CONTENTS CHAPTER, Introduction to Statistical Methods... . CHAPTER 2: Statistical Description of Systens of Particles. . CHAPTER 3: Statistical Thermodynamics»... - es Macroscopic Parameters an@ their Measurenent . . . Simple Applications of Macroscopic Thermodynamics. Basic Methods and Results of Statistical Mechanics CHAPTER 7: Simple Applications of Statisticsl Mechanics . . . CHAPTER 9: quantum Statistics of Teal gases... CHAPTER 10; Systems of Interacting Particles... 5 CHAPTER 11; Magnetisn and Lov Temperatures 66s. + CRAFTER 12; Blenentary Theory of Transport Processes « CHRETER 13: Transport Theory using the Relaxation-Tine CHAPTER 2k; Near-Exact Formation of Transport Theory Bquilfvriw: between Phases end Chemical Species. « Approxination CHAPTER 15: Irreversible Processes and Fluctuations... +... +PREFACE, ‘This manual contains solutions to the problems in Fndamentals of Statistical and Thermal Physics, by F. Reif, The problens have teen colved using only the ideas explicitly presented in this text ané in the wey e student encountering this material for the first time vould probably spproach then. Certain topics which have implications ter beyond those called for in ‘the steteuent of the probleas are not developed further here, The reader can refer to the mumerous trestments of these subjects. Except when new symbols are defined, the notation conforms to thet of the text. Tt 4s e pleasure to thank Dr. Reif for the help and encouragement he freely gave as this work vas progressing, but he has not read all of this material and is in no way responsible for its shortcomings. Sincere thanks are also due to Miss Beverly West for patiently typing the entire manuscript. would greatly appreciate your eelling errors or missions to my attention. Fe KnacksCHAPTER 1 Introduction to Statistical Methods La There are 6+6+6 = 216 ways to roll three dice. The throvs giving a sum less than or equal to 6 mr LL Le] 113 PLL! [122 [123 | 2,22 Wo. oF Permtationg 1 3 3 3 3 6 2 stnce there are a total of 20 permutations, the probability te 22, =. Le (2) Protability of obtaining one ace = (probability of an ace for one of the dice) x (probabil- 5 ity that the other dice do not show an ace) x (number of permutations) = (2)(2 - 2) 5 =@ = ke. (be) The probebility of obtaining at least one ace is one minus the probability of obtaining none, oF 6 @ = 667 (c) By the seme reasoning as in (a) we have 4 oe Lu Tae probability of a perticular sequence of digits such thet five are grecter than 5 end five are a5 less than 5 is (2) (3). Then multiplying ty the amber of permutations gives the probability srrespective of onder. 545 ser @ @ 1a (a) to xetum to the origin, the drusk must take the sane mumber of steps to the lett as to the right. ‘Taus the probability ts «@® where Nis even. (b) The drunk cannot return to the lamp post in an odd number of steps.15 (e) a (>) (Probability of being shot on the N°" trie) = (protability of surviving N-1 trials) x (provability of shooting oneself on the n*™ triet) = e®. (ce) 6 1.6 E =m? = 0 eince these ere od moments. Using 2" sm = @ &) Gr) we (@n- me eke - Mane = 16 a 30m + oka? a - Oren nt The probability of n successes out of N trials is given by the sum 22 2 wa) EE ww. 2 ayy fel jel) ml. with the restriction thet the sum is taken only over tems involving v, n tines. 2 2 2 men w(a)= Ev, Lov... Ev. re we sum over ali i... m, each sm contributes aa bya 4 eet (wy) ena : Wa) = (+) x WG) = 2 aay applying the restriction that w, mist occur n times we have “py the binomial theorem wen myn WO) = Srmeay “2 We consider the relative motion of the to @ruake, vith each simltancous step, they have a probability of 1/4 of decreasing their separation, 1/k of increasing it,and 1/2 of mainteining St by taking steps in the same direction. Let the mmber of tines each case cecurs be my and n,, respectively. Then the probability of a particular combination in N steps is 1 33 EEE? @ "Qt ayes, = 3 2The drunks meet if n, =n,» Then the probability thet they meet after N steps irrespective of the number of etepe n, vhich leave their separation unchanged Le vhere ve have inserted a paraneter x which cancels if nj=n,. We then perform the unrestricted sum over n, Rn, and choose the tem in which x cancels. By the binomial expansion, on pre Gxt eRe OT eee Vy™ nceamnesiaen mE ts ea ay sarns sone means ahi ean whan se ae ate mms Le () a Qp)FP = (en) =p oa thus (1-p)"" = oT? ©) geyr- cr)... Gr- aa) =F sence (e) wo) = aebgy ot Gay = Hot oh 110 () (e) (ce) Ll(») az (a) Dividing the tine interval + into snl] intervals At we have agein the binouial distribution for n successes in X = ¢/At trials make ¥@) - ate 2) In the Limit At +0, w(a) +4; eas in problem 1.9 where » the mean mumber of disintegra- ‘tions in the interval of time. a 2 ° w(a) 7 (o) Wa) Si = L O76 ne 21:13 We divide the plate into areas of size 0°. since b* 4s much less than the area of the plate, the probability of an atom hitting a particular element is much less than one. Clearly a <0 0 we may use the Poisson distribution 2 wea) - & vebost Les =| alk We use the Gaussian approximation to the binamial distribution. (215-200) ye ee aa 15 The probability thet @ Line is in use at eny instant is 1/30. We want N lines such that the probability that N+1 or more lines are occupied is less than .Ol vhen there are 2000 trials uring the hour. vere‘The sum may be approximated by an integral, ¥ 19 = Me ia ex [-(n-Z)°/207] an 4 vero 2 eT? ay attr a change of integration variable. The lover init may be replaced by - vith negligible error and the integral found from the tables of error functions. We fina 2.33 W = 66.67 + (2.33)(8.02) - .5 = 85 16 (a) The probability for W molecules in V is given by the binomial distribution x, (e) () mw VKH, @) vay, << Land since N, is large, we may use a Gaussian distribution. (nay =» 2 exp [-(n- 8/2 a) an (en aa)G,"2 aze unit vectors) +8204 PT Leos “A ifs ‘The second term is O because the directions are randam. Hence F =H. Lis Pia ~ OPP/R) stas(0-9) fm] (a) ‘The antennas add in phase so thet the total amplitude is B= NB, and since the intensity 4s proportions to #,°, 1, = 17r. () To find the mean intensity, we must calculate the mean square amplitude. Since amplitudes may be added vectorially rs -RE PB sf+P5 5 “eb aot ifs whore the 5,10 are unit vectors. The phases are random so the second tera is 0 and 5 xii yom 12a Stace = 0) the second tem on the right is 0 and GB) «8 GF Bate wt OQ) = As = Ms Bquating these expressions ve ind W = 108122 1.23 y_ og (2) the neon step iength is 4. EE, = ee u—— ey (oe) (@3)? = E (s,-2)? +B P 26-262) » Go =t-t=0 i ifi ‘To find the dispersion (s,-2)° , ve note that the probability that the step length is between s and s + as in the range Z-btol+visS. 5 ple (st)? as, 42 ence yee ft 4 ee ie @,-0* =f, 3 7 N42 pe? e LE. (x=) sa 525 22k a‘ -# (2) wa) = & w(e) ao = 20-8 sin o a9 | sino ae (>) w(s) ae = ee ae 12 {e) We fing the probebility that the proton is in @ and @ + 49 and thus the probability for the resulting field. sin 9 a9 From problem 1.24 w(e) 49 = _ Gucos 8 sin 9 a Stace » = Hy (3 cos%9-1) ve nave 3 am, ul)as = au(e)ag = —S2VS_ a Sal + wats(®) Tf the spin 4s anti-pareliel to the field, w(ojae « 22 a 6 vuran ab Then if either orientation is possible, ve add the probabilities and renomalize ai Vy a -Beve-H weViPou are 2 ~ 3, (oye = ele, —S4_) a Bevel ence | ikea . « ei a eve sehen = ~2u/e 1.26 ae) - [os oP u(s) 2B £ For k>0, the integral is evaluated on the path ste @ may be evaluated ty contour integration. “> ab residue (1) = 5 Q(x) = ee Pork <0 » “2 sresiaue (-1b) = $> ate) 8Hels ‘Thus Qk) = ¢ - a 7 1 -te gigy wi ii, 2 nthe tb LP act dw bk P aete & [le ° a2? ye ome “2 faces this integral my de found from tebles. Px) ox 2 ae x +e P(x) Aoes not become Gaussian because the moments s* diverge. Let From equation (1-106) and (1.10.8) we see that Pe) =e Leo a, 0)..0,0) @) vhere ae) £ as My, (5) We expand @, (x), selene tous fram (2), Pw) = z[ sou 3a) - ‘This integral my be evaluated ty the methods of section 1.11. We find Ps) exp [-(x-u)?/207} where H Peer a base e 1.28 ‘The probability that the total Gisplacenent lies in the range r to r + dr after N steps is A) ef. f wa) x, @z) where the integrel is evaluated with the restrictionWe remove the restriction on the limits ty introducing a delta function ¥e)[2eE oP ader ale é Pt) & -[ [ue a ope, EH in three dimensions o(g-Ea,)- 45 [ay © tims Pl) fe - [ ¥ et) = fle By ote a, Wa) or owas [ 1.29 EM) where a(x) = LC as ott Jor displacenents of uniform length but of renden direction w(s) = SY , sn spnerseat lm 8 coordinates. W(s) is a properly nomalized probability density since on pm pe 7 - a(s-t) _ B(s-2) EL a @ ds ae ap MEAD a [GB oy We find the Fourier transform Q(x). a(x) “Sff Be 2 u(s) = [UIT sino en an og ME atte os 8 ™ sin 9 do tke cos @ _ sin wb ra [Tage “ rea eas [ff eet ew vee have, for 3 ee as J “el WP stn 9 ak de apo HT OOF # a ‘The angular integrations are triviel and 1 oe) «ae [Ww mS JG Jo evaluate the integral, we use the identities sink’ sin kr x sixPkd ein ie ae =; sim er ssn we (E808 10a a [cos K(r-t)-cos x(rit][1-c0s aut ] = 25 13 cos K(r-L)-3 cos (rt) + cos K(mi3L)~ cos (r-32)] oe The integral of the first tvo tems in the last identity is © com u(nat)-cos R(rel) gp 3 [2 SE Eled) six? Ee) g [f semetigente ag [7 EE a making the substitutions x = (rZ) and y = E(rt), it follows thet © Jovt] sine * Jeet] sin® 3 Jf gH ss oe 3 ( Uegel senna a teeth - [ely ‘The third and fourth terms may be evaluated in the sane vay. g [> se Hesathsses wleBO) ax « B (xt-[atl) Conbining these results, we bave bp shes 2 ao o) T NW # - eM DA) ys Nope wn + wnt “ . late ut wes ist fe 34 te eatcony change f the teat reservetr ts ds! « - Sy and for the entropy chee of the extise system, OS + AS" = As - ence ask % Os, ty the second lav. 365 (2) I section 2.5 it is shom thet a(e)« Vix(z), where V 1s the volume and x (3) is independent of volume. ‘Then for tvo non-interacting species with total energy F, ite a(z) = ¢ 9, (2) 9,(8,-8) = ov 4) ©) () an a(S) = (1tysNg) la V +n ¢ + In %(5) (2) (ny, 7 = an A(z) = 3 = 2) » or BV = (NaN) aTAL 338 gp z @ - 160 m 3B ino joues ©) seal F B “fe Stace Ses = YW = - B (s13-273) = -1120 goutes/x ASjgp * My + AScgg = 190 Souter“ (v) The heat given off ty either reservoir 1s Q = me(50) = 2.09 x 10” joules. Since the entropy change of the vater is the same as in (a) we have 2.09 X10 _ 2.09 x 10° aso nn = WP 200 oe jute (c) ‘There vill te no entropy change if the systen is brought to its final temperature by inter- action with a succession of hest reservoirs differing infinitesimally in teuperature. he (a) The final tempersture is found by relating the heats, Q, exchanged in the system. The heat required for melting the ice ie mt vhere m, is the mass of the ice. Since for the other compo- nents of the system, Q = mcMT, vhere m is mass and c is the specific heat, ve have Bt + (certea ice) * (original vater) * Yeatorineter) ~ ° nb + miq,(T9273) + myo, (7.293) + m,5,(7,~293) = 0 (30) (333) + (30) (+.28) (tp-273)+(200) (#428) (7-293) +(750) (428) (75-293) = 0 ag ae so etn hime in Ba me in 28- Px » Bry * MWe 2 Byy + yo UR BS * Mate Im 93 = 16 3 18(c) The vork required 1s the ancunt of heat it vould take to raise the vater to this temperature. Wemyss Cy2y) + mee (PA) = [¢50)¢.48) + (250)(4.28) |(a93-283) = 12,750 joules 443 dqecar+ pay ty the first lew wen eR ae stmt Ve as i ze. ci o @y +f RY Ty = Vy ¥ fs Te ‘ve sedge + Ring! tadepentect of process a The spins became randomly oriented in the