilute gas in the absence of external force is = go)? ame fo(p) Gamer? (4.23) This is the Maxwell-Boltzmann distribution, the probability of finding a molecule with momentum p in the gas, under equilibrium conditions. * If a perfectly reflecting wall is introduced into the gas, fo(p) will remain unchanged because f,(p) depends only on the magnitude of p, which is un- changed by reflection from the wall. For a gas with py = 0 it is customary to define the most probable speed @ of a molecule by the value of v at which 4p?/(p) attains a maximum. We easily find p = v2mkT.. The most probable speed is therefore = (= (4.24) The root mean square speed Ujn, is defined by _ | fatpertocn) PO Ume = }-——— | = f@rfile) At room temperatures these speeds for an O, gas are of the order of magnitude of 10° cm/s. (4.25) *We have assumed, in accordance with experimental facts, that the temperature Tis indepen- dent of the average momentum pp,78 THERMODYNAMICS AND KINETIC THEORY 4pfo(p) 0 D vims Fig. 4.2 The Maxwell-Boltzmann distribution. A plot of 47p?/,(p) against v = p/m is shown in Fig. 4.2. We notice that ‘fo(P) does not vanish, as it should, when v exceeds the velocity of light c. This is because we have used Newtonian dynamics for the molecules instead of the more correct relativistic dynamics. The error is negligible at room temperatures, because 6 < c. The temperature above which relativistic dynamics must be used can be roughly estimated by putting # = c, from which we obtain kT = mc? Hence T = 10" K for H. Let us now consider the equilibrium distribution for a dilute gas in the presence of an external conservative force field given by F = -vo(r) (4.26) We assert that the equilibrium distribution function is now S(t,p) = fo(p)e #7 (4.27) where fo(p) is given by (4.23). To prove this we show that (4,27) satisfies Boltzmann’s equation. We see immediately that 4f/dt = 0 because (4.27) is independent of the time. Furthermore (f/0t).o, = 0 because $(r) is indepen- dent of p: af (Flos = eH fap, dpi d°p5 84( Py — PITS ~ Fah) = 0 Hence it is only necessary to verify that P (Peo sre,)sen <0 and this is trivial. We may absorb the factor exp(—¢/kT) in (4.27) into the density n and write F(tpp) = Sage wh ant (4.28) where n(r) = fd’pf (esp) = nye #47 (4.29) Finally we derive the thermodynamics of a dilute gas. We have defined the temperature by (4.22) and we have obtained the equation of state. By the veryTHE EQUILIBRIUM STATE OF A DILUTE GAS 79 definition of the pressure, the work done by the gas when its volume increases by dV is PdV. The internal energy is defined by U(T) = Ne = 3NKT (4.30) which is obviously a function of the temperature alone. The analog of the first law of thermodynamics now takes the form of a definition for the heat absorbed by the system: dQ = dU + Pav (4.31) It tells us that heat added to the system goes into the mechanical work P dV and the energy of molecular motion dU. From (4.31) and (4.30) we obtain for the heat capacity at constant volume Cy = INk (4.32) The analog of the second law of thermodynamics is Boltzmann’s H theorem, where we identify H with the negative of the entropy per unit volume divided by Boltzmann’s constant: Ss i (4.33) Thus the H theorem states that for a fixed volume (i.e., for an isolated gas) the entropy never decreases, which is a statement of the second law. To justify (4.33) we calculate H in equilibrium: 3 1 32 3 y= [apf oe f= n{log|n(5,) | - 3} Using the equation of state we can rewrite this as —kVHy = 4Nk log (PV5/) + constant (4.34) We recognize that the right-hand side is the entropy of an ideal gas in thermody- namics. It follows from (4.34), (4.33), and (4.31) that dS = dQ/T. Thus we have derived all of classical thermodynamics for a dilute gas; and moreover, we were able to calculate the equation of state and the specific heat. The third law of thermodynamics cannot be derived here because we have used classical mechanics and thus are obliged to confine our considerations to high temperatures. 4.3 THE METHOD OF THE MOST PROBABLE DISTRIBUTION We have noted the interesting fact that the Maxwell-Boltzmann distribution is independent of the detailed form of molecular interactions, as long as they exist. This fact endows the Maxwell-Boltzmann distribution with universality. We might suspect that as long as we are interested only in the equilibrium behavior of