SOLUTIONS TO SELECTED PROBLEMS FOR STATISTICAL MECHANICS SECOND EDITION KERSON HUANG Massachusetts Institute of Technology JOHN WILEY & SONS New York Chichester Brisbane Toronto Singapore Copyright © 1987 by John Wiley & Sons, Inc. This material may be reproduced for testing or instructional purposes by people using the text. ISBN 0 472 84827 2 Printed in the United States of America 10987654321Ll Adiabatic transformation of ideal gas: S = Const. By (1.22), which follows from the Second Law, we have y = Cp/Cy = CWP), ACV/0P), Hence av) _ 1 fav (3), * vl a The last step ts obtained by using the equation of state V=NkT/P. Thus, along an adiabatic line we have dP/P = - y dV/V. Integrating this gives the answer PV” = Const. 12 (a} In a cyclic process AU = 0. Therefore AW = AQ. which is the integral of TdS over the cycle, or the area A. The heat absorbed by the system is the area A+B. Hence the efficiency is - A. od U* AsB 7 T3B7A If the engine had operated between the highest and the lowest available temperatures, the area A would have increased, but B would have remained the same. Therefore the efficiency would increase. (b) For a arbitrary reversible cycle, the efficiency is given by the same formula as above, with A the area enclosed by the cycle in the T-S plane, and B the area beneath the cycle. If the cycle had been replaced by one that operates between the highest and lowest available temperatures, then A could only increase and B could only decrease. Therefore the efficiency could only increase. 13 In the free expansion of a real gas, no work is done, and no heat transfer takes place, by definition Therefore AU=0 by the First Law. The process cannot be represented by a path on the equation of state surface, because it is not in thermal equilibrium in the intermediate stages. The endpoints, however, are equilibrium states, and can be represented on the equation of state surface. The changes in T and V can therefore be calculated by joining the endpoints by an any reversible path with constant U. The formula AT = (6T/AV), AV merely states this fact. 1-114 The cycle is a Carnot cycle. Hence the efficiency depends only the ratio of the temperatures: y = 1-T,/T,. The work done is therefore W- nQ, = (T,/T,)Q, where Q, is the heat absorbed along the paths AB and BC. Along AB the heat absorbed is by definition L, the latent heat for 1 mole of substance, because the system transforms entirely from pure liquid to pure gas. Along BC the substance is an ideal gas al constant temperature. Hence AU=0, and the heat absorbed is equal to the work done by the system. The latter is the area under the path in the P-V diagram, or RT, log (V,/V,). Hence W = (-T,/T,) EL + RT, log (¥,/V,) ] The rest is just plugging in numbers. LS Use the Maxwell relations (A/T), = -S and (A/V), = ~ (a) Obtain ACV.T,) from P by integrating along the isotherm Ty Obtain A(V.T) for $ by integrating atong a path of constant V. We have Vv ACV,T,) = -RT, log -¥ ° 9 Vo RVTo (Te ACV,T) = casi (4) +F(V) Setting T=T, in the second equation and comparing it to the first determines F(V): FCW) = -RT, tory G may 3 [1- (b) Use P = - (@A/aT),. (c) Use W= { P dV along an isotherm.21 Water data at boiling point under 1 atm: T = 100°C = 373°K 1 = 539 cal/g = 226x 10° erg/g v, = 1671 om? v, = 1 cm? Substituting these into the Clapeyron equation gives dP/AT = 3.628 x 10° dynes/cm?/C" Hence in the neighborhood of this point AT = 276% 10° AP Using AP = -1/3.atm = -(1/3)x10° dyne/cm?, we get AT = -9.18 °C Hence the boiling point is about 90°C. 22 Let Ag denote the difference of Gibbs free energy of the two phases. The pressure at which the two phases are in equilibrium is such that dP/dT = (aAg/at)/(ddg/dp). Since this naively gives 2 » we use lHopital’s rule and differentiate numerator and denominators separately with respect to T, obtaining ap aag/at? aT ~ 9ag/aTap The denominator is Ac, the difference in the coefficient of thermal conductivity. The numerator is Ac,, the difference in specific heal al constant pressure. The latter may be shown as follows. Use the equation after (1.21): Cy = T(QV/3T}, (P/AT), Using the chain rule to rewrite (aP/3T),, we obtain Hence the analog of the Clapeyron equation reads WP/AT = dc/da Since the density is the same for the two phases, the pressure along an isotherm in the P-V diagram does not have a horizontal portion, but has a discontinuous slope at the transition volume. 