Limit of high temperatures. Since each spin hes 2 available states, for N spins ve have S(t se) =kingQ=kinA- mine () But since s¢e)-s¢o) = or ve have s(t +9) = “le AG 0 F-ea-m2) (2) where ve have eet S(0) = 0 by the third lav. From (1) and (2) Nk In 2 = c,(1-In 2) oy RS seer me AS 2 oo The entropy at tenperature T is found by evaluating 8(2) - s(0) = / SE) ar, Labeling the undtnted end ated spatome Wy a and a we Bere sy(ty) - 8,(0) = “fe E-0 F-0m2) sO) 0 =f EB ae 84(0) = $,(0) ty the thind law. since thee ase onty fy a8 mtsy magnetic atoms in the diluted case as in the other, ve mst have $,(2,) = -7 §,(7,)- Hence <2 2.7 (ttn 2) © 2h a 1CHAPFER 5 s Mestions of Macroscopic The es 5.1 (2) pv” = constant for an adiabstic quasistatic process. Substituting pV = v RI we have y , Ly wea? ym og (iy WaT eo Oe () tae entropy change of an ideal ges in a process taking it fron 7,,V, to Ty,V, vas found ta problem 4.3 Tt, Vp as evs, tng twin AS = 0 for an addanatic quasistatic process. Hence tM Mr onmit (st Thy end since In 1 = 0, it follows that ley since Ray = oyrty/ty = 7 Cy) 5.2 (a) we ['p av = aren enciosed ty curve = 31h Joules (b) Since the energy of an ideal gas is only a function of the temperature and since pV = RI, PY, 2 = = (ae an os=o,cr =e (S =) = 3 (6-2) x 10? ergs = 600 joules (c) Q= AE +¥ where AE is calculated in (b) since the energy change is independent of path. again the work 4s the area under the curve. @ = 60 + [400 + 2005 J] = 297 goutes 563 ®) tees 3) w= ['p av = acon unter curve = 1300 joutes (c) To find the heat, Q, ve first find the energy change in going from Ato C. This, of course, is independent of the peth. ag = ein = 3 n(n,-t,) = 3 (PV, ~ Py¥y) = 1500 Joules 20Ten since Q = 08 +W @ = 1500 + 1300 = 2800 joules (a) From problem 4. fou BAA s ite cos 23.6 jours 5o8 (a) ‘The total system, i.e., veter and gases, does not exchange energy with the enviroment, so its energy remains the same after the expansion. Since the vater cannot do work, its energy change is given by the heat it absorbs, AE = @= G/M, where G, is the heat capacity. The energy of the to ideal gases ts, of course, dependent only on temperature, AS = OM, vhere C is ‘the heat capacity. 28 (eater) * Sime) *E(4) =o GylteBa) + SelB) + 6 (tyty) = 0 no temperature change. (2) Let £ be the distance from the left and v the munber of moles. Mae _ Paele _ (5) (30 % By,” CGO) “3 Hence, in equilibrim 4 = 3(80-L), 2 = 60 om y, (c) Since there is no temperature change, the entropy chenge is vain. s Bu 2 | 43 = 65, +055, = Ban $F +R In 5 = 3.2 Joules/*x. 55 (a) ‘The temperature decreases, ‘The ges does work at the ext of Sts intemal enerey. (bo) The entropy of the gas increeses since the process is irreversible. (c) The system is isolated, Q = 0, and from the first lav ass = - (vv) ‘The internal energy of the gas is only e function of temperature, AE = ve,(7,-T,) - 3 (v,,) @) mms v5y(te,) tn equitttri p = 3E and sioce WY, = vit, ve bave aLSubstitution in (1) yields [0 + re 566 in ait a attodte shank w= a a) Since the process is approximately adiabatic PV” = constant = (2, + 88) ¥,7 a7 and, = +B) So - mee ee (2) (x) he Qisplacenents from the equilibrium position, “2 , are mall so we can introduce the cocr- ¥ ¥ cuoate change x - 72 +9 and expand about “2. yy Gea We keep only the first and second terms and substitute into (2). & 2 mq = -(p, +38) AZ 9 mats is the equation for bermoate motion ant the frequency may be determined by inspection. ‘roe wok [o.BE ; in? v? av, ee +e A 5.7 2(stz)a The volume elenent of atmosphere shown mist be 42 aide equiltbrius under the forees (pressure) x (area) and qzevity, Then if n de the number of particles per untt a(=)a volume, m the mass per particle, and g the acceleration of erevity, P(z4az)A-p(z)A = -n(adz)me, go. - BE we Ba-Bas, tere Foe 22,ae Q) Ince p = 2-8 Since p = nk?, Be (v) pv” = constant. substituting V = ae » ve obtain 7 pi = constant ‘Tims wt PT an + (147) 07 p? ep “ a Pat ® (c) From (1) and (2) #-G,, @) For Ny, = 26 and letting 7 = 1b, & = 5.4 aegrees/ctimeter. (a) Integrating (1) with constant T we have P=3, em busx/Rr) (e) From (3) 7 P apt 2 ug ant es at vs a °F ie oa) ° J n(n, - AZ HEE) 3) pee V7 =n, (1 Geass) 58 attie ee T H ‘ 1 L, ve have Tp >,, i.e. the temperature increases. Hence T= (ec) Fron the first lew us ® @,-?@,@,-7@,@, Substituting (2) and (3) ve tind @, DD) cer (uHt,) Hence (Zp) = O(L,,2) + a * @, & = wr - on(t-1,) @) st,)-20,2,) = | * Suef Fea B,(0'-1,) at! = -at(t-b,)? ‘0 a a n ye 8(i92) - 8(042,) f ae L ESOT es 0 oy Wr ° = ¥(2- -i,)° (2-,) hee S(Ug2) = S(2_,5,) + (2-1, - en(e-4,)® 5.15 (2) Zq= MS = a- acta Q) (>) From (2) as = 2 2th ay mm Bale, =< Equating coefficients, ve have @,-@,+» 26From (1), ve can reed off the Masrell relation ©,- Ca, -+8 since o = 9, -02, (8) = ete ‘0 Bey ss 35) 3), ~ Har + ale, - stom ~ at, If the film is stretched at constent tempersture E(x) = ) ¥ (04a) -- fF 5016 By the first lav a-@, 2Ya a) rence @,#+@ «3G, 94@ «+o Equating coefficients, we have 2) 2 (38) - ®, “@), 2¥ ‘From (1), we mey read off the Maxwell relation SS) oon ©), *@, (2 - OY) Lev sms @,-=@,-# a coe note is protuced aca om (QL) - oY vy 5017 ‘By equation (5.8.12) @,*@y* Substituting p = 2 ut (1 + 3,(t) a] ve tind @, 2180 Boo te Bro eT5.18 6 e- @,7-@,« since &, = G, and @, "Ge, => trem (5.8412) w@ 7 @e? ve beve @,-- (v) From the first lav, 6& = 745 - pav. Hence (c) For a van der Waals gas 2 5.19 S\v-») = @) me (p+ %)ra) = @ a we have le 2) -% wR? 3 ° @ . ™.%. Ge Gar eS soiving, we tits «Baty 2 (®) Substituting @ and b in (1) yields 7, =f = . () @ * 4) ( ® 5.20 To Sind the inversion curve, ve must have @,-& GS, -)-° 28> 2a (ey Tay) 2a (ros)? ‘tus e@- On eliminating v and putting the equation in tems of the dimensionless variebles of problen 5.19, 1% follows that ° pr=9-12(¥i" - ¥3) w J6-3/% 5.21 (a) Q) We have en (8) Segre + B35) ay! ae we Ze ws 30) a a Substituting these expressions into (1) ve tind a wed ore @ q = 29(>) Prem (2) 5.22 ‘the systen may be represented ty the diagram % a (0) Wy the second 1a a= - 220 pF? or naximim beat, the equlity holds and since q, = ay) {¢ follovs that a Wty «) 5.23 We have the aystea a ne a He ¥ () Wo yay = O(0-t,) + olny-ty) = Ofte, - @) (b) By the second Jaw, 22 te sraus Secu no 7 a It follove thet (c) the mextmm amount of work will be obtained vhen 7, = TT) a) - AJR JF Frea (2) w= o(nyeny 3052k To freeze an additional mass m of vater at To, heat mL must be removed from the icewater mixture nb resulting in an entropy change 45) = - The heat rejected to the body of heat capacity C ° r increases its teuperature to T, with an entropy change AS, = ¢ | + By the T, vty second lev 5, +45, = - 3 +c¢in = 20, For mintmm tenpereture increase end thus aintmm beat reJection the equality holds end it follows that ai /tc me? c The heat rejected is Q = C(T,-T,) = OT, (e | ° -1) 5. 5 ‘The probebility thet the systen occupies « stete with energy B is proportional to the mmber of states et thet enerey, (3). By the general definition of entrovy, § =k In (2), we have for the probability een) <* Q fo reise the weight a height x, an amount of energy, mex, in the form of heat, Q, mist be given off by the weter. The temperature change is found from Q = OMT = -mex Of = -nex/o wuere ¢ As the heat capectty of vater. For a nole of Liquid and x= 1c AP is on the omer of 1K, gence ve may approximate the water es a hest reservoir and find for the entropy when the weight is at height x s . 35 where S, is the entropy et height x= 0. ‘thus (1) becones 0/8, P(x) = Ae s, Here we have absorbed the tem ¢ into the constant A which is found to be XT_/ng ty the sual nommalization condition. ‘Then the protebility that the weight 1s raised to a height Lor nore is ° os, -nex/n -asi fe, o- f P(a)ax = [ =e ax ne ° L = = substitting L = 1 on anf the given values yields oe. 3h5.26 Jn the processes aD and ¢ +4 no heat ts absorbed, so by the first lav W AB, and since 63 = OMT, where C is the heat capacity, we have Way = ~ErE,) = ve, (t7) Wora = Ege) = VG, (Te2,) Hovever, in an adiabatic expansion Ty") = const. ra , y, Hence Way y Gg) 299), (2 @ o (a fr. C2 Masa * 76) 25 (GE) = 15) 2, GE The volume ts constant in process bee so no work is performed, ‘Thus & = (B,-B) = vo, (2,2) Ye + ¥en) fa" eee ® caRETER 6 Basic Methods and Results of Statistical 6.1 (a) ‘The probability that the system is ina state with energy % 1s proportional to the Boltmen factor eT, ence the ratio of the probability of being in the first excited state to the probability of being in the ground state is ny sar (>) By the definition of mean value 8 2 ate 38/2 pet pee ae Sei tS 6.2 ‘The mean energy per particle te p Be yg ttit .- Swe ee hence sor W paroles, peng tan8.3 (a) the protability thet 2 spin is perallel to the field 4s - a 1 EE a which yielés EET @ 3.66% For P = .75 ant ¥ = 30,000 gauss, (>) Prom (2), vith p= Lela x 20°3 ergs/gauss, 7 = 5.57 x 10> 64 ‘The power ebsorbed 1s proportional to the difference in the muuber of miclei in the tvo levels. Tis is, nett _ yeni * TE aS” GS SE where Nis the total mmber of mclet. Since ui << MT, ve may expand the exponentials and keep only the first two tems. Hence, aon, =n ee ° il “4 )-- cd i+B+i-E ‘Tims the absorbed power is proportional to 777. 6.5 ‘The volume element of atnosphere shown mst be in equilitrimm under the forees of the prescure and gravity. ‘Thea ig mis the mass per particle, A the area, and g the ecceleretion of gravity, we ave pletde) A - (2A = Baz a = - m(z) a ace Substituting the equation of state, p = MKT leads to --Bae) a(z) = a(oje Be 36.6 () eae As T approaches 0 the system tends to the low energy state, while in the limit of high tempera- ‘rures all states became equally probeble. The energy goes from the lw to the high temperature Limit when ¢,-¢ ~ 2 (2) me spectete best ts, 6, = (GE), toes, the slope of E o, © 3 =e on “ 220) F amy, md tae, Fan 8) To find the temperature at which F changes from the low to the high temperature limit, we evatuate 7 vere Hereyfet ete, +e : xfate | Bem, +2] E2 4) 2 n | aee visen yields on a Bp oema sl or (4) 0The heat capacity is we Meyte P* a Ll and G, +0 as 740,792. 6.7 (a) The mean energy per mole is sax, V4 ccertht 2, oF A 1+ 20% rex . L+ee x ® vhere Il, is Avogadro's number. (0) We tind the molar er ropy from the partition function Z. Clearly, Z = ~< t=Le ©“ , the oum being over states of a single mcleus. hus corse, oot and S =k (ing +68) = 3,x2n (2+ 26-6) net (2) - +3 + 20 tH) 2 - (avee 5) (c) As 7 +0, the mucieii go to the ground state, and by the general definition of entropy 8 Hx 29 =%,kln1=0 as P42, all states Decone equally probeble, @ +3 and 8 1x 1m 3 It is easily verified that expression (2) approaches these Linits. (a) Prom (1) ve eve y an, fone | = w2(1420"/)* | For large 7, oT ea and cot. 6.8 . ‘The polarization, P, is defined as Hef where aa X is the number of negative tons per unit volume, 6 @ ts the electronic charge, and 4 is the vector £ from the negative to the positive ion. Then the Oo oO 35Py 2 lel eS = me el eee ect gp. oe vbere x 4 6 ere shown in the diagram. The positive ton can have energy + $E8 or - $62, and since there are two lattice sites for each energy ve have 6.9 (a) ‘he electric field 4s found from Geuss'e Theoren if far Bee ima ee ee By symmetry, Bo = E Orr L = bg fee ae) = BF ‘The electric potential is given ty Tims (e) Tae energy of en electron st position x 1s qU(r) = -eU(x) where © is the electronte charge. Since the probability of being at x 1s proportional to the Boltmen factor, we have for the density sna s/s) i f2* Fo: ala) = o(0) oe [= sa aate/s.)] ot0) (E) 6.10 ae 2 @ molecule 4s at x is proportional to the Soltmann factor, the density is plz) = (0) exp (a2? /oxo) Q) (b) sunstituting y= 1,3+ the molecular veight, into (1) and evalusting this expression at x, (a) ™e centrifugal force mur yields the potential energy - + Since the probebility that and have 7° mye ote) ue PrP x, ote) 366.1 the meen sepazatica, Z, is found from the protability thet the separation 1s betveen x and xtixy P(x)ax ) J e-0fGe) Se Tt Ea) ae fie os GS) oa Noting that the second integral is O since the integrand is an odd fmction, and eveluating the first by Appendix Ask, we find Eee é@ + =e) Uy ‘Thus File ee Ete ae tyr ime ue a 6.12 (2) tet the aizensions of tle tox de x) yy 2 Then the volune and area are Veg Asay 422 + oe Q) Eliminating x, we have ven SE fren the coaitions for en extranm, 3 = = 0, i totlore tint (Areva) (#22) ~ 2yz (y#2e) - y (Anaya) = 0 (A-2yz) (#22) - 2yz (yt22) -22 (A-2yz) = 0 Subtracting these equations yields y = 22, Then substitution in (2) gives and from (1) ve find x = A. & (0) Free equation (2), ve have QV = yn dx tm dy toy de @) The equation of constraint is elxsyse) = ay + yt + oe A =O co) exe hag = Ayer) ax + Axtez) &y + A(Cx + 2y) a2 2 0 (5) Ad@ing (3) and (4) and noting thet the éifverentials are nov independent, ve heve ya +A(y#2z) = 0 xz + A(at2e) = 0 © xy + A(2xt2y) = 0 We multiply the first equation by x, the second by y, and the third ty 2, and ada. Bayz + M(2xy + bxe + yz) = 0 Substituting (lk) yielas a= - SBE 38and substituting \ into equations (6) gives 1-B@+e)-0 2-H (w+ 22) =0 2 - % (ex 2y) = 0 ne tiesto equations cov at x = 7 end the thing yields x =o. shen subetttutin tn the ‘ f RE ace B a3 a first and second equations gives x=4 2, y = B 6.13 Van pO) Qa p (2 sy t8 2 ¥Ee,6 Yi 2.) - eB 2, Dan vi (2) pur since 22,00) «52,02 «3, we ney site rrock 2222, @as 2,0) 257 2,022, ap 2 sts : want O2, Of 2s m2] 2 nr Man 22,00 =HEER ne, since vO) pO). 6.28 From the definition, ve have 8, 8,2 kD eine Oars pine @) substituting 2) Ep ana v2) -5 psn (a) we nave 848) °-EER, 3 5 37, = REDE, an) 22) @) For the total aysten, the entropy is =4EL2 ne, @) then from (2) ene (3) 8-(5,48,) = KEE2 inp +e ELE ina Op (2) rs Pos Gy)(e) Since -Inx2-x+1 or Inx xl, ve heve wre 2 We @) @, @ -- oe Fron (4), S-(5,'8,) = ¥ DE 2, pot since LE 2, Cp, () 22, s+ ornevs that 8-(5,48,) © 2 ZZ 2A, @a -0 ze mms § £5, + Sp. 6.15 (a) since s= Ee Ine ant sy= D2 ne) , ve nave ssent [a aeer a On m2 z . where ve have added and subtracted the term kD pin 7,(), we show that the cum of the lest two terms in (1) 4s zero. since 7,0) - ety, 22,0 = #8, - 102 then using EF, = 1, ve have Dep, .p ree +Le ange sdeinz = r : stntlenty Bp Om pCa £2), Adding, ve obtain -D2 meas 2” = r Tous (1) beconce (2) ss, -eE [ours er] endo as to > = Lyequation (2) yields (0) = wal w (0). =o vs, cuz, jess f-2] Consequently S, 2 S.CHAPTER 7 Simple Applications of Statistical Mechanics TL M8 polecule of type (2) We tabet tne positions end nenenta such that r,, and py, refer to the J i. There aze X molecules of species 4, Then the classical partition function for the mixture of ideal gases is The integretions over z yield the volume, V, while the p integrals are identical, ince there are Ny4iljs+ 1h, integrations, we have ae (tee - (yee en gh “fe = ey] heey aS The tem in brackets is independent of volume, consequently in 2 = (Nyte.s4M,) In V + In (constant) Fete L and Be PR az Oye) & Be = (rite DP = (vyteeety) BP @ () For the 1*® gas, p.v = v0, hence by (1) te (a) By the equipartition theorem the average value of the kinetic energy of a perticle is 3 z- 3x0. (0) The averege potential energy is pL |, [ses oP ae u <- f ePmet og, Ten 5 L 2k wer Bae 8 Se fos a--$a on carying out the aifferentistion, ve find a + Se13 (a) Before the partition is renoved, we have on the left, EV = vRD. After renoval the pressure a ay xD _ 2p Pe “(eb)v ~ Tb (v) The initial and final entropies of the system for different gases are i a ada ed » Wize. om fed dane] om fas dan same] ton fa GRE da ne TY Here one adds the entropies of the gases in the left and right compartments for S, vhile S, is ‘the entropy of two different gases in volume (1+b)v. 2 then a8 = SyS, = oR fein YOM) an Van | ey an GO Ss TY iy Tay © (c)_ Tn the case of identical geses, 5, is agein the om of the entropies cf the left end right compartments. Sp is the entropy of 2v moles ina volume (1+b)V. W432 + wea + veins fase] oom fa Bode oe ‘Thus Tk (a) the aysten ds isolated so its total enerey 4s constant, and since the energy of an ideal gas depends only on tenperature, we Aave 22, + AS, = GI 2,) + O(2,-,) = 0 +2, or my gk oe ‘The total volume 1s found from the equation of state Rr, yy, yee, Yee mE Wy.) Fp yt.) (2 +3 ins the fina presmure Se pg = 2G EE (ae(0) using } 32 , ve neve for the initial and final entropies of different gases Mi sore ebegea] ova eee wv fd (8. 2B) oa] a fe (8 Bau +o] vf, Ty, rer 2 +h a? R Jan (1+ vtaPe\ 3 vat Tas 2S = 8,75, vk fan (+ “iPPe (c) For identical gases [- shu] tis aE tba, #9 x a wg(2 #). puke] 2, v2? e3] 1 2 1 no 28 = yk [3a + + yaa y, sf oz ¢ | 2h 79) te Be) ae 15 We take the zero of potential eneray so thet 2 a sequent is oriented parallel to the vertical 4% contributes energy We and 4f antiparallel it contritutes fa to the total enerey of the rubber bend (Thus 4f the rubber bend were fully extended, the totel energy would be -IWa). Since the segnents are non-interacting, wa Ean Ne tenn HE “oe, WB 16 Since the total energy is additive, (24) + Uy.) = E + 0(ey.e,) where U is the energy of interection, the equizertition theor: still applies and TT ‘Te the ges is ideal, its mean energy per particle is rs o-218 For classical harmonic motion the mean energy is z B-E+iwe? ay squpartition, each of these tems contriiuter 2 in. Hence pervert 19 () ‘The mean elongation is found by equating the gravitational end restoring forces (») By the equipartition theorem Fa (ea ne 5 or (x)? = (c) 7.10 (a) Tet the restoring force be -ox. ‘Then the mean energy of K particles is BenGm+dax) By equipartition Een Gur+dm) vie BL mous o- Bem restoring force is -o°, the mean energy rer particle is iP stax the kinetic enwcay tem contributes JX8 by equipartition, ‘the mean of the potential euengy 4s sein Dw Be. fo lel]t« Sel] hy= cr oot Mae. oe Baa [Toe py where ve have made the substitution, y = 5Y/* x, ‘Tus ence ‘Then the total energy is F = We and c+ 8- fm ne “wie Since the probability of excitation is proportional to ¢ *? here n is an integer, it is clear thet the tvo parallel components are negligibly excited at 300° vhere Bu, >> 300 k. ‘The perpendicular component 4s excited since tu, << 300 kj and since 300° is in the classical region, the equizartition theoren holds and ve have for the mean energy per mole Een, Gat +3m2¥) <3 10 re o-Bens-2 me (2) consider a cube of side a. The force necessary to decrease the length of a side by da is n fe and therefore the pressure is Ap = x,fa/a”. The change in volume is AV = -2%Aa. 2 (st) 23 () the Einstein temperature is 9, = tu/k. Since w = [e/a vhere m is mess, ve heve from (1) aH -Be a The length a is found by considering that the volume per atom is u/ol, where y is the atonic @ weight, p the density, end N, is Avogeéro's mmber. ay ois a ae Substitution of m= u/N, and the given values yields 3 2.30208 ow 6, ~ 150% usTs We have = No6 uy J By(n)- By equation 7.8.14, 3 (n) Zor J = 2 becomes L y(n) = 2 (cote - Beotn 2) - 2 Soman _ cosh (a/2) 3y(n) = 2 (cota n - F cot 3) = 2 SoSBn . Sesh fale a2 05k" a) sinh?(n/2) om 2 sinh(n/2) cosh (7/2) ~ sinh sian! 2) - tee V2) cE CTE a By ~ tanh (n/2) No6 Hy ‘Thus we Tek The energy of the mgnetic moment in the field His B= -uH = -uk cos @ where 9 is the angle between the magnetic mnent and the direction of the field or z-axis. Then ‘the probability thet the magnetic moment lies in the range @ to @ + de is proportional to the Boltmann factor and the solid angle Or sin 6 a9. ‘Thus P(a)ag « ePHCPF sno ag € Hap” eFHF °F ino ao(u cos 9) and 7 f Pill 008 6 on gag x, PTs or B= BR an [oP 8 oans a 5 Tas ¥e have % to 7 Ca) @2 vere ty (7.8.28) gla) = 3[ +B om + Ba - Foon da] Tf nL and 5 >> 1 dn such a way that Jn >> 1, 3,(n) decones i 1 ak ayn) = fF conan -F@] = cotmsn- for small x Tet pi = Jn = Jeu,H8 where u = gu.J is by (7.8.2) the clucsical magnetic manent. Then (1) vecones a, «my: fos aw - 2d 1.8 (a) The energy of a magnetic moment ine field is B= y+ H. For spin} atoms n,(2,) MP Sey + Serco [bey] n(zy) PP MP ° 5a) EE 2(2,)/a(2,) > 2 ©) @aw URS - MR) +) ~ t/t), [2 (ee 3) 5 1) We have at t = 1 hour, “ge * (fee) C-hze/tne ) Since (Oye/t) 1.8 {a) The rate of change of the mmber of particles in the Ieft side of the box is au do Since the rate of effusion is Las AVA, ve have =e [LOG] - F fray] where N is the total mumber of particles. From the equation of state, ©) +7,00) we) 209 eae BOLERO vy ao mus = -£ G0 +2, - a(t) ‘Integreting,we find Py (t (0) + P(0) (0) - », aoe) Ce (©) me tnteta entrony 42 8 =O (oats + gures) oxo eats 30 In final equilitrimm, t= Ny = z 2 ¥43 « spe (Qn b+dinrec) Then AS = SS, and using (1), ve tind 34(0) + 25(0) (0) + 220) x as - 2 * t PA(0) “i]s 2p, (0) 2p,(0) -& ao Te Ry * PO) * SO SEO 527629 (2) Inside the container ¥, = 0 ty symmetry. () velocity distribution, o(y), of the molecules which have effused into the vacuum is o(@) ay = 2@) v, where £(y) is the Newell distribution. ig? a ; Lots “ av, f . ow) ; f av, = 2 ev, [ ev, [ar 0 () eee Palma ma Jo The second equality follovs because the integrations over v, and v, ere identicel in the nmera~ tor end denominstor and therefore cane: The integrals over v, axe tabulated in appendix At, 3 (zx? % so EE 2G) 7-30 (a) tm tine Gt, aolecules with velocity component v, which are in a cylinter of height v, ét with base at the aperture can escape fron the container. Molecules of Migher speed can escape from 2 larger cylinder than con molecules of lover speed, and a proportionally larger shere of ‘the fast molecules effuse. Thus the mean Kinetic energy of particles in the bean is greater ‘then in the container. fedatoe ©) _— [ere since 0(x) = £(x) ¥ cos @ and ay = v°dy sin 0 46 do, we have pe pn/2 pm Pp’ Pe ze tedo Jo" av sin 9 49 ae)(Em*) © Fy cos 6 ° fo i cr "(2 av sin 0 a9 dg) © = y coe 6 me Bf od By z [ree Ba where the integrals over v are eveluated by appendix A. Since the mean kinetic energy in the or 53‘the enclosure is € = 3 i, 1 follows thet Z, ele 1.32 When a molecule is scattered, it commtes monentun Ap, = Qnv, to the disk. The force is 4p,/t. To find the total force, ve met miltiniy Ap, /at by the mmber of molecules vith velocity in the range (y, dv) which strike the disk in time at and then integrate over all velocities. Clearly only molecules in the cone of half-engle 9, = sin R/L re fay [ae ® ra a Pp cee sin @ a8 d6)(A #(+) v cos a4) (Be 8 = [A tear The integral can be expressed in terms of the mean square speed inside the container, t.e., z [Cree ALL strike the aisk. | cemycem(- ¥ oss) me po bm PAG ‘But by equivartition we have Hence Eguilibrium between Phases and Chemical Species 8.2 By equation (8.3.8), ve have the proportionality Plos2) av at < exp [+ wya)/a,| av a2 Where V and T are the volune end teuperature of the portion of substance of mss Ny and 7, is ‘the temperature of the surrounding meditm. Erpending the Gitbs Free Energy ¢,(V,2) about the minim at ¥= 1, and =F yieide 36, i 2a,, - 1 960s) = 9608) + (ae) + CS) (OH) +B # 2 So He as, Sy in) GA) DP + Gra) OH) + (3) (28)? v @) 1 +3 ohwhene the derivatives re evaluated at 7 = % and ¥ = 7. Since ve are expanding stout « ainimm, the first derivatives sn (1) are 0. By (8447) 2, n, (=) G- Ae), (2) Since this is Oct T= 4, ve have F + Qz/en), "is the neet capacity, Cy. mes @)-3s +o eS, Qt =e Fron (2) ve also find the mixed derivative and at P= 7, a, & By. Gy @), GE),= 0 MG =o ate and since F = Weg snd C, = Mc, where cy is the specific heat per gram, it follows thet Me, @Plv,2)av ar « exp [= z hore ve have absorbed the coustent tem ¢,(T, 7,) into the nomalisstion factor, Pesfoming the ‘usual nomelication, we find Btn) a eo = E(F se) w= [= 3 (0)? - apes woes oven 8.2 (a) For the solid, In p = 23.03 - 3754/T and for the liquid In p = 19.49 - 3063/1. At the triple point, the pressures of the solid and liquid are equal. 