2-12.3 (a) Use the Clapeyron equation to calculate P,,. Approximate Av by the specific volume of the vapor, which satisfies the ideal gas law. The Clapeyron equation then can te integrated to obtain PUT) = Ce eer where m is the mass of a water molecule. The approximation that € is constant breaksdown at very low and very high T. (b) The process is indicated by the adiabatic path AB in the accompanying P-V diagram. Since the vapor is assumed to be an ideal gas, along the path PV’ = Const. or prvr 1 = Const. Therefore PAT) = PCT C/T? But the left-hand side is P,(T) exp(a/kTr), according to (2.25), where a= 2om/p. Furthermore, we have the explicit form of PCT) from part (a). Thus, after a little algebra, we obtain ~ +) pio (4) {c) In this approximation adiabatic expansion always leads to supersaturation. Referring to the accompanying figure, we can see that V>V_, because P,>P,, by use of (2.25) and the ideal gas law. 1 t 24 Write the Van der Waals equation in the form -Rt la a. V-b y? The Helmhioltz free energy is obtained by integrating this along an isotherm: A= -RT log V+ +F(T) The entropy is therefore s = -94 - Riogv-FCT) It follows that Us G+ FC- TROD) cy = Be -TeD25 Perform the integration G = - [var graphically, as shown in the accompanying figure. The principle of minimization of G shows that the system will follow the path ABC, skipping the loop entirely. IL is obvious that the point B corresponds to a line in the P-V diagram making the shaded areas equal 26 The water will not leak out because the pressure outside balances the total pressure in the solution, and is therefore greater than the partial pressure of the water. 2-3PROBLEM 2,3PROBLEM 2.5 2531 Under standard conditons the density of a gas is given by Loschmidt’s number n= 2.69x 10"? molecules/cm? The temperature is 300°K, corresponding to kT = 1/40 eV = 4x10" erg One gets for H, ans 3 “Ene 3.4.x 10 For other gases the above ratio will decrease as the root of their masses. 3.2 All molecular inteactions are electromagnetic in origin because they arise from the overlap of the electronic clouds of atoms. The atomic nuclei are kept sufficient far apart so that the strong but short-ranged nuclear forces do not play a role. The weak interactions are weaker than electromagnetic forces by the order of tol, while gravitational forces are weaker by the order of 107%, 3.3 The scattering of two hard spheres each of diameter a can be reduced tu the problem of the scattering of a point particle by a fixed hard-sphere potential of radius a (a) Refer to the accompanying figure. We have 26 +6: 7. Hence the impact parameter 6 is related to scattering angle 9 by b=asinfi=asin(6/2)= a (-ctos 6/2 The classical differential cross section is a() = orgie gs = a/4 The total cross section is ma’. (ob) The quantum mechanical total cross section in the low-energy limit is ta?, and in the high-energy limit it is 2na% It comes as no surprise that the low-energy cross section differs from the classical vatue, for the de Broglie wavelength is much greater than the diameter of the hard sphere. Bul it seem strange that the high-energy cross section is twice the classical value. 3-1The physical explanation is that half corresponds to the geometric cross section (the classical value), and the other half represents the amount of scattered wave necessary to cancel the incident wave behind the sphere, thus producing a shadow behind the sphere. For the scattering of two identical particles, however, the total cross section is only half that for the scattering from a fixed potential, because the phase space in the final state is only haif as large, owing to the fact that interchanging the two particles does not lead to a new state. In the case, the quantum mechanical total cross section in the high-energy limit agrees with the classical value, But the differential cross section still disagrees. This example shows thal we should not expect the classical description of scattering to be quantitatively correct in the subatomic world. 34 The Boltzmann transport equation is a set of coupled equations for the distribution functions f and g: If ager (2+¥,9,+ Fv, } ty = dat des a > (Ar F9,+ 07,,) g > Jeet Tig where J,, and J,, are the usual collisions integrals as given on the right-hand side of (3.36), each with their own T- matrices. Jig is the collision integral describing collisions between different types of molecules: TCP) = |e apy dps SP PIT? Pa es - 0, 8) where T is the appropriate T-matrix for the scattering. 3.5 (a) The accessible phase space consists of two horizontal strips in the p-q plane, of width 1/2, and located at the top and at the bottom of the unit square. (b) After not too long a time, the distribution looks like that in sketch (a), which can be obtained by "folding (b). After a long time, the distribution looks like that in sketch (c), which can be obtained by “folding” (d).