23.03 - 3754/t = 19.49 - 3063/r 55hence 7 » 691/3.54 = 195° (b) since an p = - E+ constant where 4 is the latent heat, ve have Legetsnation 7 3754 R = 514220 joules/aole Lapertzation” 2063 B = 25,180 joules/sole (2) teveson 7 “eubrination ~ “vaporization = 31,220 - 25,480 = 5740 joules/mole. 8.3 ‘The latent hest of sublimation is equal to the sum of the latent heats of melting and vapori- zation, Lie.) 4, = 4, +L,. Since 2 = AV (ap/a2), the Cleusius-Clapeyron equation,vhere v is ‘the volume per mole, it follows that @, = apr fe Cue lB, + hee ed] Gy) kde a 4s siace $B = SE and 05 +0 as +0 Wy the thind tev, st follows that HBO as 7-0. or 2 Buk 8.5 (2) @/t moles/sec evaporate and are swept out ty the pump. Then ty the equation of state oY om, ick, oF MT Ty () We tind the temperature at the pressure p, from the Clausius-Clepeyron eouation a L L @ “Te Taqaa 2 "as where ve have neglected ¥, since the volume per mole of the gas is much greater than that quid of the Miguid. Then using v,,, = BI/p ve find Hence8.6 ‘The intensity, I, is given by re} 2 fae Differentiating with respect to T and dividing by Iywe heve patie iz lea °2 &) Stace p is the vapor pressure, the Claustus-Clepeyron equation yields ép/al. g. ae Tyas "Yuga 7 ges Substituting into (2) and using v,., = RI/p gives aol Ter” a ey 87 nitematdating te meee inten nen ytenaa a a $-@2-@ @ fs 2 Nov £ = 0(s58,) vere (s,-8,) is the molar Sea ais toes cae 3s, | mus & -2 |e - &) , i>, = But (25/ep)q = ~(2v/2t)yy & Manvel zelation, and since the coefficient of expansion ts a= -/r (@/8t), gt fotows that a @ Differentisting wt constant p gives ; 2, ® = 65s) +2 [= -& ? > (38/80), is the specific heat at constant pressure. Thus wig Substituting (2) and (3) into (1) yields () £ € Ty) ae 2 _ Opty ryt a 7) tra8 ‘The ber moves because the higher pressure undernesth it lovers the melting point. The water is ‘hen forced up along the sides to the top of the bar and refreezes under the lover pressure. To melt a mass dm of ice, heat fam mist be conducted through the bar. The heat passing through at per unit time ts = Hee (be) & where AP ic the temperature drop across the bar and x is the thermal conductivity. Letting x be the position in the vertical direction, ve have da (be ax), and equating the rate at which heat is conducted to the rate it is absorbed in the melting process ve have ~« (0) Fab, (ve B) a) 00 is given by the Clausius-Clepeyron equation $-2-5435 BT” Tater ~ Vee’ where v is the volume per gran or I/p. Then since Ap = 2 ng/be, oA Substitution in (1) yielés 8.9 ron itis: Ginoedue-Coxperren retathon;; dy/i =iiyhiie-wp Bind a pax [3-[¥e We know £(9) end av(9), and ve can find ép/ap from the curve of vapor pressure ve. ent. ° 60 (2) aos LPS} @ & where 273.16% is the tenpereture of the reference Junction of the thermocouple. Then 2 = 273.16 =| [38h @ «| 8.10 ‘Tous We divide the substance into euall volime elenents. Te total entropy is just the sm of the entropies of each of these, or s=Ze, (SM) Boy Bmp vhere E, end 4, denote the energy and mmber of perticles in the 1" volime. If we consider 58an interchange of eneray between the i* ana j** volumes, ve have since the entropy is stationary a 2s, s-0- a+ a, a, Mi * ey ‘but since aB = -2B,, ve have as, 8s, 1 a é Ee FY Simtlarly, if we interchange particles és, 3s. wongta, + aban ay “8 ss, &, tm m- a or Betty 6 (2) The chemical potential can be found from the free energy ty 1 We consider » sxall volume elenent at height 2 over which the potential energy may be considered constent. It is clear that the addition of e constant term to the energy does not chenge the entropy of the substance in the small volime elenent. Buplicitly, the partition function vill te the free particle function times the factor e”™"5*, mB Ge 8 bow eal Lene el Hence the free energy is, letting N be the amber of particles in Av (e) ag eB o & Sa a ™* 2 &@ a P xT a Integration yielas mJ vz) = 2(c)e ee ‘The relative concentretion rensins the sane. The dissociation is described ty oo 7,0 co, Generelty, vnen the mmber of particles is conserved, 9 *K@)8.13, ‘The intensity of the I atons in the beam is proportional to their concentration n, in the oven. Since dissociation proceeds eccording +0 Ip=242 We have Q which gives Yy the equation of state. The totel pressure is p= p, +p, vhich yields on substitution at into (1) j x ae or yo (CL +NT + GP )/2K, ‘Thus, 12 the totel pressure is doubled, the ratio of fins] to initial intensities ts Ode 2p LG” anise Since K, is small ve my expand the square roots to obtein 9, 3, +1e Fis ep 2 8.28 For chemical equilibrium we beve ayy? ae: pave Letting a(pv) = V ep +p av ve heave dQ = az + a(pv)-v ap = a(z + pv) - vap = an -vap here the lest follows from the definition of enthelny, H= i+ pV. Then if p is constant do=a ) in a constant pressure process, the heat absorb: is equal to the change in enthalpy. In © chemical reaction,@ = AK = Z b,h, since exthelyy is en extensive quantity. 608.16 By the equation preceding (8.10.25) Bey te gyt Do, may (a) Substitution of n, = 2,/x into (1) ytelas Evy tne 9B (oy de yt + et) ye or Pp Pg vee BK (2) vhere ta KC) = E ae G1 +, Im 19) D mus BELO -2O, BEEZ) «, D 4 apie th " By (8:10.30) $e in 6,4 = ph vhere ¢, is the mean energy per molecule. Then multiplying gb byhyt », & x) ioe where hy" ie the enthalpy per molecule. yultiplying end dividing ty Avogedro's mumber gives Dab ag 2 a = = I) ee where b, 4, is the enthalpy per mole. 8.27 We et | be the fraction of H,0 molecules which are Gissociated. Since the pressure is pro- portionsl to the mmber of molecules, ve have Q he total pressure is the sum (2) Substituting (1) and (2) into ve find6.18 ‘In problem 8.16 it was shown that ag =? $n x(n) Using (0) tren problem 8.17 would give (Hl for the @issociation of 2 moles of HO since the reaction is 22,0428, +0,+ ease for the Gissoctation of 1 note Feane) where K,(2) ds given ty equation (3) in 8.17. since § <1, ve have ed Qe)? (ee) wa 2 a on seace a mB cde’ Sas yin | Ss found by plotting tn f ve. temperature using the given values and menmuring the slope of this curve at 1700, we find Gin ¢ = .006k. hus et 1700% an = 2 (2.99)(2700)"(.0054) = 56,000 cal/nore 6.19 (2) ‘The partition function is z= Sp where f is the partition fuction for e single nolecule. he For a Liguid we assume @ constant interaction potential -y and thet the molecule is free to move in a volume N, mms pea [dy de ote /aen nov = where the integretion is over Ty, and all b+ - Bq 2 S= hye e 3 Le PEL ay Ph vee emus dedining 6. x Hence fess] * @ (be) For on ideal gos, the partition function is x scar fe” _ ol, nc inn, = (ia i 6-2) woe Gyan a8) he Helmhols free energy is ewhere we have used Sterling's ayproxination In Wot ~ 5, In 3, - @, ‘Then hg = ge = AT (Gav, ft - ao te) ) a (c) For the Maula, we have by (1) ape et (iy Pai] ae = ED (My Ie v,S" + my on +H) hal ae (a) When the liquid is in equilibrium with the vapor, the chemical potentials are equal or He ‘Therefore aa (ay, {1 +97 +2) 4, “a(n Vo! - In B,) = -ew (tn vf" + Bn +1) ¥ ‘Thus Bev, oh s bout since p/et = x/V, we heve Ne pet oe @) (e) We calculate the molar entropy disference fron the Clausius-Clapeyron relation, Bisse @ * & * ¥, ‘5 where in the second equality ve have assumed thet the molar volme of the liquid is much less than that of the ges. Since pv, = RD we have Then using (2) in this relation ve find The molar heet of eveporation 1s +e) @) Ra if qo (2) Brea (3) & Teking the logeritim of (2), we find en# ens i+beb in oY 1+h. where v, is the volime per molecule of the vapor. 68a ’ Hence grin (4) *,. Yo z von v, and v, are evelusted at 3, (b) ze (4) ve can take v to be the volume per mole instead of the volime per molecule since ve have the ratio v,/¥,- To estinate the onler of magnitude of I/Rh, we let v, ~ 22.4 Liters /aole (05 x 10°9)°(6 x 1623) ~ 10°3 titers /aole. (a) We sind 1/2, trom og. (WJ. TE |, % catoulstea | experinental water ~O1B Liters /nole +83 cal/en°x | 1.45 cal/en"k nitrogen | .035 “3T iE benzene 087 29 -16 1.27 These results are roarkably good in view of the very simple theory considered here. CHAPTER 9 Quantum Statistics of Ideal Gases configuration | no. of states] (a) 2.5 = 1+ oP 4 oS 4 20° + 20S + ce MEP 3e | so | 38 | > . 4 a 242 ©) eS 4 @ SEE g Qrter =fala ¥ = [= 2{2[2 x{2l2[2 =» f=felats | | 9.2 (e) For an ¥D gas, we beve 28, - 1 tageon+Din(Qite *) ana 3.- eb = e T42 Hence sexnse+e er faezm aes F uywt since w=EG, and FEE, « ” a E Byer pe,)¥ Ean te s @ it follows that a +e, @) a6, a @) substituting (2) and (3) in (1) ve tind =k [z a, (0a) -42fRna+¢ ® () For the BE case nate, qageor-Lin(le 7) ana The calculation of 5 proceeds in exactly the same way as in (a). We quote the result. SE ani, - (ea) mo Ga,) (5) (c) From (1) and (5) ve cee thet in the classical Limit vhere Fl, <1 S+-kDE na, = for both FD and BE statistics. function in C/o waere aif 2 be Boo [EO fe] re) es The sm is over all positive xk, When ve use the standing wave solution, equation (9. The density of state is nov greater than in the traveling wave case, and by (9.9.25) 3, -U 43, ets ® we IE we assume thet successive tems in { differ Little from each other, ve can approximate (2) with integrals. 62 Bn? ew By Ze af Be dea Tas wo f (Fa) a 2 vy (4.3.6) 3 Hence u 2 -3 rai) 2 y which is identical to (9.10.7). gob (a) The chemical potential can be found from the Helmholtz free energy, F = -kt In 2. we (Ninf -Ninw+n) ~ 3 Where ve heve used Sterling's approximation, InN] ~ Win ney and t= % (orm) » Then ue B-aem§ a) (>) The pertition fmetion for a single molecule of a 2 dimensional gas with binding energy -<, is 2 Be, pp 2 3 2, sie Boo [- Bea Payee] = 0° Pew [- ee. fe anya, ey 2 ~ 2 eS 5 where A is the area. thus {1 =e ° 9 where ve rub A= v. 2, Hence weap Sean > (2) (c) In equilibrium » =u! end by (1) and (2) Tetting a! = 11/h and since F/et = WAV, ve find ae eft = Ph (2m x33) ee” 95 (a) wy equation (9.9.18) if Le, = 1, =Q) (e) @) of particles in state r. ty (1). For photons, Bence (e) The mean foree on the val. 4s found by multiplying the chenge of monentun per eollistoa, 2uv, ty the mumber of particles which collide vith the vell per unit tine, Z nA. Hence the pressure ts retting f= ¥ ve havewe, ut by (2) in 9.5, B= 305 ‘Tus (c) substituting 5 “9.7 ‘The probability tbat a state of energy ¢ is occupied is proportional to the Boltzmenn factor 2 M0, cance che vibrational levels have e specing lange compared to KI, ve sev that oh is small and we may neglect this contribution to the specific heat. On the other hand, ‘the spacing between rotational levels is small so that these states are appreciably excited. For a dumbbell molecule the rotetional energy should be 2 alg gy? BAA PE Abts where A is the monect of inertia and o the angular frequency. We have neglected rotation about ‘the exis of the molecule tecause the monent of inertia ie small. At room temperature, we may use the equigartion theorem yielding €_ = KT. Adding the energy of the translationel notion gives for the total energy ‘Thus the molar specific heat is a... oe 3 ont a 3-3 ° 9.8 The reaction proceeds acconding to a =H, +d, sot tn ny of mae scion teste Bn eH « From the results of section 9.12, ve can imediately write dovn the quantities ¢. In the notation of thet section,be Sa ¥ ba, a fan(2n) ur]* e = : L 2 Pe Ayer - dehy y 2 4 2 2 2 =% tena) wi? e = 5733 ae 2 pe, -} lor(majay ew Sw 2 Pm “2° where ve have assumed that molecules are predominantly in the lovest vibrational state and have ‘treated the rotational degrees of treedon classically. ‘The electronic ground state enengies ¢! are approximately equal for the three species since this quantity is altered only slightly ty the addition of « neutral particle to the neueleus (to fom D). ‘us clap wel ‘> wel, 2 similarly, the menents of inertia ane of the fom Ly p?.imes AcgW RS Fava Fo where R,y the equilibriun distance betveen nuclei, depends primarily on electromagnetic forces. 'E, , (2) 2 Ze fs then ayproxiaately the same for the three species, and ve have 2 fan, tm = OG) - ESS ©) Finally, the frequency for tvo masses coupled ty a spring of constant « is (4) Substituting the {'s into (1) and using the results (2), (3), end (4) ylelés eo rine er feta) 12 6 é Since ag = Hy, 7 FE have& Ine thermally isolated quasistatic process, there 1s no entropy change. Hence ty the first lev, 9.9 Tas 20+ +5 av substituting = Wi and p= 3H where U(r) is the energy density, ve have osta+va+tia ane fa since T= ot -Eangebanct ca SO ssnce Tea, tntegrating, ve sind - Han 8 = han gt 9.10 (s) By the Audamental themmodynamic relation ras =a +5 av ‘Then substituting E = vi and p = 5 U, we have we = seloqets = pas-iaevai+tia- iat a But since Tis only a function of 2, 6 = & an, and tt toliovs thet a-$2 a+iga a) Wwe also neve @, a- Qo @) Bowating coeftieients in (1) and (2) yields “fiw @ -19 6) an) = (8°s/en ev), it follows from (3) thetgms In TY - in H+ C where c is the constant of integration. Finely 7 <2". 9. The energy of the black body radiation in the dielectric is a-ve oot RV ems where c! ds the velocity of Light in the msterial, c! is related to the velocity of Light in veonm ty c! = c/n, n, being the index of refraction. 3 yt — geve Gm 3,2 “VS (aye € Here ois the Stefen Boltmann constant, « = 1x"/60 on? = Wealwi Hence Gy = =, = Q) Substituting v, the vohme per mole, for V in (1) gives the heat capecity per mole, ¢,'. The classical lattice heat capecity per mole is ¢, = 3R- ‘The retio of these tvo quantities is ey! wens? 5, For an order of magnitude celeulation, we can let v = 10 cx'/aole and a, find eyt/e, = 107, 5+ Ab 300K, we 9.2 - (2) the totel rate of electromagnetic radiation or pover is B= Pim =) (Gn) (20%) (6-00) (208)" = 1.200% exge/see 1.2 x 10% vats () since the totel energy/see crossing the area of a sphere of radius r! = lim mst be the seme ac that crossing the sphere of redius r = 10 a, ve have Orin 217) = Pim 2°) or PPE) = ot Ey = 5.7 x10 )C00 6 20 42 1) Ta1s = 567 x 10 tergé/sec ex” = 5.7 x 10" watts /en® (c) ‘The power spectrum has @ maximm st ‘Tus 9.23 (a) The vover given off ty the sun is =o," (tr BP) Bas the earth's murtce inthncepte sedation fom the mn ot any tind, Zones the power thet the earth absorbs is : 2, = 0 0," Gna?) 22) den son pover tht Hin wart ealts ie Pp =o T(t) Tn equilibrium, the pover incident upon the earth is equal to the power it radiates, or P,= P, 8 ug?) (2 & mus 5° (ons (ZG) = at! Cor r) @) (e) From Ba. (2) Te elk We consider the Mouid in equilibrium with its vepor (at vepor pressure p). By (7-22.13), the flux of molecules incident on the Liguid is p/VETEED , and this mst elso be the flux X” of particles escaping from the guid, Since WW cannot depend ox the conéiticns outside the liquid, this is the escaping flux et all pressures, ‘hus N= rae The mace of a water molecule is m = 16/6.02-109 = 2.99-10°°3, aus for water et 25°C where p = 23.8 mm Eg = 3.17+10" aynes/en® ve have x: ae (22.99 x 10°31. 381075: 298)! seceom pr9.15 ‘At the vapor pressure p(T), the flux of molecules of the vapor incident on the wire is by (7.22.23), 9, = 2/ JET m KP. When the metal is in equilttrium vith its vapor, the emitted flux must equal the incident flux, 9, =,- Then vhen the temperature is 7, the number of particles emitted from the wire per unit length in tine t is 2) ome fox m it But N= A/a where OY 1s the mass lost per unit length and m is the mass per molecule. son au, ple) or t vera wé ve) JE ere ve have used p= nil, and R= He 9.36 ¥, = 0 by oymetzy. ° f ay ey) v,! ty tetinition, 2 @) [ero ‘At absolute zero, the particles fil1 all the lowest states so that the distribution f(v) is just a constant ard cancels 42 () the maxim sed te ot Em, ewe ay armen, v= and (1) veces 9-27 () At] = 0 all states are fi vp to the energy p. Hence ‘the mean number of particles per state is just 1 end we have Bef eo (e) a ° 2a By (99-19) ee clots - at EG where the factor 2 is introduced since electrons have two spin states. 3 2 25 ve * Fac ae 2 ar ow do ns B) Since pw é ‘vy (9-15-10), it follows that Ee é mu Q) (c) Substituting the expression for u in (1) we have ae 342 3 8-4 °) £ Bu 2) As perticles are added, each nev particle can go only into an unfilled level of higher energy than the one tefore. Hence the energy is not proportional to Nas it vould be if particles vere added to the same level. 9.18 (a) Differentisting in 9.17 (c) gives Q) (v) again trem 9.27 (e) we tina EL £@ gS @ (c) For Cu metal, NAV = 8.4 x 10 erectrons/em), substituting into (1) where m is the mass of electron, we find F~ 10° atom. This enomous pressure shovs thet to confine e degenerate electron gos, a strong contetning volume such as the lattice of a solid 1s required even at O° 9.9 Pron the gensrel relation 14S = 2 @ = C82, we have that if the heat capacity 1s proportional to @ power of the temperature,¢ « 0° wef Bicfetent ‘Tins the entropy is proportional to the same per of the temperature as is the heet capect: (2) The heet capacity end entropy of conduction electrons in a metal is proportional to 7. Hence the ratio of the finel and inftial entropies ts 82 hoo, 5," RO (0) the energy of the radiation field inside an enclosure is proportional to 1", and the heet capacity hes e 7° dependence. Tus Iss = QY-e 4 th9.20 (2) At T= 0, the totel mmber of states within a sphere of radius x, mst equal the totel number of particles 1. ‘Tus Substituting 4 = oe" fom, ve find 2 & am? BB (ot 9) @ The aunber of particles per en’, NA is typ/u vhere N, tc Avogadro's murber, p = .95 gn/en?, and 4 = 25. From (1) we find the Fem temperature T= y/k = 36,000%R, (2) To cool 100 en or 4.13 moles of Ne from 1° to .3°K, an amount of heat @ must be removed. sf ye where cy is given by (9.16.23), ey = 28 « = Boar ped mus a= GENE of 3 at = ~.coee joules 3 Hence .0022/.8 = .0Ce7 ca’ of He” are evaporated. Note that a large amount of substance is cooled by a very small ancunt of helium, 9.22 (2) If electrons obeyed MB statistics, the susceptibility would be Ney = Mu, /kt where u, is the megnetic mazent. In the actual case, most electrons cannot change their spin orientation caly electrons nesr the top of the distribution can turn over and thus contribute to x. We expect when an external field is applied veceuse the parallel stetes are already occupy ‘then, thet the correct expression for % is Yq with N replaced ty the munber of electrons in this region, Kise: 1 Dr Gx where O 1s the Peri temperature, 7 2 ye Ba Tay mus Xe BT @) (0) since 7, 4s on the onder of 10° or 10%, (1) yields a x per mole on the orter of 10, xe electrons obeyed MB statistics, x would be changed by the factor 6Bea fb -F ‘This 1s on the onder of 100 at room texperatures. xrvente sp womerze ‘BIERCY 9.22 i hen the field E ie tumed en, the energy levels Pare 2*opposf te of the parallel spins shift ty yz while the field levels of the antiparallel spins shift ty 4 ‘The electrons T411 up these states to the Fermi energy ues shown in the figure. The magnetic monent is determined ty the number of electrons which spill over from antipersllel states to parallel states to minimize the energy. This is (u,#)o(u,) where p(u,) is the density of states at the Femi energy u,. Consequently the magnetization is m= an? oly.) BW x But stace o(u,) = 2, we have 2 = wed DEG 2a 7 2 Py s vnere a = 8 9623 If ve choose the zero of energy to be that of the electrons in the metal, the partition function of an electron in the gas outside the metal is ty (9.10.7) 2 je (erm ia) e vhere the factor 2 cours because electrons have two spin states. The chenical potential u, is ‘fund from the Helmholtz free energy. Posing =e (Ninf -NinN+4) ‘ 3 wy, = wagered (2m: x2)? & al The chenical potential inside the metal is just 1 =V,~ % and in equilibrium the chemical potentials inside and outside are equal, i.e+, p= Hae 6‘Thus 2 (on a 1a)? oT a) 9.28 Consider a situstion in which the metal is in equilibrium with an electron gas. ‘Then the enitted flux is related to the incident flux by 9, az) o, @) The electron gas outside the metal may be treated as a classical ideal gas from which it follovs 2 1é 0, = paF- a come Pe] [ex where we haved used (1) of problem 9.23. The emitted flux is then given by (1). But since the ‘that the incident flux is io eattted flux cannot depend on the conditions outside the metal, this is also the flux where equilibrim does not prevail. Thus the current density is 9, = Relics) ny? V,y where we use the notation of problem TT9.23. Tn addition, ve assume that a fraction r of electrons of ell energies are reflected. ‘Thus the electron current density is ae = (e/a) ax, aoe, = 22) fan, [7 on, We te (a3 Se am arn a + 0 [ Btn, 2hn, 2h 2) | rag the Maes ee, “Toe Senay tern, OK oF Une tom [ee tense 9 = SL SS [lax So ay € ten Boxg-aftatn a) Since V, > and, in general, | (u-V,)| >> 1, ve can use In (14x)~ x to expand the logarithm and obtein £ ele in L ey ty we Bach of these integrals is (2m/st") vf ‘by appendix A.k, and lag me (Ler 2 aor a. aa)? e ‘nay G2) (ny 9626 (a) Since the integrand in (9.17.9) 4s even, one can write where we have integrated ty parts. Since the first term on the right vanishes [xe vo Fa Q) (®) ‘This expression can be evaluated by series expansion, since e™ <1 one can write ee ee “9-5 3t 3 0 93H, eH Le = E (ay OU a ae eo Hence (1) becanes 8at Bap fet rae fa nO ° n=O (n+1) ° th Uabgea dy eget Ay ‘opm to Lag. mise Tek E ark n=O (n#1)" () o c Hg. 2 Fig. 2 wig. 3 one can use the contour ¢ of Fig. (2) to write @) o er e gf oinne Here the integrand +0 for z+. The sum in (2) is unchanged if n+-n. Hence one could equally Well write the symmetric expression (s) along the contour Cc! of Fig. (1). Adding (3) and (4) one gets then f i = his ©) chy 2 sin me But here the contour can be completed along the infinite semi-circles as shown in Fig. 9 since ‘the integrand vanishes as |z|+e, Sxcept for z = 0, there is no other singularity in the enclosed area so that the contour can be shrunk down around en infinitesine] circle ¢, surroun- O as shown in Fig. (3). For 2 = 0, — sin wz ding 2 Hence‘Thus it follovs ty (5) thet and wy (2), I =A. 9.27 (e) We expand e% in the integral, . x See = at eee wee So (#2) (ea) J = (e*n)* ” # [ls i a ps (¢ Fay? Interchanging the sun and integral yields £ ee & mn = (a? > (8) Ye? eZ as @) (b) Putting xz in (1) to denote a complex variable, we evaluate the integral on the closed contour shown in the figure. Here C! is the peth vhere z ts increased ty @ri end c" is a small cirele arcund the singularity et in. ‘Then the integral on the couplete path is zero since there are no singularities in the region bounded ty the contour. ‘But the integral is 0 at x = 4 and cancels along the inaginery axis, Hence ef ay i oe as J(eFaj(e2) J (e*42) (242) c crc" (3) where both integrals are evaluated from left to right. Along C! vhere 2 = x + ni, we have stork since © ? pate _tk(wert) comp? ay ge (P42) (e742) ve (0% 12) (2) Jeo (o%1)(e%2) 80The last integral ts Just 7(k). Thus trom (3) ve have -e" 28) Sata ee ae ot as (ea) (2%) gh (ea) (22) @) To evaluate the integral around the small circle C", we put 2 =i + { and expend the integrand in tems of £ f i ae (2) (e772) ° = 2 [or(ont)(-ax)] = ane ™ () vhere we have used e% = Liz... end the residue theoren, hen castining (1) end (5) we find f SX a ante ak 6 = @ae™s) peek ” HnTe ©) (c) Bepending (6), ve tind a(x) sa ele. ‘Then comparing coefficients vith the series in (2) we can read off the T's. We find 1, = 7°/3. 9.268 (a) According to equation (6.9+4), the probability of state 7 of the system ts “8, Pee Then the mean mumber of perticles in the state s is =i 5 2p [-B(R,E, + AZ, + oee)= anytnytee.)] = a Tew (alae; + 356 2 sno tin eestor mage wld ancl Letting Z-Lee [-B(aye, + nyen+. )- afayingte.+)] (@) we tare web g ak a where the partiel denotes taking the derivative where ¢, occurs explicitly. Zvalusting the sua (2) in the usual vay, ve obtain an.(2) thes an Ze -Ean (le) and = 5, (45,) The co ction term in (9.6.18) 4s absent showing thet if only the mean mumber of particles is fixed, the dispersion is greater than if the totel mmber is kmomn exactly. (c) For FD stetistics, the sums in (2) become (expe, [ ~(eet8€,] z-h-ere] Lord. Ee Date 8) 829.29 We can remove the restrictions on the sum over states ty inserting the Kronecker 8 function 2 = Dew [alqeyagest-)) Oy a sew Colmeymyestee)) L ong (00E 2,)(aviat)1 aa} where the sum is over n_ ++ for each r. Letting @ = ata’ and interchanging the sum and integral yields " a5" See) a @) where Eq) = Lew [-(ee,)n, - (ete, )a,--+] sia sm is cantly evaluated as in section 9.6 end aE @) <2 Oe) @ ‘To approximate (1) ve expand the logarithn of the integrand about a! - 0 where it contributes appreciably to the integral. ne ZQ) = or +n EQ) = (@Hat)n + nF (@) + a(s0") +P Bsa")? +... sot + rE (e) +iGwa)e - daa +... it Fin Z whee Ae E ue - He Biol a dot 2 a ‘Hence MZ) AZo gre (3) ‘As in section 6.8, we optimize the approximation by setting B+3,-0 or n+iBZ@ « yaa’? ana (3) becones SH E@ «Ze Substitution into (1) yields Lag? 2 = SB) (EE ays ©) Jon or an z= om + ink (e) = of -Eis where we have used (2). The ve! ue a is determined by ( 83+B eke) -1-tbm oes ° which gives = CHAPTER 10 Systems of Interacting Particles 20-1. Since o(u) du« an and for epin waves @ = An’ , it follove that o(a) am « oF ao y ae at (e0)* oF a Substituting the dimensionless variable x = Stim we obtain Then by (10.1420) oP? ax « i pecs ve J CaF ‘he integral is just © constent not involving p. Hence oy <9? « ail? ye (2) ay (20.1.18) In (1-27) (0) ao vere ase nero a, 2 (ey? But since V = 69° @ > eo Find Cy rege am - BG fon 2) oF an ° In terms of the dimensionless variables x = flim and y = Btn, this gives nee. % [i oo) foe ‘This expression can be put in terms of the function D(y) by integration by parts. &2)" 7 ms ster -8 [>a e]” - 3 free =y BL - ay an (2%) + my) “2/8 ey Hb orn Ge ) +m (9/2) @ where a, = toy. () ‘The mean energy is 2 =e PS = om + Boy) = atm + au xr 2025/2) @) (c) The extrony may be found from the relation § = k[ln 2+ 98]. then tram (1) and (2), ve bave S = Ne [-3 In (1-2) + bn(y)] -6, em tp (ee™) 40(6,/)1 30.3 For y >> 1, the upper lint in the function D(n) may be replaced ty =. Lf? Sex Dy) = 7) = 3 fe The integral is shown to be 7/15 in tables. Hence yo. For y “<1, ve can expand e™ = ltx in the denoninator Bo) <8 [ere yeu From the results of problen 10.2, we find for y >> 1, or T << @, when we use y = stim, = 9/7 8For y <1 (2 >> 9) we find, using oY 14 y 0. + In B= Ft- in aft +n = tte = Me [-3 n g/t +h) 20.4 the pressure Ss given in tems of the partition function by the relation 5 = 39> an z where by /* ‘equation (1) of problem 10.2 ao z= 32 gran (ie ) +m (0,0) yt sag Pvte,/2)][ a(@,/2) ‘thus Fen @+ ee CisDexe ai | ae 3 5 [sey] where 30(5,/2) aE In tems of 7 = (/2,) (46,/az), this becenes , Fon BEE ote For T<< 8» D(8,/t) + ant pnt Pe vee w 5 ves * For 7 >> Oy) D(6,/2) +2 10.5 Coaparing the expression for the energy Z, equation (2) in problem 10.2, vith equstion (1) im problea 10.4, we obtain sents, Gm p-nB+, Gm) 86rus 10.6 (a) Pron electrostatics, ze () the induced dipole nenent in tems of the polarizability a is x3 Bp OBER (c) the enerey of a aipole p, ina eld Et 6 a Be pbek 10.7 By equation (10.3.8) and (10.316), the log of the partition function is a 1 1 (om =i) +uanv +2 mz (¢) where n= N/V, The iret ‘wo tems are the ideal gas partition fictions while the last is the laz contribution of the interaction. Since the interaction is represented ty an edditive term in ta 15 et aah rare atte tem Sa te era 6 wit in = Bn ‘Thus the entropy per mole is S(ty2) = 6,298) + $"(25a) vere s'@) = « [En 26) -2 Ga ~ at bw -252 6] end s'(tj2) = a a(t) =a [- [8 2 £@) To show that A(T) is negative, we must show that the derivative 3/38 [r(s)/3] is positive. wee é 3 (7° oP) ap@an = [7 280 PLe PA) aa? an ee) "Sl, °F Bhs = " tut -pue®™ 2742 = 1 - G88) 5 o since (1#8u) is just the first tvo terms in the expansion of eo", Thus the integral is positive and A(2) is negative. aso ata) = i f= Pecseu]] ne? an 8710.8 From the arguments of section 10.6 we can write dom the partition function for a tvo dimensions) ges ix here ang, ox ina+3¥ 206) x(2) = [CP ate a Denoting the filn pressure by De, we yhere n = 1/A and B,(2) = - 3 10.9 (a) One cen vrite dovn the mean energy from (10.7-3) and (10.7.5) wt en, Hy Byy = “HS eo 3,(4) Here Nis the totel rusher of particles. The consistency condition is a 20) «ais © ‘We solve this equation in the given temperature limits using Fig-(10.7.1) r<7, Qa) (2) Here the lope, Mi/én JS, of the straight Line is suell end the intersection with 3, (x) is at large x vhere B(x) = 1, Thus (2) becomes -# or x = 2838 =a * * eT and ais wn (38)(2) = -20 ws? 5 Deo, @) ta this region it/2n JS is large and the intersection ie at mall x, We cannot, hovevery approxinate B(x) ty the liner tern Fea)x (eq.10.7.12 ) since this would not cross the 8Line (it/2n J8)x. Hence we must evaluate the second tera in the expansion of B(x). For sual x, x<1 substitution in B(x) = [[eeote (sex - beotn } BI yielas = 2 2,0) =} {ed ee sods - kod “A 3 a -&|} 3,(2) = 3 @a)x - (sd) GA 3 = xed (en)x - (s%4843) Ga y 3 ‘Then (2) becomes Ss y “ ? +2 [sata] ” : In the eneray (2) ve substitute B(x) to first onder and use (1) Brs(se1) eo x? B= -ws uo x 3, (x) age | - fem] = 6) Tot From (1) ve see thet 2-0 at KP = un, = 2 ny5(S+1), i.e, the energy becomes O at this point, and larger T gives imaginary x in this approximation. Fence E-0 tom (6) (b) From equations (3), (5), and (6) we have red, = pe coEe I, ° T>a, (2) . 7, ?CHAPTER 12, Magnetism and Lov Temperatures aa The meen magnetic monent is “#3, L(-ae/2z) ee 7 a-2— 2 Binz “6 Ze 28, vhere2=5e° f ue The change in entropy per unit volume is given ty 5 ° as, s-[ @ a Lo @, But from the fundanentel themofynamie relation 4B = 145 - ial, we have the vaxwell relation & ? vhere § and ¥, are the entropy and magnetic moment per unit volume. Since fi, = x= and x = 4/(t-2) ve obtain 1.3 But fron 43 = 065 - 5 av - HAR, we see thet 3) BP where v and Mare the molar volume and magnetic moment. Since M = XH and x = Aff, (1408) ] ve tind &% Mak TE (2-8, (1408)no, z and oe oe ee (r-o,(u40 BI tree (anes)? Ls (a) From the relation dBt = ras - Sav + Hal vhere BY = F - vi“/On ve obtain & .& Bye yg In the nomel state, H = Vai= 0 since X= 0 Thus (88/28)y 9 ~ 0+ In the superconducting state, or ne-Ze nus H ie independent of temperature and (35/28) (b) Since the nest capecity is given by ¢ = 1(35/22) ve have from (11.i.18) 2 oy -2S68)-£S +2 @ @ here His the critical field. (c) Wien T= 7,, the critical field ds 0. 1s but since Cjoat + 3, ve have wee He, 5 © fo setisty the condition o/f +0 as T +0 we mst set the coefficient of 7 in (2) equal to 0, ties, 2 = VE /on 2,2, gL‘Tus be we 2 arty (2) The extropy is related to the heat capacity, aS = CHT/?. Then since at To, and T=O the 1.6 entropy of the normal and superconducting states is the same, ve have Te oan 7 oar (r,)-s(0) « f° B= f° =§ 9 Fron which it follows that asa? @ (b) Since a = car, the energy st 7 r, end 140 for the normal and superconducting states is 2 Fe n. E(t.) - #,(0) -f wear = “ty on, a £,(%,) ~ £,(0) “f on? ar = But B(0,) = B(t,) and by (1) a = 37/7,7, mt ‘Thus 2,(0) = #,(0) = - LT Fron the relation 4S = C21/f ve have for the entroyy in the noma and superconducting states . 8,(2_) = §,(0) = [ “rar = 22, Je 3 ef, 8,(t,) - §,(0) = [ otar = + Since the entropy isthe sane for both states et TO and To, it ZoLlovs that on37/1.2. Hence at oP, we 7 sof,CHAPTER 12 enentery Theory of Transport Processes Ra () 6 (e) 6 ©) 6 2 (@) 4 @&) £ () 2% 23 (2) the equation of notion for an ion ine tie £ is Hence By (12.1.10), ana (0) The time to travel a distance ¥ is e-(S # ee Thus the fraction of cases in which the ion travels a distance less than ¥ is 2. The aifferential cross section is given ty (2) as wens where a is the elenent of solid angle and s ts ‘the “inpect parancter" as sham. Fron the sketch, 5 = (a, +8,) sing a e 8 = (a, +0,) cos op B Since @ = 90-6/2 and dl = 2r sin 6! 49", it follovs thet ~(a,40,) sin 9/2 Tee Ble 93(ayta,)* sin 6*/2 cos 9'/2 in Hence 2.5 By arguennts similar to those of section 12.1, one has that the probability that a molecule travels @ distance x without collision is pee where J is the meen free path. Letting P= .9 and 4 = (Ene)? yiees ng = x po /e Letting x <20 om and T = 300% gives p = 11h x 10" mm a. sh =x 12.6 The coefficient of viscosity is Q) where we have used = (2x ¢,)"4. To determine the cross section, ve note thet the volume 3 per molecule is A/Il,p where A = 39.9 gms, the atomic veight, and p = 1.65 gn ca”, the density in the solid state. Thus the radius and 25 sec, ‘Then the retio of the calculated velue of 9 to ‘the observed value, 9 = 2.27 x 107 ge ca” seo is From (1) we find q = 11x 107 ga co! Nea ops a7 The coefficient of viscosity is proportional to sinee q = si/3 Ve, and = (Gex/m)?. Thus 4 the tenperncure increas s, the teminal velocity decreases. The velocity is independent of pressure. 12.8 ‘The force on the mer cylinder is the pressure p tines the ares A= 21 Rie Boos amt okWe make the epproximation that the air at the outer cylinder is moving with it, i.e., at velocity o(RS) ~ aR, and the air at the inner cylinder is stationary. mus be, ok me aS and the torque is o-gr- FRE (b) The viscosity is given ty n = mv/3 2 c,. Since air is mainly composed of nitrogen, we det m = 28/6.02 x 10°, the mass of a nitrogen molecule. Putting o, ~ 10° ex? ana 7 = 300%, ve fina =2x10 ge and 6 = 8 ame co wg (2) We let 0, = Vac™ where x,y, and 2 are to be determined. Letting L = length, 7 = time, end M = mass, the Gimensionel equation becomes i 2 Va* We? eh But since C= FR*, it has dimensions Mf" = ple agmeagres ‘Taus which gives x+(stl)2 = 2, xt22=0,y+2 om sotving this system of equations, ve find x = ¥/i-s; hence the erose section ¢, 18 proportional wees), (0) me viscosity se given ty 9 = 28/302 c, and here c, < VW/I*, since velocity depends on the square root of the tenpereture, we have = ehh), £52) a 32.20 (2) consider a disk of radius rand width Ax at the point x. There is a pressure difference ap across the aisk giving force m=“Ap and a viscous retarding foree arr am 222) | gence ‘the condition thet the disk moves without acceleration is 95mtep = ore Oxy BER) But since ap ~ - 22(¢) ox, where the aims sign is introduced because p(x) is 2 decreasing function of x, ve have 2 BOD 6 ay my BE) Asouning thet the fluid in contact with the vallsis at rest, it follovs that oe) BO) [Frans f aut = 3 BG oe ‘u(r,x) + The mass flowing per second across a ring of radius r' and width ae! is pu(e")onrlar! where p ie the density. Then the total mass flov is Lope i. ie [ouetemtat = B82.) [ees Je ° sr -§ 2 £02) (>) For an ideal gas, the density is o(x) (u/sa)p(2) vere y is the molecular weight. Tins ‘the mass flov 4s fee Bvt) BOD [a8 nrart 4 nus e =- FS ow BA Since % 1s inlependent of x, ve obtain rh waten yielas i-% wu Let T(z,t) be the temperature et time t and position z. We consider a slab of substance of ‘thickness dz and area A. By conservation of energy, (the heat absorbed per unit time by the slab is equal to (the heat entering the slab per unit tine through the surface at 2) minus (the heat leaving per unit tine through the surface at zidz). Since the heat sbsorted per unit tine 1s, me B1/St = cA dze MT/Bt, where ¢ is the specific heat per unit mass and o is the density, we have 96Bw The wire gives off heat I°R per unit tine end length. In order that the temperature be indepen- dent of time, @ cylindrical shell between x and r 4dr must conduct all the incideat 172 heat. Thus or 22.13 (a) The heat intlux per ox height of the devar across the space between the valls is @ where r is the radius, r= 10 cn. vn tet zs vy (24 The specific heat por molecule is ¢ = (3/2) vhsle o, = nm? = bn(10"6) ex, the mean velocity is 7 = (Gut/m)/®, cnoceing en intermediate texperature T = 286°K, ve find Y= 1.2 x 1en/see. Substitution of these values into (1) yields Q = 1.2 wates/en. (b), The thermal conductivity renains approximately constant until the pressure is such that the mean free peth avproaches the dimensions of the container, I= .6 ca, At lover pressures, ‘the conductivity is roughly proportional to the number of molecules per unit volme 2. Thus ‘the heat influx is reduced ty © factor of 10 when n= — 2 — 10" notecutes/ent were, rom p = nl, ve find p= 3 x 109 mm ze. 712.14 (2) og/ay = (ny/1g) g/g) /* (2) kay = Mty/TyHy (c) Tpby/ Nyy Lis oS Qe @ «-+2? gives ¢, = 1.1.x 107) on, wr 7 > (2) ws ‘The gases ere uniformly mixed when the mean square of the displacement is on the order of the square of the ainensions of the container. We have, efter 1! collisions, Feb C@+r LER-we a hg fi ad since the second tem is zero ty statietical independence. ve 2 3 subetttusion of 7 te act sete 22.5 A molecule undergoes a momentum change of 2uv, in # collision » ‘ith the cube where u = aM/nitt, te reduced mass, Tn she fence Ss given Wy the momentum change yer collision tines the ser of sotecues wish stsite the cube par watt tins, sumed orer all velocities, > Bo ty 12 2 Foren) Pee We may approximate the exponent since ¥ >> V. Tus-Bow? -BvP sy - By? e we we (a+emv,V) L o , -2 ana Sen a 2 [ok oF" (aspan,y) ar, The first integral is just the force on a stationary wall as in section 7.14. the resistive force is thes ao Ee an ea” 2 -mivi ‘by Appendix A.4 and 7.11.13. Since we expect M >> m, u =m, end the equation of motion becomes om F vi? a ue vevjeo Ear] The velocity is reduced to half its original value in time ge Mine mer CuNPTER 13 Transport The the RelaxationsMime jpproxination BL 20 93 2 By (13.4.7) a= f oe +, The value of the integral 12 unchanged if ¥,° or vj? is substituted for v,”. gence since 2 + we obtein sf sk The quantities + and d¢/Se are fmetions only of v. Thus the substitution ay = v"av sin 9 de dp = yields ane [Tana [Bede ELE he13.2 ‘The function g becomes the Maxvell velocity distribution 2 Substitution into (2) of problen 13.1 with s = vf yields 2 o =P dr), a sf Fh on where (= Be fT aso st (65) 27 of Jo 3.3 since ¢ = Ba?’ = Be (0,26 0,2 4,5), vo bare 2 2 2 me gs a fouS ufur- 2° fey Bo, 1a apherdeal coordinates, the components of velocity Decaae U, =U sin @ cos U, =U cos 6 E uy « au ois 0 20 a9 Tuerefore 2 Pore Ted 2 ~~ ca? J cos? oa ["sin?s cosFeas [an & oF x air [toute ano ola ats oe [ar =o Pak Fe a) Bl, a per pt since [ap [sin 9 ao = im, st rotiovs that oo Ble [teow fake et13.4 Substituting the expression from problem 13.2 where into equation (1) of 13.3 yields qs okt My where [ras oo x(%), we 4.5 putting t= (“En 0,3) tanto n= nko + and using # = (Bit/m)*/* gives a BE ny BE This 2 lenger by 2 factor of 1.18 then the mean free path calculation (12.3118) and smaller ‘than the result of the rigorous calculation (1.8.33) ty @ factor of 1.20. 13.6 We assume the local equilibrium distribution 3/2 ga) op [- bam) ® where the tenpernture perenever p end the Iocel density a axe finetione of 2. Then Sn the notation of section 13.3, ae) e ed fpr Ths expression is independent of t'. Thus sie vhere the last follovs since é2(t,)/at, (03.3.5) becomes [rol ae sees @ Using (1) this expression becomes or zetrooy Fe-g8-Fg ° Tt remains to determine 3n/8e for vhich ve use the condition 3 Beil ae [he oo fever, -[Aere a EB ° ne fica Satagral te ero soe te fatgread fe an old fete of 4 Jeet hB-GE-a hy -° here ve lave cummed + inlependent of v. Ry srmetry ‘his eqution elso holds v2 ta che integrand is replaced by vy? or wy ‘Then since v> ws we have 2 Ba By vg BP Beviges RES fects-38 [ ervte-s =, ~del Ldn , 3. SB AF ae or > +b fee av - BB [8 6 av on substituting (1) and a) ere tabulated in appendix A. Lao, 3 a) a 2)? ae ee _. BE-E9 i@ G32 Be Q™ -o Lmll gs or a B78 Se «) Substitution of the equation of stete n = p/e? = pa yields 2815) 18 BOR Hae or Boo The pressure is independent of 2. 3B.7 Since there ere no external forces and f is independent of time, the Boltamann equation vecames el, ee) wa aewhere 2(°) = g is the local Maxell Aistritution of the previous problen. tetting ¢ = giz() rare lec g ve nave . , © +e BE BBS mine trons BE-#E] ‘This is identical to equation (2) of 13.6. The rest of this calculation proceeds as in that problem. 3.8 The heat flux in the e-@irection is given by a where ‘The integrsl over g is O since the integrend is an odd function of v_. Consequently Lew? sizbeW 3, yy 2g 4 == =) oy ey, env % Sieber] fer 2 bond Ye cen exploit the symmetry of the integrel by replacing v,° ty 7/3. Then the only angular Sy = Wav sin 9 a5 do which yields lnv"av when the integration over angles dependence occurs in ay is performed. Thus ve obtein 27] fs frente Pe [ent = frente? te [ante The integrals ere tabulated in appendix A.l. kefbe - =-2 a “73 7m Hence 7 Be The mean free path argument hes ehnvt-t ME, es = ‘ut/mm)/2, qaus the constent relaxation tine approxinmetion yields a since 4 + ¥r ana ¥ 163result greater than the mean free pata argument by # 1.96. 23.10 Prom problens 13.4 and 13.8 ve find 2, GAM yale 5 gta BEES where c= (3/2)u, the specific heat per molecule, The simple nean free path argument gives Experiment shows thet the ratio (5/q) (c/a) Lies between 1.3 and 2.5 (see discussion efter (22.4.13)) so thet the constant relaxation time epproximetion yields better egreenert with experiment then does the meen free path argument. fe temperature gradient, the equilibrium distrfbution of a Fermt-Direc ges (0) _ _ 2 mo 8) = Goss Bea _ In the given situetion, f is independent of time but vill depend on z because of the tenperature gradient 2/32 elong the z direction. ‘his teuperature gradient alone would ceuse the electrons to drift, but sinee no current cen flov, there is 2 redistribution so a to set up e field E(2) to counter the effect of the temperature gradient and reduce the meen drift velocity ¥, to zezo. ‘Thus the Boltaann equation becames Ve will assume that the tenperet: gradient is ou ext), 20) << gumere cl) represents « anell departure from local en me Week 2 Tt ts convenient to write this in terms of the dinenstonless paranster x = pe) = 8G mu) @)then frea (2) we find fee ur BEB e+oe6| ) 7 rensins to tint € cron te conaicion thet ¥, = 2 [ar ev, = 0 vere fis given by (¥)- The imtegrel over g is 0 since the integrand is od. Letting 7 = T, = const. for electrons near the Femi level, ve have 3, 72 de fe [een BBB a+e eq =o or BE [env ? «Breed favv,? Bo ) ‘The second integral cen be expressed in tems of n, the total mumber of electrons per unit venne. since 2 = Vee, Bek wl - kJ ee, vhere ve have integrated by perts. Since g-0 et z=, it follovs that a ee fee? B--bfeve--% ©) Proceeding to the evaluation of the first integral ia (5), we aote thet x and 86/Bx are functions 2 only of v® so that we can replace v,° by v°/3. The substitution @y = v dy sin 9 de ap yields ter Pav when mms [eer2 BBL” oo ve® Using x = (Z v°-u) this becomes integration over angles is perfomed. on 3 2 mp ax x(an)5/* 38 o Fron the proverties of the Femi distritution, ve lnoy thet d6/Sx = 0 except where e =u oF x~0. The integrand contributes appreciebly to the integral only ix this region so ve cen expend the factor x(xteu)°/? about x = 0 to approximate the integral. Also, the lover Lintt -Au may be replaced by = with negligible error. 2 sexteu) 9 m (pn)5/® (oe BE) ane, ot 2 = (en)sae (a)? om) 165Hence (7) becones 5/2 pe ae ai SB [axon ees a a Be | @ xe pe we (aR EH (%)® These integrals are the I, end I defined by equation (9.16.9). Tt is shom there that T, = 0 and Tp =7°/3- Combining the results of (5), (6), ena (8), ve obtein (aay? 3 tan crea yt f- ‘a og | #2 (9) Having found the distribution f, ve can nov calculate the heat flux @.. and (4) becomes asa Wm) = Fm (vx) where ?) @Bfevvy? st Te sntagral over g Ss zero since the integrand is 064. oo Be [fees 2 esi" ans] co Hence @, #3 ‘The calculation of these integrals is similar to the steps leading to (8). Agein v,” can be replaced ty v"/3 and the integration over angles performed to yield lm. The first integral in (20) becomes where we have expanded es before. The integral 4s I, + (5/28u)I, = 5n°/Sou. tence [eee se. -2e eat ye a) ee The second integral in (10) is [eee Be [ar F% 2 vp (2194)9/? BE oxf° (as Sey 2% Here we have neglected the squared term in the expansion since it is much less than 1. integral ts 1, + (5/2 6) Ty = he ‘Thus Combining +) ‘Thus 23.12 [er v PPS, an DP Sleyile 2 a Combining the results of the previous problen and (13-b.12), we tind /ogy, = 6.68 x 10 vate obm dee’ @ ‘+ Experimental values at 273° are (a2) results of (20), (22), and (22) and using 4 = (7/25) 320) we sma ral the aed Suact Formulation of Transport Theor es = vhere ve assume central forces. center of mass coordinates. Tas (eg) = 2 (x! 207 wieaext [= [ee oe 6 #/oqy X10" 6st | 62 | 6.09 | 67h | 6.85 | 6.88 | 8.30 | 6a watt ohm deg” CHRPDER 14 We first perfom the integration over angles ty changing tovecenes, since y= e+Hy end sey (og) = uu") ™ where y= a+, m doing the mass of the ious and m, the mass of the heavy molecules. since the meen values ¥, and ¥, are zero, it is clear thet (Gp,) = (Qp,) = 0. Hence we are left with (e2,) = uly," ¥,) 208 Jn 2a? (v8) (20,) @ (,' 18 given in terms of V_ end the scattering angles. Using the coordinate system illustrated in Fig. 14.8.1, ve see that ¥,' = Vieos(¥',z) = V cos (¥" since V' = V. Inspection of Fig. 14.8.1 yielas ¥ cos (¥"42) = o[sootu) cos 6"4sin 8'c0s 9! sat) | =, cor 9+ ¥ ein 9t cos 9! sis (¥z) ond uGr,'-¥,) = wV,(cos 6'-1)euv sin s'cos of sia (Wz) on Substituting into (2) ve cbtin, since f cos g'ag" = 0, pen nm ra J | w(v,'-v,)o(vse")sin ataa'ap'=emv, | (cos 6'-1)o(v,e")sin 9'ae" ovo vo For bard spheres, o ie constant and a onw,s [ (cos o'-1)sin 649" = -ln uo 6 where 0, 4s the total cross section. Zzuation (1) then simplifies to 7 rf By ai 2) suo, | [vy 2, Oe Se @) zh 2 le ae -Z voere Bye Ft © Pay 2 2, E (x 2er Fev, -0) ee age? PE Orne) or Here u is the mean 2 component of velocity of the ions. To avoid carrying repititious constants ve ast ° a= a ge ® 8f can be simplified by making the approxination that v, >> uy then 2 nee Pe 8 ey ee wy) Equation (3) becomes 2 2 2/2 pp ~(onPoayr,?) = p,) = ney, ( *5) [Per rae weg oe yy ©) We again express v and v, in relative coordinates 2(cea, 2,2) (com? 4c,2°) ‘Tas Fs ae? = (ete )e® eS a Se oF + a7,® = (orm sel as On completing the square this yields (cn, -a,) -oas| 2 ESEar 1] _ 23)? oe tae) (cr, )® (om) 1 (oa) Po St e > aa) where (6) K+ sy, (1) ey, Ve We wish to put the integral (5) in temas of ¥ and the variable K defined ty (6). Tt has been shoe (2.2.6) tant ay, ae = ale Or. my tems of ve nave say a0 oy s easy ° thet J (gy, bees fe 2 san aS Foe A lea dap ath The first tvo tems in the brackets give integrations over odd functions and hence do not con- ‘tribute to the integral. Changing to spherical coordinates gives 5/2 4 “— “inp Mag Se afro ea (oo Pe [ets She integrals are found in appendix A. and ve obtein 18(22,)e- 288 og amy ir [or ( (ore) 94] (je Be e.d) -$o, my gk EEE fee SE The mouentun balance equation is then 3 ne€ + (ap,) =0 which gives Since j = neu = 0,,€ , we have el 2 (2) We will assume the distribution function 2 = 2°) (140) a) where £9) wate) EH) exe [-232 4] @) Te 4s shown in problen 13.6 that the condition ¥, = 0 yields the relation 2-28 © (0) The 20! amann equation (1!.7.12) becomes vel) 2) 0) pz 3c), Because the ton ts and there ere no exterel f 125, ve ere left with gel) 5) (2) 35 (0) vey (BB EB) ze a BO OB) -Poq are l rear on using (2),(3), and (24.7.10). Tt reunins to determine the function ¢. The left side of (i) leads us to expect that @ good approximation will recult if ve choose i day, (her) novhere A and c are constants. © must satisfy the restrictions (14.7.14) to be @ good approximation. These become fee 20°) v, (aan) = 0 Pe) vy ae?) [oct Proc The first and third integrels ere zero beceuse the integrands are odd. Similarly only the v_ component of y in the second relation will give a non-zero integral. detemine a. Thet is, 3/2 ané oeav,a- BA) 6) ‘We sll use the procedure of section 1s.8 to evaluate the constent A. Multiplying (8) by 9 and integrating over ¥ yields B [by An Pa - Beye al Pf be Ayaat 2), ver, 0-2 ‘The integrel on the coe%9 ein oto f'n a ‘The integral of the second term in (7) vas evaluated previously. The third tem is eesily show to be 7n/Sém. Thus the integral becomes (8) 2 (e+ -22 Be 2 +5) = 5 oe Ye split the right side of (6) into an integration over the angle @' end over y and y,. We madefine oa fare ak, @ BA] ‘Then using (8), equation (6) becomes E2GR-FE-s () Jo evaluste J, ve express a[r_(1-9*]] in center of masa coordinates (vs have reintroduced anys). By (4.7.12), (Lew!?) + v1 (ary?) 7 (deen) = vy, (2-0) a ; EU, we have By )(-00%eet -@ E) v (ar) + (er, a(e, + By) oc 2en - EV )4(6, og? - ag af, Q-e)) = 2 0," 28" - ve-¥) 2) carrying out the product in (10) ve find on opm geo [aot [ "sim etastav etiattel tated tay ye (9, Jo ve a aly eal where the ccordinate systen is shown in Fig. 14.8.1, We notice that, except for constants, the ret integral is (18.8.7). the second integral involves only 2 change of the inex x to y but is othervise the same as the first. Consequently, vy (1.8.20), these tems yield doe wiley, +6%) a Fa 9, Wiley + Vs) a2) where 6, is given ty (1h.8.21). 4 #8 etven Wy (8.8.21) Tt rentins to ind er an _ -of aot [ssn otaote ve (v,'2-1,2) (2) ovo By (1.8.18) cos7'421,V sin steos oteoeg' (Po2)+ veta%ataos%@t (f.2)?7,2en and i ao'(v, 129.2) = an v2 (coe%et-a) + mv ain®or(P-2)? (3) To eliminate £, ve write + GD? +@9° or 9? - 148-9? and (13) becomes = 1,2(2 cos®ot-sin®ot-2)nteineat = Gary? + a7) sin®ar ‘The lest tem in J is then (G4) end (12) end (14) give Vv y? TB oar (6,87, + iV, t6,7,° = 5) 3 2 wey (,(eW = We now eveluste ‘The evaluation of this integrel is streightforvard though teat In the center of mass systen ay @y, = Be yy (2.2.6) eoutetity By 22,8 a apn 9 Facto Be AA,2E (6,Piehy 5, HH e802) we PE BAA? 4S 0 Fhe $0 8,27] an) x sxsin eC, (°Y nan ea stmpta fon (a8) 2h the stag sre the Wanted nee entourtered im this theory. We quete the result of integrating over s. Tn (18) the terms appear in the a3order that they eppear in (17) [el er ee] » pee f [ndene- = yy 2 Sy 23.5 +B +S Ere] ‘he integral becomes on subsfituting a = pm/5, a we “gr 28-L +B] a 2 e+ 2 [Pao ee af (=. TB veeosts - 2 2) stn 6.20 a, ot “BCP el Vee a eae se EVE vaca 8 - 2 (8 myf_2) es\ 7 Be=(Z) »@) -- Mer a % we)> where @, is given ty (14.8.26). substitution inte (18) yields 2 2 = 2-8 Te aay s7e “1 and ty (9) 2 am W2 “ena Qo & 32 na z= 20) bs ey” Y, “oe To find the coefficient of thermal conductivity, we eveluste the heat shu =a, m)) = Be fbx 2) (rseyy sta Be [abe 2 ve? sha [Fx Ba-B 8 ~, [5.8 2 e [ee (3 nkHence 13 (2) Hence the Boltemann equation gives 2 value fer w/q greater then the nea free path caleulation vy 8 factor of 245 ©) Exo eserad}| ore | a | xe Calowlsted 2780 | -237 Tiperinental 7785 | -250 an], ve nave [ereur-[ea Performing the integration over angles yields we 2)” Poe Pans OM ome ] and by appendix 4.4 this is5/e we” =] Comparison vith (9.20.10) shove that except for a constant, this {s -S/k where S is the entropy per unit volume of an ide AS (e) Ditgerentiating the function x yields 2 f 2 ¥ Gn a) a) ‘De/dt can be found from the Zoltmann equation. We shall assume thet there are no external forces so that the distribution function should depend only on the velocity and tine. Then the Boltmann equation becanes = -[fen aa! Vo (2y'f" ~ 2,2) @ Substitution of (2) into (1) yielés SH LPe Ll dy dy, aff fees This integral is invarient under the interchange of ¥ and y, because @ is invariant under this aa'vo(2,"2"-£,2) (In £42) @) Amterchange. When the resulting expression 4s added to (3) ve have gwiifr 3, 1 tet g-2/ f fee @uy aa! Volt, '2-2,2)(1n 2,242) @) Sintlarly, this integral is taverient 4f the initial and final velocities are interchanged because ¢ 4s inverient under the inverse collision, i.e., o(yy¥ 3x, 'v") = a(x; te" >y. 2) £. aa! vie (2,2 tf) (anf, tth42) m Bah BePu! = By dy But Ve" and by (24.2.8), ea Eff fer By, aa! vo (2,f-#,"#")(an £, "2" + 2) 6) Adding (4) and (5) gives a & - fff By, a! vo (eye-r2) (00 sy tta 2) (6) 6() tetting r,!2' = y and f)f = x, we see that since (In y - In x)(y-#) > 0, the integrand im (6) 4s greeter than zero unless 2,12" = Hence au/at <0 where the equelity holds vhen the integrand identically vanishes. 1b6 The equiltbrism condition és ween aay, + ym, + 3a, +o? @) Tais can be written ix the fom Inf = -at(yey,)* + an cr where the constants A', C' and the constant vector v contain the constants in (1). “a'r, Hence fe=cre ~ yy is cleerly the meen velocity viich can be set equal to zero without lose of generality. To a ey ae he a 2% Sat [eekete we [Poe Ea? ohh f eye of “var o & sr ae @y £ which Letting @ = (3/2)xE, ve find A' = m/2kT. The constant C' is easily found fromm = gives C' = n(GB) showing thet £ is the Masvell distritution. 5a Let the friction force depend on 8, vy ant 9 in the manner peat ngth, T = time, end M = mass becomes teen the dineasionai equetion vhere L sar? =) gate) = Solution of this system of equations yieléx xeyazel, and fe qey Thus xty-2 = 1, col, yee = aT15.2 Since J, = R here H, 1s Avogadro's number and Ris the gas constant, we have from (15.6.11), my nal, or HL: 3ma(x") Substituting R = 8.32 x 10" ergs note” x"? ena the given values yields 1, = 7.0 x 10% molecules mole, 83 (2) Tae energy of en ion in the Mela at point z is - els. se€ (24az) Bence alzeis) a = lteter @) (0) The flux is given by an | Dfn(ztaz) - n(z)) oz cry thea tron (2) 5, = -ap pee (©) d,cavemé (@) cms 15.4 ew = ov + BH) @ Substitution of v(t) = u(t)e7* into (2) gives Bebe rs) Hence aul) +2 [er ter(eryact Jo Since u(o) = v(e) 4 follows that * verge Tt a Bet [Marne 5 By dividing the tine interval t inte N successive intervals such that t = Nr, we can replace the Amtegral in (2) of 15.4 ty the sum of integrals over the intervals of length 7 between +, and ustpg? Then t! = ker $5 where Kk is on integer and at" = as. peace vge Te TERE PT slo or eye) a mF Jo oS yore) 2 f ©? 3" (erts) as k=O ado In the integral, s <1 or 7 < e!= 1 since 7 is chosen so thet T> 1 and X(s) +0 for s >> 1%, # can be neglected compared ‘to T and the Limits replaced ty t=. BLBy the results of 15.8, @ = 2kt yt/m, Tt follows that yaaa [7 xO) © 1 (a) We integrate the Langevin equation z He -v e B P(t) [OO arn free ok [renee Since 7 is enell, ve can replace v ty the initial velocity v, in the first integrel on the right over the interval 1. and obtain apt oven 2 orege + BL ee ees soiree @) and BH -yvyr since T= 0. (eon)? = (7 vgn? = ar vr BE =O = Betyt/a @) where we heve used the result of 15.8 and kept only terms to first order in T. (0) From (1), keeping tems to lovest onder in 7 and noting that odd mouants of G are 0, ve find GP = arvr © Gy Zeng Since G = 1 2 should be Proportional to 1°. ene (4v)° end (Av)* are proportional to 1°. (2) Fron (2), @r)? = - er Paya 35.22 From eq. (2) of 154 (w(o)v(t)) = (v7(0)) e°7* Gia fae sow) rt . OPEN) 7 + SE ovloy) Pe) ae" But since #'(t*) is rendom, the second term on the right is 0. By equipartition 12(F(0)) = Aa me (r(o)e(e)) = Ee? ‘end einee (v(o)v(-t)} = (v(o)v(t)), we have for all t (o(o)ete)) = el*l 15.13 Squaring equation (2) of 15.4 yielas Oe) = eke wo, Per eterna EE Pee Morcenecerners wove and H(t) = + FP anaf ere oneyer(es) avn @ wo vo since (F'(t!)) = 0. The corzelation function in the integral is only « Suction of the tine @ifference s = ¢"'~t', Melting this change of variable yields [ar Poon) Ger(enderters) ate =f aeef ae 07(2 48) (2) where K(s) = (Ft(t*)p (tHe) = (F\(o)F"(c))- The evaluetion of this integral is similar to that of problem 15.10, Thus interchanging the order of integration and reading the Limite off the Giegram of problen 15-10 with t substituted for r yields Paes ay oP 8) gr5) 2 Peas [PatreZ2t)g¢) « P “asl” cele Oo} Le Je k(s) f “as “Sera ° 2rt_278) pt ag er (t-s) S, as o7x(s) eS ds o¥x(s) a) Since K(s) 4s only appreciable when ys << 1, ve can put e”© = 1 in the above and find fas lo) ED 5 Pau wpe) ED, CDP ae te)» ED ae me) a vot = Substitution in (1) ylelés -eyt) pe ety er £ as x(s) ast se, (=) = kt/e ty equipertition and Ye) -£- oe - as K(s) Fence regis f as x(s) as in (15.8.8) 13p.k (a) We via denote the Fourier coefficient of F'(+) vy F'(o) and that of v (t) wv (0). thet ‘ss Pr(t) - [ise F'(o) & ana v(t) = [ce v(u) au @) Substitution in the Langevin equation gives (a) + 2 F1(0) or (0) =) Pro) Denoting the spectral densities of FY end v ty J,,(o) and J,(o), ve have from (25.35.11) Syr(o) = ¥ ler(@)|? = F falta) vf)? = 2° Pas?) F lx(o) |? or Tpsle) = 2°(740") 3,,(0) (2) (0) ay 5.20.9) H{2) = (v(o)v(a)) = Eel @) mus Sy(e) = Bf le) 8 as “iE [Coco oes [core ayo) = FS [rar tote] -s[25] ) (c) Substitution of (1) into (2) gives Sp(s) = Emer 7 oe I.) = 2750 2 This result depends on o < (r*)"1, where 1 is the conrelation tine of the fluctuation force, since in deriving (3), one used a tine scale such thet 1 >> 1°. Consequently, ar 1 >> un". 22h